WorldWideScience

Sample records for physisorption

  1. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  2. CALCULATION OF PHYSISORPTION ENERGIES OF

    African Journals Online (AJOL)

    but it may naturally arise through semi-quantum mechanical treatment of the admolecule - surface electrostatic interaction. For the physisorption of molecules with permanent dipole moment it is reasonable, in our opinion, to represent the admolecule by a classical dipole so as to avoid overlap of the admolecule and solid ...

  3. Modeling the physisorption of graphene on metals

    Science.gov (United States)

    Tao, Jianmin; Tang, Hong; Patra, Abhirup; Bhattarai, Puskar; Perdew, John P.

    2018-04-01

    Many processes of technological and fundamental importance occur on surfaces. Adsorption is one of these phenomena that has received the most attention. However, it presents a great challenge to conventional density functional theory. Starting with the Lifshitz-Zaremba-Kohn second-order perturbation theory, here we develop a long-range van der Waals (vdW) correction for physisorption of graphene on metals. The model importantly includes quadrupole-surface interaction and screening effects. The results show that, when the vdW correction is combined with the Perdew-Burke-Enzerhof functional, it yields adsorption energies in good agreement with the random-phase approximation, significantly improving upon other vdW methods. We also find that, compared with the leading-order interaction, the higher-order quadrupole-surface correction accounts for about 25 % of the total vdW correction, suggesting the importance of the higher-order term.

  4. Physisorption of SDS in a Hydrocarbon Nanoporous Polymer

    DEFF Research Database (Denmark)

    Li, Li; Wang, Yanwei; Vigild, Martin Etchells

    2010-01-01

    Surface modification of nanoporous 1,2-polybutadiene of pore diameter similar to 15 nm was accomplished by physisorption of sodium dodecyl sulfate (SDS) in water. Loading of the aqueous solution and the accompanying physisorption of SDS into the hydrophobic nanoporous films were investigated in a...

  5. Hydrogen storage by physisorption on porous materials

    Energy Technology Data Exchange (ETDEWEB)

    Panella, B.

    2006-09-13

    A great challenge for commercializing hydrogen powered vehicles is on-board hydrogen storage using economic and secure systems. A possible solution is hydrogen storage in light-weight solid materials. Here three principle storage mechanisms can be distinguished: i) absorption of hydrogen in metals ii) formation of compounds with ionic character, like complex hydrides and iii) physisorption (or physical adsorption) of hydrogen molecules on porous materials. Physical adsorption exhibits several advantages over chemical hydrogen storage as for example the complete reversibility and the fast kinetics. Two classes of porous materials were investigated for physical hydrogen storage, i.e. different carbon nanostructures and crystalline metal-organic frameworks possessing extremely high specific surface area. Hydrogen adsorption isotherms were measured using a Sieverts' apparatus both at room temperature and at 77 K at pressures up to the saturation regime. Additionally, the adsorption sites of hydrogen in these porous materials were identified using thermal desorption spectroscopy extended to very low temperatures (down to 20 K). Furthermore, the adsorbed hydrogen phase was studied in various materials using Raman spectroscopy at different pressures and temperatures. The results show that the maximum hydrogen storage capacity of porous materials correlates linearly with the specific surface area and is independent of structure and composition. In addition the pore structure of the adsorbent plays an important role for hydrogen storage since the adsorption sites for H2 could be assigned to pores possessing different dimensions. Accordingly it was shown that small pores are necessary to reach high storage capacities already at low pressures. This new understanding may help to tailor and optimize new porous materials for hydrogen storage. (orig.)

  6. Hydrogen storage by physisorption on porous materials

    Energy Technology Data Exchange (ETDEWEB)

    Panella, B

    2006-09-13

    A great challenge for commercializing hydrogen powered vehicles is on-board hydrogen storage using economic and secure systems. A possible solution is hydrogen storage in light-weight solid materials. Here three principle storage mechanisms can be distinguished: i) absorption of hydrogen in metals ii) formation of compounds with ionic character, like complex hydrides and iii) physisorption (or physical adsorption) of hydrogen molecules on porous materials. Physical adsorption exhibits several advantages over chemical hydrogen storage as for example the complete reversibility and the fast kinetics. Two classes of porous materials were investigated for physical hydrogen storage, i.e. different carbon nanostructures and crystalline metal-organic frameworks possessing extremely high specific surface area. Hydrogen adsorption isotherms were measured using a Sieverts' apparatus both at room temperature and at 77 K at pressures up to the saturation regime. Additionally, the adsorption sites of hydrogen in these porous materials were identified using thermal desorption spectroscopy extended to very low temperatures (down to 20 K). Furthermore, the adsorbed hydrogen phase was studied in various materials using Raman spectroscopy at different pressures and temperatures. The results show that the maximum hydrogen storage capacity of porous materials correlates linearly with the specific surface area and is independent of structure and composition. In addition the pore structure of the adsorbent plays an important role for hydrogen storage since the adsorption sites for H2 could be assigned to pores possessing different dimensions. Accordingly it was shown that small pores are necessary to reach high storage capacities already at low pressures. This new understanding may help to tailor and optimize new porous materials for hydrogen storage. (orig.)

  7. Physisorption of molecular hydrogen on carbon nanotube with vacant defects

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Gang; Shen, Huaze; Wang, Enge; Xu, Limei, E-mail: limei.xu@pku.edu.cn [International Center for Quantum Materials and School of Physics, Peking University, Beijing 100871 (China); Collaborative Innovation Center of Quantum Matter, Beijing (China); Tangpanitanon, Jirawat [University of Cambridge, Cambridge, Cambridgeshire CB2 1TP (United Kingdom); Wen, Bo [International Center for Quantum Materials and School of Physics, Peking University, Beijing 100871 (China); Beijing Computational Science Research Center, Heqing Street, Haidian District, Beijing 100084 (China); Xue, Jianming [State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing 100871 (China); Center for Applied Physics and Technology, Peking University, Beijing 100871 (China)

    2014-05-28

    Physisorption of molecular hydrogen on single-walled carbon nanotubes (SWCNTs) is important for its engineering applications and hydrogen energy storage. Using molecular dynamics simulation, we study the physisorption of molecular hydrogen on a SWCNT with a vacant defect, focusing on the effect of the vacant defect size and external parameters such as temperature and pressure. We find that hydrogen can be physisorbed inside a SWCNT through a vacant defect when the defect size is above a threshold. By controlling the size of the defects, we are able to extract hydrogen molecules from a gas mixture and store them inside the SWCNT. We also find that external parameters, such as low temperature and high pressure, enhance the physisorption of hydrogen molecules inside the SWCNT. In addition, the storage efficiency can be improved by introducing more defects, i.e., reducing the number of carbon atoms on the SWCNT.

  8. Physisorption of molecular hydrogen on carbon nanotube with vacant defects

    Science.gov (United States)

    Sun, Gang; Tangpanitanon, Jirawat; Shen, Huaze; Wen, Bo; Xue, Jianming; Wang, Enge; Xu, Limei

    2014-05-01

    Physisorption of molecular hydrogen on single-walled carbon nanotubes (SWCNTs) is important for its engineering applications and hydrogen energy storage. Using molecular dynamics simulation, we study the physisorption of molecular hydrogen on a SWCNT with a vacant defect, focusing on the effect of the vacant defect size and external parameters such as temperature and pressure. We find that hydrogen can be physisorbed inside a SWCNT through a vacant defect when the defect size is above a threshold. By controlling the size of the defects, we are able to extract hydrogen molecules from a gas mixture and store them inside the SWCNT. We also find that external parameters, such as low temperature and high pressure, enhance the physisorption of hydrogen molecules inside the SWCNT. In addition, the storage efficiency can be improved by introducing more defects, i.e., reducing the number of carbon atoms on the SWCNT.

  9. Physisorption of molecular hydrogen on carbon nanotube with vacant defects

    International Nuclear Information System (INIS)

    Sun, Gang; Shen, Huaze; Wang, Enge; Xu, Limei; Tangpanitanon, Jirawat; Wen, Bo; Xue, Jianming

    2014-01-01

    Physisorption of molecular hydrogen on single-walled carbon nanotubes (SWCNTs) is important for its engineering applications and hydrogen energy storage. Using molecular dynamics simulation, we study the physisorption of molecular hydrogen on a SWCNT with a vacant defect, focusing on the effect of the vacant defect size and external parameters such as temperature and pressure. We find that hydrogen can be physisorbed inside a SWCNT through a vacant defect when the defect size is above a threshold. By controlling the size of the defects, we are able to extract hydrogen molecules from a gas mixture and store them inside the SWCNT. We also find that external parameters, such as low temperature and high pressure, enhance the physisorption of hydrogen molecules inside the SWCNT. In addition, the storage efficiency can be improved by introducing more defects, i.e., reducing the number of carbon atoms on the SWCNT

  10. Recognizing Physisorption and Chemisorption in Carbon Nanotubes Gas Sensors by Double Exponential Fitting of the Response.

    Science.gov (United States)

    Calvi, Andrea; Ferrari, Alberto; Sbuelz, Luca; Goldoni, Andrea; Modesti, Silvio

    2016-05-19

    Multi-walled carbon nanotubes (CNTs) have been grown in situ on a SiO 2 substrate and used as gas sensors. For this purpose, the voltage response of the CNTs as a function of time has been used to detect H 2 and CO 2 at various concentrations by supplying a constant current to the system. The analysis of both adsorptions and desorptions curves has revealed two different exponential behaviours for each curve. The study of the characteristic times, obtained from the fitting of the data, has allowed us to identify separately chemisorption and physisorption processes on the CNTs.

  11. Chemi- vs physisorption in the radical functionalization of single-walled carbon nanotubes under microwaves

    Directory of Open Access Journals (Sweden)

    Victor Mamane

    2014-04-01

    Full Text Available The effect of microwaves on the functionalization of single-walled carbon nanotubes (SWNTs by the diazonium method was studied. The usage of a new approach led to the identification of the strength of the interaction (physical or chemical between the functional groups and the carbon nanotube surface. Moreover, the nature (chemical formula of the adsorbed/grafted functional groups was determined. According to thermogravimetric analysis coupled with mass spectrometry and Raman spectroscopy, the optimal functionalization level was reached after 5 min of reaction. Prolonged reaction times can lead to undesired reactions such as defunctionalization, solvent addition and polymerization of the grafted functions. The strength (chemi- vs physisorption of the bonds between the grafted functional groups and the SWNTs is discussed showing the occurrence of physical adsorption as a consequence of defunctionalization after 15 min of reaction under microwaves. Several chemical mechanisms of grafting could be identified, and it was possible to distinguish conditions leading to the desired chemical grafting from those leading to undesired reactions such as physisorption and polymerization.

  12. Role of physisorption states in molecular scattering: a semilocal density-functional theory study on O2/Ag(111).

    Science.gov (United States)

    Goikoetxea, I; Meyer, J; Juaristi, J I; Alducin, M; Reuter, K

    2014-04-18

    We simulate the scattering of O2 from Ag(111) with classical dynamics simulations performed on a six-dimensional potential energy surface calculated within semilocal density-functional theory. The enigmatic experimental trends that originally required the conjecture of two types of repulsive walls, arising from a physisorption and chemisorption part of the interaction potential, are fully reproduced. Given the inadequate description of the physisorption properties in semilocal density-functional theory, our work casts severe doubts on the prevalent notion to use molecular scattering data as indirect evidence for the existence of such states.

  13. A molecular dynamics study of Lennard-Jones physisorption on W(100)

    International Nuclear Information System (INIS)

    Broughton, J.Q.

    1980-01-01

    The physisorption of Xe on W(100) was modeled by Lennard-Jones pair-wise interaction potentials and the dynamics of coverages ranging from one to four adlayers obtained by molecular dynamics simulation. At 115 K, the first two layers were well-ordered and each adsorbed with c(2 x 2) symmetry. Further adsorption produced a surface similar to that of a distorted Xe(100) face. In accord with the work of Broughton and Woodcock, the top layers of the three- and four-adlayer coverages were rough and had liquid-like diffusion coefficients. The potential energies of all layers other than the first were similar, thus corroborating one of the postulates of BET theory. Generally, the effect of adsorbing a layer was to reduce the entropy of all those beneath. (orig.)

  14. DFT Study of PH3 Physisorption and Chemisorptions on Boron Nitride Nanotubes

    Science.gov (United States)

    Rakhshi, Mahdi; Mohsennia, Mohsen; Rasa, Hossein

    2018-03-01

    The adsorption of PH3 molecules on the NiB,N-doped(4,4) and (5,5) BNNTS surfaces has been investigated using density functional theory (DFT). The adsorption energies, geometric and electronic structures of the adsorbed systems were studied to judge the possible application of NiB,N-doped BNNTS in PH3 monitoring systems. Our calculated results showed that NiB,N-doped BNNTS had much higher adsorption energy and shorter binding distances than pure BNNTS owning to chemisorptions of the PH3 molecule. The obtained density of states (DOS) and frontier orbitals demonstrated that the orbital hybridization was obvious between the PH3 molecule and NiB,N-doped BNNTS. However, due to weak physisorption according to the total electron density maps, there was no evidence for hybridization between PH3 molecule and pure BNNTS. It was shown that after doping of Ni atom, the primary symmetry of BNNTS decreased which enhanced the chemical activity of BNNTS towards PH3 molecules. According to the obtained results, we highlight the high potential application of NiB,N-doped BNNTS in the design and fabrication of PH3 sensing devices.

  15. Quasi physisorptive two dimensional tungsten oxide nanosheets with extraordinary sensitivity and selectivity to NO2.

    Science.gov (United States)

    Khan, Hareem; Zavabeti, Ali; Wang, Yichao; Harrison, Christopher J; Carey, Benjamin J; Mohiuddin, Md; Chrimes, Adam F; De Castro, Isabela Alves; Zhang, Bao Yue; Sabri, Ylias M; Bhargava, Suresh K; Ou, Jian Zhen; Daeneke, Torben; Russo, Salvy P; Li, Yongxiang; Kalantar-Zadeh, Kourosh

    2017-12-14

    Attributing to their distinct thickness and surface dependent physicochemical properties, two dimensional (2D) nanostructures have become an area of increasing interest for interfacial interactions. Effectively, properties such as high surface-to-volume ratio, modulated surface activities and increased control of oxygen vacancies make these types of materials particularly suitable for gas-sensing applications. This work reports a facile wet-chemical synthesis of 2D tungsten oxide nanosheets by sonication of tungsten particles in an acidic environment and thermal annealing thereafter. The resultant product of large nanosheets with intrinsic substoichiometric properties is shown to be highly sensitive and selective to nitrogen dioxide (NO 2 ) gas, which is a major pollutant. The strong synergy between polar NO 2 molecules and tungsten oxide surface and also abundance of active surface sites on the nanosheets for molecule interactions contribute to the exceptionally sensitive and selective response. An extraordinary response factor of ∼30 is demonstrated to ultralow 40 parts per billion (ppb) NO 2 at a relatively low operating temperature of 150 °C, within the physisorption temperature band for tungsten oxide. Selectivity to NO 2 is demonstrated and the theory behind it is discussed. The structural, morphological and compositional characteristics of the synthesised and annealed materials are extensively characterised and electronic band structures are proposed. The demonstrated 2D tungsten oxide based sensing device holds the greatest promise for producing future commercial low-cost, sensitive and selective NO 2 gas sensors.

  16. Physisorption of an electron in deep surface potentials off a dielectric surface

    International Nuclear Information System (INIS)

    Heinisch, R. L.; Bronold, F. X.; Fehske, H.

    2011-01-01

    We study phonon-mediated adsorption and desorption of an electron at dielectric surfaces with deep polarization-induced surface potentials where multiphonon transitions are responsible for electron energy relaxation. Focusing on multiphonon processes due to the nonlinearity of the coupling between the external electron and the acoustic bulk phonon triggering the transitions between surface states, we calculate electron desorption times for graphite, MgO, CaO, Al 2 O 3 , and SiO 2 and electron sticking coefficients for Al 2 O 3 , CaO, and SiO 2 . To reveal the kinetic stages of electron physisorption, we moreover study the time evolution of the image-state occupancy and the energy-resolved desorption flux. Depending on the potential depth and the surface temperature, we identify two generic scenarios: (i) adsorption via trapping in shallow image states followed by relaxation to the lowest image state and desorption from that state via a cascade through the second strongly bound image state in not too deep potentials, and (ii) adsorption via trapping in shallow image states but followed by a relaxation bottleneck retarding the transition to the lowest image state and desorption from that state via a one-step process to the continuum in deep potentials.

  17. Physisorption of helium on a TiO{sub 2}(110) surface: Periodic and finite cluster approaches

    Energy Technology Data Exchange (ETDEWEB)

    Lara-Castells, Maria Pilar de, E-mail: Pilar.deLara.Castells@csic.es [Instituto de Fisica Fundamental (C.S.I.C.), Serrano 123, E-28006 Madrid (Spain); Aguirre, Nestor F. [Instituto de Fisica Fundamental (C.S.I.C.), Serrano 123, E-28006 Madrid (Spain); Mitrushchenkov, Alexander O. [Universite Paris-Est, Laboratoire Modelisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallee (France)

    2012-05-03

    Graphical abstract: The physisorption of helium on the TiO{sub 2}(110) surface is explored by using finite cluster and periodic approaches (see left panel). Once the basis set is specifically tailored to minimize the BSSE (rigth panel), DFT periodic calculations using the PBE functional (left panel) yield interaction potentials in good agreement with those obtained using post-HF methods as the LMP2 treatment (see left panel). Highlights: Black-Right-Pointing-Pointer He/TiO{sub 2}(110) is a simplest example of physisorption on transition-metal oxide surfaces. Black-Right-Pointing-Pointer Optimized basis sets that minimize the BSSE are better suited for physisorption problems. Black-Right-Pointing-Pointer FCI benchmarks on the He{sub 2} bound-state assess the Counterpoise scheme reliability. Black-Right-Pointing-Pointer Periodic DFT-PBE and post-HF results on H-saturated clusters compare satisfactorily. Black-Right-Pointing-Pointer Correlation energies by using embedded and H-saturated clusters agree well. - Abstract: As a proto-typical case of physisorption on an extended transition-metal oxide surface, the interaction of a helium atom with a TiO{sub 2}(110) - (1 Multiplication-Sign 1) surface is studied here by using finite cluster and periodic approaches and both wave-function-based (post-Hartree-Fock) quantum chemistry methods and density functional theory. Both classical and advanced finite cluster approaches, based on localized Wannier orbitals combined with one-particle embedding potentials, are applied to provide (reference) coupled-cluster and second-order Moeller-Plesset interaction energies. It is shown that, once the basis set is specifically tailored to minimize the basis set superposition error, periodic calculations using the Perdew-Burke-Ernzerhof functional yield short and medium-range interaction potentials in very reasonable agreement with those obtained using the correlated wave-function-based methods, while small long-range dispersion corrections

  18. Evaluation of a density functional with account of van der Waals forces using experimental data of H2 physisorption on Cu(111)

    DEFF Research Database (Denmark)

    Lee, Kyuho; Kelkkanen, Kari André; Berland, Kristian

    2011-01-01

    Detailed experimental data for physisorption potential-energy curves of H2 on low-indexed faces of Cu challenge theory. Recently, density-functional theory has been developed to also account for nonlocal correlation effects, including van der Waals forces. We show that one functional, denoted vd...

  19. Molecular dynamics investigation of the physisorption and interfacial characteristics of NBR chains on carbon nanotubes with different characteristics

    Directory of Open Access Journals (Sweden)

    Kun Li

    2017-07-01

    Full Text Available The present study investigates the physisorption and interfacial interactions between multiwalled carbon nanotubes (MWNTs with different characteristics, including different numbers of walls and different functional groups, and acrylonitrile-butadiene rubber (NBR polymer chains based on molecular dynamics simulations performed using modeled MWNT/NBR compound systems. The effects of the initial orientation of NBR chains and their relative distances to nanotubes, number of nanotube layers, and the surface functional groups of nanotubes on nanotube/polymer interactions are examined. Analysis is conducted according to the final configuration obtained in conjunction with the binding energy (Eb, radius of gyration (Rg and end-to-end distance (h. The results show that the final conformations of NBR chains adsorbed on MWNT surfaces is associated with the initial relative angle of the NBR chains and their distance from the nanotubes. For non-functionalized MWNTs, Eb is almost directly proportional to Rg under equivalent parameters. Moreover, it is observed that functional groups hinder the wrapping of NBR chains on the MWNT surfaces. This indicates that functional groups do not always benefit the macro-mechanical properties of the composites. Moreover, the type of the major interaction force has been dramatically changed into electrostatic force from vdW force because of functionalization.

  20. Molecular dynamics investigation of the physisorption and interfacial characteristics of NBR chains on carbon nanotubes with different characteristics

    Science.gov (United States)

    Li, Kun; Gu, Boqin

    2017-07-01

    The present study investigates the physisorption and interfacial interactions between multiwalled carbon nanotubes (MWNTs) with different characteristics, including different numbers of walls and different functional groups, and acrylonitrile-butadiene rubber (NBR) polymer chains based on molecular dynamics simulations performed using modeled MWNT/NBR compound systems. The effects of the initial orientation of NBR chains and their relative distances to nanotubes, number of nanotube layers, and the surface functional groups of nanotubes on nanotube/polymer interactions are examined. Analysis is conducted according to the final configuration obtained in conjunction with the binding energy (Eb), radius of gyration (Rg) and end-to-end distance (h). The results show that the final conformations of NBR chains adsorbed on MWNT surfaces is associated with the initial relative angle of the NBR chains and their distance from the nanotubes. For non-functionalized MWNTs, Eb is almost directly proportional to Rg under equivalent parameters. Moreover, it is observed that functional groups hinder the wrapping of NBR chains on the MWNT surfaces. This indicates that functional groups do not always benefit the macro-mechanical properties of the composites. Moreover, the type of the major interaction force has been dramatically changed into electrostatic force from vdW force because of functionalization.

  1. Neutron scattering and physisorption

    International Nuclear Information System (INIS)

    Marlow, I.; Thomas, R.K.; Trewern, T.D.

    1977-01-01

    Neutron scattering experiments on methane and ammonia adsorbed on a graphitized carbon black are described. Diffraction from adsorbed deuterated methane shows that, at a coverage of 0.7, it forms an epitaxial layer with a √3x√3 structure. Between 50 and 60 K it undergoes a phase transition from two-dimensional solid to liquid (bulk melting point=89.7 K). Similar results are obtained for deuterated methane on a sample of graphon intercalated with potassium. From the effect of adsorbed methane on the intensities of 001 peaks of both substrates the carbon atom of the methane is estimated to be 3.3+-0.2 A from the surface. Ammonia-d 3 on graphon behaves quite differently from methane. It follows a type III isotherm and at low temperatures desorbs from the surface to form bulk ammonia. This has anomalous melting properties which are shown to be related to adsorption isobars for the system. The detailed interpretation of the results emphasizes the close link between adsorption and heterogeneous nucleation. Quasielastic experiments on the ammonia-graphon system show that the adsorbed ammonia is undergoing translational diffusion on the surface which is much faster than in the bulk. This is attributed to the breaking up of the hydrogen bonded network normally present in t

  2. Use of X-ray absorption near edge structure (XANES) to identify physisorption and chemisorption of phosphate onto ferrihydrite-modified diatomite.

    Science.gov (United States)

    Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

    2012-02-15

    This paper presents a novel technique integrating bulk-sensitive and surface-sensitive XANES methods to distinguish between physisorption and chemisorption for phosphate adsorption onto ferrihydrite-modified diatomite (FHMD). XANES P K-edge, L-edge, and Fe M-edge spectra were obtained for reference samples (K(2)HPO(4) and FePO(4)·2H(2)O) and test samples (phosphate adsorbed onto FHMD (FHMD-Ps) and Si-containing ferrihydrite (FHYD-Ps)). A resolvable pre-edge peak in the P K-edge spectra of FHMD-Ps and FHYD-Ps provided direct evidence for the formation of P-O-Fe(III) coordination and the occurrence of chemisorption. The resemblance between the P L-edge spectra of K(2)HPO(4) and FHMD-Ps and the marked difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O indicated the intact existence of the adsorbate and the adsorbent. The similarity between Fe M-edge spectra of FHMD and FHMD-Ps and the difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O confirmed the findings from P L-edge analyses. Therefore, chemisorption and physisorption coexisted during phosphate adsorption onto FHMD. Phosphate chemisorption occurred in the deeper zone of FHMD (from 50 nm to 5 μm); whereas physisorption occurred in the zone of FHMD shallower than 50 nm since the probing depth of XANES P K-edge method is 5 μm and that of P L-edge and Fe M-edge methods is 50 nm. Copyright © 2011 Elsevier Inc. All rights reserved.

  3. In situ emulsification microextraction using a dicationic ionic liquid followed by magnetic assisted physisorption for determination of lead prior to micro-sampling flame atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Shokri, Masood; Beiraghi, Asadollah; Seidi, Shahram

    2015-01-01

    For the first time, a simple and efficient in situ emulsification microextraction method using a dicationic ionic liquid followed by magnetic assisted physisorption was presented to determine trace amounts of lead. In this method, 400 μL of 1.0 mol L −1 lithium bis (trifluoromethylsulfonyl) imide aqueous solution, Li[NTf 2 ], was added into the sample solution containing 100 μL of 1.0 mol L −1 1,3-(propyl-1,3-diyl) bis (3-methylimidazolium) chloride, [pbmim]Cl 2 , to form a water immiscible ionic liquid, [pbmim][NTf 2 ] 2 . This new in situ formed dicationic ionic liquid was applied as the acceptor phase to extract the lead-ammonium pyrrolidinedithiocarbamate (Pb-APDC) complexes from the sample solution. Subsequently, 30 mg of Fe 3 O 4 magnetic nanoparticles (MNPs) were added into the sample solution to collect the fine droplets of [pbmim][NTf 2 ] 2 , physisorptively. Finally, MNPs were eluted by acetonitrile, separated by an external magnetic field and the obtained eluent was subjected to micro-sampling flame atomic absorption spectrometry (FAAS) for further analysis. Comparing with other microextraction methods, no special devices and centrifugation step are required. Parameters influencing the extraction efficiency such as extraction time, pH, concentration of chelating agent, amount of MNPs and coexisting interferences were studied. Under the optimized conditions, this method showed high extraction recovery of 93% with low LOD of 0.7 μg L −1 . Good linearity was obtained in the range of 2.5–150 μg L −1 with determination coefficient (r 2 ) of 0.9921. Relative standard deviation (RSD%) for seven repeated measurements at the concentration of 10 μg L −1 was 4.1%. Finally, this method was successfully applied for determination of lead in some water and plant samples. - Highlights: • A dicationic ionic liquid was used as the extraction solvent, for the first time. • A simple and efficient in situ emulsification microextraction

  4. Design and Development for Capacitive Humidity Sensor Applications of Lead-Free Ca,Mg,Fe,Ti-Oxides-Based Electro-Ceramics with Improved Sensing Properties via Physisorption

    Science.gov (United States)

    Tripathy, Ashis; Pramanik, Sumit; Manna, Ayan; Bhuyan, Satyanarayan; Azrin Shah, Nabila Farhana; Radzi, Zamri; Abu Osman, Noor Azuan

    2016-01-01

    Despite the many attractive potential uses of ceramic materials as humidity sensors, some unavoidable drawbacks, including toxicity, poor biocompatibility, long response and recovery times, low sensitivity and high hysteresis have stymied the use of these materials in advanced applications. Therefore, in present investigation, we developed a capacitive humidity sensor using lead-free Ca,Mg,Fe,Ti-Oxide (CMFTO)-based electro-ceramics with perovskite structures synthesized by solid-state step-sintering. This technique helps maintain the submicron size porous morphology of the developed lead-free CMFTO electro-ceramics while providing enhanced water physisorption behaviour. In comparison with conventional capacitive humidity sensors, the presented CMFTO-based humidity sensor shows a high sensitivity of up to 3000% compared to other materials, even at lower signal frequency. The best also shows a rapid response (14.5 s) and recovery (34.27 s), and very low hysteresis (3.2%) in a 33%–95% relative humidity range which are much lower values than those of existing conventional sensors. Therefore, CMFTO nano-electro-ceramics appear to be very promising materials for fabricating high-performance capacitive humidity sensors. PMID:27455263

  5. Enhanced Hydrogen Dipole Physisorption, Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Channing [California Inst. of Technology (CalTech), Pasadena, CA (United States)

    2014-01-03

    The hydrogen gas adsorption effort at Caltech was designed to probe and apply our understanding of known interactions between molecular hydrogen and adsorbent surfaces as part of a materials development effort to enable room temperature storage of hydrogen at nominal pressure. The work we have performed over the past five years has been tailored to address the outstanding issues associated with weak hydrogen sorbent interactions in order to find an adequate solution for storage tank technology.

  6. Hydrogen Storage using Physisorption : Modified Carbon Nanofibers and Related Materials

    NARCIS (Netherlands)

    Nijkamp, Marije Gessien

    2002-01-01

    This thesis describes our research on adsorbent systems for hydrogen storage for small scale, mobile application. Hydrogen storage is a key element in the change-over from the less efficient and polluting internal combustion engine to the pollution-free operating hydrogen fuel cell. In general,

  7. Synthesis and Thermodynamic Studies of Physisorptive Energy Storage Materials

    Science.gov (United States)

    Stadie, Nicholas

    Physical adsorption of hydrogen or other chemical fuels on the surface of carbonaceous materials offers a promising avenue for energy storage applications. The addition of a well-chosen sorbent material to a compressed gas tank increases the volumetric energy density of the system while still permitting fast refueling, simplicity of design, complete reversibility, high cyclability, and low overall cost of materials. While physical adsorption is most effective at temperatures below ambient, effective storage technologies are possible at room temperature and modestly high pressure. A volumetric Sieverts apparatus was designed, constructed, and commissioned to accurately measure adsorption uptake at high pressures and an appropriate thermodynamic treatment of the experimental data is presented. In Chapter 1, the problem of energy storage is introduced in the context of hydrogen as an ideal alternative fuel for future mobile vehicle applications, and with methane in mind as a near-term solution. The theory of physical adsorption that is relevant to this work is covered in Chapter 2. In-depth studies of two classes of materials are presented in the final chapters. Chapter 3 presents a study of the dissociative "hydrogen spillover" effect in the context of its viability as a practical hydrogen storage solution at room temperature. Chapters 4-5 deal with zeolite-templated carbon, an extremely high surface-area material which shows promise for hydrogen and methane storage applications. Studies of hydrogen adsorption at high pressure (Chapter 4) and anomalous thermodynamic properties of methane adsorption (Chapter 5) on ZTCs are presented. The concluding chapter discusses the impact of and possible future directions for this work.

  8. Scattering, Adsorption, and Langmuir-Hinshelwood Desorption Models for Physisorptive and Chemisorptive Gas-Surface Systems

    Science.gov (United States)

    2013-09-01

    quantum effects by incorporating Zero- Point Energy ( ZPE ) in the initial conditions [19; 108]. Desorption calculations, in order to be incorporated...TST Transition State Theory TTPD Threshold Temperature-Programmed Desorption UHV Ultra-High Vacuum XHV Extreme-High Vacuum ZPE Zero-Point Energy 141

  9. The effect of concentration of H2 physisorption on the current ...

    Indian Academy of Sciences (India)

    2016-09-06

    Sep 6, 2016 ... mission spectrum exhibits a great depression for a wide range of energies. As the H2 concentration increases, the transmis- sion for energies greater than 0.55 eV is suppressed as a function of concentration (figure 8a). Figure 8b shows that for energies in the interval of 0–0.55 eV, early transmission of the ...

  10. Rheological properties of epoxy/MWCNT suspensions associated with the surface modification of MWCNT by physisorption of aromatic ionic salts

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Yu-Hsun [Institute of Polymer Science and Engineering, National Taiwan University, Taipei 106, Taiwan (China); Lin, King-Fu, E-mail: kflin@ntu.edu.tw [Institute of Polymer Science and Engineering, National Taiwan University, Taipei 106, Taiwan (China); Department of Materials Science and Engineering, National Taiwan University, Taipei 106, Taiwan (China)

    2016-04-15

    The multi-walled carbon nanotubes (MWCNTs) physisorbed by aromatic ionic salts such as 10-methyl-acridinium iodide (MAcI) were found to well disperse in diglycidyl ether of bisphenol-A epoxy resin. As they were subjected to the rheological study at 30 °C, the gelation of epoxy/MWCNT-MAcI suspension occurred at 0.75 wt% MWCNT-MAcI, which was less than that using pristine MWCNT. As to the viscosity measurements, the dilation effect that the viscosity of epoxy/MWCNT suspension increases with shear rate was found and more pronounced by incorporating MWCNT-MAcI. According to the Thomas-modified Einstein viscosity equation, the dilation effect was attributed to the excess amount of epoxy resin trapping in the aggregated domain of MWCNT. By increasing the shear rate to a certain point, the shear thinning effect that the viscosity decreases with shear rate was also observed. Interestingly, the transition point that the dilation effect changes to shear thinning effect shifted to lower shear rate as the content of MWCNT increased and/or MWCNT-MAcI was incorporated. Notably, better dispersion and less aggregated domains for the suspensions with MWCNT-MAcI compared to pristine MWCNT were further supported by small angle x-ray scattering and transmission electron microscopy. - Highlights: • Dilation effect that viscosity of epoxy/MWCNT suspension increases with shear rate was discovered. • Dilation effect was attributed to the excess epoxy resin trapping in the aggregated domain of MWCNT. • The transition point that the dilation effect changes to shear thinning effect was observed.

  11. A fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture using physisorption.

    KAUST Repository

    Bhatt, Prashant; Belmabkhout, Youssef; Cadiau, Amandine; Adil, Karim; Shekhah, Osama; Shkurenko, Aleksander; Barbour, Leonard J.; Eddaoudi, Mohamed

    2016-01-01

    The development of functional solid-state materials for carbon capture at low carbon dioxide (CO2) concentrations, from con-fined spaces (<0.5 %) and particularly from air (400 ppm), is of prime importance with respect to energy and environment sustainability. Herein, we report the deliberate construction of a hydrolytically stable fluorinated metal-organic framework (MOF), NbOFFIVE-1-Ni, with the proper pore system (size, shape and functionality), ideal for efficient and effective traces carbon dioxide removal. Markedly, the CO2-selective NbOFFIVE-1-Ni exhibits the highest CO2 gravimetric and volumetric uptake (ca. 1.3 mmol/g and 51.4 cm3.cm-3) for physical adsorbents at 400 ppm CO2 and 298 K. Practically, the NbOFFIVE-1-Ni affords the complete CO2 desorption at 328 K under vacuum with an associated moderate energy input of 54 kJ/mol, typical for the full CO2 desorption in reference physical adsorbents but considerably lower than the conventional chemical sorbents. Noticeably, the contracted square-like channels, affording the close proximity of the fluorine centers, permitted the enhancement of the CO2-framework interactions and subsequently the attainment of an unprecedented CO2-selectivity at very low CO2 concentrations. The precise localization of the adsorbed CO2 at the vicinity of the periodically aligned fluorine centers, promoting the selective adsorption of CO2, is evidenced by the single-crystal X-ray diffraction study on the NbOFFIVE-1-Ni hosting CO2 molecules. Cyclic CO2/N2 mixed-gas column breakthrough experiments under dry and humid conditions corroborate the excellent CO2-selectivity under practical carbon capture conditions. Pertinently, the no-table hydrolytic stability positions the NbOFFIVE-1-Ni as the new benchmark adsorbent for direct air capture and CO2 removal from confined spaces.

  12. Computational study of physisorption and chemisorption of polypyrrole on H-terminated (111) and (100) nanodiamond facets

    Czech Academy of Sciences Publication Activity Database

    Matunová, Petra; Jirásek, Vít; Rezek, Bohuslav

    2016-01-01

    Roč. 213, č. 10 (2016), 2672-2679 ISSN 1862-6300 R&D Projects: GA ČR GA15-01809S Institutional support: RVO:68378271 Keywords : density functional theory * nanodiamonds * nanoparticles * polypyrrole * charge transfer Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.775, year: 2016

  13. Chemical treatment effect on physi-sorption properties of nano-fibres: an experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Kayiran, S.B.; Darkrim, F.L.; Gicquel, A. [Paris-Nord Univ., Laboratoire d' Ingenierie des Materiaux et des Hautes Pressions UPR 1311, 93 - Villetaneuse (France); Bernier, P. [Groupe de Dynamique des Phases Condensees, UMR5581 UMII, 34 - Montpellier (France); Gadelle, P. [Universite Joseph Fourier ENSEEG, 38 - St Martin d' Heres (France); Levesque, D. [Paris-11 Univ., Laboratoire de Physique theorique UMR 8627, 91 - Orsay (France)

    2003-09-01

    In this work, we have realized experimental studies of gas adsorption in purified and raw graphitic nano-fibres (GNFs) obtained by CVD method, at a pressure of 20 MPa and a temperature of 293 K. The structural characterizations of these adsorbents have been evaluated by X-ray diffraction, transmission electronic microscopy, specific surface area measurements at 77 K, chemical analysis and Raman spectroscopy. We have also realized Monte Carlo simulations of hydrogen adsorption in GNF model. The results of the simulations, realized in the Grand Canonical ensemble, are compared to experimental data. (authors)

  14. A fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture using physisorption.

    KAUST Repository

    Bhatt, Prashant

    2016-07-08

    The development of functional solid-state materials for carbon capture at low carbon dioxide (CO2) concentrations, from con-fined spaces (<0.5 %) and particularly from air (400 ppm), is of prime importance with respect to energy and environment sustainability. Herein, we report the deliberate construction of a hydrolytically stable fluorinated metal-organic framework (MOF), NbOFFIVE-1-Ni, with the proper pore system (size, shape and functionality), ideal for efficient and effective traces carbon dioxide removal. Markedly, the CO2-selective NbOFFIVE-1-Ni exhibits the highest CO2 gravimetric and volumetric uptake (ca. 1.3 mmol/g and 51.4 cm3.cm-3) for physical adsorbents at 400 ppm CO2 and 298 K. Practically, the NbOFFIVE-1-Ni affords the complete CO2 desorption at 328 K under vacuum with an associated moderate energy input of 54 kJ/mol, typical for the full CO2 desorption in reference physical adsorbents but considerably lower than the conventional chemical sorbents. Noticeably, the contracted square-like channels, affording the close proximity of the fluorine centers, permitted the enhancement of the CO2-framework interactions and subsequently the attainment of an unprecedented CO2-selectivity at very low CO2 concentrations. The precise localization of the adsorbed CO2 at the vicinity of the periodically aligned fluorine centers, promoting the selective adsorption of CO2, is evidenced by the single-crystal X-ray diffraction study on the NbOFFIVE-1-Ni hosting CO2 molecules. Cyclic CO2/N2 mixed-gas column breakthrough experiments under dry and humid conditions corroborate the excellent CO2-selectivity under practical carbon capture conditions. Pertinently, the no-table hydrolytic stability positions the NbOFFIVE-1-Ni as the new benchmark adsorbent for direct air capture and CO2 removal from confined spaces.

  15. Physisorption of functionalized gold nanoparticles on AlGaN/GaN high electron mobility transistors for sensing applications.

    Science.gov (United States)

    Makowski, M S; Kim, S; Gaillard, M; Janes, D; Manfra, M J; Bryan, I; Sitar, Z; Arellano, C; Xie, J; Collazo, R; Ivanisevic, A

    2013-02-18

    AlGaN/GaN high electron mobility transistors (HEMTs) were used to measure electrical characteristics of physisorbed gold nanoparticles (Au NPs) functionalized with alkanethiols with a terminal methyl, amine, or carboxyl functional group. Additional alkanethiol was physisorbed onto the NP treated devices to distinguish between the effects of the Au NPs and alkanethiols on HEMT operation. Scanning Kelvin probe microscopy and electrical measurements were used to characterize the treatment effects. The HEMTs were operated near threshold voltage due to the greatest sensitivity in this region. The Au NP/HEMT system electrically detected functional group differences on adsorbed NPs which is pertinent to biosensor applications.

  16. Physisorption of three amine terminated molecules (TMBDA, BDA, TFBDA) on the Au(111) Surface: The Role of van der Waals Interaction

    Science.gov (United States)

    Aminpour, Maral; Le, Duy; Rahman, Talat S.

    2012-02-01

    Recently, the electronic properties and alignment of tetramethyl-1,4-benzenediamine (TMBDA), 1,4-benzenediamine (BDA) and tetrafluro-1,4-benzenediamine (TFBDA) molecules were studied experimentally. Discrepancies were found for both the binding energy and the molecule tilt angle with respect to the surface, when results were compared with density functional theory calculations [1]. We have included the effect of vdW interactions both between the molecules and the Au(111) surface and find binding energies which are in very good agreement with experiments. We also find that at low coverages each of these molecules would adsorb almost parallel to the surface. N-Au bond lengths and charge redistribution on adsorption of the molecules are also analyzed. Our calculations are based on DFT using vdW-DF exchange correlation functionals. For BDA (since we are aware of experimental data), we show that for higher coverage, inclusion of intermolecular van der Waals interaction leads to tilting of the molecules with respect to the surface and formation of line structures. Our results demonstrate the central role played by intermolecular interaction in pattern formation on this surface.[4pt] [1] M. Dell'Angela et al, Nano Lett. 2010, 10, 2470; M. Kamenetska et al, J. Phys. Chem. C, 2011, 115, 12625

  17. Physisorption and desorption of H2, HD and D2 on amorphous solid water ice. Effect on mixing isotopologue on statistical population of adsorption sites.

    Science.gov (United States)

    Amiaud, Lionel; Fillion, Jean-Hugues; Dulieu, François; Momeni, Anouchah; Lemaire, Jean-Louis

    2015-11-28

    We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

  18. Pentacene on Au(1 1 1), Ag(1 1 1) and Cu(1 1 1): From physisorption to chemisorption.

    Science.gov (United States)

    Lu, Meng-Chao; Wang, Rong-Bin; Yang, Ao; Duhm, Steffen

    2016-03-09

    We measured the electronic and the molecular surface structure of pentacene deposited on the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy (UPS) and low-energy electron diffraction (LEED). Pentacene is almost flat-lying in monolayers on all three substrates and highly ordered on Au(1 1 1) and on Cu(1 1 1). On Ag(1 1 1), however, weak chemisorption leads to almost disordered monolayers, both, at room temperature and at 78 K. On Cu(1 1 1) pentacene is strongly chemisorbed and the lowest unoccupied molecular orbital becomes observable in UPS by a charge transfer from the substrate. On Ag(1 1 1) and Cu(1 1 1) multilayers adopt a tilted orientation and a high degree of crystallinity. On Au(1 1 1), most likely, also in multilayers the molecular short and long axes are parallel to the substrate, leading to a distinctively different electronic structure than on Ag(1 1 1) and Cu(1 1 1). Overall, it could be demonstrated that the substrate not only determines the geometric and electronic characteristics of molecular monolayer films but also plays a crucial role for multilayer film growth.

  19. Hydrogen adsorption and desorption in carbon nanotube systems and its mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Shiraishi, M.; Takenobu, T.; Ata, M. [Materials Laboratories, SONY Corporation, Shin-Sakuragaoka 2-1-1, Hodogaya-ku, 240-0036, Yokohama (Japan); Kataura, H. [Department of Physics, Faculty of Science, Tokyo Metropolitan University, Minami-Osawa, Hachioji, 192-0397, Tokyo (Japan)

    2004-04-01

    The hydrogen physisorption properties in single-walled carbon nanotube (SWNT) based materials were characterized. The SWNTs were highly purified and three useful pores for hydrogen physisorption were activated. Hydrogen was physisorbed in intra-tube pores at room temperature and the capacity was estimated to be about 0.3-0.4 wt. % at room temperature. The adsorption capacity can be explained by the Langmuir model. The intra-tube pores have large adsorption potential and this induces hydrogen physisorption at comparatively higher temperatures. This fact indicates the importance of fabricating sub-nanometer ordered pores for this phenomena. (orig.)

  20. Non-oxidative methane dehydroaromatization reaction over highly ...

    Indian Academy of Sciences (India)

    Pradeep Kumar Budde

    2018-03-02

    Mar 2, 2018 ... damental science to advanced engineering technology for conversion of .... C using an automatic micropore physisorption ana- lyzer (Micrometrics ASAP ..... MoO2 species with methane to form molybdenum car- bide species.

  1. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene

    KAUST Repository

    Cui, X.; Chen, K.; Xing, H.; Yang, Q.; Krishna, R.; Bao, Z.; Wu, H.; Zhou, W.; Dong, Xinglong; Han, Y.; Li, B.; Ren, Q.; Zaworotko, M. J.; Chen, B.

    2016-01-01

    The trade-off between physical adsorption capacity and selectivity of porous materials is a major barrier for efficient gas separation and purification through physisorption. We report control over pore chemistry and size in metal coordination

  2. Effect of Fe doping on low temperature deNOx activity of high-performance vanadia-anatase nanoparticles

    DEFF Research Database (Denmark)

    Schill, Leonhard; Putluru, Siva Sankar Reddy; Jensen, Anker Degn

    2014-01-01

    VFe/TiO2 catalysts have been prepared using a sol-gel based method. Fe was introduced using 3 different methods. The resulting substances were characterized with N2-physisorption, NH3-TPD, H2-TPR, XPS and XRD. Extrudates of the VFe/TiO2 powders were prepared using sepiolite (20 wt.%) as binder. T...

  3. Comparative study of electronic and magnetic properties of Pc ( = Fe, Co) molecules physisorbed on 2D MoS and graphene

    KAUST Repository

    Haldar, Soumyajyoti

    2017-09-13

    In this paper, we have done a comparative study of electronic and magnetic properties of iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc) molecules physisorbed on monolayer of MoS$_2$ and graphene by using density functional theory. Various different types of physisorption sites have been considered for both surfaces. Our calculations reveal that the $M$Pc molecules prefer the S-top position on MoS$_2$. However, on graphene, FePc molecule prefers the bridge position while CoPc molecule prefers the top position. The $M$Pc molecules are physisorbed strongly on the MoS$_2$ surface than the graphene ($\\\\sim$ 2.5 eV higher physisorption energy). Analysis of magnetic properties indicates the presence of strong spin dipole moment opposite to the spin moment and hence a huge reduction of effective spin moment can be observed. Our calculations of magnetic anisotropy energies using both variational approach and $2^{nd}$ order perturbation approach indicate no significant changes after physisorption. In case of FePc, an out-of-plane easy axis and in case of CoPc, an in-plane easy axis can be seen. Calculations of work function indicate a reduction of MoS$_2$ work function $\\\\sim$ 1 eV due to physisorption of $M$Pc molecules while it does not change significantly in case of graphene.

  4. A theoretical study on the influence of gas adsorption on interparticle forces in powders

    NARCIS (Netherlands)

    Cottaar, E.J.E.; Rietema, K.

    1986-01-01

    Using data from the literature and some additional experiments it is investigated whether the interparticle forces in general and more specifically the cohesion between particles are influenced by the physisorption of gases. In this otherwise theoretical study the force to be applied to a particle

  5. Borazine-boron nitride hybrid hydrogen storage system

    Science.gov (United States)

    Narula, Chaitanya K [Knoxville, TN; Simonson, J Michael [Knoxville, TN; Maya, Leon [Knoxville, TN; Paine, Robert T [Albuquerque, NM

    2008-04-22

    A hybrid hydrogen storage composition includes a first phase and a second phase adsorbed on the first phase, the first phase including BN for storing hydrogen by physisorption and the second phase including a borazane-borazine system for storing hydrogen in combined form as a hydride.

  6. Vapor phase versus liquid phase grafting of meso-porous alumina

    NARCIS (Netherlands)

    Sripathi, V.G.P.; Mojet, Barbara; Nijmeijer, Arian; Benes, Nieck Edwin

    2013-01-01

    Functionalization of meso-porous c-alumina has been performed by grafting of 3-Aminopropyltrimethoxysilane (3APTMS) simultaneously from either the liquid phase or from the vapor phase. In both cases, after grafting nitrogen physisorption indicates that the materials remain meso-porous with

  7. Sorption pumps and storage for gases

    Science.gov (United States)

    Haaland, Peter; Bethel, Dylan

    2016-08-16

    A method and system for filling gas storage vessels from a source operates by cooling a sorbent, opening a valve to transfer gas by physisorption, regulating the sorbent temperature to achieve the desired degree of filling, closing the valve connecting to the gas source, and warming the tank, sorbent, and gas to provide a predetermined pressure at room temperature.

  8. Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran

    DEFF Research Database (Denmark)

    Sádaba, Irantzu; Gorbanev, Yury; Kegnæs, Søren

    2013-01-01

    on the four different zeolite supports H-beta, H-Y, H-mordenite, and H-ZSM-5 with 1–10 wt% vanadia loading were prepared and characterized by nitrogen physisorption, X-ray powder diffraction, scanning electron  microscopy, ammonia temperature-programmed desorption, Raman spectroscopy and UV...

  9. Hairy foam" : carbon nanofibers grown on solid foam. A fully accessible, high surface area, graphitic catalyst support

    NARCIS (Netherlands)

    Wenmakers, P.W.A.M.; Schaaf, van der J.; Kuster, B.F.M.; Schouten, J.C.

    2008-01-01

    This paper describes the synthesis of carbon nanofibers (CNFs) on solid carbon foam ("Hairy Foam") by catalytic decompn. of ethylene. The effect of nickel loading on fiber diam. and morphol., CNF coverage, and fiber layer thickness is studied using SEM and N2/Kr-physisorption. The surface area

  10. Experimental and theoretical IR study of methanol and ethanol converson over H-SAPO-34

    NARCIS (Netherlands)

    Hemelsoet, K.L.J.; Ghysels, A.; Mores, D.; De Wispelaere, K.; Van Speybroeck, V.; Weckhuysen, B.M.; Waroquier, M.

    2011-01-01

    Theoretical and experimental IR data are combined to gain insight into the methanol and ethanol conversion over an acidic H-SAPO-34 catalyst. The theoretical simulations use a large finite cluster and the initial physisorption energy of both alcohols is calculated. Dispersive contributions turn out

  11. Theoretical study of n-alkane adsorption on metal surfaces

    DEFF Research Database (Denmark)

    Morikawa, Yoshitada; Ishii, Hisao; Seki, Kazuhiko

    2004-01-01

    The interaction between n-alkane and metal surfaces has been studied by means of density-functional theoretical calculations within a generalized gradient approximation (GGA). We demonstrate that although the GGA cannot reproduce the physisorption energy well, our calculations can reproduce the e...

  12. A Kinetic Insight into the Activation of n -Octane with Alkaline-Earth ...

    African Journals Online (AJOL)

    Alkaline-earth metal hydroxyapatites are prepared by the co-precipitation method and characterized using XRD, ICP,NH3-TPD, SEM-EDX, TEM and N2 physisorption analysis. The metal present in the hydroxyapatite influences the acidity of the catalyst. Oxidative dehydrogenation reactions carried out in a continuous flow ...

  13. Permeability of two-dimensional graphene and hexagonal-boron nitride to hydrogen atom

    Science.gov (United States)

    Gupta, Varun; Kumar, Ankit; Ray, Nirat

    2018-05-01

    The permeability of atomic hydrogen in monolayer hexagonal Boron Nitride(h-BN) and graphene has been studied using first-principles density functional theory based simulations. For the specific cases of physisorption and chemisoroption, barrier heights are calculated using the nudged elastic band approach. We find that the barrier potential for physisorption through the ring is lower for graphene than h-BN. In the case of chemisorption, where the H atom passes through by making bonds with the atoms in the ring, the barrier potential for the graphene was found to be higher than that of h-BN. We conclude that the penetration of H atom with notable kinetic energy (graphene as compared to h-BN. Whereas through chemisorption, lower kinetic energy (>3eV) H-atoms have a higher chance to penetrate through h-BN than graphene.

  14. Hydrogen adsorption in new carbon materials

    Energy Technology Data Exchange (ETDEWEB)

    Zubizarreta, L.; Arenillas, A.; Rubiera, F.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain)

    2006-07-01

    Hydrogen physi-sorption on porous carbon materials is one among the different technologies which could be used for hydrogen storage. In addition hydrogen spillover on a carbon supports can enhance the hydrogen adsorption capacities obtained by physi-sorption. In this study two different carbon supports were synthesised: carbon gels and carbon microspheres. Carbon microspheres were doped with Ni(NO{sub 3}){sub 2} to study the hydrogen spillover on carbon support. The texture of the materials was characterised by CO{sub 2} adsorption at 0 C and their hydrogen storage capacity was evaluated at -196 and 10 C with a Micromeritics Tristar 3000, and at room temperature with a high pressure gravimetric analyser. (authors)

  15. Hydrogen adsorption in new carbon materials

    International Nuclear Information System (INIS)

    Zubizarreta, L.; Arenillas, A.; Rubiera, F.; Pis, J.J.

    2006-01-01

    Hydrogen physi-sorption on porous carbon materials is one among the different technologies which could be used for hydrogen storage. In addition hydrogen spillover on a carbon supports can enhance the hydrogen adsorption capacities obtained by physi-sorption. In this study two different carbon supports were synthesised: carbon gels and carbon microspheres. Carbon microspheres were doped with Ni(NO 3 ) 2 to study the hydrogen spillover on carbon support. The texture of the materials was characterised by CO 2 adsorption at 0 C and their hydrogen storage capacity was evaluated at -196 and 10 C with a Micromeritics Tristar 3000, and at room temperature with a high pressure gravimetric analyser. (authors)

  16. Elucidation of the Corrosion Inhibition of Mild Steel in 1.0 M HCl by Catechin Monomers from Commercial Green Tea Extracts

    Science.gov (United States)

    Nofrizal, S.; Rahim, Afidah A.; Saad, Bahruddin; Bothi Raja, P.; Shah, Affaizza M.; Yahya, S.

    2012-04-01

    The inhibitive action of commercial green tea extracts on mild steel (MS) in a 1.0 M hydrochloric acid solution was investigated by weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). A high-performance liquid chromatographic (HPLC) analysis showed conclusively that of the eight catechin monomers and caffeine found in the original extracts, only four components were responsible for the inhibition of MS. The decreasing adsorption capacity of monomers on MS is related to the stereochemistry of molecules and the number of phenolic groups, and it is as follows: epigallocatechin gallate > epicatechin gallate > epigallocatechin > epicatechin. Adsorption of green tea extract constituent was found to follow Langmuir adsorption isotherm and the calculated Gibb's free energy values indicated the physisorption of inhibitor over MS surface. Physisorption was supported well by the potential zero charge (PZC) and molecular surface energy-level calculations.

  17. Capacitance and surface of carbons in supercapacitors

    OpenAIRE

    Lobato Ortega, Belén; Suárez Fernández, Loreto; Guardia, Laura; Álvarez Centeno, Teresa

    2017-01-01

    This research is focused in the missing link between the specific surface area of carbons surface and their electrochemical capacitance. Current protocols used for the characterization of carbons applied in supercapacitors electrodes induce inconsistencies in the values of the interfacial capacitance (in F m−2), which is hindering the optimization of supercapacitors. The constraints of both the physisorption of N2 at 77 K and the standard methods used for the isotherm analysis frequently lead...

  18. Hydrogen storage in porous carbons: modelling and performance improvements

    International Nuclear Information System (INIS)

    Pellenq, R.J.M.; Maresca, O.; Marinelli, F.; Duclaux, L.; Azais, P.; Conard, J.

    2006-01-01

    In this work, we aim at exploring using ab initio calculations, the various ways allowing for an efficient hydrogen docking in carbon porous materials. Firstly, the influence of surface curvature on the chemisorption of atomic hydrogen is considered. Then it is shown that electro-donor elements such as lithium or potassium used as dopant of the carbon substrate induce a strong physi-sorption for H 2 , allowing its storage at ambient temperature under moderate pressure. (authors)

  19. A high rotational barrier for physisorbed hydrogen in an fcu-metal-organic framework

    KAUST Repository

    Pham, Tony T.; Forrest, Katherine A.; Georgiev, Peter A L; Lohstroh, Wiebke; Xue, Dongxu; Hogan, Adam; Eddaoudi, Mohamed; Space, Brian; Eckert, Juergen

    2014-01-01

    A combined inelastic neutron scattering (INS) and theoretical study of H2 sorption in Y-FTZB, a recently reported metal-organic framework (MOF) with fcu topology, reveals that the strongest binding site in the MOF causes a high barrier to rotation on the sorbed H2. This rotational barrier for H2 is the highest yet of reported MOF materials based on physisorption. This journal is

  20. Molecular dynamics simulation aiming at interfacial characteristics of polymer chains on nanotubes with different layers

    Science.gov (United States)

    Li, Kun; Gu, Boqin; Zhu, Wanfu

    2017-03-01

    A molecular dynamics (MD) simulations study is performed on multiwalled carbon nanotubes (MWNTs)/acrylonitrile-butadiene rubber (NBR) composites. The physisorption and interfacial characteristics between the various MWNTs and polymer macromolecular chains are identified. The effects of nanotube layers on the nanotubes/polymer interactions are examined. Each of the situation result and surface features is characterized by binding energy (Eb). It is shown that the binding energy (Eb) increase with the number of layers.

  1. Seed-assisted sol-gel synthesis and characterization of nanoparticular V2O5/anatase

    DEFF Research Database (Denmark)

    Kunov-Kruse, Andreas Jonas; Kristensen, Steffen Buus; Riisager, Anders

    2009-01-01

    -ray powder diffraction, transmission electron microscopy and nitrogen physisorption. The synthesized high-surface area anatase particles allowed a loading of up to 15 wt.% vanadia without exceeding monolayer coverage of V2O5 in contrast to typical analogous industrial catalysts which only can accommodate 3......-5 wt.% vanadia. These materials are promising candidates for improved catalysts for, e.g., oxidation reactions and selective catalytic reduction of NO (X) in flue gases....

  2. A Quantum Mechanical Analysis of the Electronic Response of BN Nanocluster to Formaldehyde

    OpenAIRE

    Vahabi, Vahid; Soleymanabadi, Hamed

    2016-01-01

    Abstract: It has been previously demonstrated that the electronic properties of pristine BN nanotubes and graphene-like sheets are not sensitive toward presence of H2CO gas. Here, the adsorption of H2CO on the external surface of B12N12 nano-cage is studied using X3LYP and Minnesota density functional calculations. Three different adsorption behaviors were found including physisorption, chemisorption, and chemical functionalization. Gibbs free energy changes at room temperature and 1 atm pres...

  3. Surface Functionalization of Orthopedic Titanium Implants with Bone Sialoprotein.

    Directory of Open Access Journals (Sweden)

    Andreas Baranowski

    Full Text Available Orthopedic implant failure due to aseptic loosening and mechanical instability remains a major problem in total joint replacement. Improving osseointegration at the bone-implant interface may reduce micromotion and loosening. Bone sialoprotein (BSP has been shown to enhance bone formation when coated onto titanium femoral implants and in rat calvarial defect models. However, the most appropriate method of BSP coating, the necessary level of BSP coating, and the effect of BSP coating on cell behavior remain largely unknown. In this study, BSP was covalently coupled to titanium surfaces via an aminosilane linker (APTES, and its properties were compared to BSP applied to titanium via physisorption and untreated titanium. Cell functions were examined using primary human osteoblasts (hOBs and L929 mouse fibroblasts. Gene expression of specific bone turnover markers at the RNA level was detected at different intervals. Cell adhesion to titanium surfaces treated with BSP via physisorption was not significantly different from that of untreated titanium at any time point, whereas BSP application via covalent coupling caused reduced cell adhesion during the first few hours in culture. Cell migration was increased on titanium disks that were treated with higher concentrations of BSP solution, independent of the coating method. During the early phases of hOB proliferation, a suppressive effect of BSP was observed independent of its concentration, particularly when BSP was applied to the titanium surface via physisorption. Although alkaline phosphatase activity was reduced in the BSP-coated titanium groups after 4 days in culture, increased calcium deposition was observed after 21 days. In particular, the gene expression level of RUNX2 was upregulated by BSP. The increase in calcium deposition and the stimulation of cell differentiation induced by BSP highlight its potential as a surface modifier that could enhance the osseointegration of orthopedic implants

  4. A peculiar bonding of sulphur at the Nb(001) surface

    Czech Academy of Sciences Publication Activity Database

    Huger, E.; Zelený, Martin; Káňa, Tomáš; Osuch, K.; Šob, Mojmír

    2008-01-01

    Roč. 83, č. 2 (2008), 26001/1-26001/6 ISSN 0295-5075 R&D Projects: GA MŠk OC 147; GA AV ČR IAA1041302; GA ČR GD106/05/H008 Institutional research plan: CEZ:AV0Z20410507 Keywords : Electron spectroscopy * Chemisorption/physisorption * Surface electronic density of states Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.203, year: 2008

  5. Hydrogen storage in pure and Li-doped carbon nanopores: combined effects of concavity and doping.

    Science.gov (United States)

    Cabria, I; López, M J; Alonso, J A

    2008-04-14

    Density functional calculations are reported for the adsorption of molecular hydrogen on carbon nanopores. Two models for the pores have been considered: (i) The inner walls of (7,7) carbon nanotubes and (ii) the highly curved inner surface of nanotubes capped on one end. The effect of Li doping is investigated in all cases. The hydrogen physisorption energies increase due to the concavity effect inside the clean nanotubes and on the bottom of the capped nanotubes. Li doping also enhances the physisorption energies. The sum of those two effects leads to an increase by a factor of almost 3 with respect to the physisorption in the outer wall of undoped nanotubes and in flat graphene. Application of a quantum-thermodynamical model to clean cylindrical pores of diameter 9.5 A, the diameter of the (7,7) tube, indicates that cylindrical pores of this size can store enough hydrogen to reach the volumetric and gravimetric goals of the Department of Energy at 77 K and low pressures, although not at 300 K. The results are useful to explain the experiments on porous carbons. Optimizations of the pore size, concavity, and doping appear as promising alternatives for achieving the goals at room temperature.

  6. Normal Mode Analysis in Zeolites: Toward an Efficient Calculation of Adsorption Entropies.

    Science.gov (United States)

    De Moor, Bart A; Ghysels, An; Reyniers, Marie-Françoise; Van Speybroeck, Veronique; Waroquier, Michel; Marin, Guy B

    2011-04-12

    An efficient procedure for normal-mode analysis of extended systems, such as zeolites, is developed and illustrated for the physisorption and chemisorption of n-octane and isobutene in H-ZSM-22 and H-FAU using periodic DFT calculations employing the Vienna Ab Initio Simulation Package. Physisorption and chemisorption entropies resulting from partial Hessian vibrational analysis (PHVA) differ at most 10 J mol(-1) K(-1) from those resulting from full Hessian vibrational analysis, even for PHVA schemes in which only a very limited number of atoms are considered free. To acquire a well-conditioned Hessian, much tighter optimization criteria than commonly used for electronic energy calculations in zeolites are required, i.e., at least an energy cutoff of 400 eV, maximum force of 0.02 eV/Å, and self-consistent field loop convergence criteria of 10(-8) eV. For loosely bonded complexes the mobile adsorbate method is applied, in which frequency contributions originating from translational or rotational motions of the adsorbate are removed from the total partition function and replaced by free translational and/or rotational contributions. The frequencies corresponding with these translational and rotational modes can be selected unambiguously based on a mobile block Hessian-PHVA calculation, allowing the prediction of physisorption entropies within an accuracy of 10-15 J mol(-1) K(-1) as compared to experimental values. The approach presented in this study is useful for studies on other extended catalytic systems.

  7. The interstellar carbonaceous aromatic matter as a trap for molecular hydrogen

    Science.gov (United States)

    Pauzat, F.; Lattelais, M.; Ellinger, Y.; Minot, C.

    2011-04-01

    We report a theoretical study of the physisorption of molecular hydrogen, H2, on a major component of the interstellar dust, namely, the polyaromatic carbonaceous grains. Going beyond the model of the polycyclic aromatic hydrocarbon freeflyers and its theoretical treatment within the super molecule approach, we consider the graphene surface in a Density Functional Theory periodic approach using plane-wave expansions. The physisorption energy of isolated H2 on that flat and rigid support is determined to be attractive by ˜0.75 kcal mol-1 and practically independent of the orientation with respect to the infinite surface. Since this energy is also not affected by the position (over a ring centre, a carbon atom or the middle of a carbon-carbon bond), we can conclude that H2 is able to move freely like a ball rolling on the graphene support. We also investigate the conditions for multiple physisorption. It leads to a monolayer of H2 molecules where the corresponding interaction energy per H2 amounts to a potential depth of ˜1 kcal mol-1, close to the available experimental estimates ranging from 1.1 to 1.2 kcal mol-1. We show that the most energetically favourable coverage, which corresponds to an arrangement of the H2 molecules, the closest possible to the dimer configuration, leads to a surface density of ˜0.8 × 1015 molecule cm-2. Finally, assuming that 15-20 per cent of the interstellar carbon is locked in aromatic systems, one obtains ˜10-5 of the interstellar hydrogen trapped as H2 on such types of surfaces.

  8. Physical adsorption: rare-gas atoms on solid surfaces. Final report, June 1, 1980-September 30, 1982

    International Nuclear Information System (INIS)

    Cole, M.W.

    1982-09-01

    The areas of major progress are a quantitative understanding of band structure effects for He on graphite, the substrate modification of the He-He interaction on graphite, the nature of a universal physisorption potential, and the asymptotic coefficient C 3 of the van der Waals interaction between an atom and a surface. These calculations have been largely confirmed by very precise experiments, indicating the growing sophistication of this field. Their conclusions can be generalized and extended to a variety of other systems and problems

  9. Combing and self-assembly phenomena in dry films of Taxol-stabilized microtubules

    Directory of Open Access Journals (Sweden)

    Rose Franck

    2007-01-01

    Full Text Available AbstractMicrotubules are filamentous proteins that act as a substrate for the translocation of motor proteins. As such, they may be envisioned as a scaffold for the self-assembly of functional materials and devices. Physisorption, self-assembly and combing are here investigated as a potential prelude to microtubule-templated self-assembly. Dense films of self-assembled microtubules were successfully produced, as well as patterns of both dendritic and non-dendritic bundles of microtubules. They are presented in the present paper and the mechanism of their formation is discussed.

  10. Materials for carbon dioxide separation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Qingqing

    2014-10-01

    The CO{sub 2} adsorption capacities at room temperature have been investigated by comparing carbon nanotubes, fullerene, graphenes, graphite and granular activated carbons. It turned out that the amount of the micropore surface area was dominating the CO{sub 2} adsorption ability. Another promising class of materials for CO{sub 2} capture and separation are CaO derived from the eggshells. Two aspects were studied in present work: a new hybrid materials synthesized by doping the CaTiO{sub 3} and the relationship between physisorption and chemisorption properties of CaO-based materials.

  11. Ab initio calculations on hydrogen storage in porous carbons

    International Nuclear Information System (INIS)

    Maresca, O.; Marinelli, F.; Pellenq, R.J.M.; Duclaux, L.; Azais, Ph.; Conard, J.

    2005-01-01

    We have investigated through ab initio computations the possible ways to achieve efficient hydrogen storage on carbons. Firstly, we have considered how the curvature of a carbon surface could affect the chemisorption of atomic H 0 Secondly, we show that electron donor elements such as Li and K, used as dopants for the carbon substrate, strongly enhance the physi-sorption energy of H 2 , allowing in principle its storage in this type of material at room temperature under mild conditions of pressure. (authors)

  12. High performance vanadia-anatase nanoparticle catalysts for the selective catalytic reduction of NO by ammonia

    DEFF Research Database (Denmark)

    Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas; Riisager, Anders

    2011-01-01

    Highly active nanoparticle SCR deNO(x) catalysts composed of amorphous vanadia on crystalline anatase have been prepared by a sol-gel, co-precipitation method using decomposable crystallization seeds. The catalysts were characterized by means of XRPD, TEM/SEM, FT-IR, nitrogen physisorption and NH(3......) catalysts reported in the literature in the examined temperature range of 200-400 degrees C. The catalysts showed very high resistivity towards potassium poisoning maintaining a 15-30 times higher activity than the equally poisoned industrial reference catalyst, upon impregnation by 280 mu mole potassium....../g of catalyst. (C) 2011 Elsevier Inc. All rights reserved....

  13. Dispersive and Covalent Interactions between Graphene and Metal Surfaces from the Random Phase Approximation

    DEFF Research Database (Denmark)

    Olsen, Thomas; Yan, Jun; Mortensen, Jens Jørgen

    2011-01-01

    We calculate the potential energy surfaces for graphene adsorbed on Cu(111), Ni(111), and Co(0001) using density functional theory and the random phase approximation (RPA). For these adsorption systems covalent and dispersive interactions are equally important and while commonly used approximations...... for exchange-correlation functionals give inadequate descriptions of either van der Waals or chemical bonds, RPA accounts accurately for both. It is found that the adsorption is a delicate competition between a weak chemisorption minimum close to the surface and a physisorption minimum further from the surface....

  14. A theoretical study of symmetry-breaking organic overlayers on single- and bi-layer graphene

    Science.gov (United States)

    Morales-Cifuentes, Josue; Einstein, T. L.

    2013-03-01

    An ``overlayer'' of molecules that breaks the AB symmetry of graphene can produce (modify) a band gap in single- (bi-) layer graphene.[2] Since the triangular shaped trimesic acid (TMA) molecule forms two familiar symmetry breaking configurations, we are motivated to model TMA physisorption on graphene surfaces in conjunction with experiments by Groce et al. at UMD. Using VASP, with ab initio van der Waals density functionals (vdW-DF), we simulate adsorption of TMA onto a graphene surface in several symmetry-breaking arrangements in order to predict/understand the effect of TMA adsorption on experimental observables. Supported by NSF-MRSEC Grant DMR 05-20471.

  15. Methane storage in metal-organic frameworks.

    Science.gov (United States)

    He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2014-08-21

    Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodology and the emerging porous metal-organic frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-organic frameworks for methane storage.

  16. Tuning dispersion correction in DFT-D2 for metal-molecule interactions: A tailored reparameterization strategy for the adsorption of aromatic systems on Ag(1 1 1)

    Science.gov (United States)

    Schiavo, Eduardo; Muñoz-García, Ana B.; Barone, Vincenzo; Vittadini, Andrea; Casarin, Maurizio; Forrer, Daniel; Pavone, Michele

    2018-02-01

    Common local and semi-local density functionals poorly describe the molecular physisorption on metal surfaces due to the lack of dispersion interactions. In the last decade, several correction schemes have been proposed to amend this fundamental flaw of Density Functional Theory. Using the prototypical case of aromatic molecules adsorbed on Ag(1 1 1), we discuss the accuracy of different dispersion-correction methods and present a reparameterization strategy for the simple and effective DFT-D2. For the adsorption of different aromatic systems on the same metallic substrate, good results at feasible computational costs are achieved by means of a fitting procedure against MP2 data.

  17. Materials for carbon dioxide separation

    International Nuclear Information System (INIS)

    Xu, Qingqing

    2014-01-01

    The CO 2 adsorption capacities at room temperature have been investigated by comparing carbon nanotubes, fullerene, graphenes, graphite and granular activated carbons. It turned out that the amount of the micropore surface area was dominating the CO 2 adsorption ability. Another promising class of materials for CO 2 capture and separation are CaO derived from the eggshells. Two aspects were studied in present work: a new hybrid materials synthesized by doping the CaTiO 3 and the relationship between physisorption and chemisorption properties of CaO-based materials.

  18. CoFe2O4 nanocrystalline powders prepared by citrate-gel methods: Synthesis, structure and magnetic properties

    International Nuclear Information System (INIS)

    Cannas, C.; Falqui, A.; Musinu, A.; Peddis, D.; Piccaluga, G.

    2006-01-01

    Nanocrystalline CoFe 2 O 4 powders were prepared by decomposition of metal ion citrate precursors. Four samples were synthesized from precursor solutions having different pH values in the range 2 physisorption and Transmission Electron Microscopy. Magnetic properties were explored by a SQUID magnetometer. Three out of the four samples, coming from solutions of pH 2, 4 and 7, were produced by an autocombustion reaction and are very similar as regards average size of the nanoparticles (about 20 nm), their morphology and the magnetic properties, while the fourth sample was produced by a slower thermal decomposition and is composed of smaller nanoparticles (about 10 nm)

  19. Impact of incomplete metal coverage on the electrical properties of metal-CNT contacts: A large-scale ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Fediai, Artem, E-mail: artem.fediai@nano.tu-dresden.de; Ryndyk, Dmitry A. [Institute for Materials Science and Max Bergman Center of Biomaterials, TU Dresden, 01062 Dresden (Germany); Center for Advancing Electronics Dresden, TU Dresden, 01062 Dresden (Germany); Seifert, Gotthard [Theoretical Chemistry, TU Dresden, 01062 Dresden (Germany); Center for Advancing Electronics Dresden, TU Dresden, 01062 Dresden (Germany); Dresden Center for Computational Materials Science, TU Dresden, 01062 Dresden (Germany); Mothes, Sven; Schroter, Michael; Claus, Martin [Chair for Electron Devices and Integrated Circuits, TU Dresden, 01062 Dresden (Germany); Center for Advancing Electronics Dresden, TU Dresden, 01062 Dresden (Germany); Cuniberti, Gianaurelio [Institute for Materials Science and Max Bergman Center of Biomaterials, TU Dresden, 01062 Dresden (Germany); Center for Advancing Electronics Dresden, TU Dresden, 01062 Dresden (Germany); Dresden Center for Computational Materials Science, TU Dresden, 01062 Dresden (Germany)

    2016-09-05

    Using a dedicated combination of the non-equilibrium Green function formalism and large-scale density functional theory calculations, we investigated how incomplete metal coverage influences two of the most important electrical properties of carbon nanotube (CNT)-based transistors: contact resistance and its scaling with contact length, and maximum current. These quantities have been derived from parameter-free simulations of atomic systems that are as close as possible to experimental geometries. Physical mechanisms that govern these dependences have been identified for various metals, representing different CNT-metal interaction strengths from chemisorption to physisorption. Our results pave the way for an application-oriented design of CNT-metal contacts.

  20. Pushing nanoparticles of La0.7Sr0.3MnO3

    International Nuclear Information System (INIS)

    Ma, Y.-R.; Liou Yung; Yao, Y.-D.

    2004-01-01

    Pushing nanoparticles of La 0.7 Sr 0.3 MnO 3 (LSMO) on a native SiO 2 surface using atomic force microscopy (AFM) in the tapping mode is presented. The pushing is accompanied by a repulsive tip-sample interaction between the AFM tip and the LSMO nanoparticles and the physisorption of the LSMO on the SiO 2 surface. The AFM images show scratch artifacts on the surface, indicating that artificial scratches are strongly related to the pushing of the LSMO nanoparticles. A possible approach to pushing nanoparticles is proposed

  1. Non-oxidic nanoscale composites: single-crystalline titanium carbide nanocubes in hierarchical porous carbon monoliths.

    Science.gov (United States)

    Sonnenburg, Kirstin; Smarsly, Bernd M; Brezesinski, Torsten

    2009-05-07

    We report the preparation of nanoscale carbon-titanium carbide composites with carbide contents of up to 80 wt%. The synthesis yields single-crystalline TiC nanocubes 20-30 nm in diameter embedded in a hierarchical porous carbon matrix. These composites were generated in the form of cylindrical monoliths but can be produced in various shapes using modern sol-gel and nanocasting methods in conjunction with carbothermal reduction. The monolithic material is characterized by a combination of microscopy, diffraction and physisorption. Overall, the results presented in this work represent a concrete design template for the synthesis of non-oxidic nanoscale composites with high surface areas.

  2. Physisorbed H{sub 2}@Cu(100) surface: Potential and spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, Eddy; Houriez, Céline; Mitrushchenkov, Alexander O.; Guitou, Marie; Chambaud, Gilberte, E-mail: gilberte.chambaud@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Echelle, UMR 8208 CNRS, 5 Boulevard Descartes, Champs sur Marne, F-77454 Marne-la-Vallée (France)

    2015-02-07

    Using an embedding approach, a 2-D potential energy function has been calculated to describe the physisorption interaction of H{sub 2} with a Cu(100) surface. For this purpose, a cluster model of the system calculated with highly correlated wavefunctions is combined with a periodic Density-Functional-Theory method using van der Waals-DF2 functional. Rotational and vibrational energy levels of physisorbed H{sub 2}, as well as D{sub 2} and HD, are calculated using the 2D embedding corrected potential energy function. The calculated transitions are in a very good agreement with Electron-Energy-Loss-Spectroscopy observations.

  3. Characteristics of Heavy Metals Adsorption Cu, Pb and Cd Using Synthetics Zeolite Zsm-5

    OpenAIRE

    Priyadi,; Iskandar,; Suwardi,; Mukti, Rino Rakhmata

    2015-01-01

    It is generally known that zeolite has potential for heavy metal adsorption. The objectives of this study were to synthesize and characterize zeolite ZSM-5 and to figure out the adsorption capacity of zeolite ZSM-5 for heavy metals of Cu2+, Pb2+ and Cd2+. Characterization of zeolite ZSM-5 included some variables i.e. crystal structure (XRD), morphology (SEM), specific surface area and total pore volume (N2 physisorption). Adsorption capacity of zeolite ZSM-5 was analysed using a batch system...

  4. Adsorption of O2 on a (4, 2) carbon nanotube

    International Nuclear Information System (INIS)

    Liu, H J; Zhai, J P; Chan, C T; Tang, Z K

    2007-01-01

    The physisorption and chemisorption of O 2 on the outer wall of a (4, 2) carbon nanotube have been studied by density functional calculations. The minimum-energy paths from physisorbed products to chemisorbed products are calculated by the nudged elastic band technique. Our theoretical calculations and experimentally measured Raman spectra both indicate that the (4, 2) tube is less air stable than the (5, 0) tube, which could be used to select a single chirality from a mixture of these 4 A tubes

  5. Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

    Science.gov (United States)

    Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

    2018-03-01

    We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

  6. Advanced nanostructured materials as media for hydrogen storage

    International Nuclear Information System (INIS)

    David, E.; Niculescu, V.; Armeanu, A.; Sandru, C.; Constantinescu, M.; Sisu, C.

    2005-01-01

    Full text: In a future sustainable energy system based on renewable energy, environmentally harmless energy carriers like hydrogen, will be of crucial importance. One of the major impediments for the transition to a hydrogen based energy system is the lack of satisfactory hydrogen storage alternatives. Hydrogen storage in nanostructured materials has been proposed as a solution for adequate hydrogen storage for a number of applications, in particular for transportation. This paper is a preliminary study with the focus on possibilities for hydrogen storage in zeolites, alumina and nanostructured carbon materials. The adsorption properties of these materials were evaluated in correlation with their internal structure. From N 2 physisorption data the BET surface area (S BET ) , total pore volume (PV), micropore volume (MPV) and total surface area (S t ) were derived. H 2 physisorption measurements were performed at 77 K and a pressure value of 1 bar. From these data the adsorption capacities of sorbent materials were determined. Apparently the microporous adsorbents, e.g activated carbons, display appreciable sorption capacities. Based on their micropore volume, carbon-based sorbents have the largest adsorption capacity for H 2 , over 230 cm 3 (STP)/g, at the previous conditions. By increasing the micropore volume (∼ 1 cm 3 /g) of sorbents and optimizing the adsorption conditions it is expected to obtain an adsorption capacity of ∼ 560 cm 3 (STP)/g, close to targets set for mobile applications. (authors)

  7. Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by Mixed-Linker Synthesis

    KAUST Repository

    Thompson, Joshua A.

    2012-05-22

    Zeolitic imidazolate frameworks (ZIFs) are a subclass of nanoporous metal-organic frameworks (MOFs) that exhibit zeolite-like structural topologies and have interesting molecular recognition properties, such as molecular sieving and gate-opening effects associated with their pore apertures. The synthesis and characterization of hybrid ZIFs with mixed linkers in the framework are described in this work, producing materials with properties distinctly different from the parent frameworks (ZIF-8, ZIF-90, and ZIF-7). NMR spectroscopy is used to assess the relative amounts of the different linkers included in the frameworks, whereas nitrogen physisorption shows the evolution of the effective pore size distribution in materials resulting from the framework hybridization. X-ray diffraction shows these hybrid materials to be crystalline. In the case of ZIF-8-90 hybrids, the cubic space group of the parent frameworks is continuously maintained, whereas in the case of the ZIF-7-8 hybrids there is a transition from a cubic to a rhombohedral space group. Nitrogen physisorption data reveal that the hybrid materials exhibit substantial changes in gate-opening phenomena, either occurring at continuously tunable partial pressures of nitrogen (ZIF-8-90 hybrids) or loss of gate-opening effects to yield more rigid frameworks (ZIF-7-8 hybrids). With this synthetic approach, significant alterations in MOF properties may be realized to suit a desired separation or catalytic process. © 2012 American Chemical Society.

  8. Polymer nanocomposite patterning by dip-pen nanolithography

    International Nuclear Information System (INIS)

    Kandemir, Ayse Cagil; Ma, Huan; Reiser, Alain; Spolenak, Ralph; Erdem, Derya

    2016-01-01

    The ultimate aim of this study is to construct polymer nanocomposite patterns by dip-pen nanolithography (DPN). Recent investigations have revealed the effect of the amount of ink (Laplace pressure) on the mechanism of liquid ink writing. In this study it is shown that not only the amount of ink, but also physisorption and surface diffusion are relevant. After a few writing steps, physisorption and surface diffusion outweigh the influence of the amount of ink, allowing consistent patterning governed by dwell times and writing speeds. Polymer matrices can be utilized as a delivery medium to deposit functional particles. DPN patterning of polymer nanocomposites allows for local tuning of the functionality and mechanical strength of the written patterns in high resolution, with the benefit of pattern flexibility. Typically polymer matrices with volatile components are used as a delivery medium for nanoparticle deposition, with subsequent removal of loosely bound matrix material by heating or oxygen plasma. In our study, nanocomposite patterns were constructed, and the differences between polymer and nanocomposite patterning were investigated. Cross-sectional SEM and TEM analysis confirmed that nanoparticles can be deposited with the liquid-polymer ink and are evenly distributed in the polymer matrix. (paper)

  9. Use of a La(III)-modified bentonite for effective phosphate removal from aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Kuroki, Vivian; Bosco, Giulianna E. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Rua Santa Adélia, 166, Santo André CEP 09210-170, SP (Brazil); Fadini, Pedro S.; Mozeto, Antonio A. [Laboratório de Biogeoquímica Ambiental, Núcleo de Estudos, Diagnósticos e Intervenções Ambientais, Departamento de Química, Universidade Federal de São Carlos, Cx. Postal 676, São Carlos CEP 13565-905, SP (Brazil); Cestari, Antonio R. [Department of Chemistry/CCET, Universidade Federal de Sergipe, São Cristóvão CEP 49100-000, SE (Brazil); Carvalho, Wagner A., E-mail: wagner.carvalho@ufabc.edu.br [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Rua Santa Adélia, 166, Santo André CEP 09210-170, SP (Brazil)

    2014-06-01

    Highlights: • A phosphate adsorbent was prepared from unpurified natural bentonite. • Physisorption was found to the main phosphate interaction mechanism. • The retention has reached 95% of the phosphate present in solution at room temperature. • The rate sorption was about 4 times faster than commercial phosphate adsorbents. - Abstract: A bentonite from the Northeast Brazilian region was modified with lanthanum (NT-25La) using an ion exchange process. Lanthanum incorporation in the natural clay, as well as the properties of the clay materials, were confirmed by X-ray diffraction, X-ray fluorescence, specific surface area and scanning electron microscopy (SEM/EDX). Phosphate adsorption equilibrium and kinetic tests were performed at different temperatures. The adsorption data have shown that NT-25La reaches equilibrium between modified clay and phosphate solution within 60 min of contact. The phosphate retention at room temperature reached 95%, when initial phosphate concentration in solution was 5 mg L{sup −1}. A kinetic-order variable model provided satisfactory fitting of the kinetic data. Adsorption of phosphate was best described by a Langmuir isotherm, with maximum phosphate sorption capacity of 14.0 mg g{sup −1}. Two distinct adsorption mechanisms were observed that may influence the adsorption processes. The investigation pointed out that the phosphate adsorption occurs via physisorption processes and that the use of NT-25La provides a maximum phosphate sorption capacity higher than many commercial adsorbents.

  10. Chemisorption-induced n-doping of MoS2 by oxygen

    International Nuclear Information System (INIS)

    Qi, Long; Wang, Ying; Wu, Yihong; Shen, Lei

    2016-01-01

    Both chemisorption and physisorption affect the electronic properties of two-dimensional materials, such as MoS 2 , but it remains a challenge to probe their respective roles experimentally. Through repeated in-situ electrical measurements of few-layer MoS 2 field-effect transistors in an ultrahigh vacuum system with well-controlled oxygen partial pressure (6 × 10 −8 mbar–3 × 10 −7 mbar), we were able to study the effect of chemisorption on surface defects separately from physically adsorbed oxygen molecules. It is found that chemisorption of oxygen results in n-doping in the channel but negligible effect on mobility and on/off ratio of the MoS 2 transistors. These results are in disagreement with the previous reports on p-doping and degradation of the device's performance when both chemisorption and physisorption are present. Through the analysis of adsorption-desorption kinetics and the first-principles calculations of electronic properties, we show that the experimentally observed n-doping effect originates from dissociative adsorption of oxygen at the surface defects of MoS 2 , which lowers the conduction band edge locally and makes the MoS 2 channel more n-type-like as compared to the as-fabricated devices

  11. Adsorption properties of fission gases Xe and Kr on pristine and doped graphene: A first principle DFT study

    Science.gov (United States)

    Vazhappilly, Tijo; Ghanty, Tapan K.; Jagatap, B. N.

    2017-07-01

    Graphene has excellent adsorption properties due to large surface area and has been used in applications related to gas sorption and separation. The separation of radioactive noble gases using graphene is an interesting area of research relevant to nuclear waste management. Radioactive noble gases Xe and Kr are present in the off-gas streams from nuclear fission reactors and spent nuclear fuel reprocessing plants. The entrapment of these volatile fission gases is important in the context of nuclear safety. The separation of Xe from Kr is extremely difficult, and energy intensive cryogenic distillation is generally employed. Physisorption based separation techniques using porous materials is a cost effective alternative to expensive cryogenic distillation. Thus, adsorption of noble gases on graphene is relevant for fundamental understanding of physisorption process. The properties of graphene can be tuned by doping and incorporation of defects. In this regard, we study the binding affinity of Xe and Kr in pristine and doped graphene sheets. We employ first principle calculations using density functional theory, corrected for dispersion interactions. The structural parameters obtained from the current study show excellent agreement with the available theoretical and experimental observations on similar systems. Noble gas adsorption energies on pristine graphene match very well with the available literature. Our results show that the binding energy of fission gases Xe and Kr on graphene can be considerably improved through doping the lattice with a heteroatom.

  12. Biofunctionalization of scaffold material with nano-scaled diamond particles physisorbed with angiogenic factors enhances vessel growth after implantation.

    Science.gov (United States)

    Schimke, Magdalena M; Stigler, Robert; Wu, Xujun; Waag, Thilo; Buschmann, Peter; Kern, Johann; Untergasser, Gerold; Rasse, Michael; Steinmüller-Nethl, Doris; Krueger, Anke; Lepperdinger, Günter

    2016-04-01

    Biofunctionalized scaffold facilitates complete healing of large defects. Biological constraints are induction and ingrowth of vessels. Angiogenic growth factors such as vascular endothelial growth factor or angiopoietin-1 can be bound to nano-scaled diamond particles. Corresponding bioactivities need to be examined after biofunctionalization. We therefore determined the physisorptive capacity of distinctly manufactured, differently sized nDP and the corresponding activities of bound factors. The properties of biofunctionalized nDPs were investigated on cultivated human mesenchymal stem cells and on the developing chicken embryo chorio-allantoic membrane. Eventually porous bone substitution material was coated with nDP to generate an interface that allows biofactor physisorption. Angiopoietin-1 was applied shortly before scaffold implantation into an osseous defect in sheep calvaria. Biofunctionalized scaffolds exhibited significantly increased rates of angiogenesis already one month after implantation. Conclusively, nDP can be used to ease functionalization of synthetic biomaterials. With the advances in nanotechnology, many nano-sized materials have been used in the biomedical field. This is also true for nano-diamond particles (nDP). In this article, the authors investigated the physical properties of functionalized nano-diamond particles in both in-vitro and in-vivo settings. The positive findings would help improve understanding of these nanomaterials in regenerative medicine. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Removal of malachite green by using an invasive marine alga Caulerpa racemosa var. cylindracea

    International Nuclear Information System (INIS)

    Bekci, Zehra; Seki, Yoldas; Cavas, Levent

    2009-01-01

    The biosorption of a cationic dye, malachite green oxalate (MG) from aqueous solution onto an invasive marine alga Caulerpa racemosa var. cylindracea (CRC) was investigated at different temperatures (298, 308 and 318 K). The dye adsorption onto CRC was confirmed by FTIR analysis. Equilibrium data were analyzed using Freundlich, Langmuir and Dubinin-Radushkevich (DR) equations. All of the isotherm parameters were calculated. The Freundlich model gave a better conformity than Langmuir equation. The mean free energy values (E) from DR isotherm were also estimated. In order to clarify the sorption kinetic, the fit of pseudo-first-order kinetic model, second-order kinetic model and intraparticle diffusion model were investigated. It was obtained that the biosorption process followed the pseudo-second-order rate kinetics. From thermodynamic studies the free energy changes were found to be -7.078, -9.848 and -10.864 kJ mol -1 for 298, 308 and 318 K, respectively. This implied the spontaneous nature of biosorption and the type of adsorption as physisorption. Activation energy value for MG sorption (E a ) was found to be 37.14 kJ mol -1 . It could be also derived that this result supported physisorption as a type of adsorption

  14. Aqueous lubricating properties of charged (ABC) and neutral (ABA) triblock copolymer chains

    DEFF Research Database (Denmark)

    Røn, Troels; Javakhishvili, Irakli; Patil, Navin J.

    2014-01-01

    Application of charged polymer chains as additives for lubricating neutral surfaces in aqueous envi- ronment, especially via polymer physisorption, is generally impeded by the electrostatic repulsion be- tween adjacent polymers on the surface. In this study, we have investigated the adsorption an...... improvement compared to fully charged polymer chains, e.g. poly(acrylic acid)- block -poly(2-methoxyethyl acrylate) (PAA- b -PMEA), which is attributed to dilution of charged moieties on the surface and subsequent improvement of the lubricating fi lm stability......Application of charged polymer chains as additives for lubricating neutral surfaces in aqueous envi- ronment, especially via polymer physisorption, is generally impeded by the electrostatic repulsion be- tween adjacent polymers on the surface. In this study, we have investigated the adsorption...... and aqueous lubricating properties of an amphiphilic triblock copolymer, comprised of a neutral poly(ethylene glycol) (PEG) block, a hydrophobic poly(2-methoxyethyl acrylate) (PMEA) block, and a charged poly(methacrylic acid) (PMAA) block, namely PEG- b -PMEA- b -PMAA. After adsorption onto a nonpolar...

  15. Study on the associated removal of pollutants from coal-firing flue gas using biomass activated carbon pellets

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Cuiping; Yuan, Wanli [Qingdao Univ., Shandong (China). Electrical and Mechanical Engineering College; Qi, Haiying [Tsinghua Univ., Beijing (China). Dept. of Thermal Engineering

    2013-07-01

    A pilot-scale multi-layer system was developed for the adsorption of SO{sub 2}/NO{sub x}/Hg from flue gas (real flue gases of an heating boiler house) at various operating conditions, including operating temperature and activated carbon materials. Excellent SO{sub 2}/NO{sub x}/Hg removal efficiency was achieved with the multi-layer design with carbons pellets. The SO{sub 2} removal efficiency achieved with the first layer adsorption bed clearly decreased as the operating temperature was increased due to the decrease of physisorption performance. The NO{sub x} removal efficiency measured at the second layer adsorption bed was very higher when the particle carbon impregnated with NH{sub 3}. The higher amounts of Hg absorbed by cotton-seed-skin activated carbon (CSAC) were mainly contributed by chlorinated congeners content. The simultaneously removal of SO{sub 2}/NO{sub x}/Hg was optimization characterized with different carbon layer functions. Overall, The alkali function group and chloride content in CSAC impelled not only the outstanding physisorption but also better chemisorptions. The system for simultaneously removal of multi-pollutant-gas with biomass activated carbon pellets in multi-layer reactor was achieved and the removal results indicated was strongly depended on the activated carbon material and operating temperature.

  16. Adsorption of Pb(II) present in aqueous solution on calcium, strontium and barium hydroxy apatites

    International Nuclear Information System (INIS)

    Vilchis G, J.

    2013-01-01

    Calcium, strontium and barium hydroxy apatites were successfully synthesized by chemical precipitation method, the obtained powders were characterized by the techniques of X-ray diffraction (XRD), scanning electron microscopy (Sem), semi-quantitative elemental analysis (EDS), infrared spectroscopy (IR), and N 2 physisorption studies, complementary to these analytical techniques, was determined the surface fractal dimension (Df), and the amount of surface active sites of the materials, in order to know application as ceramic for water remediation. The ability of Pb(II) ion adsorption present in aqueous solution on the hydroxy apatites synthesized by batch type experiments was studied as a function of contact time, concentration of the adsorbate and temperature. The maximum lead adsorption efficiencies obtained were 0.31, 0.32 and 0.26 mg/g for calcium, strontium and barium hydroxy apatites respectively, achieved an equilibrium time of 20 minutes in the three solid-liquid systems studied. Experimental data were adequately adjusted at the adsorption kinetic model pseudo-second order, for the three cases. Moreover, experimental data of the strontium and calcium hydroxy apatites were adjusted to the Langmuir adsorption isotherm, indicating that the adsorption was through a monolayer, whereas barium hydroxyapatite was adjusted to the Freundlich adsorption isotherm, indicating a multilayer adsorption. The thermodynamic parameters obtained during adsorption studies as a function of temperature showed physisorption, exothermic and spontaneous processes respectively. The results showed that the calcium hydroxyapatite, strontium and barium are an alternative for the Pb(II) ion adsorption present in wastewaters. (Author)

  17. Utilization of m-Phenylenediamine-Furfural Resin for Removal of Cu(II from Aqueous Solution-A Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Tariq S. Najim

    2010-01-01

    Full Text Available m-Phenylenediamine was condensed with furfural in absence of catalyst at room temperature. The produced m-phenylenediamine-furfural resin was used for the removal of Cu(II from aqueous solution. The pH for the optimum removal of Cu(II was 6. The negative values of Gibbs free energy at low concentration of Cu(II (20, 30 ppm indicative of the spontaneous adsorption process, while, at higher Cu(II concentration (40,50 ppm the positive and weak values of ∆G° indicate that the process is feasible but non spontaneous. The values of ∆H° were positive indicating that the sorption process is endothermic. On the other hand, the values of activation energy (Ea were inconsistent with the values of ∆H° both are positive and lie in the range of physisorption. The entropy ∆S° of the process was positive indicative of the randomness of the Cu(II ions at the solid / liquid interface. The values of sticking probability S* were less than one which indicate a preferable adsorption process and the mechanism is physisorption.

  18. SeO2 adsorption on CaO surface: DFT study on the adsorption of a single SeO2 molecule

    Science.gov (United States)

    Fan, Yaming; Zhuo, Yuqun; Lou, Yu; Zhu, Zhenwu; Li, Liangliang

    2017-08-01

    Selenium is a hazardous element in coal. During coal combustion, most of the selenium will convert to SeO2 in the flue gas. Ca-based adsorbents, especially CaO, have been considered as a potential sorbent to adsorb SeO2 due to its low cost. In this paper, the adsorption mechanisms of single SeO2 on CaO surface were investigated by density functional theory (DFT) calculation. Both the physisorption and chemisorption structures were determined. It has been identified that the adsorption of SeO2 on CaO surface is primarily chemisorption, while physisorption takes effects at the initial stage of the process. Under O2 atmosphere, selenate is hard to form. Most of the adsorption products are selenite. Additionally, the electron density maps were obtained to reveal the surface active sites. The partial density of states (PDOS) was calculated for analyzing the electronic structural change of SeO2 and CaO surface during adsorption. The results provide fundamental information of the adsorption process, which could be meaningful for the development of new absorbents.

  19. Amide mediated enhancement of sorption efficiency of trivalent f-elements on functionalized carbon nanotube: evidence of physiosorption

    International Nuclear Information System (INIS)

    Gupta, Nishesh K.; Sengupta, Arijit; Rane, Vinayak G.; Kadam, R.M.

    2017-01-01

    Amide Functionalized multi-walled carbon nanotube (CNT-DHA) was found to enhance the sorption efficiency of trivalent lanthanides and actinides from aqueous acidic solution. Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models were employed to understand the sorption mechanism revealing the predominance of Fruendlich isotherm. The sorption energy evaluated from D-R isotherm revealed the sorption process is physisorption, which was confirmed by the no shift in the IR frequency of amide functionality of carbon nanotube on sorption. The EPR spectra of the Gd"3"+ sorbed on carbon nanotube also showed no perturbation on the local environment of Gd"3"+ on sorption again revealing the physisorption. Analysis of the sorption kinetics through Lagergren's first order kinetics, intra particle diffusion model and pseudo second order kinetics revealed that the sorption kinetics followed pseudo second order kinetics for Am"3"+ and Eu"3"+ with rate constants 4.04E-05mg g"-"1 min"-"1 and 8.27E-05 mg g"-"1 min"-"1 respectively. The radiolytic stability of CNT-DHA was evaluated and found to be satisfactory. EDTA was found to strip the trivalent lanthanides and actinides almost quantitatively. (author)

  20. Detection of 2,4-dinitrotoluene by graphene oxide: first principles study

    Science.gov (United States)

    Abdollahi, Hassan; Kari, Akbar; Samaeifar, Fatemeh

    2018-05-01

    The surface of graphene oxide (GO) with different oxidation level is widely used in gas sensing applications. Otherwise, detection of 2,4-dinitrotoluene (DNT) have been extensively attend as a high explosive and environmental sources by various methods. Atomic level modelling are widely employed to explain the sensing mechanism at a microscopic level. The present work is an attempt to apply density functional theory (DFT) to investigate the structural and electronic properties of GO and adsorption of oxygen atom and hydroxyl on graphene surface. The focus is on the adsorption mechanisms of DNT molecule on the GO monolayer surface to detect DNT molecule. The calculated adsorption energy of DNT molecule on the GO surface indicates physisorption mechanism with ‑0.7 eV adsorption energy. Moreover, basis-set superposition errors correction based on off site orbitals consideration leads to ‑0.4 eV adsorption energy which it is more in the physisorption regime. Consequently, the results could shed more light to design and fabrication an efficient DNT sensor based on GO layers.

  1. SeO{sub 2} adsorption on CaO surface: DFT study on the adsorption of a single SeO{sub 2} molecule

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Yaming; Zhuo, Yuqun; Lou, Yu; Zhu, Zhenwu [Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084 (China); Li, Liangliang [Key Laboratory of Advanced Materials, Department of Material Science and Engineering, Tsinghua University, Beijing 100084 (China)

    2017-08-15

    Highlights: • Adsorption mechanisms of SeO{sub 2} on CaO surface under O{sub 2} were firstly studied by DFT. • The adsorption energies, bond length and electron density maps were calculated. • The electronic structure changes upon adsorption were studied. - Abstract: Selenium is a hazardous element in coal. During coal combustion, most of the selenium will convert to SeO{sub 2} in the flue gas. Ca-based adsorbents, especially CaO, have been considered as a potential sorbent to adsorb SeO{sub 2} due to its low cost. In this paper, the adsorption mechanisms of single SeO{sub 2} on CaO surface were investigated by density functional theory (DFT) calculation. Both the physisorption and chemisorption structures were determined. It has been identified that the adsorption of SeO{sub 2} on CaO surface is primarily chemisorption, while physisorption takes effects at the initial stage of the process. Under O{sub 2} atmosphere, selenate is hard to form. Most of the adsorption products are selenite. Additionally, the electron density maps were obtained to reveal the surface active sites. The partial density of states (PDOS) was calculated for analyzing the electronic structural change of SeO{sub 2} and CaO surface during adsorption. The results provide fundamental information of the adsorption process, which could be meaningful for the development of new absorbents.

  2. Tip-surface interactions at redox responsive poly(ferrocenylsilane) (PFS) interface by AFM-based force spectroscopy

    International Nuclear Information System (INIS)

    Chung Hongjing; Song Jing; Vancso, G. Julius

    2009-01-01

    Poly(ferrocenylsilanes) (PFS) belong to the class of redox responsive organometallic polymers. Atomic force microscopy (AFM)-based single molecule force spectroscopy (SMFS) was used earlier to study single chain PFS response and redox energy driven single chain PFS molecular motors. Here we present further AFM investigations of force interactions between tip and a grafted PFS surface under potential control in electrochemical redox cycles. Typical tip-Au interaction is considered as reference in the force measurements. First the electrostatic component in the diffused double layer (DL) in NaClO 4 electrolyte environment was considered for a 'grafted to' PFS, which dominated the interplay between the tip and sample surface. The DL forces can also hinder the physisorption of PFS chain onto the tip when the voltage was applied at -0.1 V. On the other hand, if the tip contacted the PFS surface prior to the electrochemical process, physisorption of PFS chains governed the overall interaction regardless of subsequently applied surface potential. In addition, prolonged contact time, t c , may also contribute to the stability of tip-PFS bridging and detection of electrostatic forces between the tip-PFS interface. The results showed that tip-substrate interaction forces without PFS grafts have negligibly small force contributions under similar, electrochemically controlled, conditions used in single PFS chain based molecular motors.

  3. Influence of the synthesis parameters on the physico-chemical and catalytic properties of cerium oxide for application in the synthesis of diethyl carbonate

    International Nuclear Information System (INIS)

    Leino, Ewelina; Kumar, Narendra; Mäki-Arvela, Päivi; Aho, Atte; Kordás, Krisztián; Leino, Anne-Riikka; Shchukarev, Andrey; Murzin, Dmitry Yu.; Mikkola, Jyri-Pekka

    2013-01-01

    Synthesis of cerium (IV) oxide by means of room temperature precipitation method was carried out. The effect of preparation variables such as synthesis time, calcination temperature and pH of the solution on resulting CeO 2 properties was discussed. Moreover, the comparison of CeO 2 samples prepared in a static and rotation mode of synthesis is presented. The solid catalysts were characterized by means of X-ray powder diffraction, scanning electron microscopy, transmission electron microscope, nitrogen physisorption, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy using pyridine as a probe molecule and temperature programmed desorption of CO 2 . Significant variations in physico-chemical properties of CeO 2 by varying the preparation conditions were observed. Furthermore, the catalytic performances of CeO 2 catalysts were compared in the synthesis of diethyl carbonate starting from ethanol and CO 2 using butylene oxide as a dehydrating agent. The dependence of CeO 2 properties on its catalytic activity is evaluated in detail. - Highlights: • Synthesis of cerium (IV) oxide by precipitation method. • Influence of synthesis time, calcination temperature, mode of stirring and solution pH on properties. • Characterization by XRD, SEM, TEM, nitrogen physisorption, XPS, FTIR. • Catalytic performance diethyl carbonate synthesis from ethanol and CO 2

  4. A theoretical study of hydrogen atoms adsorption and diffusion on PuO_2 (110) surface

    International Nuclear Information System (INIS)

    Yu, H.L.; Tang, T.; Zheng, S.T.; Shi, Y.; Qiu, R.Z.; Luo, W.H.; Meng, D.Q.

    2016-01-01

    The mechanisms of adsorption and diffusion of hydrogen atoms on the PuO_2 (110) surface are investigated by density functional theory corrected for onsite Coulombic interactions (GGA + U). In order to find out the energetically more favorable adsorption site and optimum diffusion path, adsorption energy of atomic H on various sites and the diffusion energy barrier are derived and compared. Our results show that both chemisorption and physisorption exist for H atoms adsorption configurations on PuO_2 (110) surface. Two processes for H diffusion are investigated using the climbing nudged-elastic-band (cNEB) approach. We have identified two diffusion mechanisms, leading to migration of atomic H on the surface and diffusion from surface to subsurface. The energy barriers indicate that it is energetically more favorable for H atom to be on the surface. Hydrogen permeation through purity PuO_2 surface is mainly inhibited from hydrogen atom diffusion from surface to subsurface. - Highlights: • H atoms adsorption on PuO_2 (110) surface are investigated by GGA + U. • Both chemisorption and physisorption exist for H atoms adsorption configurations. • H atoms migration into PuO_2 (100) surface are inhibited with the barrier of 2.15 eV. • H atoms diffusion on PuO_2 (110) surface are difficult at room temperature.

  5. Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

    Science.gov (United States)

    He, Xin; Kim, Seong H

    2018-02-20

    Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

  6. Coated kapok fiber for removal of spilled oil

    International Nuclear Information System (INIS)

    Wang, Jintao; Zheng, Yian; Wang, Aiqin

    2013-01-01

    Highlights: ► A low-cost and biodegradable oil absorbent based on kapok fiber was prepared. ► The polymer-coated kapok fiber showed higher oil sorption capacity. ► Coated kapok fiber can be reused and the absorbed oil can be easily recovered. ► Adsorption of oil is spontaneous and exothermic physisorption and chemisorption. -- Abstract: Based on raw kapok fiber, two kinds of oil absorbers with high sorption capacity were prepared by a facile solution–immersion process. The coated polymer with low surface energy and rough fiber surface play important role in the retention of oil. The as-prepared fiber can quickly absorb gasoline, diesel, soybean oil, and paraffin oil up to above 74.5%, 66.8%, 64.4% and 47.8% of oil sorption capacity of raw fiber, respectively. The absorbed oils can be easily recovered by a simple vacuum filtration and the recovered coated-fiber still can be used for several cycles without obvious loss in oil sorption capacity. The thermodynamic study indicates that the adsorption process is spontaneous and exothermic, with complex physisorption and chemisorption. The results suggest that the coated fiber can be used as a low-cost alternative for the removal of oil spilled on water surface

  7. Cloning single wall carbon nanotubes for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Tour, James M [Rice Univ., Houston, TX (United States); Kittrell, Carter [Rice Univ., Houston, TX (United States)

    2012-08-30

    The purpose of this research is to development the technology required for producing 3-D nano-engineered frameworks for hydrogen storage based on sp2 carbon media, which will have high gravimetric and especially high volumetric uptake of hydrogen, and in an aligned fibrous array that will take advantage of the exceptionally high thermal conductivity of sp2 carbon materials to speed up the fueling process while minimizing or eliminating the need for internal cooling systems. A limitation for nearly all storage media using physisorption of the hydrogen molecule is the large amount of surface area (SA) occupied by each H2 molecule due to its large zero-point vibrational energy. This creates a conundrum that in order to maximize SA, the physisorption media is made more tenuous and the density is decreased, usually well below 1 kg/L, so that there comes a tradeoff between volumetric and gravimetric uptake. Our major goal was to develop a new type of media with high density H2 uptake, which favors volumetric storage and which, in turn, has the capability to meet the ultimate DoE H2 goals.

  8. Efficient visible-light photocatalytic activity by band alignment in mesoporous ternary polyoxometalate-Ag2S-CdS semiconductors

    Science.gov (United States)

    Kornarakis, I.; Lykakis, I. N.; Vordos, N.; Armatas, G. S.

    2014-07-01

    Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster anions with different reduction potentials, such as PW12O403-, SiW12O404- and PMo12O403-, were employed as electron acceptors in these ternary heterojunction photocatalysts. Characterization by small-angle X-ray scattering, X-ray diffraction, transmission electron microscopy and N2 physisorption measurements showed hexagonal arrays of POM-Ag2S-CdS hybrid nanorods with large internal BET surface areas and uniform mesopores. The Keggin structure of the incorporated POM clusters was also verified by elemental X-ray spectroscopy microanalysis, infrared and diffuse-reflectance ultraviolet-visible spectroscopy. These new porous materials were implemented as visible-light-driven photocatalysts, displaying exceptional high activity in aerobic oxidation of various para-substituted benzyl alcohols to the corresponding carbonyl compounds. Our experiments show that the spatial separation of photogenerated electrons and holes at CdS through the potential gradient along the CdS-Ag2S-POM interfaces is responsible for the increased photocatalytic activity.Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster

  9. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACOUES SURFACES

    Energy Technology Data Exchange (ETDEWEB)

    Radisav D. Vidic

    2002-05-01

    The first part of this study evaluated the application of a versatile optical technique to study the adsorption and desorption of model adsorbates representative of volatile polar (acetone) and non-polar (propane) organic compounds on a model carbonaceous surface under ultra high vacuum (UHV) conditions. The results showed the strong correlation between optical differential reflectance (ODR) and adsorbate coverage determined by temperature programmed desorption (TPD). ODR technique was proved to be a powerful tool to investigate surface adsorption and desorption from UHV to high pressure conditions. The effects of chemical functionality and surface morphology on the adsorption/desorption behavior of acetone, propane and mercury were investigated for two model carbonaceous surfaces, namely air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG. They can be removed by thermal treatment (> 500 K). The presence of these groups almost completely suppresses propane adsorption at 90K and removal of these groups leads to dramatic increase in adsorption capacity. The amount of acetone adsorbed is independent of surface heat treatment and depends only on total exposure. The effects of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area, as well as higher energy binding sites. Mercury adsorption at 100 K on HOPG surfaces with and without chemical functionalities and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from HOPG surface enhances mercury physisorption. Plasma oxidation of HOPG provides additional surface area for mercury adsorption. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms, physisorption below 348 K and chemisorption above 348 K. No significant impact of oxygen functionalities was observed in the chemisorption region. The key findings of this study

  10. Interaction study on bovine serum albumin physically binding to silver nanoparticles: Evolution from discrete conjugates to protein coronas

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Jun; Zhong, Ruibo; Li, Wanrong; Liu, Yushuang; Bai, Zhijun; Yin, Jun; Liu, Jingran; Gong, Pei [Agricultural Nanocenter, School of Life Science, Inner Mongolia Agricultural University, 306 Zhaowuda Road, Hohhot 010018 (China); Zhao, Xinmin, E-mail: zhao.xinmin@hotmail.com [School of Foreign Language, Inner Mongolia Agricultural University, 306 Zhaowuda Road, Hohhot 010018 (China); Zhang, Feng, E-mail: fengzhang1978@hotmail.com [Agricultural Nanocenter, School of Life Science, Inner Mongolia Agricultural University, 306 Zhaowuda Road, Hohhot 010018 (China)

    2015-12-30

    Graphical abstract: With the non-uniform coating of amphiphilic polymer, the silver nanoparticles (AgNPs) can form protein coronas which can become discrete protein–nanoparticle conjugates when controlling the protein–nanoparticle molar ratios. The protein's conformational changes upon binding NPs was also studied by both circular dichroism and three-dimensional fluorescence spectroscopy. - Highlights: • The amphiphilic polymer coating can not only transfer hydrophobic NPs into water soluble, but also providing a thick shell responsible for the strong physisorption to proteins without significantly changing their spatial conformations. • NP with discrete proteins can be simply obtained by a simple mixing procedure followed by a gel electrophoresis separation, and the resulting conjugates are robust enough to resist common separation techniques like gel electrophoresis. • In combination with the universal amphiphilic polymer coating strategy and the physisorption mediated protein–NP conjugation, proteins like BSA can be effectively conjugated to different materials such as noble metal, semiconductor and magnetic NPs. • In contrast to chemical coupling methods, the physisorption mediated protein–NP conjugation holds facile, robust and reversible advantages, which may find wide applications in nano-biomedicine field. - Abstract: The nanostructures formed by inorganic nanoparticles together with organic molecules especially biomolecules have attracted increasing attention from both industries and researching fields due to their unique hybrid properties. In this paper, we systemically studied the interactions between amphiphilic polymer coated silver nanoparticles and bovine serum albumins by employing the fluorescence quenching approach in combination with the Stern-Volmer and Hill equations. The binding affinity was determined to 1.30 × 10{sup 7} M{sup −1} and the interaction was spontaneously driven by mainly the van der Waals force and

  11. Morphology and adsorption of chromium ion on uranium 1,2,4,5-benzenetetracarboxylic acid metal organic framework (MOF

    Directory of Open Access Journals (Sweden)

    Vala Remy M.K.

    2016-01-01

    Full Text Available In this paper, we report the synthesis of metal organic framework of uranium 1,2,4,5-benzene tetracarboxylic acid (U-H4btec MOF by solvothermal method. The obtained MOF was characterized by Fourier transform infrared spectroscopy (FTIR, Scanning electron microscopy (SEM, Transmission electron microscopy (TEM, X-ray diffraction spectroscopy (XRD, Energy dispersive spectroscopy (EDS, thermogravimetric and differential thermogravimetric analysis (TGA/DTA. The morphology of the uranium 1,2,4,5-benzene tetracarboxylic acid MOF observed by SEM, revealed the presence of flaky porous structure. Adsorption of Cr3+ from aqueous solution onto the uranium 1,2,4,5-benzene tetracarboxylic acid MOF was systematically studied. Langmuir and Freundlich adsorption isotherms were applied to determine the adsorption capacity of the MOF to form a monolayer. Kinetic determination of the adsorption of Cr3+ suggested both chemisorption and physisorption probably due to the presence of carbonyl groups within the MOF and its porous structure.

  12. An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water Electro-oxidation at Neutral pH

    KAUST Repository

    Chen, Ba-Tian

    2016-06-14

    The synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine is described. Hydrophobicity was identified as the key variable in mediating the catalytic competence of the complexes. The change in this parameter correlates with both the conformational mobility of the ligand core and the structural changes in the local solvent environment around the metal site. The optimal Co complex identified is hydrophobic, because of three semifluorinated side chains. It catalyzes water electro-oxidation efficiently at neutral pH, with an overpotential of 390 mV and a turnover frequency (TOF) of 1.83 s-1 in the absence of soluble Co salts. The catalyst can be immobilized through physisorption, and it remains stable in prolonged electrolysis experiments. © 2016 American Chemical Society.

  13. Mesoporous zeolite and zeotype single crystals synthesized in fluoride media

    DEFF Research Database (Denmark)

    Egeblad, Kresten; Kustova, Marina; Klitgaard, Søren Kegnæs

    2007-01-01

    We report the synthesis and characterization of a series of new mesoporous zeolite and zeotype materials made available by combining new and improved procedures for directly introducing carbon into reaction mixtures with the fluoride route for conventional zeolite synthesis. The mesoporous...... materials were all prepared by hydrothermal crystallization of gels adsorbed on carbon matrices which were subsequently removed by combustion. The procedures presented here resulted in mesoporous zeolite and zeotypes materials with MFI, MEL, BEA, AFI and CHA framework structures. All samples were...... characterized by XRPD, SEM, TEM and N-2 physisorption measurements. For the zeolite materials it A as found that mesoporous MFI and MEL structured single crystals could indeed be crystallized from fluoride media using an improved carbon-templating approach. More importantly, it was found that mesoporous BEA...

  14. Synthesis of mesoporous zeolite catalysts by in situ formation of carbon template over nickel nanoparticles

    DEFF Research Database (Denmark)

    Abildstrøm, Jacob Oskar; Kegnæs, Marina; Hytoft, Glen

    2016-01-01

    A novel synthesis procedure for the preparation of the hierarchical zeolite materials with MFI structure based on the carbon templating method with in situ generated carbon template is presented in this study. Through chemical vapour deposition of coke on nickel nanoparticles supported on silica...... oxide, a carbon-silica composite is obtained and exploited as a combined carbon template/silica source for zeolite synthesis. This approach has several advantages in comparison with conventional carbon templating methods, where relatively complicated preparative strategies involving multistep...... impregnation procedures and rather expensive chemicals are used. Removal of the carbon template by combustion results in zeolite single crystals with intracrystalline pore volumes between 0.28 and 0.48 cm3/g. The prepared zeolites are characterized by XRD, SEM, TEM and physisorption analysis. The isomerization...

  15. Effect of the platinum content on the microstructure and micropore size distribution of Pt/alumina-pillared clays.

    Science.gov (United States)

    Barrera-Vargas, M; Valencia-Rios, J; Vicente, M A; Korili, S A; Gil, A

    2005-12-15

    The aim of this work is to study the effect of the platinum content (0-1.8 wt % Pt) on the microstructure of an alumina-pillared clay. For this purpose, the nitrogen physisorption data at -196 degrees C, the micropore size distributions of the supported platinum catalysts, and the hydrogen chemisorption results at 30 degrees C have been analyzed and compared. The preparation of the catalysts has modified the textural properties of the Al-pillared clay support, giving rise to a loss of surface area and micropore volume. After reduction at 420 degrees C, the presence of dispersed metallic platinum with mean crystallite size in the 22-55 A range has been found by hydrogen adsorption. Comparison of all results reveals that the platinum species block the micropore entrances by steric hindrance to nitrogen access as the platinum content increases.

  16. Ab initio modeling of Al adsorption on CaF2 surfaces

    International Nuclear Information System (INIS)

    Barzilai, S.; Argaman, N.; Froumin, N.; Fuks, D.; Frage, N.

    2008-01-01

    Ab initio simulations of the adsorption of Al atoms on CaF 2 (0 0 1) and (1 1 1) surfaces have been performed for supercells with 7 different atomic configurations, using density functional theory. For (1 1 1) surfaces, a repulsive interaction was observed for most configurations, while a weak attraction was obtained when the Al atom was placed above F atoms. For the Ca-terminated (0 0 1) surface, the adsorption energy was about 5 times larger, whereas for the F-terminated (0 0 1) surface it was about 20 times greater. The comparative analysis indicates that the (0 0 1) surfaces are reactive and have a strong Al adatom bonding (chemisorption), especially for the F-terminated substrate. On the contrary, the (1 1 1) plane may be considered as non-reactive (physisorption), having a weak bonding of the Al adatom above the F site

  17. Mean-field theory of active electrolytes: Dynamic adsorption and overscreening

    Science.gov (United States)

    Frydel, Derek; Podgornik, Rudolf

    2018-05-01

    We investigate active electrolytes within the mean-field level of description. The focus is on how the double-layer structure of passive, thermalized charges is affected by active dynamics of constituting ions. One feature of active dynamics is that particles adhere to hard surfaces, regardless of chemical properties of a surface and specifically in complete absence of any chemisorption or physisorption. To carry out the mean-field analysis of the system that is out of equilibrium, we develop the "mean-field simulation" technique, where the simulated system consists of charged parallel sheets moving on a line and obeying active dynamics, with the interaction strength rescaled by the number of sheets. The mean-field limit becomes exact in the limit of an infinite number of movable sheets.

  18. Incorporation of metals (Pt-Ni-Ru) in the zeolite ZSM-5 through ion exchange competitive: synthesis and characterization

    International Nuclear Information System (INIS)

    Barbosa, A.S.; Rodrigues, M.G.F.

    2012-01-01

    Zeolites are very important materials due to their high specific surface area. Moreover, they are suitable for use as catalyst support. Noble metals supported on zeolites have been widely used as catalysts in the petrochemical industry. This paper was prepared and characterized, a powder aiming its use in heterogeneous catalysis. Support was used as ZSM-5 and the method of incorporation of the metals (Ru-PtNi) was competitive ion exchange. The materials (ZSM-5 and Pt-Ni-Ru/ZSM-5) were characterized by spectrophotometry Energy Dispersive X-ray (EDX), X-Ray Diffraction (XRD) and nitrogen physisorption (BET method). Based on the results of X-ray diffraction, it is possible to demonstrate the preservation of the structure of zeolite ZSM-5 after the competitive ion Exchange with metals (Ru-Pt-Ni) and calcination. The dispersion of metals on ZSM-5 did not change the textural characteristics of the zeolite. (author)

  19. An Energy Conservation Approach to Adsorbate-Induced Surface Stress and the Extraction of Binding Energy Using Nanomechanics

    Energy Technology Data Exchange (ETDEWEB)

    Pinnaduwage, Lal A [ORNL; Boiadjiev, Vassil I [ORNL; Fernando, G. W. [University of Connecticut, Storrs; Hawk, J. E. [Oak Ridge National Laboratory (ORNL); Wijewardhana, L.C. R. [University of Cincinnati; Gehl, Anthony C [ORNL

    2008-01-01

    Microcantilevers are ideally-suited for the study of surface phenomena due to their large surface-to-volume ratios, which amplify surface effects. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. When the excess energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such experiments were conducted for three binding processes in vapor phase experiments: physisorption, hydrogen bonding, and chemisorption. To our knowledge, such an energy conservation approach has not been taken into account in adsorbate-induced surface effect investigations. Furthermore, these experiments illustrate that detailed molecular-level information on binding energies can be extracted from this simple micromechanical sensor.

  20. Photocatalytic activity of TiO2 doped with boron and vanadium

    International Nuclear Information System (INIS)

    Bettinelli, M.; Dallacasa, V.; Falcomer, D.; Fornasiero, P.; Gombac, V.; Montini, T.; Romano, L.; Speghini, A.

    2007-01-01

    Boron (B)- and vanadium (V)-doped TiO 2 photocatalysts were synthesized using modified sol-gel reaction processes and characterized by X-ray diffraction (XRD), Raman spectroscopy and N 2 physisorption (BET). The photocatalytic activities were evaluated by monitoring the degradation of methylene blue (MB). The results showed that the materials possess high surface area. The addition of B favored the transformation of anatase to rutile, while in the presence of V, anatase was the only phase detected. The MB degradation on V-doped TiO 2 was significantly affected by the preparation method. In fact while the presence of V in the bulk did not influence strongly the photoreactivity under visible irradiation, an increase of surface V doping lead to improved photodegradation of MB. The degradation of MB dye indicated that the photocatalytic activities of TiO 2 increased as the boron doping increased, with high conversion efficiency for 9 mol% B doping

  1. Energy storage device including a redox-enhanced electrolyte

    Science.gov (United States)

    Stucky, Galen; Evanko, Brian; Parker, Nicholas; Vonlanthen, David; Auston, David; Boettcher, Shannon; Chun, Sang-Eun; Ji, Xiulei; Wang, Bao; Wang, Xingfeng; Chandrabose, Raghu Subash

    2017-08-08

    An electrical double layer capacitor (EDLC) energy storage device is provided that includes at least two electrodes and a redox-enhanced electrolyte including two redox couples such that there is a different one of the redox couples for each of the electrodes. When charged, the charge is stored in Faradaic reactions with the at least two redox couples in the electrolyte and in a double-layer capacitance of a porous carbon material that comprises at least one of the electrodes, and a self-discharge of the energy storage device is mitigated by at least one of electrostatic attraction, adsorption, physisorption, and chemisorption of a redox couple onto the porous carbon material.

  2. CO2 capture by ionic liquids - an answer to anthropogenic CO2 emissions?

    Science.gov (United States)

    Sanglard, Pauline; Vorlet, Olivier; Marti, Roger; Naef, Olivier; Vanoli, Ennio

    2013-01-01

    Ionic liquids (ILs) are efficient solvents for the selective removal of CO2 from flue gas. Conventional, offthe-shelf ILs are limited in use to physisorption, which restricts their absorption capacity. After adding a chemical functionality like amines or alcohols, absorption of CO2 occurs mainly by chemisorption. This greatly enhances CO2 absorption and makes ILs suitable for potential industrial applications. By carefully choosing the anion and the cation of the IL, equimolar absorption of CO2 is possible. This paper reviews the current state of the art of CO2 capture by ILs and presents the current research in this field performed at the ChemTech Institute of the Ecole d'Ingénieurs et d'Architectes de Fribourg.

  3. Heterogeneous catalysis afford biodiesel of babassu, castor oil and blends

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, Lee M.G. de; Abreu, Wiury C. de; Silva, Maria das Gracas de O. e; Matos, Jose Milton E. de; Moura, Carla V.R. de; Moura, Edmilson M. de, E-mail: mmoura@ufpi.edu.br [Universidade Federal do Piaui (UFPI), Teresina, PI (Brazil). Departamento de Quimica; Lima, Jose Renato de O.; Oliveira, Jose Eduardo de [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP/IQ/CEMPEQC), Araraquara, SP (Brazil). Instituto de Quimica. Centro de Monitoramento e Pesquisa da Qualidade de Combustiveis, Biocombustiveis, Petroleo e Derivados

    2013-04-15

    This work describes the preparation of babassu, castor oil biodiesel and mixtures in various proportions of these oils, using alkaline compounds of strontium (SrCO{sub 3} + SrO + Sr (OH){sub 2}) as heterogeneous catalysts. The mixture of oils of these oleaginous sources was used in the production of biodiesel with quality parameters that meet current legislation. The catalyst was characterized by X-ray diffractometry (XDR), physisorption of gas (BET method), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). The viscometric technique was used to monitor the optimization.The transesterification reactions performed using strontium compounds reached conversion rates of 97.2% babassu biodiesel (BB), 96.4% castor oil biodiesel (COB) and 95.3% Babassu/Castor Oil Biodiesel 4:1 (BBCO41). (author)

  4. The regeneration viability evaluation of zinc on bofe clay columns

    International Nuclear Information System (INIS)

    Araujo, A.L.P. de; Silva, M.G.C da; Gimenes, M.L.; Barros, M.A.S.D.

    2011-01-01

    In this study, the Bofe bentonite clay, calcined at 500 °C was used for removal of zinc in porous bed with multiple cycles of adsorption-desorption. The natural and calcined clay was characterized by N 2 physisorption (BET method), X-ray diffraction (XRD) and thermal analysis). The experiments for the removal of zinc were carried out at room temperature (25 °C) with particle diameter of 0.855 mm and a flow rate of 3 mL/min. The results indicated that over the four cycles of adsorption/desorption of which was submitted, the clay has not lost the capacity for adsorption of metal and that this process may be feasible to replace or complement conventional treatments to remove metals, since that clay was able to reduce the concentration of zinc to the amount recommended by Resolution Nº 357/2005 of CONAMA (5 mg.L -1 ). (author)

  5. Gas Sensing Properties of Ordered Mesoporous SnO2

    Directory of Open Access Journals (Sweden)

    Michael Tiemann

    2006-04-01

    Full Text Available We report on the synthesis and CO gas-sensing properties of mesoporoustin(IV oxides (SnO2. For the synthesis cetyltrimethylammonium bromide (CTABr wasused as a structure-directing agent; the resulting SnO2 powders were applied as films tocommercially available sensor substrates by drop coating. Nitrogen physisorption showsspecific surface areas up to 160 m2·g-1 and mean pore diameters of about 4 nm, as verifiedby TEM. The film conductance was measured in dependence on the CO concentration inhumid synthetic air at a constant temperature of 300 °C. The sensors show a high sensitivityat low CO concentrations and turn out to be largely insensitive towards changes in therelative humidity. We compare the materials with commercially available SnO2-basedsensors.

  6. Adsorption of Methyl Red by water-hyacinth (Eichornia crassipes) biomass.

    Science.gov (United States)

    Tarawou, Temi; Horsfall, Michael; Vicente, José L

    2007-09-01

    The surface characteristics and adsorbent properties of biomass, obtained from low-cost and environmentally problematic water hyacinth, were determined. Optimum conditions for the elimination of the industrial dye Methyl Red (1) from aqueous solution were established by means of a batch adsorption technique. The ultimate adsorption capacity of water-hyacinth biomass in terms of the elimination of 1 was calculated from a Langmuir-type isotherm as 8.85x10(-2) mol g(-1) at 30 degrees and at an optimum solution pH of 8.0. Dye elimination was found to be associated with strong electrostatic forces (physisorption), the overall process being slightly endergonic (deltaG>0). Our study shows that water hyacinth has a great potential of removing color from wastewater and other dye-polluted aquatic systems.

  7. Thermally modified bentonite clay for copper removal

    International Nuclear Information System (INIS)

    Bertagnolli, C.; Kleinübing, S.J.; Silva, M.G.C.

    2011-01-01

    Bentonite clay coming from Pernambuco was thermally modified in order to increase its affinity and capacity in the copper removal in porous bed. The application of this procedure is justified by the low cost of clay, their abundance and affinity for various metal ions. Thermally treatment modifies the clay adsorption properties enables its use in porous bed system, with the increase in surface area and mechanical strength. The material was characterized by x-ray diffraction, thermogravimetric analysis and N_2 physisorption. Then tests were carried out for adsorption of copper in various experimental conditions and evaluated the mass transfer zone, useful and total adsorbed removal amounts and total copper removal percentage. The results showed that the clay treated at higher temperature showed higher copper removal. (author)

  8. Removal of Pyrethrin from Aqueous Effluents by Adsorptive Micellar Flocculation

    Directory of Open Access Journals (Sweden)

    Pardon K. Kuipa

    2015-01-01

    Full Text Available The equilibrium adsorption of pyrethrin onto aggregates formed by the flocculation of micelles of the surfactant sodium dodecyl sulphate (SDS with aluminium sulphate is reported. The experimental results were analysed using different adsorption isotherms (Langmuir, Freundlich, Redlich-Peterson, Sips, Radke-Prausnitz, Temkin, linear equilibrium, and the Dubin-Radushkevich isotherms. The Freundlich and linear equilibrium isotherms best describe the adsorption of pyrethrin onto SDS micellar flocs, with the Freundlich adsorption constant, KF, and the mass distribution coefficient, KD, of 64.266 ((mg/g(L/mg1/n and 119.65 L/g, respectively. Applicability of the Freundlich adsorption model suggests that heterogeneous surface adsorption affects the adsorption. The mean free energy value estimated using the Dubinin-Radushkevich isotherm was 0.136 kJ/mol indicating that physisorption may be predominant in the adsorption process.

  9. Synthesis, characterization and catalytic properties of nanocrystaline Y{sub 2}O{sub 3}-coated TiO{sub 2} in the ethanol dehydration reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fajardo, Humberto Vieira [Universidade Federal de Ouro Preto (UFOP), MG (Brazil). Departamento de Quimica; Longo, Elson [Universidade Estadual Paulista (UNESP), Araraquara, SP (Brazil). Departamento de Fisico-Quimica; Leite, Edson Roberto; Libanori, Rafael [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica; Probst, Luiz Fernando Dias [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Departamento de Quimica; Carreno, Neftali Lenin Villarreal [Universidade Federal de Pelotas (UFPel), RS (Brazil). Departamento de Quimica Analitica e Inorganica

    2012-03-15

    In the present study, TiO{sub 2} nano powder was partially coated with Y{sub 2}O{sub 3} precursors generated by a sol-gel modified route. The system of nanocoated particles formed an ultra thin structure on the TiO{sub 2} surfaces. The modified nanoparticles were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) analysis, Zeta potential and surface area through N{sub 2} physisorption measurements. Bioethanol dehydration was used as a probe reaction to investigate the modifications on the nanoparticles surface. The process led to the obtainment of nanoparticles with important surface characteristics and catalytic behavior in the bioethanol dehydration reaction, with improved activity and particular selectivity in comparison to their non-coated analogs. The ethylene production was disfavored and selectivity toward acetaldehyde, hydrogen and ethane increased over modified nanoparticles. (author)

  10. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene

    KAUST Repository

    Cui, X.

    2016-05-20

    The trade-off between physical adsorption capacity and selectivity of porous materials is a major barrier for efficient gas separation and purification through physisorption. We report control over pore chemistry and size in metal coordination networks with hexafluorosilicate and organic linkers for the purpose of preferential binding and orderly assembly of acetylene molecules through cooperative host-guest and/or guest-guest interactions. The specific binding sites for acetylene are validated by modeling and neutron powder diffraction studies. The energies associated with these binding interactions afford high adsorption capacity (2.1 millimoles per gram at 0.025 bar) and selectivity (39.7 to 44.8) for acetylene at ambient conditions. Their efficiency for the separation of acetylene/ethylene mixtures is demonstrated by experimental breakthrough curves (0.73 millimoles per gram from a 1/99 mixture).

  11. Mesoporous C/CrN and C/VN Nanocomposites Obtained by One-Pot Soft-Templating Process

    Directory of Open Access Journals (Sweden)

    Julien Kiener

    2016-07-01

    Full Text Available Nanocomposites of ordered mesoporous carbon associated with chromium nitride (CrN or vanadium nitride (VN nanoparticles were obtained by a simple one-pot synthesis based on the solvent evaporation induced self-assembly (EISA process using Pluronic triblock surfactant as soft-template and a phenol-based resin (resol as carbon precursor. These nanocomposites were characterized by X-ray diffraction, nitrogen physisorption and Transmission Electron Microscopy (TEM techniques. Electron tomography (or 3D-TEM technique was particularly useful for providing direct insight on the internal architecture of C/CrN nanocomposite. Nanocomposites showed a very well organized hexagonal mesoporous carbon structure and a relatively high concentration of nanoparticles well distributed in the porous network. The chromium and vanadium nitrides/mesoporous carbon nanocomposites could have many potential applications in catalysis, Li-ion batteries, and supercapacitors.

  12. The Effect of Acidic and Redox Properties of V2O5/CeO2-ZrO2 Catalysts in Selective Catalytic Reduction of NO by NH3

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Riisager, Anders; Fehrmann, Rasmus

    2009-01-01

    V2O5 supported ZrO2 and CeO2–ZrO2 catalysts were prepared and characterized by N2 physisorption, XRPD, TPR, and NH3-TPD methods. The influence of calcination temperature from 400 to 600 °C on crystallinity, acidic and redox properties were studied and compared with the catalytic activity...... in the selective catalytic reduction (SCR) of NO with ammonia. The surface area of the catalysts decreased gradually with increasing calcination temperature. The SCR activity of V2O5/ZrO2 catalysts was found to be related with the support crystallinity, whereas V2O5/CeO2–ZrO2 catalysts were also dependent...... on acidic and redox properties of the catalyst. The V2O5/CeO2–ZrO2 catalysts showed high activity and selectivity for reduction of NO with NH3....

  13. Heteropoly acid promoted V2O5/TiO2 catalysts for NO abatement with ammonia in alkali containing flue gases

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Jensen, Anker Degn; Riisager, Anders

    2011-01-01

    V2O5/TiO2 and heteropoly acid promoted V2O5/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD and NH3-TPD. The influence of the calcination temperature from 400 to 700 1C on crystallinity and acidic properties was studied and compared with the activity for the selective...... catalytic reduction (SCR) of NO with ammonia. The SCR activity of heteropoly acid promoted catalysts was found to be much higher than for unpromoted catalysts. The stability of heteropoly acid promoted catalysts is dependent on calcination temperature and there is a gradual decrease in SCR activity...... and acidity with increase in calcination temperatures. Furthermore, the heteropoly acid promoted V2O5/TiO2 catalysts showed excellent alkali deactivation resistance and might therefore be alternative deNOx catalysts in biomass fired power plants....

  14. Application of activated carbon derived from scrap tires for adsorption of Rhodamine B.

    Science.gov (United States)

    Li, Li; Liu, Shuangxi; Zhu, Tan

    2010-01-01

    Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate the adsorption characteristics of the activated pyrolytic tire char (APTC) for Rhodamine B (RhB). Systematic research including equilibrium, kinetics and thermodynamic studies was performed. The results showed that APTC was a potential adsorbent for RhB with a higher adsorption capacity than most adsorbents. Solution pH and temperature exert significant influence while ionic strength showed little effect on the adsorption process. The adsorption equilibrium data obey Langmuir isotherm and the kinetic data were well described by the pseudo second-order kinetic model. The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption process. Thermodynamic study confirmed that the adsorption was a physisorption process with spontaneous, endothermic and random characteristics.

  15. Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

    Science.gov (United States)

    Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

    2017-09-11

    Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log K ow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN activated carbon.

  16. Interference-Blind Microfluidic Sensor for Ascorbic Acid Determination by UV/vis Spectroscopy

    DEFF Research Database (Denmark)

    Bi, Hongyan; Oliveira Fernandes, Ana Carolina; Cardoso, Susana

    2016-01-01

    A microfluidic sensor is developed and targeted at specific ingredients determination in drug/food/beverage matrices. The surface of a serpentine polydimethylsiloxane (PDMS) microchannel is modified by enzyme via physisorption. When solutions containing target ingredients pass through...... the microfluidic channel, enzyme-catalyzed reaction occurs and only converts the target molecules to its products. The whole process is monitored by an end-channel UV/vis spectroscopic detection. Ascorbate oxidase and L-ascorbic acid (AA) are taken as enzyme-substrate model in this study to investigate......, specific, and accurate, and can be potentially used for fast quantification of ingredient in samples with complex matrix background. It is promising to be widely spread in food industry and quality control department...

  17. A Novel Schiff Base of 3-acetyl-4-hydroxy-6-methyl-(2Hpyran-2-one and 2,2'-(ethylenedioxydiethylamine as Potential Corrosion Inhibitor for Mild Steel in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Jonnie N. Asegbeloyin

    2015-05-01

    Full Text Available The corrosion inhibition activity of a newly synthesized Schiff base (SB from 3-acetyl-4-hydroxy-6-methyl-(2H-pyran-2-one and 2,2'-(ethylenedioxydiethylamine was investigated on the corrosion of mild steel in 1 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopic techniques. Ultraviolet-visible (UV-vis and Raman spectroscopic techniques were used to study the chemical interactions between SB and mild steel surface. SB was found to be a relatively good inhibitor of mild steel corrosion in 1 M HCl. The inhibition efficiency increases with increase in concentration of SB. The inhibition activity of SB was ascribed to its adsorption onto mild steel surface, through physisorption and chemisorption, and described by the Langmuir adsorption model. Quantum chemical calculations indicated the presence of atomic sites with potential nucleophilic and electrophilic characteristics with which SB can establish electronic interactions with the charged mild steel surface.

  18. Baphia nitida Leaves Extract as a Green Corrosion Inhibitor for the Corrosion of Mild Steel in Acidic Media

    Directory of Open Access Journals (Sweden)

    V. O. Njoku

    2014-01-01

    Full Text Available The inhibiting effect of Baphia nitida (BN leaves extract on the corrosion of mild steel in 1 M H2SO4 and 2 M HCl was studied at different temperatures using gasometric and weight loss techniques. The results showed that the leaves extract is a good inhibitor for mild steel corrosion in both acid media and better performances were obtained in 2 M HCl solutions. Inhibition efficiency was found to increase with increasing inhibitor concentration and decreasing temperature. The addition of halides to the extract enhanced the inhibition efficiency due to synergistic effect which improved adsorption of cationic species present in the extract and was in the order KCl < KBr < KI suggesting possible role of radii of the halide ions. Thermodynamic parameters determined showed that the adsorption of BN on the metal surface is an exothermic and spontaneous process and that the adsorption was via a physisorption mechanism.

  19. Assembly of porous hierarchical copolymers/resin proppants: New approaches to smart proppant immobilization via molecular anchors.

    Science.gov (United States)

    Alexander, Shirin; Dunnill, Charles W; Barron, Andrew R

    2016-03-15

    The assembly of temperature/pH sensitive complex microparticle structures through chemisorption and physisorption provides a responsive system that offers application as routes to immobilization of proppants in-situ. Thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) along with energy dispersive X-ray analysis (EDX) have been used to characterize a series of bi-functionalized monolayers and/or multilayers grown on alumina microparticles and investigate the reactive nature of both temperature sensitive cross-linker (epoxy resin) with the layers and pH-responsive bridging layer (polyetheramine). The bifunctional acids, behaving as molecular anchors, allow for a controlled reaction with a cross-linker (resin or polymer) with the formation of networks, which is either irreversible or reversible based on the nature of the cross-linker. The networks results in formation of porous hierarchical particles that offer a potential route to the creation of immobile proppant pack. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. Lithium, rubidium and cesium ion removal using potassium iron(III) hexacyanoferrate(II) supported on polymethylmethacrylate

    International Nuclear Information System (INIS)

    Shabana Taj; Din Muhammad; Ashraf Chaudhry, M.; Muhammad Mazhar

    2011-01-01

    Potassium iron(III) hexacyanoferrate(II) supported on poly methyl methacrylate, has been developed and investigated for the removal of lithium, rubidium and cesium ions. The material is capable of sorbing maximum quantities of these ions from 5.0, 2.5 and 4.5 M HNO 3 solutions respectively. Sorption studies, conducted individually for each metal ion, under optimized conditions, demonstrated that it was predominantly physisorption in the case of lithium ion while shifting to chemisorption with increasing ionic size. Distribution coefficient (K d ) values followed the order Cs + > Rb + > Li + at low concentrations of metal ions. Following these findings Cs + can preferably be removed from 1.5 to 5 M HNO 3 nuclear waste solutions. (author)

  1. Van der Waals interaction between a molecule and a spherical cavity in a metal: Nonlocality and anisotropy effects

    International Nuclear Information System (INIS)

    Labani, B.; Boustimi, M.; Baudon, J.

    1997-01-01

    The electric response field of a small spherical metallic cavity to a molecule characterized by fluctuating dipolar and quadrupolar moments is built from spherical tensor theory. The electric susceptibility of the field gradient between the two points inside the metallic cavity is formulated by a general expression of the van der Waals energy between the two partners. The induction contribution is introduced by using the field gradient susceptibilities of the cavity at zero frequency. In order to illustrate the nonlocal effects as well as the importance of the curvature of the metallic cavity on the magnitude of the physisorption energy, we present numerical results for typical systems (HF, HCl on Ag, Al, and Cu). copyright 1997 The American Physical Society

  2. CO{sub 2} capture by adsorption with nitrogen enriched carbons

    Energy Technology Data Exchange (ETDEWEB)

    M.G. Plaza; C. Pevida; A. Arenillas; F. Rubiera; J.J. Pis [Instituto Nacional del Carbon (CSIC), Oviedo (Spain)

    2007-09-15

    The success of CO{sub 2} capture with solid sorbents is dependent on the development of a low cost sorbent with high CO{sub 2} selectivity and adsorption capacity. Immobilised amines are expected to offer the benefits of liquid amines in the typical absorption process, with the added advantages that solids are easy to handle and that they do not give rise to corrosion problems. In this work, different alkylamines were evaluated as a potential source of basic sites for CO{sub 2} capture, and a commercial activated carbon was used as a preliminary support in order to study the effect of the impregnation. The amine coating increased the basicity and nitrogen content of the carbon. However, it drastically reduced the microporous volume of the activated carbon, which is chiefly responsible for CO{sub 2} physisorption, thus decreasing the capacity of raw carbon at room temperature. 33 refs., 7 figs., 3 tabs.

  3. Non-covalent functionalization of single wall carbon nanotubes and graphene by a conjugated polymer

    KAUST Repository

    Jiwuer, Jilili

    2014-07-07

    We report first-principles calculations on the binding of poly[(9,9-bis-(6-bromohexylfluorene-2,7-diyl)-co-(benzene-1,4-diyl)] to a (8,0) single wall carbon nanotube (SWCNT) and to graphene. Considering different relative orientations of the subsystems, we find for the generalized gradient approximation a non-binding state, whereas the local density approximation predicts reasonable binding energies. The results coincide after inclusion of van der Waals corrections, which demonstrates a weak interaction between the polymer and SWCNT/graphene, mostly of van der Waals type. Accordingly, the density of states shows essentially no hybridization. The physisorption mechanism explains recent experimental observations and suggests that the conjugated polymer can be used for non-covalent functionalization.

  4. Influence of the particle size of zeolite HZSM-5 on the catalytic performance in the ethene-to-propene reaction

    Energy Technology Data Exchange (ETDEWEB)

    Follmann, S.; Ernst, S. [Kaiserslautern Univ. (Germany). Dept. of Chemistry; Vetter, A.; Ripperger, S. [Kaiserslautern Univ. (Germany). Dept. of Mechanical and Process Engineering

    2013-11-01

    In this study, HZSM-5-type zeolites with comparable nSi/nAl-ratios but different crystallite sizes (6 {mu}m, 27 {mu}m, 40 {mu}m and 62 {mu}m) were synthesized and their physicochemical properties characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and nitrogen physisorption. Their catalytic properties were explored in the acid-catalyzed conversion of ethene to propene (and higher hydrocarbons). The results show that there is a significant influence of the crystallite size of the zeolite catalyst on the activity and time-on-steam stability. While the yields of short-chain olefins do not significantly differ for all materials investigated, the formation of aromatics is significantly suppressed over the catalyst with the largest crystallite size. (orig.)

  5. Hydrogen Adsorption on Nanoporous Biocarbon

    Science.gov (United States)

    Wood, M. B.; Burress, J. W.; Lapilli, C. M.; Pfeifer, P.; Shah, P. S.; Suppes, G. J.; Dillon, A. C.; Parilla, P. A.

    2007-03-01

    As a part of the Alliance for Collaborative Research in Alternative Fuel Technology (http://all-craft.missouri.edu) we study activated carbons made from corncob, optimized for storing methane and hydrogen (H2) by physisorption at low pressure. We report here: (a) storage capacities of 73-91 g H2/kg carbon at 77 K and 47 bar, validated in three different laboratories (the 2010 DOE target is 60 g H2/kg system); (b) binding energies from H2 adsorption isotherms (c) temperature-programmed desorption data; (d) degree of graphitization of the carbon surface from Raman spectra; (e) pore structure of carbon from nitrogen and methane adsorption isotherms, and small-angle x-ray scattering. The structural analysis shows that the carbon is highly microporous and that the pore space is highly correlated (micropores do not scatter independently).

  6. Sub-ambient carbon dioxide adsorption properties of nitrogen doped graphene

    Energy Technology Data Exchange (ETDEWEB)

    Tamilarasan, P.; Ramaprabhu, Sundara, E-mail: ramp@iitm.ac.in [Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai 600036 (India)

    2015-04-14

    Carbon dioxide adsorption on carbon surface can be enhanced by doping the surface with heterogeneous atoms, which can increase local surface affinity. This study presents the carbon dioxide adsorption properties of nitrogen doped graphene at low pressures (<100 kPa). Graphene was exposed to nitrogen plasma, which dopes nitrogen atoms into carbon hexagonal lattice, mainly in pyridinic and pyrrolic forms. It is found that nitrogen doping significantly improves the CO{sub 2} adsorption capacity at all temperatures, due to the enrichment of local Lewis basic sites. In general, isotherm and thermodynamic parameters suggest that doped nitrogen sites have nearly same adsorption energy of surface defects and residual functional groups. The isosteric heat of adsorption remains in physisorption range, which falls with surface coverage, suggesting the distribution of magnitude of adsorption energy. The absolute values of isosteric heat and entropy of adsorption are slightly increased upon nitrogen doping.

  7. An enhanced hydrogen adsorption enthalpy for fluoride intercalated graphite compounds.

    Science.gov (United States)

    Cheng, Hansong; Sha, Xianwei; Chen, Liang; Cooper, Alan C; Foo, Maw-Lin; Lau, Garret C; Bailey, Wade H; Pez, Guido P

    2009-12-16

    We present a combined theoretical and experimental study on H(2) physisorption in partially fluorinated graphite. This material, first predicted computationally using ab initio molecular dynamics simulation and subsequently synthesized and characterized experimentally, represents a novel class of "acceptor type" graphite intercalated compounds that exhibit significantly higher isosteric heat of adsorption for H(2) at near ambient temperatures than previously demonstrated for commonly available porous carbon-based materials. The unusually strong interaction arises from the semi-ionic nature of the C-F bonds. Although a high H(2) storage capacity (>4 wt %) at room temperature is predicted not to be feasible due to the low heat of adsorption, enhanced storage properties can be envisaged by doping the graphitic host with appropriate species to promote higher levels of charge transfer from graphene to F(-) anions.

  8. Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst.

    Science.gov (United States)

    Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

    2017-04-01

    Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O 2 at room temperature to an acidic RuO 2 /γ-Al 2 O 3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO 2 and acidic sites on the γ-Al 2 O 3 and with physisorption of multiple ammonia molecules.

  9. Removal of Congo red dye from aqueous solutions using a halloysite-magnetite-based composite.

    Science.gov (United States)

    Ferrarini, F; Bonetto, L R; Crespo, Janaina S; Giovanela, M

    2016-01-01

    Adsorption has been considered as one of the most effective methods to remove dyes from aqueous solutions due to its ease of operation, high efficiency and wide adaptability. In view of all these aspects, this study aimed to evaluate the adsorption capacity of a halloysite-magnetite-based composite in the removal of Congo red dye from aqueous solutions. The effects of stirring rate, pH, initial dye concentration and contact time were investigated. The results revealed that the adsorption kinetics followed the pseudo-second-order model, and equilibrium was well represented by the Brunauer-Emmett-Teller isotherm. The thermodynamic data showed that dye adsorption onto the composite was spontaneous and endothermic and occurred by physisorption. Finally, the composite could also be regenerated at least four times by calcination and was shown to be a promising adsorbent for the removal of this dye.

  10. Synthesis, characterization and catalytic properties of nanocrystaline Y2O3-coated TiO2 in the ethanol dehydration reaction

    International Nuclear Information System (INIS)

    Fajardo, Humberto Vieira; Longo, Elson; Leite, Edson Roberto; Libanori, Rafael; Probst, Luiz Fernando Dias; Carreno, Neftali Lenin Villarreal

    2012-01-01

    In the present study, TiO 2 nano powder was partially coated with Y 2 O 3 precursors generated by a sol-gel modified route. The system of nanocoated particles formed an ultra thin structure on the TiO 2 surfaces. The modified nanoparticles were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) analysis, Zeta potential and surface area through N 2 physisorption measurements. Bioethanol dehydration was used as a probe reaction to investigate the modifications on the nanoparticles surface. The process led to the obtainment of nanoparticles with important surface characteristics and catalytic behavior in the bioethanol dehydration reaction, with improved activity and particular selectivity in comparison to their non-coated analogs. The ethylene production was disfavored and selectivity toward acetaldehyde, hydrogen and ethane increased over modified nanoparticles. (author)

  11. Adsorption site of ammonia on copper-exchanged Y-type zeolite under coexisting water vapor. Temperature-programed desorption and infrared adsorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Kasaoka, S.; Sasaoka, E.; Shiraga, T.; Ono, Y.

    1978-03-01

    Sodium Y zeolites were copper-exchanged with cupric nitrate in water, in aqueous ammonia, and in aqueous ammonia/ammonium chloride, and calcined at 500/sup 0/C. Temperature-programed desorption and IR spectroscopy showed three types of adsorption sites for 0.1-1.0% ammonia gas from nitrogen containing 0-12% water vapor: physisorption, adsorption as tetraamminocopper(II) on copper(II) sites (type 2 site), and adsorption as ammonium ion on hydroxyl sites (type 3 site). Adsorption on type 2 sites occurred only at high ammonia concentration; desorption occurred around 175/sup 0/C. Type 3 sites consisted of Cu(OH)/sup +/ and Al(OH)/sup +/, adsorbed ammonia from low concentrations, and at temperatures above 200/sup 0/C, were probably the active sites for the reduction of nitric oxide by ammonia.

  12. Durability and photophysical properties of surfactant-covered porous silicon particles in aqueous suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Balaguer, M.; Pastor, E.; Matveeva, E.; Chirvony, V.S. [Nanophotonics Technology Center, Universidad Politecnica de Valencia, Cami de Vera s/n, 46022 Valencia (Spain); Bychto, L. [Nanophotonics Technology Center, Universidad Politecnica de Valencia, Cami de Vera s/n, 46022 Valencia (Spain); Department of Electronics and Computer Sciences, Koszalin University of Technology, Sniadeckich 2, 75-453 Koszalin (Poland); Atienzar, P.; Miranda, M.A. [Instituto de Tecnologia Quimica CSIC-UPV, Universidad Politecnica de Valencia, Av. de los Naranjos s/n, 46022 Valencia (Spain)

    2008-11-15

    With the aim to impart hydrophilic properties to porous silicon (PSi) containing luminescent Si nanocrystals the PSi surface has been modified by a non-ionic surfactant (undecylenic acid) either physically (by physisorption) or chemically (through Si-C bond). PSi luminescence spectra and reversible quenching of the luminescence by molecular oxygen have been studied as a function of time elapsed after PSi surface immersion in water. The data obtained indicate that Si nanocrystal surface oxidation, which is realized in water, is accompanied by an appearance of a new type of luminescence centres, which are quenched by molecular oxygen differently than free excitons. SiO-related surface states are suggested to be responsible for the observed effect. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. Adsorption Behavior and Kinetic Characteristic of Cibacron Brilliant Red 3B-A by Granular Activated Carbon

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jong Jib [Kongju National University, Cheonan (Korea, Republic of)

    2014-08-15

    In this paper, the adsorption behavior and kinetic characteristics of cibacron brilliant red 3B-A from aqueous solution using granular activated carbon were investigated. The effect of various parameters such as adsorbent dose, pH, initial concentration, contact time and temperature on the adsorption system were studied. Base on the estimated Langmuir constant (R{sub L}) and Freundlich constant (1/n), This process could be employed as effective treatment method. From the Temkin constant (B) and Dubinin-Radushkevich constant (E), This adsorption process is physical adsorption. From kinetic experiments, the adsorption process followed the pseudo second order model with good correlation. Base on the Gibbs free energy and enthalpy, the adsorption of cibacron brilliant red 3B-A onto granular activated carbon was physisorption and endothermic in nature.

  14. Breakthrough of toluene vapours in granular activated carbon filled packed bed reactor

    International Nuclear Information System (INIS)

    Mohan, N.; Kannan, G.K.; Upendra, S.; Subha, R.; Kumar, N.S.

    2009-01-01

    The objective of this research was to determine the toluene removal efficiency and breakthrough time using commercially available coconut shell-based granular activated carbon in packed bed reactor. To study the effect of toluene removal and break point time of the granular activated carbon (GAC), the parameters studied were bed lengths (2, 3, and 4 cm), concentrations (5, 10, and 15 mg l -1 ) and flow rates (20, 40, and 60 ml/min). The maximum percentage removal of 90% was achieved and the maximum carbon capacity for 5 mg l -1 of toluene, 60 ml/min flow rate and 3 cm bed length shows 607.14 mg/g. The results of dynamic adsorption in a packed bed were consistent with those of equilibrium adsorption by gravimetric method. The breakthrough time and quantity shows that GAC with appropriate surface area can be utilized for air cleaning filters. The result shows that the physisorption plays main role in toluene removal.

  15. Adsorption Behavior and Kinetic Characteristic of Cibacron Brilliant Red 3B-A by Granular Activated Carbon

    International Nuclear Information System (INIS)

    Lee, Jong Jib

    2014-01-01

    In this paper, the adsorption behavior and kinetic characteristics of cibacron brilliant red 3B-A from aqueous solution using granular activated carbon were investigated. The effect of various parameters such as adsorbent dose, pH, initial concentration, contact time and temperature on the adsorption system were studied. Base on the estimated Langmuir constant (R L ) and Freundlich constant (1/n), This process could be employed as effective treatment method. From the Temkin constant (B) and Dubinin-Radushkevich constant (E), This adsorption process is physical adsorption. From kinetic experiments, the adsorption process followed the pseudo second order model with good correlation. Base on the Gibbs free energy and enthalpy, the adsorption of cibacron brilliant red 3B-A onto granular activated carbon was physisorption and endothermic in nature

  16. Agro-waste biosorbents: Effect of physico-chemical properties on atrazine and imidacloprid sorption.

    Science.gov (United States)

    Mandal, Abhishek; Singh, Neera; Nain, Lata

    2017-09-02

    Low cost agro-waste biosorbents namely eucalyptus bark (EB), corn cob (CC), bamboo chips (BC), rice straw (RS) and rice husk (RH) were characterized and used to study atrazine and imidacloprid sorption. Adsorption studies suggested that biosorbents greatly varied in their pesticide sorption behaviour. The EB was the best biosorbent to sorb both atrazine and imidacloprid with K F values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values imidacloprid sorption parameter [K F .(1/n)] with the physicochemical properties of the biosorbents suggested that atrazine adsorption correlated significantly to the aromaticity, polarity, surface area, fractal dimension, lacunarity and relative C-O band intensity parameters of biosorbents. Probably, both physisorption and electrostatic interactions were responsible for the pesticide sorption. The eucalyptus bark can be exploited as low cost adsorbent for the removal of these pesticides as well as a component of on-farm biopurification systems.

  17. Hydrogenation of Levulinic Acid over Nickel Catalysts Supported on Aluminum Oxide to Prepare γ-Valerolactone

    Directory of Open Access Journals (Sweden)

    Jie Fu

    2015-12-01

    Full Text Available Four types of nickel catalysts supported on aluminum oxide (Ni/Al2O3 with different nickel loadings were synthesized using the co-precipitation method and were used for the hydrogenation of levulinic acid (LA to prepare γ-valerolactone (GVL. The synthesized Ni/Al2O3 catalysts exhibited excellent catalytic activity in dioxane, and the activity of the catalysts was excellent even after being used four times in dioxane. The catalytic activity in dioxane as a solvent was found to be superior to the activity in water. Nitrogen physisorption, X-ray diffraction, and transmission electron microscopy were employed to characterize the fresh and used catalysts. The effects of the nickel loading, temperature, hydrogen pressure, and substrate/catalyst ratio on the catalytic activity were investigated.

  18. Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders

    2011-01-01

    Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...... be suitable for biomass fired power plant SCR applications....

  19. {beta}-TCP porous pellets as an orthopaedic drug delivery system: ibuprofen/carrier physicochemical interactions

    Energy Technology Data Exchange (ETDEWEB)

    Baradari, Hiba; Damia, Chantal; Dutreih-Colas, Maggy; Champion, Eric; Chulia, Dominique; Viana, Marylene, E-mail: hiva.baradari@etu.unilim.fr [SPCTS-Centre Europeen de la Ceramique, 12 Rue Atlantis, 87068 Limoges CEDEX (France)

    2011-10-15

    Calcium phosphate bone substitute materials can be loaded with active substances for in situ, targeted drug administration. In this study, porous {beta}-TCP pellets were investigated as an anti-inflammatory drug carrier. Porous {beta}-TCP pellets were impregnated with an ethanolic solution of ibuprofen. The effects of contact time and concentration of ibuprofen solution on drug adsorption were studied. The ibuprofen adsorption equilibrium time was found to be one hour. The adsorption isotherms fitted to the Freundlich model, suggesting that the interaction between ibuprofen and {beta}-TCP is weak. The physicochemical characterizations of loaded pellets confirmed that the reversible physisorption of ibuprofen on {beta}-TCP pellets is due to Van der Waals forces, and this property was associated with the 100% ibuprofen release.

  20. Influence of Rare Earth Doping on the Structural and Catalytic Properties of Nanostructured Tin Oxide

    Directory of Open Access Journals (Sweden)

    Maciel Adeilton

    2008-01-01

    Full Text Available AbstractNanoparticles of tin oxide, doped with Ce and Y, were prepared using the polymeric precursor method. The structural variations of the tin oxide nanoparticles were characterized by means of nitrogen physisorption, carbon dioxide chemisorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The synthesized samples, undoped and doped with the rare earths, were used to promote the ethanol steam reforming reaction. The SnO2-based nanoparticles were shown to be active catalysts for the ethanol steam reforming. The surface properties, such as surface area, basicity/base strength distribution, and catalytic activity/selectivity, were influenced by the rare earth doping of SnO2and also by the annealing temperatures. Doping led to chemical and micro-structural variations at the surface of the SnO2particles. Changes in the catalytic properties of the samples, such as selectivity toward ethylene, may be ascribed to different dopings and annealing temperatures.

  1. Research and development of a helium-4 based solar neutrino detector

    International Nuclear Information System (INIS)

    Lanou, R.E.; Maris, H.J.; Seidel, G.M.

    1990-12-01

    We report on work accomplished in the first 30 months of a research and development program to investigate the feasibility of a new technique to detect solar neutrinos in superfluid helium. Accomplishments include the successful completion of design, construction and operation of the entire cryogenic, mechanical and electronic apparatus. During the last several months we have begun a series of experiments in superfluid helium to test the method. Experimental results include the first observation of the combined physical processes essential to the detection technique: ballistic roton generation by energetic charged particles, quantum evaporation of helium at a free surface and bolometric detection of the evaporated helium by physisorption on a cold silicon wafer. Additional results are also presented

  2. Graphene-induced band gap renormalization in polythiophene: a many-body perturbation study

    Science.gov (United States)

    Marsusi, F.; Fedorov, I. A.; Gerivani, S.

    2018-01-01

    Density functional theory and many-body perturbation theory at the G0W0 level are employed to study the electronic properties of polythiophene (PT) adsorbed on the graphene surface. Analysis of the charge density difference shows that substrate-adsorbate interaction leads to a strong physisorption and interfacial electric dipole moment formation. The electrostatic potential displays a  -0.19 eV shift in the graphene work function from its initial value of 4.53 eV, as the result of the interaction. The LDA band gap of the polymer does not show any change. However, the band structure exhibits weak orbital hybridizations resulting from slight overlapping between the polymer and graphene states wave functions. The interfacial polarization effects on the band gap and levels alignment are investigated at the G0W0 level and show a notable reduction of PT band gap compared to that of the isolated chain.

  3. Investigating the mesostructure of ordered porous silica nanocomposites by transmission electron microscopy techniques

    Energy Technology Data Exchange (ETDEWEB)

    Bullita, S.; Casula, M. F., E-mail: casulaf@unica.it [INSTM and Department of Chemical and Geological Science, University of Cagliari, Monserrato (Canada) (Italy); Piludu, M. [Department of Biomedical Sciences, University of Cagliari, Monserrato (Canada) (Italy); Falqui, A. [INSTM and Department of Chemical and Geological Science, University of Cagliari, Monserrato (Canada) Italy and KAUST-King Abdullah University of Science and Technology, Jeddah (Saudi Arabia); Carta, D. [INSTM and Department of Chemical and Geological Science, University of Cagliari, Monserrato (Canada), Italy and Faculty of Physical Sciences and Engineering, University of Southampton, Southampton (United Kingdom); Corrias, A. [INSTM and Department of Chemical and Geological Science, University of Cagliari, Monserrato (Canada) Italy and School of Physical Sciences, Ingram Building, University of Kent, Canterbury (United Kingdom)

    2014-10-21

    Nanocomposites made out of FeCo alloy nanocrystals supported onto pre-formed mesoporous ordered silica which features a cubic arrangement of pores (SBA-16) were investigated. Information on the effect of the nanocrystals on the mesostructure (i.e. pore arrangement symmetry, pore size, and shape) were deduced by a multitechnique approach including N2 physisorption, low angle X-ray diffraction, and Transmission electron microscopy. It is shown that advanced transmission electron microscopy techniques are required, however, to gain direct evidence on key compositional and textural features of the nanocomposites. In particular, electron tomography and microtomy techniques make clear that the FeCo nanocrystals are located within the pores of the SBA-16 silica, and that the ordered mesostructure of the nanocomposite is retained throughout the observed specimen.

  4. Nanodevices for generating power from molecules and batteryless sensing

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yinmin; Wang, Xianying; Hamza, Alex V.

    2017-01-03

    A nanoconverter or nanosensor is disclosed capable of directly generating electricity through physisorption interactions with molecules that are dipole containing organic species in a molecule interaction zone. High surface-to-volume ratio semiconductor nanowires or nanotubes (such as ZnO, silicon, carbon, etc.) are grown either aligned or randomly-aligned on a substrate. Epoxy or other nonconductive polymers are used to seal portions of the nanowires or nanotubes to create molecule noninteraction zones. By correlating certain molecule species to voltages generated, a nanosensor may quickly identify which species is detected. Nanoconverters in a series parallel arrangement may be constructed in planar, stacked, or rolled arrays to supply power to nano- and micro-devices without use of external batteries. In some cases breath, from human or other life forms, contain sufficient molecules to power a nanoconverter. A membrane permeable to certain molecules around the molecule interaction zone increases specific molecule nanosensor selectivity response.

  5. Theoretical Investigation of CO{sub 2} Adsorption on Graphene

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kunjoon; Kim, Seungjoon [Hannam Univ., Daejeon (Korea, Republic of)

    2013-10-15

    The adsorption of carbon dioxide on graphene sheets was theoretically investigated using density functional theory (DFT) and MP{sub 2} calculations. Geometric parameters and adsorption energies were computed at various levels of theory. The CO{sub 2} chemisorption energies on graphene-C{sub 40} assuming high pressure are predicted to be 71.2-72.1 kcal/mol for the lactone systems depending on various C-O orientations at the UCAM-B3LYP level of theory. Physisorption energies of CO{sub 2} on graphene were predicted to be 2.1 and 3.3 kcal/mol, respectively, at the single-point UMP2/6-31G{sup **} level of theory for perpendicular and parallel orientations.

  6. Composition, texture and methane potential of cellulosic residues from Lewis acids organosolv pulping of wheat straw.

    Science.gov (United States)

    Constant, Sandra; Barakat, Abdellatif; Robitzer, Mike; Di Renzo, Francesco; Dumas, Claire; Quignard, Françoise

    2016-09-01

    Cellulosic pulps have been successfully isolated from wheat straw through a Lewis acids organosolv treatment. The use of Lewis acids with different hardness produced pulps with different delignification degrees. The cellulosic residue was characterised by chemical composition, X-ray diffraction, FT-IR spectroscopy, N2 physisorption, scanning electron microscopy and potential for anaerobic digestibility. Surface area and pore volume increased with the hardness of the Lewis acid, in correspondence with the decrease of the amount of lignin and hemicellulose in the pulp. The non linearity of the correlation between porosity and composition suggests that an agglomeration of cellulose fibrils occurs in the early stages of pulping. All organosolv pulps presented a significantly higher methane potential than the parent straw. A methane evolution of 295Ncm(3)/g OM was reached by a moderate improvement of the accessibility of the native straw. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Chemisorption and Diffusion of H on a Graphene Sheet and Single-Wall Carbon Nanotubes

    Science.gov (United States)

    Srivastava, Deepak; Dzegilenko, Fedor; Menon, Madhu

    2000-01-01

    Recent experiments on hydrogen storage in single wall nanotubes and nanotube bundles have reported large fractional weight of stored molecular hydrogen which are not in agreement with theoretical estimates based of simulation of hydrogen storage by physisorption mechanisms. Hydrogen storage in catalytically doped nanotube bundles indicate that atomic H might undergo chemisorption changing the basic nature of the storage mechanism under investigation by many groups. Using a generalized tight-binding molecular dynamics (GTBMD) method for reactive C-H dynamics, we investigate chemisorption and diffusion of atomic H on graphene sheet and C nanotubes. Effective potential energy surfaces (EPS) for chemisorption and diffusion are calculated for graphene sheet and nanotubes of different curvatures. Analysis of the activation barriers and quantum rate constants, computed via wave-packet dynamics method, will be discussed in this presentation.

  8. Understanding the role of thiol and disulfide self-assembled DNA receptor monolayers for biosensing applications.

    Science.gov (United States)

    Carrascosa, Laura G; Martínez, Lidia; Huttel, Yves; Román, Elisa; Lechuga, Laura M

    2010-09-01

    A detailed study of the immobilization of three differently sulfur-modified DNA receptors for biosensing applications is presented. The three receptors are DNA-(CH)n-SH-, DNA-(CH)n-SS-(CH)n-DNA, and DNA-(CH)n-SS-DMTO. Nanomechanical and surface plasmon resonance biosensors and fluorescence and radiolabelling techniques were used for the experimental evaluation. The results highlight the critical role of sulfur linker type in DNA self-assembly, affecting the kinetic adsorption and spatial distribution of DNA chains within the monolayer and the extent of chemisorption and physisorption. A spacer (mercaptohexanol, MCH) is used to evaluate the relative efficiencies of chemisorption of the three receptors by analysing the extent to which MCH can remove physisorbed molecules from each type of monolayer. It is demonstrated that -SH derivatization is the most suitable for biosensing purposes as it results in densely packed monolayers with the lowest ratio of physisorbed probes.

  9. Study of Coating Geometries and Photoluminescence Properties of Metal Nanoparticles/Graphite Composites

    Directory of Open Access Journals (Sweden)

    Pasquale Barone

    2014-01-01

    Full Text Available In this work we present the results of a study of growth and characterization of metal nanoparticles (Ag, Au, and Co/carbon surfaces. The nanoparticles grew by laser ablation technique and their dimensions were controlled by light scattering study and AFM microscopy before their insertion on graphite surface. Nanoparticles appear randomly disposed on carbon surfaces aggregating to form big particles only in the case of silver. The different behavior of metal nanoparticles on carbon surface was explained in terms of different metal wetting of surface, in agreement with previous theoretical results of He et al. Chemical information, obtained by X-ray photoelectron spectroscopy, indicated that the doping process is a simple physisorption while the interfacial interaction between particles and carbon layers causes local defects in graphite structure and the appearance of a strong photoluminescence signal for all composites. Moreover, the visible optical absorption decreases about 10% indicating the progressive metallization of carbon surface.

  10. Reducibility of ceria-lanthana mixed oxides under temperature programmed hydrogen and inert gas flow conditions

    International Nuclear Information System (INIS)

    Bernal, S.; Blanco, G.; Cifredo, G.; Perez-Omil, J.A.; Pintado, J.M.; Rodriguez-Izquierdo, J.M.

    1997-01-01

    The present paper deals with the preparation and characterization of La/Ce mixed oxides, with La molar contents of 20, 36 and 57%. We carry out the study of the structural, textural and redox properties of the mixed oxides, comparing our results with those for pure ceria. For this aim we use temperature programmed reduction (TPR), temperature programmed desorption (TPD), nitrogen physisorption at 77 K, X-ray diffraction and high resolution electron microscopy. The mixed oxides are more easy to reduce in a flow of hydrogen than ceria. Moreover, in an inert gas flow they release oxygen in higher amounts and at lower temperatures than pure CeO 2 . The textural stability of the mixed oxides is also improved by incorporation of lanthana. All these properties make the ceria-lanthana mixed oxides interesting alternative candidates to substitute ceria in three-way catalyst formulations. (orig.)

  11. Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al2O3 catalysts

    International Nuclear Information System (INIS)

    Dominguez-Crespo, M.A.; Diaz-Garcia, L.; Arce-Estrada, E.M.; Torres-Huerta, A.M.; Cortez de la Paz, M.T.

    2006-01-01

    Four NiMo catalyst supported on Al 2 O 3 with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 A for HDS and HDN

  12. Support effects on hydrotreating activity of NiMo catalysts

    International Nuclear Information System (INIS)

    Dominguez-Crespo, M.A.; Arce-Estrada, E.M.; Torres-Huerta, A.M.; Diaz-Garcia, L.; Cortez de la Paz, M.T.

    2007-01-01

    The effect of the gamma alumina particle size on the catalytic activity of NiMoS x catalysts prepared by precipitation method of aluminum acetate at pH = 10 was studied. The structural characterization of the supports was measured by using XRD, pyridine FTIR-TPD and nitrogen physisorption. NiMo catalysts were characterized during the preparation steps (annealing and sulfidation) using transmission electron microscopy (TEM). Hydrogen TPR studies of the NiMo catalysts were also carried out in order to correlate their hydrogenating properties and their catalytic functionality. Catalytic tests were carried out in a pilot plant at 613, 633 and 653 K temperatures. The results showed that the rate constants of hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatizing (HDA) at 613-653 K decreased in the following order: A > B > C corresponding to the increase of NiMoS particle size associated to these catalysts

  13. Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al 2O 3 catalysts

    Science.gov (United States)

    Domínguez-Crespo, M. A.; Díaz-García, L.; Arce-Estrada, E. M.; Torres-Huerta, A. M.; Cortéz-De la Paz, M. T.

    2006-11-01

    Four NiMo catalyst supported on Al 2O 3 with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 Å for HDS and HDN.

  14. Porous Silicates Modified with Zirconium Oxide and Sulfate Ions for Alcohol Dehydration Reactions

    Directory of Open Access Journals (Sweden)

    Heriberto Esteban Benito

    2015-01-01

    Full Text Available Porous silicates were synthesized by a nonhydrothermal method, using sodium silicate as a source of silica and cetyltrimethylammonium bromide as a template agent. Catalysts were characterized using thermogravimetric analysis, N2 physisorption, X-ray diffraction, FTIR spectroscopy, pyridine adsorption, potentiometric titration with n-butylamine, scanning electronic microscopy, and transmission electronic microscopy. The surface area of the materials synthesized was greater than 800 m2/g. The introduction of zirconium atoms within the porous silicates increased their acid strength from −42 to 115 mV, while the addition of sulfate ions raised this value to 470 mV. The catalytic activity for the dehydration of alcohols yields conversions of up to 70% for ethanol and 30% for methanol.

  15. Pre-treatment of desalination feed seawater by Jordanian Tripoli, Pozzolana and Feldspar: batch experiments

    Directory of Open Access Journals (Sweden)

    AIMAN E. AL-RAWAJFEH

    2011-06-01

    Full Text Available In this research, composites of layered double hydroxide (LDH with three Jordanian natural raw materials: Tripoli (T, Pozzolana (P and Feldspar (F were prepared by co-precipitation and have been used for feed seawater pre-treatment. The data reveals that percent adsorption decreased with increase in initial concentration, but the actual amount of adsorbed ions per unit mass of LDH/T-P-F increased with increase in metal ion concentrations. The values of ΔG were negative and within 21 to 26 kJ/mol, while the values of and ΔS were positive, with ΔH within the range of 0.1 to 25 kJ/mol. The values of ΔH, ΔS and ΔG indicate the favorability of physisorption and show that the LDH/T-P-F composites have a considerable potential as adsorbents for the removal of ions from seawater.

  16. Photosensitized Oxidation of 9,10-Dimethylanthracene on Dye-Doped Silica Composites

    Directory of Open Access Journals (Sweden)

    Elim Albiter

    2012-01-01

    Full Text Available A series of cationic dyes, methylene blue (MB, safranin O (SF, toluidine blue (TB, and neutral red (NR, were successfully incorporated into a silica matrix by using ultrasound irradiation during the Stöber process. Several analyses were performed, including scanning dynamic light scattering (DLS, electron microscopy (SEM, nitrogen physisorption, FTIR spectroscopy, UV-vis, and diffuse reflectance spectroscopy. The entrapped dyes on silica were evaluated in singlet oxygen (1O2 generation under visible light irradiation, by means of the photosensitized oxidation of 9,10-dimethylanthracene (DMA. According to the results, the photocatalytic performance of the silica composites was improved, and the leakage of the dye from the particles was suppressed. Among these four different types of dye-doped silica composites, the SiO2-SF composite showed the most efficient delivery of 1O2.

  17. Performance of Cobalt-Based Fischer-Tropsch Synthesis Catalysts Using Dielectric-Barrier Discharge Plasma as an Alternative to Thermal Calcination

    International Nuclear Information System (INIS)

    Bai Suli; Huang Chengdu; Lv Jing; Li Zhenhua

    2012-01-01

    Co-based catalysts were prepared by using dielectric-barrier discharge (DBD) plasma as an alternative method to conventional thermal calcination. The characterization results of N 2 -physisorption, temperature programmed reduction (TPR), transmission electron microscope (TEM), and X-ray diffraction (XRD) indicated that the catalysts prepared by DBD plasma had a higher specific surface area, lower reduction temperature, smaller particle size and higher cobalt dispersion as compared to calcined catalysts. The DBD plasma method can prevent the sintering and aggregation of active particles on the support due to the decreased treatment time (0.5 h) at lower temperature compared to the longer thermal calcination at higher temperature (at 500° C for 5 h). As a result, the catalytic performance of the Fischer-Tropsch synthesis on DBD plasma treated Co/SiO 2 catalyst showed an enhanced activity, C 5+ selectivity and catalytic stability as compared to the conventional thermal calcined Co/SiO 2 catalyst.

  18. Vastly enhancing the chemical stability of phosphorene by employing an electric field.

    Science.gov (United States)

    Gao, Junfeng; Zhang, Gang; Zhang, Yong-Wei

    2017-03-23

    Currently, a major hurdle preventing phosphorene from various electronic applications is its rapid oxidation under ambient conditions. Thus how to enhance its chemical stability by suppressing oxidation becomes an urgent task. Here, we reveal a highly effective procedure to suppress the oxidation of phosphorene by employing a suitable van der Waals (vdW) substrate and a vertical electric field. Our first-principles study shows that the phosphorene-MoSe 2 vdW heterostructure is able to reverse the stability of physisorption and chemisorption of molecular O 2 on phosphorene. With further application of a vertical electric field of -0.6 V Å -1 , the energy barrier for oxidation is able to further increase to 0.91 eV, leading to a 10 5 times enhancement in its lifetime compared with that without using the procedure at room temperature. Our work presents a viable strategy to vastly enhance the chemical stability of phosphorene in air.

  19. Porous carbons prepared by direct carbonization of MOFs for supercapacitors

    Science.gov (United States)

    Yan, Xinlong; Li, Xuejin; Yan, Zifeng; Komarneni, Sridhar

    2014-07-01

    Three porous carbons were prepared by direct carbonization of HKUST-1, MOF-5 and Al-PCP without additional carbon precursors. The carbon samples obtained by carbonization at 1073 K were characterized by XRD, TEM and N2 physisorption techniques followed by testing for electrochemical performance. The BET surface areas of the three carbons were in the range of 50-1103 m2/g. As electrode materials for supercapacitor, the MOF-5 and Al-PCP derived carbons displayed the ideal capacitor behavior, whereas the HKUST-1 derived carbon showed poor capacitive behavior at various sweep rates and current densities. Among those carbon samples, Al-PCP derived carbons exhibited highest specific capacitance (232.8 F/g) in 30% KOH solution at the current density of 100 mA/g.

  20. A Comparative Characterization of the HPA-MCM-48 Type Catalysts Produced by the Direct Hydrothermal and Room Temperature Synthesis Methods

    International Nuclear Information System (INIS)

    Gucbilmez, Y.; Calis, I.; Yargic, A. S.

    2012-01-01

    MCM-48 type support materials synthesized by the direct hydrothermal synthesis (HTS) and room temperature synthesis (RTS) methods were incorporated with tungstophosphoric acid (TPA) in the range of 10-40 wt% by using a wet impregnation technique in methanol solutions. Resulting HPA-MCM-48 catalysts were characterized by the XRD, Nitrogen Physisorption, SEM, TEM, EDS, and FT-IR methods in order to determine the effects of different initial synthesis conditions on the catalyst properties. RTS samples were found to have better crystalline structures, higher BET surface areas, and higher BJH pore volumes than HTS samples. They also had slightly higher TPA incorporation, except for the 40 wt% samples, as evidenced by the EDS results. Keggin ion structure was preserved, for both methods, even at the highest acid loading of 40 wt%. It was concluded that the simpler and more economical RTS method was more successful than the HTS method for hetero poly acid incorporation into MCM-48 type materials

  1. High surface area V-Mo-N materials synthesized from amine intercalated foams

    International Nuclear Information System (INIS)

    Krawiec, Piotr; Narayan Panda, Rabi; Kockrick, Emanuel; Geiger, Dorin; Kaskel, Stefan

    2008-01-01

    Nanocrystalline ternary V-Mo nitrides were prepared via nitridation of amine intercalated oxide foams or bulk ternary oxides. Specific surface areas were in the range between 40 and 198 m 2 g -1 and strongly depended on the preparation method (foam or bulk oxide). Foamed precursors were favorable for vanadium rich materials, while for molybdenum rich samples bulk ternary oxides resulted in higher specific surface areas. The materials were characterized via nitrogen physisorption at 77 K, X-ray diffraction patterns, electron microscopy, and elemental analysis. - Graphical abstract: Nanocrystalline ternary V-Mo nitrides were prepared via nitridation of amine intercalated oxide foams or bulk ternary oxides. Foamed precursors were favorable for vanadium rich materials, while for molybdenum rich samples bulk ternary oxides resulted in higher specific surface areas

  2. Applications of core level spectroscopy to adsorbates

    International Nuclear Information System (INIS)

    Nilsson, Anders

    2002-01-01

    In the following review different applications of core-level spectroscopy to atomic and molecular adsorbates will be shown. Core-holes are created through core-level ionization and X-ray absorption processes and the core-hole decays by radiant and non-radiant processes. This forms the basis for X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, Auger electron spectroscopy and X-ray emission spectroscopy. We will demonstrate how we can use the different methods to obtain information about the chemical state, local geometric structure, nature of chemical bonding and dynamics in electron transfer processes. The adsorption of N 2 and CO on Ni(100) will be used as prototype systems for chemisorption while N 2 on graphite and Ar on Pt for physisorption

  3. Organic Vapour Sensing Properties of Area-Ordered and Size-Controlled Silicon Nanopillar

    Directory of Open Access Journals (Sweden)

    Wei Li

    2016-11-01

    Full Text Available Here, a silicon nanopillar array (Si-NPA was fabricated. It was studied as a room-temperature organic vapour sensor, and the ethanol and acetone gas sensing properties were detected with I-V curves. I-V curves show that these Si-NPA gas sensors are sensitive to ethanol and acetone organic vapours. The turn-on threshold voltage is about 0.5 V and the operating voltage is 3 V. With 1% ethanol gas vapour, the response time is 5 s, and the recovery time is 15 s. Furthermore, an evaluation of the gas sensor stability for Si-NPA was performed. The gas stability results are acceptable for practical detections. These excellent sensing characteristics can mainly be attributed to the change of the overall dielectric constant of Si-NPA caused by the physisorption of gas molecules on the pillars, and the filling of the gas vapour in the voids.

  4. Non-covalent functionalization of single wall carbon nanotubes and graphene by a conjugated polymer

    KAUST Repository

    Jiwuer, Jilili; Abdurahman, Ayjamal; Gü lseren, Oğuz; Schwingenschlö gl, Udo

    2014-01-01

    We report first-principles calculations on the binding of poly[(9,9-bis-(6-bromohexylfluorene-2,7-diyl)-co-(benzene-1,4-diyl)] to a (8,0) single wall carbon nanotube (SWCNT) and to graphene. Considering different relative orientations of the subsystems, we find for the generalized gradient approximation a non-binding state, whereas the local density approximation predicts reasonable binding energies. The results coincide after inclusion of van der Waals corrections, which demonstrates a weak interaction between the polymer and SWCNT/graphene, mostly of van der Waals type. Accordingly, the density of states shows essentially no hybridization. The physisorption mechanism explains recent experimental observations and suggests that the conjugated polymer can be used for non-covalent functionalization.

  5. Heterogeneous catalysis afford biodiesel of babassu, castor oil and blends

    International Nuclear Information System (INIS)

    Carvalho, Lee M.G. de; Abreu, Wiury C. de; Silva, Maria das Gracas de O. e; Matos, Jose Milton E. de; Moura, Carla V.R. de; Moura, Edmilson M. de; Lima, Jose Renato de O.; Oliveira, Jose Eduardo de

    2013-01-01

    This work describes the preparation of babassu, castor oil biodiesel and mixtures in various proportions of these oils, using alkaline compounds of strontium (SrCO 3 + SrO + Sr (OH) 2 ) as heterogeneous catalysts. The mixture of oils of these oleaginous sources was used in the production of biodiesel with quality parameters that meet current legislation. The catalyst was characterized by X-ray diffractometry (XDR), physisorption of gas (BET method), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). The viscometric technique was used to monitor the optimization.The transesterification reactions performed using strontium compounds reached conversion rates of 97.2% babassu biodiesel (BB), 96.4% castor oil biodiesel (COB) and 95.3% Babassu/Castor Oil Biodiesel 4:1 (BBCO41). (author)

  6. CO2 Capacity Sorbent Analysis Using Volumetric Measurement Approach

    Science.gov (United States)

    Huang, Roger; Richardson, Tra-My Justine; Belancik, Grace; Jan, Darrell; Knox, Jim

    2017-01-01

    In support of air revitalization system sorbent selection for future space missions, Ames Research Center (ARC) has performed CO2 capacity tests on various solid sorbents to complement structural strength tests conducted at Marshall Space Flight Center (MSFC). The materials of interest are: Grace Davison Grade 544 13X, Honeywell UOP APG III, LiLSX VSA-10, BASF 13X, and Grace Davison Grade 522 5A. CO2 capacity was for all sorbent materials using a Micromeritics ASAP 2020 Physisorption Volumetric Analysis machine to produce 0C, 10C, 25C, 50C, and 75C isotherms. These data are to be used for modeling data and to provide a basis for continued sorbent research. The volumetric analysis method proved to be effective in generating consistent and repeatable data for the 13X sorbents, but the method needs to be refined to tailor to different sorbents.

  7. An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water Electro-oxidation at Neutral pH

    KAUST Repository

    Chen, Batian; Morlanes, Natalia Sanchez; Adogla, Enoch; Takanabe, Kazuhiro; Rodionov, Valentin

    2016-01-01

    The synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine is described. Hydrophobicity was identified as the key variable in mediating the catalytic competence of the complexes. The change in this parameter correlates with both the conformational mobility of the ligand core and the structural changes in the local solvent environment around the metal site. The optimal Co complex identified is hydrophobic, because of three semifluorinated side chains. It catalyzes water electro-oxidation efficiently at neutral pH, with an overpotential of 390 mV and a turnover frequency (TOF) of 1.83 s-1 in the absence of soluble Co salts. The catalyst can be immobilized through physisorption, and it remains stable in prolonged electrolysis experiments. © 2016 American Chemical Society.

  8. Synthesis, characterization and photo catalytic activity of titanium oxide modified with nitrogen; Sintesis, caracterizacion y actividad fotocatalitica de oxido de titanio modificado con nitrogeno

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez Enriquez, J. M.; Garcia Alamilla, R.; Garcia Serrano, L. A.; Cueto Hernandez, A.

    2011-07-01

    Titanium oxides (TiO{sub 2}) were synthesized by precipitation of titanium tetrachloride (TiCl{sub 4}) using ammonium hydroxide (NH{sub 4}OH). The synthesized materials were characterized by means of nitrogen physisorption, X-ray diffraction, infrared spectroscopy, U.V.-visible diffuse reflectance spectroscopy and the photo catalytic activity of the samples were measured by the degradation of the methyl orange. By means of this synthesis method we have doped the titanium oxide structure with nitrogen (N-TiO{sub 2}), stabilizing the anatase phase and obtaining meso porous and nanocrystalline materials. The titanium oxide with higher specific surface area (132 m{sup 2}/g) degraded the azo-compound to 100% in 180 min of reaction. (Author) 33 refs.

  9. Facile NOx interconversion over preoxidized Ag(111)

    Science.gov (United States)

    Klacar, S.; Martin, N. M.; Gustafson, J.; Blomberg, S.; Liu, Z.; Axnanda, S.; Chang, R.; Lundgren, E.; Grönbeck, H.

    2013-11-01

    X-ray photoelectron spectroscopy and density functional theory calculations are used to investigate NO adsorption at low (100 K) and room temperature (RT) over preoxidized Ag(111). At 100 K, the data indicates presence of NO and N2O2, with little or no nitrite/nitrate formation. This is consistent with the calculated surface core level shifts and the pronounced barrier for nitrite formation. At RT, the recorded spectra indicate a complex interconversion between adsorbed species with an initial formation of a p(4 × 4) nitrate overlayer. With increasing NO pressure, the experimental results are best rationalized by partial nitrate decomposition into nitrites and subsequent NO physisorption, which leads to the formation of N2O3-like species.

  10. Polycyclic Aromatic Hydrocarbons Adsorption onto Graphene: A DFT and AIMD Study

    Directory of Open Access Journals (Sweden)

    Bing Li

    2018-05-01

    Full Text Available Density functional theory (DFT calculations and ab-initio molecular dynamics (AIMD simulations were performed to understand graphene and its interaction with polycyclic aromatic hydrocarbons (PAHs molecules. The adsorption energy was predicted to increase with the number of aromatic rings in the adsorbates, and linearly correlate with the hydrophobicity of PAHs. Additionally, the analysis of the electronic properties showed that PAHs behave as mild n-dopants and introduce electrons into graphene; but do not remarkably modify the band gap of graphene, indicating that the interaction between PAHs and graphene is physisorption. We have also discovered highly sensitive strain dependence on the adsorption strength of PAHs onto graphene surface. The AIMD simulation indicated that a sensitive and fast adsorption process of PAHs can be achieved by choosing graphene as the adsorbent. These findings are anticipated to shed light on the future development of graphene-based materials with potential applications in the capture and removal of persistent aromatic pollutants.

  11. Charge transfer processes during ion scattering and stimulated desorption of secondary ions from gas-condensed dielectric surfaces

    CERN Document Server

    Souda, R

    2002-01-01

    The ion emission mechanism from weakly-interacting solid surfaces has been investigated. The H sup + ion captures a valence electron via transient chemisorption, so that the ion neutralization probability is related to the nature of bonding of adsorbates. The H sup + ion is scattered from physisorbed Ar at any coverage whereas the H sup + yield from solid H sub 2 O decays considerably due to covalency in the hydrogen bond. In electron- and ion-stimulated desorption, the ion ejection probability is correlated intimately with the physisorption/chemisorption of parent atoms or molecules. The emission of F sup + ions is rather exceptional because they arise from the screened F 2s core-hole state followed by the ionization via the intra-atomic Auger decay after bond breakage. In electron-stimulated desorption of H sub 2 O, hydrated protons are emitted effectively from nanoclusters formed on a solid Ar substrate due to Coulomb repulsion between confined valence holes.

  12. Porous Aluminum Oxide and Magnesium Oxide Films Using Organic Hydrogels as Structure Matrices

    Directory of Open Access Journals (Sweden)

    Zimei Chen

    2018-03-01

    Full Text Available We describe the synthesis of mesoporous Al2O3 and MgO layers on silicon wafer substrates by using poly(dimethylacrylamide hydrogels as porogenic matrices. Hydrogel films are prepared by spreading the polymer through spin-coating, followed by photo-cross-linking and anchoring to the substrate surface. The metal oxides are obtained by swelling the hydrogels in the respective metal nitrate solutions and subsequent thermal conversion. Combustion of the hydrogel results in mesoporous metal oxide layers with thicknesses in the μm range and high specific surface areas up to 558 m2∙g−1. Materials are characterized by SEM, FIB ablation, EDX, and Kr physisorption porosimetry.

  13. Effect of Ti content in the photo catalytic behavior of Fe/TiO2-SiO2 systems

    International Nuclear Information System (INIS)

    Leon C, A.; Portillo V, N.; Hernandez P, I.; May L, M.; Gonzalez R, L.; Luna P, R.; Suarez P, R.

    2013-01-01

    In this work we report the synthesis of Fe/TiO 2 -SiO 2 systems with different concentrations of TiO 2 in order to determine the influence of titanium content on the structural, textural, optical properties and their photo catalytic behavior. The materials were synthesized by the sol-gel method and their modification was carried out by incipient impregnation. All samples were characterized be means of X-ray diffraction, N 2 physisorption (Bet method), Dr-UV-Vis and Raman spectroscopy. The modifications of the structural and optical properties are discussed on the basis of long-range order reduction, suggesting the formation of highly dispersed TiO 2 species. On the other hand, it was observed that the energy of the optical band gap decreases by introducing Fe. On the basis of these phenomena, the photo catalytic activity was measured, employing the degradation of orange II azo dye as a model reaction. (Author)

  14. Preparation of resveratrol-loaded nanoporous silica materials with different structures

    Science.gov (United States)

    Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

    2014-11-01

    Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound.

  15. Adsorption of diclofenac and nimesulide on activated carbon: Statistical physics modeling and effect of adsorbate size

    Science.gov (United States)

    Sellaoui, Lotfi; Mechi, Nesrine; Lima, Éder Cláudio; Dotto, Guilherme Luiz; Ben Lamine, Abdelmottaleb

    2017-10-01

    Based on statistical physics elements, the equilibrium adsorption of diclofenac (DFC) and nimesulide (NM) on activated carbon was analyzed by a multilayer model with saturation. The paper aimed to describe experimentally and theoretically the adsorption process and study the effect of adsorbate size using the model parameters. From numerical simulation, the number of molecules per site showed that the adsorbate molecules (DFC and NM) were mostly anchored in both sides of the pore walls. The receptor sites density increase suggested that additional sites appeared during the process, to participate in DFC and NM adsorption. The description of the adsorption energy behavior indicated that the process was physisorption. Finally, by a model parameters correlation, the size effect of the adsorbate was deduced indicating that the molecule dimension has a negligible effect on the DFC and NM adsorption.

  16. β-TCP porous pellets as an orthopaedic drug delivery system: ibuprofen/carrier physicochemical interactions

    International Nuclear Information System (INIS)

    Baradari, Hiba; Damia, Chantal; Dutreih-Colas, Maggy; Champion, Eric; Chulia, Dominique; Viana, Marylene

    2011-01-01

    Calcium phosphate bone substitute materials can be loaded with active substances for in situ, targeted drug administration. In this study, porous β-TCP pellets were investigated as an anti-inflammatory drug carrier. Porous β-TCP pellets were impregnated with an ethanolic solution of ibuprofen. The effects of contact time and concentration of ibuprofen solution on drug adsorption were studied. The ibuprofen adsorption equilibrium time was found to be one hour. The adsorption isotherms fitted to the Freundlich model, suggesting that the interaction between ibuprofen and β-TCP is weak. The physicochemical characterizations of loaded pellets confirmed that the reversible physisorption of ibuprofen on β-TCP pellets is due to Van der Waals forces, and this property was associated with the 100% ibuprofen release.

  17. Titanium embedded cage structure formation in AlnTi+ clusters and their interaction with Ar

    International Nuclear Information System (INIS)

    Torres, M. B.; Vega, A.; Balbás, L. C.; Aguilera-Granja, F.

    2014-01-01

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al n Ti + [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n c determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al n Ti + , experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al n Ti + (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n c = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n c = 21) and their neutral counterparts (n c = 20). For the Al n Ti + · Ar complexes, and for n n Ti + clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support to the experimental technique used. For n c = 21, the smallest size of endohedral Ti doped cationic clusters, the Ar binding energy decreases drastically, whereas the Ar-cluster distance increases substantially, point to Ar physisorption, as assumed by the experimentalists. Calculated Ar adsorption energies agree well with available experimental binding

  18. Removal of element mercury by medicine residue derived biochars in presence of various gas compositions

    International Nuclear Information System (INIS)

    Li, Guoliang; Shen, Boxiong; Li, Yongwang; Zhao, Bin; Wang, Fumei; He, Chuan; Wang, Yinyin; Zhang, Min

    2015-01-01

    Highlights: • Both physisorption and chemisorption of Hg 0 occurred on the surface of M6WN5. • Chemisorption process was an absolute predominant route for Hg 0 removal by M6WN5. • The effect of NO, H 2 O, SO 2 and O 2 on Hg 0 removal by M6WN5 was investigated. • M6WN5 demonstrated to be a promising Hg 0 sorbent in flue gas. - Abstract: Pyrolyzed biochars from an industrial medicinal residue waste were modified by microwave activation and NH 4 Cl impregnation. Mercury adsorption of different modified biochars was investigated in a quartz fixed-bed reactor. The results indicated that both physisorption and chemisorption of Hg 0 occurred on the surface of M6WN5 which was modified both microwave and 5 wt.% NH 4 Cl loading, and exothermic chemisorption process was a dominant route for Hg 0 removal. Microwave activation improved pore properties and NH 4 Cl impregnation introduced good active sites for biochars. The presence of NO and O 2 increased Hg 0 adsorption whereas H 2 O inhibited Hg 0 adsorption greatly. A converse effect of SO 2 was observed on Hg 0 removal, namely, low concentration of SO 2 promoted Hg 0 removal obviously whereas high concentration of SO 2 suppressed Hg 0 removal. The Hg 0 removal by M6WN5 was mainly due to the reaction of the C−Cl with Hg 0 to form HgCl 2 , and the active state of C−Cl * groups might be an intermediate group in this process. Thermodynamic analysis showed that mercury adsorption by the biochars was exothermic process and apparent adsorption energy was 43.3 kJ/mol in the range of chemisorption. In spite of low specific surface area, M6WN5 proved to be a promising Hg 0 sorbent in flue gas when compared with other sorbents

  19. The influence of alizarin and fluorescein on the photoactivity of Ni, Pt and Ru-doped TiO2 layers

    International Nuclear Information System (INIS)

    Rosu, Marcela-Corina; Suciu, Ramona-Crina; Lazar, Mihaela D.; Bratu, I.

    2013-01-01

    Highlights: ► The Ni, Pt, Ru-doped TiO 2 materials and sensitized with alizarin and fluorescein dyes were prepared by wet chemical route. ► The samples were characterized by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N 2 physisorption measurements. ► A combined influence of the dopants and dyes was observed, leading to a beneficial effect to TiO 2 photoactivity. -- Abstract: The doping with different metal ions and sensitization with organic compounds are two well known methods used to improve the photoactivity of TiO 2 . In this respect, the metallic ions-doped TiO 2 samples were prepared by embedding Ni, Pt and Ru ions into TiO 2 crystalline network and then, each sample was sensitized with alizarin and fluorescein dyes. The qualitative evaluation of prepared TiO 2 -based materials was made by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N 2 physisorption measurements. The optoelectronic properties investigated by UV–vis spectroscopy show that the optical response of Ni-doped TiO 2 layer shifts to visible. The X-ray spectra do not show peaks of nickel, platinum and ruthenium oxide crystals or pure metals. The FT/IR spectra proved the presence of dye molecules adsorbed on titania nanoparticles surface. These results demonstrated that the studied dopants and dyes have potential to promote modified TiO 2 -based materials as good candidates to be used in photolectrocatalytic processes

  20. Mechanism of amitriptyline adsorption on Ca-montmorillonite (SAz-2)

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Po-Hsiang [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Jiang, Wei-Teh, E-mail: atwtj@mail.ncku.edu.tw [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Li, Zhaohui, E-mail: li@uwp.edu [Department of Geosciences, University of Wisconsin – Parkside, 900 Wood Road, Kenosha, WI 53144 (United States); Kuo, Chung-Yih [Department of Public Health, College of Health Care and Management, Chung Shan Medical University, No. 110, Sec. 1, Chien-kuo N Road, Taichung 40242, Taiwan (China); Jean, Jiin-Shuh [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Chen, Wan-Ru [Department of Environmental Engineering, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Lv, Guocheng [School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China)

    2014-07-30

    Graphical abstract: XRD patterns to show AMI intercalation into SAz-2 vs. direct mixing of the same amount of AMI with SAz-2. - Highlights: • Ca-montmorillonite is proven to be an efficient adsorbent or sink for amitriptyline. • The high adsorption capacity is accompanied with intercalation into interlayers. • The adsorption is mainly governed by a cation exchange mechanism. • Horizontal mono- and bi-layer conformations occur at low and high adsorption levels. • The process is an endothermic physisorption at high adsorption levels. - Abstract: The uptake of amitriptyline (AMI) from aqueous environment by Ca-montmorillonite (SAz-2) was studied in a batch system under different physicochemical conditions. The adsorbent was characterized by X-ray diffraction and Fourier transform infrared (FTIR) analyses. The AMI adsorption on SAz-2 obeyed the Langmuir isotherm with a capacity of 330 mg/g (1.05 mmol/g) at pH 6–7. The adsorption kinetics was fast, almost reaching equilibrium in 2 h, and followed a pseudo-second-order kinetic model. Desorption of exchangeable cations correlated with the AMI adsorption well, indicating that cation exchange was the major mechanism. X-ray diffraction patterns showing significant expansions of the d{sub 0} {sub 0} {sub 1} spacing and characteristic FTIR band shifts toward higher frequencies after AMI adsorption onto SAz-2 indicated that the adsorbed AMI molecules were intercalated into the interlayers of the mineral. Thermodynamic parameters based on partitioning coefficients suggested that the AMI adsorption was an endothermic physisorption at high adsorption levels. At low and higher AMI adsorption levels, the intercalated AMI molecules take a horizontal monolayer and bilayer conformation, respectively. The higher adsorption capacity suggested that SAz-2 could be a good candidate to remove AMI from wastewater and would be an important environmental sink for the fate and transport of AMI in soils and groundwater.

  1. Adsorption of Pb(II) present in aqueous solution on calcium, strontium and barium hydroxy apatites; Adsorcion de Pb(II) presente en solucion acuosa sobre hidroxiapatitas de calcio, estroncio y bario

    Energy Technology Data Exchange (ETDEWEB)

    Vilchis G, J.

    2013-07-01

    Calcium, strontium and barium hydroxy apatites were successfully synthesized by chemical precipitation method, the obtained powders were characterized by the techniques of X-ray diffraction (XRD), scanning electron microscopy (Sem), semi-quantitative elemental analysis (EDS), infrared spectroscopy (IR), and N{sub 2} physisorption studies, complementary to these analytical techniques, was determined the surface fractal dimension (Df), and the amount of surface active sites of the materials, in order to know application as ceramic for water remediation. The ability of Pb(II) ion adsorption present in aqueous solution on the hydroxy apatites synthesized by batch type experiments was studied as a function of contact time, concentration of the adsorbate and temperature. The maximum lead adsorption efficiencies obtained were 0.31, 0.32 and 0.26 mg/g for calcium, strontium and barium hydroxy apatites respectively, achieved an equilibrium time of 20 minutes in the three solid-liquid systems studied. Experimental data were adequately adjusted at the adsorption kinetic model pseudo-second order, for the three cases. Moreover, experimental data of the strontium and calcium hydroxy apatites were adjusted to the Langmuir adsorption isotherm, indicating that the adsorption was through a monolayer, whereas barium hydroxyapatite was adjusted to the Freundlich adsorption isotherm, indicating a multilayer adsorption. The thermodynamic parameters obtained during adsorption studies as a function of temperature showed physisorption, exothermic and spontaneous processes respectively. The results showed that the calcium hydroxyapatite, strontium and barium are an alternative for the Pb(II) ion adsorption present in wastewaters. (Author)

  2. A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

    International Nuclear Information System (INIS)

    Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu; Chou, Lingjun; Zhuo, Shuping

    2017-01-01

    Highlights: • A novel mesoporous ZrO_2/SO_4"2"− has been prepared via a facile one-pot EISA strategy. • The M-ZrO_2/SO_4"2"− exhibited excellent textural and acidic properties. • The introduced S species were homogeneously dispersed in mesoporous skeleton. • The M-ZrO_2/SO_4"2"− exhibited excellent catalytic performance and reusability. - Abstract: In this paper, a novel mesoporous sulfated zirconium (M-ZrO_2/SO_4"2"−) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N_2-physisorption and TEM characterization techniques indicated that M-ZrO_2/SO_4"2"− possessed distinct mesostructure with big specific surface area (133.5 m"2 g"−"1), large pore volume (0.18 cm"3 g"−"1) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N_2-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO_4"2"−, improved the textural properties of prepared materials. In addition, the NH_3-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO_2/SO_4"2"− even evacuated at 400 °C. Furthermore, the M-ZrO_2/SO_4"2"− was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  3. Towards modelling the vibrational signatures of functionalized surfaces: carboxylic acids on H-Si(111) surfaces

    Science.gov (United States)

    Giresse Tetsassi Feugmo, Conrard; Champagne, Benoît; Caudano, Yves; Cecchet, Francesca; Chabal, Yves J.; Liégeois, Vincent

    2012-03-01

    In this work, we investigate the adsorption process of two carboxylic acids (stearic and undecylenic) on a H-Si(111) surface via the calculation of structural and energy changes as well as the simulation of their IR and Raman spectra. The two molecules adsorb differently at the surface since the stearic acid simply physisorbs while the undecylenic acid undergoes a chemical reaction with the hydrogen atoms of the surface. This difference is observed in the change of geometry during the adsorption. Indeed, the chemisorption of the undecylenic acid has a bigger impact on the structure than the physisorption of the stearic acid. Consistently, the former is also characterized by a larger value of adsorption energy and a smaller value of the tilting angle with respect to the normal plane. For both the IR and Raman signatures, the spectra of both molecules adsorbed at the surface are in a first approximation the superposition of the spectra of the Si cluster and of the carboxylic acid considered individually. The main deviation from this simple observation is the peak of the stretching Si-H (ν(Si-H)) mode, which is split into two peaks upon adsorption. As expected, the splitting is bigger for the chemisorption than the physisorption. The modes corresponding to atomic displacements close to the adsorption site display a frequency upshift by a dozen wavenumbers. One can also see the disappearance of the peaks associated with the C=C double bond when the undecylenic acid chemisorbs at the surface. The Raman and IR spectra are complementary and one can observe here that the most active Raman modes are generally IR inactive. Two exceptions to this are the two ν(Si-H) modes which are active in both spectroscopies. Finally, we compare our simulated spectra with some experimental measurements and we find an overall good agreement.

  4. Towards modelling the vibrational signatures of functionalized surfaces: carboxylic acids on H-Si(111) surfaces

    International Nuclear Information System (INIS)

    Tetsassi Feugmo, Conrard Giresse; Champagne, Benoît; Liégeois, Vincent; Caudano, Yves; Cecchet, Francesca; Chabal, Yves J

    2012-01-01

    In this work, we investigate the adsorption process of two carboxylic acids (stearic and undecylenic) on a H-Si(111) surface via the calculation of structural and energy changes as well as the simulation of their IR and Raman spectra. The two molecules adsorb differently at the surface since the stearic acid simply physisorbs while the undecylenic acid undergoes a chemical reaction with the hydrogen atoms of the surface. This difference is observed in the change of geometry during the adsorption. Indeed, the chemisorption of the undecylenic acid has a bigger impact on the structure than the physisorption of the stearic acid. Consistently, the former is also characterized by a larger value of adsorption energy and a smaller value of the tilting angle with respect to the normal plane. For both the IR and Raman signatures, the spectra of both molecules adsorbed at the surface are in a first approximation the superposition of the spectra of the Si cluster and of the carboxylic acid considered individually. The main deviation from this simple observation is the peak of the stretching Si-H (ν(Si-H)) mode, which is split into two peaks upon adsorption. As expected, the splitting is bigger for the chemisorption than the physisorption. The modes corresponding to atomic displacements close to the adsorption site display a frequency upshift by a dozen wavenumbers. One can also see the disappearance of the peaks associated with the C=C double bond when the undecylenic acid chemisorbs at the surface. The Raman and IR spectra are complementary and one can observe here that the most active Raman modes are generally IR inactive. Two exceptions to this are the two ν(Si-H) modes which are active in both spectroscopies. Finally, we compare our simulated spectra with some experimental measurements and we find an overall good agreement. (paper)

  5. Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

    International Nuclear Information System (INIS)

    Pershina, V.; Borschevsky, A.; Iliaš, M.; Türler, A.

    2014-01-01

    With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl 4 , MOCl 2 , MCl 6 − , and MOCl 4 2 with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl 4 , the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔH sub , of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔH sub (RfCl 4 ) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl 2 on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl 4 on quartz by chemical forces, formation of the MOCl 2 or MOCl 4 2− complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl 4 on a chlorinated quartz surface, formation of the MCl 6 2− surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the “one-atom-at-a-time” gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations

  6. Mechanism of amitriptyline adsorption on Ca-montmorillonite (SAz-2)

    International Nuclear Information System (INIS)

    Chang, Po-Hsiang; Jiang, Wei-Teh; Li, Zhaohui; Kuo, Chung-Yih; Jean, Jiin-Shuh; Chen, Wan-Ru; Lv, Guocheng

    2014-01-01

    Graphical abstract: XRD patterns to show AMI intercalation into SAz-2 vs. direct mixing of the same amount of AMI with SAz-2. - Highlights: • Ca-montmorillonite is proven to be an efficient adsorbent or sink for amitriptyline. • The high adsorption capacity is accompanied with intercalation into interlayers. • The adsorption is mainly governed by a cation exchange mechanism. • Horizontal mono- and bi-layer conformations occur at low and high adsorption levels. • The process is an endothermic physisorption at high adsorption levels. - Abstract: The uptake of amitriptyline (AMI) from aqueous environment by Ca-montmorillonite (SAz-2) was studied in a batch system under different physicochemical conditions. The adsorbent was characterized by X-ray diffraction and Fourier transform infrared (FTIR) analyses. The AMI adsorption on SAz-2 obeyed the Langmuir isotherm with a capacity of 330 mg/g (1.05 mmol/g) at pH 6–7. The adsorption kinetics was fast, almost reaching equilibrium in 2 h, and followed a pseudo-second-order kinetic model. Desorption of exchangeable cations correlated with the AMI adsorption well, indicating that cation exchange was the major mechanism. X-ray diffraction patterns showing significant expansions of the d 0 0 1 spacing and characteristic FTIR band shifts toward higher frequencies after AMI adsorption onto SAz-2 indicated that the adsorbed AMI molecules were intercalated into the interlayers of the mineral. Thermodynamic parameters based on partitioning coefficients suggested that the AMI adsorption was an endothermic physisorption at high adsorption levels. At low and higher AMI adsorption levels, the intercalated AMI molecules take a horizontal monolayer and bilayer conformation, respectively. The higher adsorption capacity suggested that SAz-2 could be a good candidate to remove AMI from wastewater and would be an important environmental sink for the fate and transport of AMI in soils and groundwater

  7. Adsorption properties of fission gases Xe and Kr on pristine and doped graphene: A first principle DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Vazhappilly, Tijo, E-mail: tijoj@barc.gov.in [Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Ghanty, Tapan K., E-mail: tapang@barc.gov.in [Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Homi Bhabha National Institute, Training School Complex, Anushakti Nagar, Mumbai 400094 (India); Jagatap, B.N. [Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2017-07-15

    Graphene has excellent adsorption properties due to large surface area and has been used in applications related to gas sorption and separation. The separation of radioactive noble gases using graphene is an interesting area of research relevant to nuclear waste management. Radioactive noble gases Xe and Kr are present in the off-gas streams from nuclear fission reactors and spent nuclear fuel reprocessing plants. The entrapment of these volatile fission gases is important in the context of nuclear safety. The separation of Xe from Kr is extremely difficult, and energy intensive cryogenic distillation is generally employed. Physisorption based separation techniques using porous materials is a cost effective alternative to expensive cryogenic distillation. Thus, adsorption of noble gases on graphene is relevant for fundamental understanding of physisorption process. The properties of graphene can be tuned by doping and incorporation of defects. In this regard, we study the binding affinity of Xe and Kr in pristine and doped graphene sheets. We employ first principle calculations using density functional theory, corrected for dispersion interactions. The structural parameters obtained from the current study show excellent agreement with the available theoretical and experimental observations on similar systems. Noble gas adsorption energies on pristine graphene match very well with the available literature. Our results show that the binding energy of fission gases Xe and Kr on graphene can be considerably improved through doping the lattice with a heteroatom. - Graphical abstract: The adsorption of radioactive fission gases Xe and Kr on pristine/doped graphene is an interesting topic in the context of nuclear waste management. Previous experimental and computational studies about Xe/Kr adsorption on graphene were limited to only on pristine graphene. The doping by hetero atom changes the electronic properties of graphene and creates active sites in the lattice. Based

  8. Heat cascading regenerative sorption heat pump

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1995-01-01

    A simple heat cascading regenerative sorption heat pump process with rejected or waste heat from a higher temperature chemisorption circuit (HTCC) powering a lower temperature physisorption circuit (LTPC) which provides a 30% total improvement over simple regenerative physisorption compression heat pumps when ammonia is both the chemisorbate and physisorbate, and a total improvement of 50% or more for LTPC having two pressure stages. The HTCC contains ammonia and a chemisorbent therefor contained in a plurality of canisters, a condenser-evaporator-radiator system, and a heater, operatively connected together. The LTPC contains ammonia and a physisorbent therefor contained in a plurality of compressors, a condenser-evaporator-radiator system, operatively connected together. A closed heat transfer circuit (CHTC) is provided which contains a flowing heat transfer liquid (FHTL) in thermal communication with each canister and each compressor for cascading heat from the HTCC to the LTPC. Heat is regenerated within the LTPC by transferring heat from one compressor to another. In one embodiment the regeneration is performed by another CHTC containing another FHTL in thermal communication with each compressor. In another embodiment the HTCC powers a lower temperature ammonia water absorption circuit (LTAWAC) which contains a generator-absorber system containing the absorbent, and a condenser-evaporator-radiator system, operatively connected together. The absorbent is water or an absorbent aqueous solution. A CHTC is provided which contains a FHTL in thermal communication with the generator for cascading heat from the HTCC to the LTAWAC. Heat is regenerated within the LTAWAC by transferring heat from the generator to the absorber. The chemical composition of the chemisorbent is different than the chemical composition of the physisorbent, and the absorbent. The chemical composition of the FHTL is different than the chemisorbent, the physisorbent, the absorbent, and ammonia.

  9. Solar hydrogen hybrid system with carbon storage

    International Nuclear Information System (INIS)

    Zini, G.; Marazzi, R.; Pedrazzi, S.; Tartarini, P.

    2009-01-01

    A complete solar hydrogen hybrid system has been developed to convert, store and use energy from renewable energy sources. The theoretical model has been implemented in a dynamic model-based software environment and applied to real data to simulate its functioning over a one-year period. Results are used to study system design and performance. A photovoltaic sub-system directly drives a residential load and, if a surplus of energy is available, an electrolyzer to produce hydrogen which is stored in a cluster of nitrogen-cooled tanks filled with AX-21 activated carbons. When the power converted from the sun is not sufficient to cover load needs, hydrogen is desorbed from activated carbon tanks and sent to the fuel-cell sub-system so to obtain electrical energy. A set of sub-systems (bus-bar, buck- and boost-converters, inverter, control circuits), handle the electrical power according to a Programmable Logic Control unit so that the load can be driven with adequate Quality of Service. Hydrogen storage is achieved through physisorption (weak van der Waals interactions) between carbon atoms and hydrogen molecules occurring at low temperature (77 K) in carbon porous solids at relatively low pressures. Storage modeling has been developed using a Langmuir-Freundlich 1st type isotherm and experimental data available in literature. Physisorption storage provides safer operations along with good gravimetric (10.8% at 6 MPa) and volumetric (32.5 g/l at 6 MPa) storage capacities at costs that can be comparable to, or smaller than, ordinary storage techniques (compression or liquefaction). Several test runs have been performed on residential user data-sets: the system is capable of providing grid independence and can be designed to yield a surplus production of hydrogen which can be used to recharge electric car batteries or fill tanks for non-stationary uses. (author)

  10. The influence of alizarin and fluorescein on the photoactivity of Ni, Pt and Ru-doped TiO{sub 2} layers

    Energy Technology Data Exchange (ETDEWEB)

    Rosu, Marcela-Corina, E-mail: marcela.rosu@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293, Cluj-Napoca (Romania); Suciu, Ramona-Crina; Lazar, Mihaela D.; Bratu, I. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293, Cluj-Napoca (Romania)

    2013-04-20

    Highlights: ► The Ni, Pt, Ru-doped TiO{sub 2} materials and sensitized with alizarin and fluorescein dyes were prepared by wet chemical route. ► The samples were characterized by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N{sub 2} physisorption measurements. ► A combined influence of the dopants and dyes was observed, leading to a beneficial effect to TiO{sub 2} photoactivity. -- Abstract: The doping with different metal ions and sensitization with organic compounds are two well known methods used to improve the photoactivity of TiO{sub 2}. In this respect, the metallic ions-doped TiO{sub 2} samples were prepared by embedding Ni, Pt and Ru ions into TiO{sub 2} crystalline network and then, each sample was sensitized with alizarin and fluorescein dyes. The qualitative evaluation of prepared TiO{sub 2}-based materials was made by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N{sub 2} physisorption measurements. The optoelectronic properties investigated by UV–vis spectroscopy show that the optical response of Ni-doped TiO{sub 2} layer shifts to visible. The X-ray spectra do not show peaks of nickel, platinum and ruthenium oxide crystals or pure metals. The FT/IR spectra proved the presence of dye molecules adsorbed on titania nanoparticles surface. These results demonstrated that the studied dopants and dyes have potential to promote modified TiO{sub 2}-based materials as good candidates to be used in photolectrocatalytic processes.

  11. Scanning force microscopy and fluorescence microscopy of microcontact printed antibodies and antibody fragments.

    Science.gov (United States)

    LaGraff, John R; Chu-LaGraff, Quynh

    2006-05-09

    Unlabeled primary immunoglobulin G (IgG) antibodies and its F(ab')2 and Fc fragments were attached to oxygen-plasma-cleaned glass substrates using either microcontact printing (MCP) or physical adsorption during bath application from dilute solutions. Fluorescently labeled secondary IgGs were then bound to surface-immobilized IgG, and the relative surface coverage was determined by measuring the fluorescence intensity. Results indicated that the surface coverage of IgG increased with increasing protein solution concentration for both MCP and bath-applied IgG and that a greater concentration of IgG was transferred to a glass substrate using MCP than during physisorption during bath applications. Scanning force microscopy (SFM) showed that patterned MCP IgG monolayers were 5 nm in height, indicating that IgG molecules lie flat on the substrate. After incubation with a secondary IgG, the overall line thickness increased to around 15 nm, indicating that the secondary IgG was in a more vertical orientation with respect to the substrate. The surface roughness of these MCP patterned IgG bilayers as measured by SFM was observed to increase with increasing surface coverage. Physisorption of IgG to both unmodified patterned polydimethylsiloxane (PDMS) stamps and plasma-cleaned glass substrates was modeled by Langmuir adsorption kinetics yielding IgG binding constants of K(MCP) = 1.7(2) x 10(7) M(-1) and K(bath) = 7.8(7) x 10(5) M(-1), respectively. MCP experiments involving primary F(ab')2 and Fc fragments incubated in fluorescently labeled fragment-specific secondary IgGs were carried out to test for the function and orientation of IgG. Finally, possible origins of MCP stamping defects such as pits, pull outs, droplets, and reverse protein transfer are discussed.

  12. From Fundamental Understanding To Predicting New Nanomaterials For High Capacity Hydrogen/Methane Storage and Carbon Capture

    Energy Technology Data Exchange (ETDEWEB)

    Yildirim, Taner [Univ. of Pennsylvania, Philadelphia, PA (United States)

    2015-03-03

    On-board hydrogen/methane storage in fuel cell-powered vehicles is a major component of the national need to achieve energy independence and protect the environment. The main obstacles in hydrogen storage are slow kinetics, poor reversibility and high dehydrogenation temperatures for the chemical hydrides; and very low desorption temperatures/energies for the physisorption materials (MOF’s, porous carbons). Similarly, the current methane storage technologies are mainly based on physisorption in porous materials but the gravimetric and volumetric storage capacities are below the target values. Finally, carbon capture, a critical component of the mitigation of CO2 emissions from industrial plants, also suffers from similar problems. The solid-absorbers such as MOFs are either not stable against real flue-gas conditions and/or do not have large enough CO2 capture capacity to be practical and cost effective. In this project, we addressed these challenges using a unique combination of computational, synthetic and experimental methods. The main scope of our research was to achieve fundamental understanding of the chemical and structural interactions governing the storage and release of hydrogen/methane and carbon capture in a wide spectrum of candidate materials. We studied the effect of scaffolding and doping of the candidate materials on their storage and dynamics properties. We reviewed current progress, challenges and prospect in closely related fields of hydrogen/methane storage and carbon capture.[1-5] For example, for physisorption based storage materials, we show that tap-densities or simply pressing MOFs into pellet forms reduce the uptake capacities by half and therefore packing MOFs is one of the most important challenges going forward. For room temperature hydrogen storage application of MOFs, we argue that MOFs are the most promising scaffold materials for Ammonia-Borane (AB) because of their unique interior active metal-centers for AB binding and well

  13. Alternating current impedance spectroscopic analysis of biofunctionalized vertically-aligned silica nanospring surface for biosensor applications

    Science.gov (United States)

    Timalsina, Yukta P.

    In this dissertation, a process of vertically-aligned (silica) nanosprings (VANS) based biosensor development is presented. Alternating current (AC) impedance spectroscopy has been used to analyze sensor response as a function of saline phosphate (SP) buffer and biological solutions. The sensor is a parallel plate capacitor consisting of two glass substrates coated with indium tin oxide (ITO), where the VANS [or randomly-aligned nanosprings (RANS)] grown on one substrate serve as the dielectric spacer layer. The response of a VANS device as a function of ionic concentration in SP buffer was examined and an equivalent circuit model was developed. The results demonstrated that VANS sensors exhibited greater sensitivity to the changes in SP concentration relative to the ITO sensors, which serve as controls. The biofunctionalized VANS surface via physisorption and the cross-linker method demonstrates the repeatability, specificity, and selectivity of the binding. The physisorption of biotinylated immunoglobulin G (B-IgG) onto the VANS surface simplifies the whole sensing procedure for the detection of glucose oxidase, since the avidin-conjugated glucose oxidase (Av-GOx) can directly be immobilized on the B-IgG. The cross linker method involves the covalent attachment of antibodies onto the functionalized VANS surface via imine bond. The experiments revealed that the VANS sensor response is solely the result of the interaction of target molecule i.e. mouse IgG with the probe layer, i.e. goat antimouse IgG (GalphaM IgG). It was determined that VANS-based sensors exhibit a greater magnitude of change between successive bio-layers relative to the controls above 100 Hz, which indicates that the addition of biomolecules inhibits the diffusion of ions and changes the effective dielectric response of the VANS via biomolecular polarization. The study of ionic transport in nanosprings suggested that conductance follows a scaling law. It was demonstrated that a VANS-based device

  14. A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu [School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (China); Chou, Lingjun, E-mail: ljchou@licp.cas.cn [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 (China); Zhuo, Shuping, E-mail: zhuosp_academic@yahoo.com [School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (China)

    2017-07-31

    Highlights: • A novel mesoporous ZrO{sub 2}/SO{sub 4}{sup 2−} has been prepared via a facile one-pot EISA strategy. • The M-ZrO{sub 2}/SO{sub 4}{sup 2−} exhibited excellent textural and acidic properties. • The introduced S species were homogeneously dispersed in mesoporous skeleton. • The M-ZrO{sub 2}/SO{sub 4}{sup 2−} exhibited excellent catalytic performance and reusability. - Abstract: In this paper, a novel mesoporous sulfated zirconium (M-ZrO{sub 2}/SO{sub 4}{sup 2−}) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N{sub 2}-physisorption and TEM characterization techniques indicated that M-ZrO{sub 2}/SO{sub 4}{sup 2−} possessed distinct mesostructure with big specific surface area (133.5 m{sup 2} g{sup −1}), large pore volume (0.18 cm{sup 3} g{sup −1}) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N{sub 2}-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO{sub 4}{sup 2−}, improved the textural properties of prepared materials. In addition, the NH{sub 3}-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO{sub 2}/SO{sub 4}{sup 2−} even evacuated at 400 °C. Furthermore, the M-ZrO{sub 2}/SO{sub 4}{sup 2−} was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  15. Preparation of ZnO/SiO{sub 2} gel composites and their performance of H{sub 2}S removal at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Guoqiang [Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Huang, Zheng-Hong, E-mail: zhhuang@tsinghua.edu.cn [Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Kang, Feiyu [Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Institute of Advanced Materials Research, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)

    2012-05-15

    Graphical abstract: The ZnO/SiO{sub 2} gel composites exhibit mixed type isotherms, in which the initial part is type I, and intermediate and high relative pressures are type IV with a hysteresis loop of type H2. The breakthrough time of ZnO/SiO{sub 2} composites first increased sharply up to 400 Degree-Sign C with the H{sub 2}S breakthrough capacity is up to 96.4 mg/g, and then decrease dramatically with further rising of temperature beyond 500 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer High surface area ZnO/SiO{sub 2} gel composites were prepared by co-sol-gel method. Black-Right-Pointing-Pointer The active phase (ZnO) well disperses in the composites. Black-Right-Pointing-Pointer The highest H{sub 2}S adsorption capacity of the composites reaches up to 96.4 mg/g. Black-Right-Pointing-Pointer Both physisorption and the active phase reactivation governed the H{sub 2}S removal process. - Abstract: ZnO/SiO{sub 2} gel composites with different active component loading were prepared by sol-gel method combined with ambient drying process, followed by thermal treatment. The gel composites were characterized by scanning electron microscopy (SEM), nitrogen adsorption, X-ray diffraction (XRD), FTIR and X-ray photoelectron spectroscopy (XPS), and their performances for H{sub 2}S removal were evaluated by dynamic testing at room temperature. The as prepared materials exhibited high surface area with multimodal pore size distributions in micropore and mesopore region. The porous properties were significantly influenced both by the ZnO loading ratio and the treated temperature. The gel composites showed a high performance for H{sub 2}S removal, with the highest H{sub 2}S adsorption capacity of 96.4 mg/g for the sample treated at 400 Degree-Sign C with 30 wt% ZnO. Both physisorption and the active phase reactivation governed the H{sub 2}S removal process. It needs to optimize the composites' porous structure and active component loading amount.

  16. Factors affecting the removal of ammonia from air on carbonaceous materials: Investigation of reactive adsorption mechanism

    Science.gov (United States)

    Petit, Camille

    Air pollution related to the release of industrial toxic gases, represents one of the main concerns of our modern world owing to its detrimental effect on the environment. To tackle this growing issue, efficient ways to reduce/control the release of pollutants are required. Adsorption of gases on porous materials appears as a potential solution. However, the physisorption of small molecules of gases such as ammonia is limited at ambient conditions. For their removal, adsorbents providing strong adsorption forces must be used/developed. In this study, new carbon-based materials are prepared and tested for ammonia adsorption at ambient conditions. Characterization of the adsorbents' texture and surface chemistry is performed before and after exposure to ammonia to identify the features responsible for high adsorption capacity and for controlling the mechanisms of retention. The characterization techniques include: nitrogen adsorption, thermal analysis, potentiometric titration, FT-IR spectroscopy, X-ray diffraction, Energy Dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Electron Microscopy. The results obtained indicate that ammonia removal is governed by the adsorbent's surface chemistry. On the contrary, porosity (and thus physisorption) plays a secondary role in this process, unless strong dispersive forces are provided by the adsorbent. The surface chemistry features responsible for the enhanced ammonia adsorption include the presence of oxygen-(carboxyl, hydroxyl, epoxy) and sulfur- (sulfonic) containing groups. Metallic species improve the breakthrough capacity as well as they lead to the formation of Lewis acid-base interactions, hydrogen-bonding or complexation. In addition to the latter three mechanisms, ammonia is retained on the adsorbent surface via Bronsted acid-base interactions or via specific reactions with the adsorbent's functionalities leading to the incorporation of ammonia into the adsorbent's matrix. Another mechanism

  17. Design and synthesis of vanadium hydrazide gels for Kubas-type hydrogen adsorption: a new class of hydrogen storage materials.

    Science.gov (United States)

    Hoang, Tuan K A; Webb, Michael I; Mai, Hung V; Hamaed, Ahmad; Walsby, Charles J; Trudeau, Michel; Antonelli, David M

    2010-08-25

    In this paper we demonstrate that the Kubas interaction, a nondissociative form of weak hydrogen chemisorption with binding enthalpies in the ideal 20-30 kJ/mol range for room-temperature hydrogen storage, can be exploited in the design of a new class of hydrogen storage materials which avoid the shortcomings of hydrides and physisorpion materials. This was accomplished through the synthesis of novel vanadium hydrazide gels that use low-coordinate V centers as the principal Kubas H(2) binding sites with only a negligible contribution from physisorption. Materials were synthesized at vanadium-to-hydrazine ratios of 4:3, 1:1, 1:1.5, and 1:2 and characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption, elemental analysis, infrared spectroscopy, and electron paramagnetic resonance spectroscopy. The material with the highest capacity possesses an excess reversible storage of 4.04 wt % at 77 K and 85 bar, corresponding to a true volumetric adsorption of 80 kg H(2)/m(3) and an excess volumetric adsorption of 60.01 kg/m(3). These values are in the range of the ultimate U.S. Department of Energy goal for volumetric density (70 kg/m(3)) as well as the best physisorption material studied to date (49 kg H(2)/m(3) for MOF-177). This material also displays a surprisingly high volumetric density of 23.2 kg H(2)/m(3) at room temperature and 85 bar--roughly 3 times higher than that of compressed gas and approaching the DOE 2010 goal of 28 kg H(2)/m(3). These materials possess linear isotherms and enthalpies that rise on coverage and have little or no kinetic barrier to adsorption or desorption. In a practical system these materials would use pressure instead of temperature as a toggle and can thus be used in compressed gas tanks, currently employed in many hydrogen test vehicles, to dramatically increase the amount of hydrogen stored and therefore the range of any vehicle.

  18. Adsorption of Pb(II) ions present in aqueous solution on the oxy hydroxides: boehmite (γ-AIOOH), goethite (α-FeOOH) and manganite (γ-MnOOH); Adsorcion de iones Pb(II) presentes en solucion acuosa sobre los oxihidroxidos: boehmita (γ-AlOOH), goetita (α-FeOOH) y manganita (γ-MnOOH)

    Energy Technology Data Exchange (ETDEWEB)

    Arreola L, J. E.

    2013-07-01

    Boehmite, goethite and manganite were synthesized by different methods and characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric study , N{sub 2} physisorption measurements, scanning electron microscopy (Sem), semiquantitative elemental analysis (EDS), as well as additional studies were determined the surface active sites concentration and zero point of charge. Furthermore, we studied the Pb(II) ion adsorption capacity present in aqueous solution on these synthesized materials by batch-type experiments at room temperature, as a function of contact time between the phases liquid-solid system (adsorption kinetics), initial concentration of the adsorbate (adsorption isotherms), ph and temperature. The adsorption equilibrium time of adsorption processes in these studied systems was found at 60 minutes for boehmite and 30 minutes for goethite and manganite respectively after contacting the solid-liquid phase systems. The adsorption capacity of the lead ions on these adsorbent materials depended of lead concentration, ph and temperature of the systems. Were evaluated lead adsorption capacities in these materials to different contact times using an initial concentration of 20 mg/L of Pb(II) ions at ph = 4, the results of three systems were adjusted to second pseudo kinetic model order. With respect to the study of the adsorbate concentration effect, boehmite-Pb(II) and goethite-Pb(II) systems were adjusted to Langmuir isotherm model which proposes that the adsorption is carried out in a monolayer, moreover manganite-Pb(II) system was adjusted Temp kin isotherm model, which assumes that the adsorption heat of all the molecules in the layer decreases linearly with coverage due to adsorbent-adsorbate interactions and adsorption is characterized by a uniform distribution of the binding energies. Were studied the ph effect of Pb(II) ions solution on the adsorption capacity of such adsorbents, it was found that as the ph increases lead

  19. Assessing the performance of dispersionless and dispersion-accounting methods: helium interaction with cluster models of the TiO2(110) surface.

    Science.gov (United States)

    de Lara-Castells, María Pilar; Stoll, Hermann; Mitrushchenkov, Alexander O

    2014-08-21

    As a prototypical dispersion-dominated physisorption problem, we analyze here the performance of dispersionless and dispersion-accounting methodologies on the helium interaction with cluster models of the TiO2(110) surface. A special focus has been given to the dispersionless density functional dlDF and the dlDF+Das construction for the total interaction energy (K. Pernal, R. Podeswa, K. Patkowski, and K. Szalewicz, Phys. Rev. Lett. 2009, 109, 263201), where Das is an effective interatomic pairwise functional form for the dispersion. Likewise, the performance of symmetry-adapted perturbation theory (SAPT) method is evaluated, where the interacting monomers are described by density functional theory (DFT) with the dlDF, PBE, and PBE0 functionals. Our benchmarks include CCSD(T)-F12b calculations and comparative analysis on the nuclear bound states supported by the He-cluster potentials. Moreover, intra- and intermonomer correlation contributions to the physisorption interaction are analyzed through the method of increments (H. Stoll, J. Chem. Phys. 1992, 97, 8449) at the CCSD(T) level of theory. This method is further applied in conjunction with a partitioning of the Hartree-Fock interaction energy to estimate individual interaction energy components, comparing them with those obtained using the different SAPT(DFT) approaches. The cluster size evolution of dispersionless and dispersion-accounting energy components is then discussed, revealing the reduced role of the dispersionless interaction and intramonomer correlation when the extended nature of the surface is better accounted for. On the contrary, both post-Hartree-Fock and SAPT(DFT) results clearly demonstrate the high-transferability character of the effective pairwise dispersion interaction whatever the cluster model is. Our contribution also illustrates how the method of increments can be used as a valuable tool not only to achieve the accuracy of CCSD(T) calculations using large cluster models but also to

  20. Removal of element mercury by medicine residue derived biochars in presence of various gas compositions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Guoliang [School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401 (China); College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Shen, Boxiong, E-mail: shenbx@nankai.edu.cn [School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401 (China); College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Li, Yongwang [College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhao, Bin [School of Chemical Engineering, Hebei University of Technology, Tianjin 300401 (China); Wang, Fumei; He, Chuan; Wang, Yinyin; Zhang, Min [College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

    2015-11-15

    Highlights: • Both physisorption and chemisorption of Hg{sup 0} occurred on the surface of M6WN5. • Chemisorption process was an absolute predominant route for Hg{sup 0} removal by M6WN5. • The effect of NO, H{sub 2}O, SO{sub 2} and O{sub 2} on Hg{sup 0} removal by M6WN5 was investigated. • M6WN5 demonstrated to be a promising Hg{sup 0} sorbent in flue gas. - Abstract: Pyrolyzed biochars from an industrial medicinal residue waste were modified by microwave activation and NH{sub 4}Cl impregnation. Mercury adsorption of different modified biochars was investigated in a quartz fixed-bed reactor. The results indicated that both physisorption and chemisorption of Hg{sup 0} occurred on the surface of M6WN5 which was modified both microwave and 5 wt.% NH{sub 4}Cl loading, and exothermic chemisorption process was a dominant route for Hg{sup 0} removal. Microwave activation improved pore properties and NH{sub 4}Cl impregnation introduced good active sites for biochars. The presence of NO and O{sub 2} increased Hg{sup 0} adsorption whereas H{sub 2}O inhibited Hg{sup 0} adsorption greatly. A converse effect of SO{sub 2} was observed on Hg{sup 0} removal, namely, low concentration of SO{sub 2} promoted Hg{sup 0} removal obviously whereas high concentration of SO{sub 2} suppressed Hg{sup 0} removal. The Hg{sup 0} removal by M6WN5 was mainly due to the reaction of the C−Cl with Hg{sup 0} to form HgCl{sub 2}, and the active state of C−Cl{sup *} groups might be an intermediate group in this process. Thermodynamic analysis showed that mercury adsorption by the biochars was exothermic process and apparent adsorption energy was 43.3 kJ/mol in the range of chemisorption. In spite of low specific surface area, M6WN5 proved to be a promising Hg{sup 0} sorbent in flue gas when compared with other sorbents.

  1. Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Pershina, V., E-mail: V.Pershina@gsi.de [GSI Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, Darmstadt D-64291 (Germany); Borschevsky, A. [Helmholtz Institute Mainz, Mainz D-55128, Germany and Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Private Bag 102904, 0745 North Shore MSC, Auckland (New Zealand); Iliaš, M. [Department of Chemistry, Faculty of Natural Sciences, Matej Bel University, Tajovského 40, SK-974 00 Banská Bystrica (Slovakia); Türler, A. [Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland and Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland)

    2014-08-14

    With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl{sub 4}, MOCl{sub 2}, MCl{sub 6}{sup −}, and MOCl{sub 4}{sup 2} with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl{sub 4}, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔH{sub sub}, of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔH{sub sub}(RfCl{sub 4}) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl{sub 2} on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl{sub 4} on quartz by chemical forces, formation of the MOCl{sub 2} or MOCl{sub 4}{sup 2−} complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl{sub 4} on a chlorinated quartz surface, formation of the MCl{sub 6}{sup 2−} surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the “one-atom-at-a-time” gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.

  2. Adsorption of Pb(II) ions present in aqueous solution on the oxy hydroxides: boehmite (γ-AIOOH), goethite (α-FeOOH) and manganite (γ-MnOOH)

    International Nuclear Information System (INIS)

    Arreola L, J. E.

    2013-01-01

    Boehmite, goethite and manganite were synthesized by different methods and characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric study , N 2 physisorption measurements, scanning electron microscopy (Sem), semiquantitative elemental analysis (EDS), as well as additional studies were determined the surface active sites concentration and zero point of charge. Furthermore, we studied the Pb(II) ion adsorption capacity present in aqueous solution on these synthesized materials by batch-type experiments at room temperature, as a function of contact time between the phases liquid-solid system (adsorption kinetics), initial concentration of the adsorbate (adsorption isotherms), ph and temperature. The adsorption equilibrium time of adsorption processes in these studied systems was found at 60 minutes for boehmite and 30 minutes for goethite and manganite respectively after contacting the solid-liquid phase systems. The adsorption capacity of the lead ions on these adsorbent materials depended of lead concentration, ph and temperature of the systems. Were evaluated lead adsorption capacities in these materials to different contact times using an initial concentration of 20 mg/L of Pb(II) ions at ph = 4, the results of three systems were adjusted to second pseudo kinetic model order. With respect to the study of the adsorbate concentration effect, boehmite-Pb(II) and goethite-Pb(II) systems were adjusted to Langmuir isotherm model which proposes that the adsorption is carried out in a monolayer, moreover manganite-Pb(II) system was adjusted Temp kin isotherm model, which assumes that the adsorption heat of all the molecules in the layer decreases linearly with coverage due to adsorbent-adsorbate interactions and adsorption is characterized by a uniform distribution of the binding energies. Were studied the ph effect of Pb(II) ions solution on the adsorption capacity of such adsorbents, it was found that as the ph increases lead solution

  3. Titanium embedded cage structure formation in Al{sub n}Ti{sup +} clusters and their interaction with Ar

    Energy Technology Data Exchange (ETDEWEB)

    Torres, M. B., E-mail: begonia@ubu.es [Departamento de Matemáticas y Computación, Universidad de Burgos, 09006 Burgos (Spain); Vega, A.; Balbás, L. C. [Departamento de Física Teórica, Universidad de Valladolid, 47011 Valladolid (Spain); Aguilera-Granja, F. [Instituto de Física, Universidad de San Luis Potosí, 78000 San Luis de Potosí (Mexico)

    2014-05-07

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al{sub n}Ti{sup +} [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n{sub c} determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al{sub n}Ti{sup +}, experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al{sub n}Ti{sup +} (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n{sub c} = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n{sub c} = 21) and their neutral counterparts (n{sub c} = 20). For the Al {sub n} Ti {sup +} · Ar complexes, and for n < 21, the preferred Ar adsorption site is on top of the exohedral Ti atom, with adsorption energy in very good agreement with the experimental value. Instead, for n = 21, the Ar adsorption occurs on the top an Al atom with very low absorption energy. For all sizes the geometry of the Al{sub n}Ti{sup +} clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support

  4. Cobalt separation present in aqueous solution using shell tamarind as bio sorbent

    International Nuclear Information System (INIS)

    Hernandez L, J.

    2014-01-01

    In this work a new carbonaceous material is presented with improved adsorption properties obtained by a heart treatment about 5 min from the shell tamarind. It was found that the samples obtained carbonaceous adsorbents are effective in removing Co 2+ (41 mg / g) ions in aqueous solutions. These samples were prepared from tamarind shell, urea, ammonium nitrate and water. The solution was subjected to a combustion process at different temperatures. Carbonaceous samples prepared in this manner were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (Sem) and surface area measurements by Physisorption of N 2 . Changes in structure, morphology and texture were studied. The results show that this material is of great importance to the applications of adsorption of metal ions. The measurements of specific surface area (Bet) were 2.35 to 203.76 m 2 g -1 with pore diameters between 2.31 and 15.63 nm, indicating that the samples obtained are predominantly meso porous. The combustion process of the solution proved to be advantageous to improve the textural properties of the tamarind shell. The obtained carbonaceous material plays an important role in adsorption to remove cobalt in aqueous solutions. (Author)

  5. Nanomaterials driven energy, environmental and biomedical research

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Prakash C.; Srinivasan, Sesha S.; Wilson, Jeremiah F. [Department of Physics, College of Arts and Sciences, Tuskegee University, Tuskegee, AL 36088 (United States)

    2014-03-31

    We have developed state-of-the-art nanomaterials such as nanofibers, nanotubes, nanoparticles, nanocatalysts and nanostructures for clean energy, environmental and biomedical research. Energy can neither be created nor be destroyed, but it can be converted from one form to another. Based on this principle, chemical energy such as hydrogen has been produced from water electrolysis at a much lower voltage using RuO{sub 2} nanoparticles on the Si wafer substrate. Once the hydrogen is produced from the clean sources such as solar energy and water, it has to be stored by physisorption or chemisorption processes on to the solid state systems. For the successful physical adsorption of hydrogen molecule, we have developed novel polyaniline nanostructures via chemical templating and electrospinning routes. Chemical or complex hydrides involving nano MgH{sub 2} and transition metal nanocatalysts have been synthesized to tailor both the thermodynamics and kinetics of hydrogen (chemi) sorption respectively. Utilization of solar energy (UV-Vis) and a coupling of novel semiconductor oxide nanoparticles have been recently demonstrated with enhancement in photo-oxidation and/or photo-reduction processes for the water/air detoxification and sustainable liquid fuel production respectively. Magnetic nanoparticles such as ZnFe{sub 2}O{sub 4} have been synthesized and optimized for biomedical applications such as targeted drug delivery and tumor diagnostic sensing (MRI)

  6. Theoretical predictions of properties and gas-phase chromatography behaviour of carbonyl complexes of group-6 elements Cr, Mo, W, and element 106, Sg.

    Science.gov (United States)

    Pershina, V; Anton, J

    2013-05-07

    Fully relativistic, four-component density functional theory electronic structure calculations were performed for M(CO)6 of group-6 elements Cr, Mo, W, and element 106, Sg, with an aim to predict their adsorption behaviour in the gas-phase chromatography experiments. It was shown that seaborgium hexacarbonyl has a longer M-CO bond, smaller ionization potential, and larger polarizability than the other group-6 molecules. This is explained by the increasing relativistic expansion and destabilization of the (n - 1)d AOs with increasing Z in the group. Using results of the calculations, adsorption enthalpies of the group-6 hexacarbonyls on a quartz surface were predicted via a model of physisorption. According to the results, -ΔHads should decrease from Mo to W, while it should be almost equal--within the experimental error bars--for W and Sg. Thus, we expect that in the future gas-phase chromatography experiments it will be almost impossible--what concerns ΔHads--to distinguish between the W and Sg hexacarbonyls by their deposition on quartz.

  7. Electronic properties and gas adsorption behaviour of pristine, silicon-, and boron-doped (8, 0) single-walled carbon nanotube: A first principles study.

    Science.gov (United States)

    Azam, Mohd Asyadi; Alias, Farizul Muiz; Tack, Liew Weng; Seman, Raja Noor Amalina Raja; Taib, Mohamad Fariz Mohamad

    2017-08-01

    Carbon nanotubes (CNTs) have received enormous attention due to their fascinating properties to be used in various applications including electronics, sensing, energy storage and conversion. The first principles calculations within density functional theory (DFT) have been carried out in order to investigate the structural, electronic and optical properties of un-doped and doped CNT nanostructures. O 2 , CO 2 , and CH 3 OH have been chosen as gas molecules to study the adsorption properties based on zigzag (8,0) SWCNTs. The results demonstrate that the adsorption of O 2 , CO 2, and CH 3 OH gas molecules on pristine, Si-doped and B-doped SWCNTs are either physisorption or chemisorption. Moreover, the electronic properties indicating SWCNT shows significant improvement toward gas adsorption which provides the impact of selecting the best gas sensor materials towards detecting gas molecule. Therefore, these pristine, Si-, and B-doped SWCNTs can be considered to be very good potential candidates for sensing application. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. Enhanced Biosensor Platforms for Detecting the Atherosclerotic Biomarker VCAM1 Based on Bioconjugation with Uniformly Oriented VCAM1-Targeting Nanobodies

    Directory of Open Access Journals (Sweden)

    Duy Tien Ta

    2016-07-01

    Full Text Available Surface bioconjugation of biomolecules has gained enormous attention for developing advanced biomaterials including biosensors. While conventional immobilization (by physisorption or covalent couplings using the functional groups of the endogenous amino acids usually results in surfaces with low activity, reproducibility and reusability, the application of methods that allow for a covalent and uniformly oriented coupling can circumvent these limitations. In this study, the nanobody targeting Vascular Cell Adhesion Molecule-1 (NbVCAM1, an atherosclerotic biomarker, is engineered with a C-terminal alkyne function via Expressed Protein Ligation (EPL. Conjugation of this nanobody to azidified silicon wafers and Biacore™ C1 sensor chips is achieved via Copper(I-catalyzed azide-alkyne cycloaddition (CuAAC “click” chemistry to detect VCAM1 binding via ellipsometry and surface plasmon resonance (SPR, respectively. The resulting surfaces, covered with uniformly oriented nanobodies, clearly show an increased antigen binding affinity, sensitivity, detection limit, quantitation limit and reusability as compared to surfaces prepared by random conjugation. These findings demonstrate the added value of a combined EPL and CuAAC approach as it results in strong control over the surface orientation of the nanobodies and an improved detecting power of their targets—a must for the development of advanced miniaturized, multi-biomarker biosensor platforms.

  9. The effect of the shape of single, sub-ms voltage pulses on the rates of surface immobilization and hybridization of DNA

    International Nuclear Information System (INIS)

    Cabeca, R; Rodrigues, M; Chu, V; Conde, J P; Prazeres, D M F

    2009-01-01

    Electric fields generated by single square and sinusoidal voltage pulses with amplitudes below 2 V were used to assist the covalent immobilization of single-stranded, thiolated DNA probes, onto a chemically functionalized SiO 2 surface and to assist the specific hybridization of single-stranded DNA targets with immobilized complementary probes. The single-stranded immobilized DNA probes were either covalently immobilized (chemisorption) or electrostatically adsorbed (physisorption) to a chemically functionalized surface. Comparing the speed of electric field assisted immobilization and hybridization with the corresponding control reactions (without electric field), an increase of several orders of magnitude is observed, with the reaction timescaled down from 1 to 2 h to a range between 100 ns and 1 ms. The influence of the shape of the voltage pulse (square versus sinusoidal) and its duration were studied for both immobilization and hybridization reactions. The results show that pulsed electric fields are a useful tool to achieve temporal and spatial control of surface immobilization and hybridization reactions of DNA.

  10. Methylene blue biosorption by pericarp of corn, alfalfa, and agave bagasse wastes.

    Science.gov (United States)

    Rosas-Castor, José M; Garza-González, María T; García-Reyes, Refugio B; Soto-Regalado, Eduardo; Cerino-Córdova, Felipe J; García-González, Alcione; Loredo-Medrano, José A

    2014-01-01

    The presence of dyes in effluent is a matter of concern due to their toxicologic and aesthetical effects. In this research, locally available agro-industrial wastes (Zea mays pericarp, ZMP; Agave tequilana bagasse, ATB; and Medicago sativa waste, MSW) were used as alternative low-cost adsorbents for the removal of methylene blue (MB) from aqueous solutions. The adsorbents were characterized physically and chemically by Fourier transform infrared, scanning electron microscopy, potentiometric titrations, and N2 physisorption. MB adsorption experiments were carried out in batch systems and experimental data were used to calculate the adsorption isotherm model parameters (Langmuir, Freundlich, and Temkin) and the adsorption kinetic model parameters (pseudo-first- and pseudo-second-order models). MB-loaded biosorbents were desorbed with deionized water, ethanol (10% and 50% v/v), hydrochloric acid (0.01 and 0.05 N), and sodium hydroxide (0.1 N) at room temperature, and the best eluent was used in various adsorption-desorption cycles. The selected agricultural wastes can be considered as promising adsorbents for dye uptake from water since they exhibit considerable MB adsorption capacity (MSW 202.6 mg g(-1), ATB 156.2mg g(-1), and ZMP 110.9mg g(-1)), but it is lower than that reported for activated carbon; however, the biosorbents show higher adsorption rate than powdered activated carbon. Furthermore, the adsorbents can be economically regenerated with HCl solutions and reused for seven adsorption-desorption cycles.

  11. Structural, vibrational and morphological properties of layered double hydroxides containing Ni{sup 2+}, Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+} cations

    Energy Technology Data Exchange (ETDEWEB)

    Bezerra, Débora M. [Instituto de Química de São Carlos, Universidade de São Paulo, CP 780, CEP 13566-590 São Carlos, SP (Brazil); Rodrigues, João E.F.S. [Instituto de Física de São Carlos, Universidade de São Paulo, CP 780, CEP 13560-970 São Carlos, SP (Brazil); Assaf, Elisabete M., E-mail: eassaf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, CP 780, CEP 13566-590 São Carlos, SP (Brazil)

    2017-03-15

    Layered double hydroxides are anionic clays with formula [M{sup II}{sub 1−x} M{sup III}{sub x}(OH){sub 2}]{sup q+}[A{sup n−}]{sub q/n}·mH{sub 2}O, finding possible uses as catalyst support, adsorbents and so on. In this paper, we address the phase formation of layered double hydroxides containing Ni{sup 2+}, Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+} cations, namely, NiZn-Al, NiZn-AlZr and NiZn-Zr compositions obtained by the coprecipitation method. Such systems were characterized by X-ray diffraction, confirming the phase formation for NiZn-Al and NiZn-AlZr samples. Infrared and Raman spectroscopies elucidated the anion and water molecules occurrence in the interlayer. Nitrogen physisorption (BET method) determined the presence of pores and specific surface area. The isotherm shapes were Type IV, according to the IUPAC, and represent a mesoporous structure. A morphological study was performed by means of scanning and transmission electron microscopies, and particle size values of 120, 131 and 235 nm for NiZn-Al, NiZn-AlZr and NiZn-Zr, respectively, were determined. Thermogravimetric analysis of the decomposition of the systems revealed that their complete disintegration occurred at ~ 450 °C and resulted in mixed oxides.

  12. Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste

    International Nuclear Information System (INIS)

    Olgun, Asim; Atar, Necip

    2009-01-01

    In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73 mg g -1 , respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23 kJ/mol for BY 28 and 18.15 kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents

  13. Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste

    Energy Technology Data Exchange (ETDEWEB)

    Olgun, Asim [Department of Chemistry, Faculty of Arts and science, University of Dumlupinar, Kuetahya (Turkey)], E-mail: aolgun@dumlupinar.edu.tr; Atar, Necip [Department of Chemistry, Faculty of Arts and science, University of Dumlupinar, Kuetahya (Turkey)

    2009-01-15

    In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73 mg g{sup -1}, respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23 kJ/mol for BY 28 and 18.15 kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents.

  14. Mesoporous MEL, BEA, and FAU zeolite crystals obtained by in situ formation of carbon template over metal nanoparticles

    DEFF Research Database (Denmark)

    Abildstrøm, Jacob Oskar; Ali, Zahra Nasrudin; Mentzel, Uffe Vie

    2016-01-01

    Here, we report the synthesis and characterization of hierarchical zeolite materials with MEL, BEA and FAU structures. The synthesis is based on the carbon templating method with an in situ-generated carbon template. Through the decomposition of methane and deposition of coke over nickel nanopart......Here, we report the synthesis and characterization of hierarchical zeolite materials with MEL, BEA and FAU structures. The synthesis is based on the carbon templating method with an in situ-generated carbon template. Through the decomposition of methane and deposition of coke over nickel...... nanoparticles supported on silica, a carbon–silica composite is obtained and exploited as a combined carbon template/silica source for the zeolite synthesis. The mesoporous zeolite materials were all prepared by hydrothermal crystallization in alkaline media followed by removal of the carbon template...... by combustion, which results in zeolite single crystals with intracrystalline pore volumes of up to 0.44 cm3 g−1. The prepared zeolite structures are characterized by XRD, SEM, TEM and N2 physisorption measurements....

  15. The effect of positioning cations on acidity and stability of the framework structure of Y zeolite

    Science.gov (United States)

    Deng, Changshun; Zhang, Junji; Dong, Lihui; Huang, Meina; Bin Li; Jin, Guangzhou; Gao, Junbin; Zhang, Feiyue; Fan, Minguang; Zhang, Luoming; Gong, Yanjun

    2016-01-01

    The investigation on the modification of NaY zeolite on LaHY and AEHY (AE refers Ca and Sr and the molar ratio of Ca and Sr is 1:1) zeolites was proformed by XRD, N2-physisorption (BET), XRF, XPS, NH3-TPD, Py-IR, hydrothermal stability, and catalytic cracking test. These results indicate that HY zeolite with ultra low content Na can be obtained from NaY zeolite through four exchange four calcination method. The positioning capability of La3+ in sodalite cage is much better than that of AE2+ and about 12 La3+ can be well coordinated in sodalite cages of one unit cell of Y zeolite. Appropriate acid amount and strength favor the formation of propylene and La3+ is more suitable for the catalytic cracking of cyclohexane than that of AE2+. Our results not only elaborate the variation of the strong and weak acid sites as well as the Brönsted and Lewis acid sites with the change of exchanged ion content but also explore the influence of hydrothermal aging of LaHY and AEHY zeolites and find the optimum ion exchange content for the most reserved acid sites. At last, the coordination state and stabilization of ion exchanged Y zeolites were discussed in detail. PMID:26987306

  16. Efficient removal of cobalt from aqueous solution by zinc oxide nanoparticles. Kinetic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Khezami, L.; Modwi, A. [Al Imam Mohammad Ibn Saud Islamic Univ. (IMSIU), Riyadh (Saudi Arabia). Dept. of Chemistry; Taha, Kamal K. [Al Imam Mohammad Ibn Saud Islamic Univ. (IMSIU), Riyadh (Saudi Arabia). Dept. of Chemistry; Univ. of Bahri, Khartoum (Sudan). College of Applied and Industrial Sciences

    2017-08-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg.g{sup -1} of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  17. Photocatalytic degradation of bisphenol A in the presence of Ce–ZnO: Evolution of kinetics, toxicity and photodegradation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Bechambi, Olfa [Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie des Matériaux et Catalyse, 2092, Tunis (Tunisia); Jlaiel, Lobna [Laboratoire de Bioprocédés Environnementaux, Centre de Biotechnologie de Sfax, B.P. 1177, 3018 Sfax (Tunisia); Najjar, Wahiba, E-mail: najjarwahiba2014@gmail.com [Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie des Matériaux et Catalyse, 2092, Tunis (Tunisia); Sayadi, Sami [Laboratoire de Bioprocédés Environnementaux, Centre de Biotechnologie de Sfax, B.P. 1177, 3018 Sfax (Tunisia)

    2016-04-15

    Ce–ZnO (2 mol %) and undoped ZnO catalysts have been synthesized through hydrothermal method and characterized by X-ray diffraction (XRD), Nitrogen physisorption at 77 K; Fourier transformed infrared spectroscopy (FTIR), UV–Visible spectroscopy, Photoluminescence spectra (PL), and Raman spectroscopy. Ce-doping reduces the average crystallite size, increases the BET surface area, shifts the absorption edge, reduces the electron–hole recombination and consequently improves photodegradation efficiency of Bisphenol A (BPA) in the presence of UV irradiation and hydrogen peroxide. The photocatalytic optimum conditions were established by studying the influence of various operational parameters including catalyst concentration, initial BPA concentration, H{sub 2}O{sub 2} concentration and initial pH. Under optimum conditions, Ce–ZnO (2%) achieved 100% BPA degradation and 61% BPA mineralization after 24 h of UV irradiation. BPA degradation reaction followed pseudo first-order kinetics according to the Langmuir–Hinshelwood model. Based on the identified intermediate products, the possible mechanism for BPA photodegradation is proposed. Toxicity under the optimum condition was also evaluated. - Graphical abstract: Proposed photocatalytic degradation pathway of BPA in the presence of Ce– ZnO (2%)/UV/H{sub 2}O{sub 2} system. - Highlights: • Influence of different parameters on the degradation and mineralization of BPA. • Identification of possible degradation products. • Toxicity tests conducted with Vibrio fischeri. • Simple and direct photodegradation mechanism of BPA is proposed.

  18. Concentration quenching and photostability in Eu(dbm)3phen embedded in mesoporous silica nanoparticles

    International Nuclear Information System (INIS)

    Moretti, Elisa; Talon, Aldo; Storaro, Loretta; Le Donne, Alessia; Binetti, Simona; Benedetti, Alvise; Polizzi, Stefano

    2014-01-01

    Ordered mesoporous silica nanoparticles (MSNs) were impregnated with different loadings of the luminescent complex tris(dibenzoylmethane) mono(1,10-phenanthroline)europium(III) (Eu(dbm) 3 phen), with the aim of increasing the luminescence by avoiding concentration quenching and having mainly in mind the application as spectral converter for multi-crystalline silicon solar cells. The morphological, structural and luminescence properties of the impregnated silica nanoparticles were characterized by N 2 physisorption, X-ray diffraction, transmission electron microscopy, infrared spectroscopy, UV–visible spectroscopy and photoluminescence excitation and emission measurements. Photostability was tested under 1 sun (1000 W/m 2 ) illumination for 24 h and the related effects were inspected by UV–visible and photoluminescence spectroscopies. Impregnation of the complex into 50–70 nm MSNs with pore size tailored around 2.9 nm depressed concentration quenching and allowed the use of complex loadings as high as 23 wt%. Sunlight irradiation caused a marked increase in the luminescence intensity. -- Highlights: • Mesoporous silica nanoparticles tailored to the size of Eu 3+ (dbm) 3 phen molecules. • Concentration quenching avoided up to 23 wt% of Eu 3+ (dbm) 3 phen/silica. • Sun irradiation increased luminescence intensity by two order of magnitudes

  19. On the use of mesophase pitch for the preparation of hierarchical porous carbon monoliths by nanocasting

    Directory of Open Access Journals (Sweden)

    Philipp Adelhelm, Karin Cabrera and Bernd M Smarsly

    2012-01-01

    Full Text Available A detailed study is given on the synthesis of a hierarchical porous carbon, possessing both meso- and macropores, using a mesophase pitch (MP as the carbon precursor. This carbon material is prepared by the nanocasting approach involving the replication of a porous silica monolith (hard templating. While this carbon material has already been tested in energy storage applications, various detailed aspects of its formation and structure are addressed in this study. Scanning electron microscopy (SEM, Hg porosimetry and N2 physisorption are used to characterize the morphology and porosity of the carbon replica. A novel approach for the detailed analysis of wide-angle x-ray scattering (WAXS from non-graphitic carbons is applied to quantitatively compare the graphene microstructures of carbons prepared using MP and furfuryl alcohol (FA. This WAXS analysis underlines the importance of the carbon precursor in the synthesis of templated porous carbon materials via the nanocasting route. Our study demonstrates that a mesophase pitch is a superior precursor whenever a high-purity, low-micropore-content and well-developed graphene structure is desired.

  20. Silylated Co/SBA-15 catalysts for Fischer-Tropsch synthesis

    International Nuclear Information System (INIS)

    Jia Lihong; Jia Litao; Li Debao; Hou Bo; Wang Jungang; Sun Yuhan

    2011-01-01

    A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N 2 physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH 3 ) 3 species even after calcinations and H 2 reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH 3 ) 3 for the re-adsorption of α-olefins. -- Graphical abstract: The silylation of an SBA-15 before cobalt impregnation enhanced the reducibility of cobalt oxides on an SBA-15-supported cobalt catalyst and consequently increased the catalytic activity for Fischer-Tropsch synthesis. Display Omitted

  1. Development of highly microporous activated carbon from the alcoholic beverage industry organic by-products

    International Nuclear Information System (INIS)

    Nieto-Delgado, C.; Terrones, M.; Rangel-Mendez, J.R.

    2011-01-01

    This work has the aim to employ the agave bagasse, a waste from Tequila and Mescal industries, to obtain a product of high commercial value such as activated carbon. The activated carbon production methodology was based on a chemical activation, by using ZnCl 2 and H 3 PO 4 as activating agent and agave bagasse as a natural source of carbon. The activation temperature (150-450 o C), activation time (0-60 min) and weight ratio of activating agent to precursor (0.2-4) were studied. The produced carbon materials were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and nitrogen physisorption at -196 o C. In addition, the activating agent recovery was evaluated. We were able to obtain highly microporous activated carbons with micropore volumes between 0.24 and 1.20 cm 3 /g and a surface area within 300 and 2139 m 2 /g. These results demonstrated the feasibility to treat the industrial wastes of the Tequila and Mescal industries, being this wastes an excellent precursor to produce highly microporous activated carbons that can be processed at low activation temperatures in short times, with the possibility of recycling the activating agent.

  2. Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, Eric [College of Engineering, Purdue University, West Lafayette, IN 47907 (United States); Dailly, Anne [Chemical and Environmental Sciences Laboratory, General Motors Corporation, Warren, MI 48090 (United States)], E-mail: poirierem@gmail.com, E-mail: anne.dailly@gm.com

    2009-05-20

    Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn{sub 4}O(1,3,5-benzenetribenzoate){sub 2}, MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g{sup -1}. An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid. These liquid state properties observed under supercritical conditions reveal a remarkable effect of nanoscale confinement. The entire set of adsorption isotherms can be well described using a micropore filling model. The latter is used, in particular, to determine the absolute amounts adsorbed and the adsorption enthalpy. When expressed in terms of absolute adsorption, the isotherms show considerable hydrogen storage capacities, reaching up to 125 mg g{sup -1} at 50 K and 25 bar. The adsorption enthalpies are calculated as a function of fractional filling and range from 3 to 5 kJ mol{sup -1} in magnitude, in accordance with physisorption. These results are discussed with respect to a similar analysis performed on another Zn-based MOF, Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}, IRMOF-1, presented recently. It is found that both materials adsorb hydrogen by similar mechanisms.

  3. Collision of hydrogen molecules interacting with two grapheme sheets

    Directory of Open Access Journals (Sweden)

    Malivuk-Gak Dragana

    2017-01-01

    Full Text Available It have been performed the computational experiments with two hydrogen molecules and two graphene sheets. Hydrogen - hydrogen and hydrogen - carbon interactions are described by Lennard - Jones potential. Equations of motion of the wave packet centre are solved numerically. The initial molecule velocity was determined by temperature and collisions occur in central point between two sheets. The molecules after collision stay near or get far away of graphene sheets. Then one can find what temperatures, graphene sheet sizes and their distances are favourable for hydrogen storage. It is found that quantum corrections of the molecule classical trajectories are not significant here. Those investigations of possibility of hydrogen storage by physisorption are of interest for improvement of the fuel cell systems. The main disadvantages of computational experiments are: (1 it cannot compute with very large number of C atoms, (2 it is assumed that carbon atoms are placed always in their equilibrium positions and (3 the changes of wave packet width are not considered.

  4. Synthesis of Fe–Cu/TiO{sub 2} nanostructure and its use in construction of a sensitive and selective sensor for metformin determination

    Energy Technology Data Exchange (ETDEWEB)

    Gholivand, Mohammad Bagher, E-mail: mbgholivand@yahoo.com; Shamsipur, Mojtaba; Paimard, Giti; Feyzi, Mostafa; Jafari, Fataneh

    2014-09-01

    A carbon paste electrode modified with Fe-Cu/TiO{sub 2} was prepared and used for low level determination of metformin (MET) using square wave adsorptive stripping voltammetry (SWAdSV). The Fe-Cu/TiO{sub 2} nanoparticle was synthesized by a modified sol–gel method. The surface structure and composition of nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction analysis (XRD) and N{sub 2} physisorption. Also, electrochemical properties of the prepared nanocomposite modified electrode were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques. Under optimized conditions, the modified electrode exhibited a linear response over the concentration range of 15 nM to 75 μM MET, with a detection limit of 3 nM. The proposed sensor exhibited a high sensitivity, good selectivity and was successfully applied for MET determination in real samples such as human urine and pharmaceutical formulations. - Highlights: • A carbon paste modified electrode for determination of MET was developed. • The synthesized Fe-Cu/TiO{sub 2} nanocomposite was used as a modifier. • The sensor was successfully applied for MET determination in real samples. • Square wave adsorptive stripping voltammetric method was used for MET determination.

  5. Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts.

    Science.gov (United States)

    Xia, Zhenyuan; Leonardi, Francesca; Gobbi, Marco; Liu, Yi; Bellani, Vittorio; Liscio, Andrea; Kovtun, Alessandro; Li, Rongjin; Feng, Xinliang; Orgiu, Emanuele; Samorì, Paolo; Treossi, Emanuele; Palermo, Vincenzo

    2016-07-26

    We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

  6. Adsorption of strontium on different sodium-enriched bentonites

    Directory of Open Access Journals (Sweden)

    Marinović Sanja R.

    2017-01-01

    Full Text Available Bentonites from three different deposits (Wyoming, TX, USA and Bogovina, Serbia with similar cation exchange capacities were sodium enriched and tested as adsorbents for Sr2+ in aqueous solutions. X-Ray diffraction analysis confirmed successful Na-exchange. The textural properties of the bentonite samples were determined using low-temperature the nitrogen physisorption method. Significant differences in the textural properties between the different sodium enriched bentonites were found. Adsorption was investigated with respect to adsorbent dosage, pH, contact time and the initial concentration of Sr2+. The adsorption capacity increased with pH. In the pH range from 4.0–8.5, the amount of adsorbed Sr2+ was almost constant but 2–3 times smaller than at pH ≈11. Further experiments were performed at the unadjusted pH since extreme alkaline conditions are environmentally hostile and inapplicable in real systems. The adsorption capacity of all the investigated adsorbents toward Sr2+ was similar under the investigated conditions, regardless of significant differences in the specific surface areas. It was shown and confirmed by the Dubinin–Radushkevich model that the cation exchange mechanism was the dominant mechanism of Sr2+ adsorption. Their developed microporous structures contributed to the Sr2+ adsorption process. The adsorption kinetics obeyed the pseudo-second-order model. The isotherm data were best fitted with the Langmuir isotherm model. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III 45001

  7. Basic dye removal from aqueous solutions by dodecylsulfate- and dodecyl benzene sulfonate-intercalated hydrotalcite

    Energy Technology Data Exchange (ETDEWEB)

    Bouraada, Mohamed; Lafjah, Mama [Laboratoire de valorisation des materiaux, University of Mostaganem, B.P. 227, Mostaganem R.P. (Algeria); Ouali, Mohand Said [Laboratoire de valorisation des materiaux, University of Mostaganem, B.P. 227, Mostaganem R.P. (Algeria)], E-mail: ouali@univ-mosta.dz; Menorval, Louis Charles de [LAMMI (CNRS-UMR5072), Universite Montpellier II, 2 Place Eugene Bataillon, Case Courrier 015, 34095 Montpellier cedex 5 (France)

    2008-05-30

    Dodecylsulfate- and dodecyl benzene sulfonate-hydrotalcites were prepared by calcination-rehydratation method. The surfactants intercalation in the interlayer space of hydrotalcite were checked by PXRD and FTIR spectroscopy where the resulting materials were found to be similar to those reported in the literature and were used to remove a basic dye (safranine) from aqueous solutions. The sorption kinetics data fitted the pseudo second order model. The isotherms were established and the parameters calculated. The sorption data fitted the Langmuir model with good values of the determination coefficient. The thermodynamic parameters calculated from Van't Hoff plots gave a low value of {delta}G{sup o} (<-20 kJ mol{sup -1}) indicating a spontaneous physisorption process. Two regeneration cycles were processed by acetone extraction leading to the same removal capacity of the obtained materials as the original surfactant-intercalated hydrotalcites. The UV-vis spectra of the recovered extracts were similar to the spectrum of safranine, which means that the dye was recovered without any modification.

  8. Adsorption of carbon dioxide in porous magnesium oxides; Adsorcion de dioxido de carbono en oxidos de magnesio porosos

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez B, E.

    2016-07-01

    Mg O powders were synthesized by chemical solution combustion and treated by mechanical milling, and separately were doped with Fe and Ni. The obtained powders were characterized by the X-ray diffraction (DRX) technique, scanning electron microscopy (Sem), elementary semi-quantitative analysis (EDS), N{sub 2} physisorption measurements and infrared spectroscopy (IR). It was studied the CO{sub 2} adsorption capacity in the synthesized materials as a function of temperature, pressure and saturation time. The results show that the CO{sub 2} adsorption capacities on respective materials were 0.39 mmol/g in Mg O powders synthesized by chemical solution combustion, 1.61 mmol/g in Mg O powders treated by mechanical milling during 2.5 h, 0.90 mmol/g in Mg O powders doped with Fe by milling during 2.5 h and 1.50 mmol/g for Mg O powders doped with Ni milling during 7.5 h, at 25 degrees Celsius, 1 atm and 30 min of saturation time. The results showed that the powders treated by mechanical milling are efficient for CO{sub 2} adsorption and are an alternative of advanced materials to be used as potential adsorbent materials and contribute to reduce the global warming. (Author)

  9. Adsorption of rhodamine B by acid activated carbon-Kinetic, thermodynamic and equilibrium studies

    Directory of Open Access Journals (Sweden)

    Shanmugam Arivoli

    2009-08-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste by acid treatment was tested for its efficiency in removing Rhodamine B (RDB. The parameters studied include agitation time, initial dye concentration, carbon dose, pH and temperature. The adsorption followed first order kinetics and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plots were 40.161, 35.700, 38.462 and 37.979 mg/g respectively at an initial pH of 7.0 at 30, 40, 50 and 60 0C. The temperature variation study showed that the RDB adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the RDB solutions. Almost 85% removal of RDB was observed at 60 0C. The Langmuir and Freundlich isotherms obtained, positive ?H0 value, pH dependent results and desorption of dye in mineral acid suggest that the adsorption of RDB by Banana bark carbon involves physisorption mechanism.

  10. Surface fractal dimensions and textural properties of mesoporous alkaline-earth hydroxyapatites

    International Nuclear Information System (INIS)

    Vilchis-Granados, J.; Granados-Correa, F.; Barrera-Díaz, C.E.

    2013-01-01

    This work examines the surface fractal dimensions (D f ) and textural properties of three different alkaline-earth hydroxyapatites. Calcium, strontium and barium hydroxyapatite compounds were successfully synthesized via chemical precipitation method and characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, and N 2 -physisorption measurements. Surface fractal dimensions were determined using single N 2 -adsorption/desorption isotherms method to quantify the irregular surface of as-prepared compounds. The obtained materials were also characterized through their surface hydroxyl group content, determined by the mass titration method. It was found that the D f values for the three materials covered the range of 0.77 ± 0.04–2.33 ± 0.11; these results indicated that the materials tend to have smooth surfaces, except the irregular surface of barium hydroxyapatite. Moreover, regarding the synthesized calcium hydroxyapatite exhibited better textural properties compared with the synthesized strontium and barium hydroxyapatites for adsorbent purposes. However, barium hydroxyapatite shows irregular surface, indicating a high population of active sites across the surface, in comparison with the others studied hydroxyapatites. Finally, the results showed a linear correlation between the surface hydroxyl group content at the external surface of materials and their surface fractal dimensions.

  11. The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate

    Directory of Open Access Journals (Sweden)

    Paulina Arellanes-Lozada

    2014-08-01

    Full Text Available Compounds of poly(ionic liquids (PILs, derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium (PImC12, poly(1-vinyl-3-octylimidazolium (PImC8 and poly(1-vinyl-3-butylimidazolium (PImC4 hexafluorophosphate were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1–1 M H2SO4 by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir’s isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC12 > PImC8 > PImC4 to reach 61% for PImC12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs’ partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.

  12. An energy conservation approach to adsorbate-induced surface stress and the extraction of binding energy using nanomechanics

    Science.gov (United States)

    Pinnaduwage, Lal A.; Boiadjiev, Vassil I.; Hawk, John E.; Gehl, Anthony C.; Fernando, Gayanath W.; Rohana Wijewardhana, L. C.

    2008-03-01

    Surface stress induced by molecular adsorption in three different binding processes has been studied experimentally using a microcantilever sensor. A comprehensive free-energy analysis based on an energy conservation approach is proposed to explain the experimental observations. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. The released binding energy appears to be almost exclusively channeled to the surface energy, and energy distribution to other channels, including heat, appears to be inactive for this micromechanical system. When this excess surface energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such vapor phase experiments were conducted for three binding processes: physisorption, hydrogen bonding, and chemisorption. Binding energies for these three processes were also estimated.

  13. An energy conservation approach to adsorbate-induced surface stress and the extraction of binding energy using nanomechanics

    Energy Technology Data Exchange (ETDEWEB)

    Pinnaduwage, Lal A; Boiadjiev, Vassil I; Hawk, John E; Gehl, Anthony C [Oak Ridge National Laboratory, PO Box 2008, Oak Ridge, TN 37831-6122 (United States); Fernando, Gayanath W [Physics Department, University of Connecticut, Storrs, CT 06269 (United States); Wijewardhana, L C Rohana [Physics Department, University of Cincinnati, Cincinnati, OH 45221 (United States)

    2008-03-12

    Surface stress induced by molecular adsorption in three different binding processes has been studied experimentally using a microcantilever sensor. A comprehensive free-energy analysis based on an energy conservation approach is proposed to explain the experimental observations. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. The released binding energy appears to be almost exclusively channeled to the surface energy, and energy distribution to other channels, including heat, appears to be inactive for this micromechanical system. When this excess surface energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such vapor phase experiments were conducted for three binding processes: physisorption, hydrogen bonding, and chemisorption. Binding energies for these three processes were also estimated.

  14. Spontaneous dissociation of Co2(CO8 and autocatalytic growth of Co on SiO2: A combined experimental and theoretical investigation

    Directory of Open Access Journals (Sweden)

    Kaliappan Muthukumar

    2012-07-01

    Full Text Available We present experimental results and theoretical simulations of the adsorption behavior of the metal–organic precursor Co2(CO8 on SiO2 surfaces after application of two different pretreatment steps, namely by air plasma cleaning or a focused electron beam pre-irradiation. We observe a spontaneous dissociation of the precursor molecules as well as autodeposition of cobalt on the pretreated SiO2 surfaces. We also find that the differences in metal content and relative stability of these deposits depend on the pretreatment conditions of the substrate. Transport measurements of these deposits are also presented. We are led to assume that the degree of passivation of the SiO2 surface by hydroxyl groups is an important controlling factor in the dissociation process. Our calculations of various slab settings, using dispersion-corrected density functional theory, support this assumption. We observe physisorption of the precursor molecule on a fully hydroxylated SiO2 surface (untreated surface and chemisorption on a partially hydroxylated SiO2 surface (pretreated surface with a spontaneous dissociation of the precursor molecule. In view of these calculations, we discuss the origin of this dissociation and the subsequent autocatalysis.

  15. Chemical trends of Schottky barrier behavior on monolayer hexagonal B, Al, and Ga nitrides

    Science.gov (United States)

    Lu, Haichang; Guo, Yuzheng; Robertson, John

    2016-08-01

    The Schottky Barrier Heights (SBH) of metal layers on top of monolayer hexagonal X-nitrides (X = B, Al, Ga, and h-XN) are calculated using supercells and density functional theory so as to understand the chemical trends of contact formation on graphene and the 2D layered semiconductors such as the transition metal dichalcogenides. The Fermi level pinning factor S of SBHs on h-BN is calculated to be nearly 1, indicating no pinning. For h-AlN and h-GaN, the calculated pinning factor is about 0.63, less than for h-BN. We attribute this to the formation of stronger, chemisorptive bonds between the nitrides and the contact metal layer. Generally, the h-BN layer remains in a planar sp2 geometry and has weak physisorptive bonds to the metals, whereas h-AlN and h-GaN buckle out of their planar geometry which enables them to form the chemisorptive bonds to the metals.

  16. Influences of doping Cr/Fe/Ta on the performance of Ni/CeO{sub 2} catalyst under microwave irradiation in dry reforming of CH{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Odedairo, Taiwo [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia); Ma, Jun [School of Engineering, University of South Australia, Mawson Lakes, SA (Australia); Chen, Jiuling, E-mail: cjlchen@yahoo.com [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia); Wang, Shaobin [Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia); Zhu, Zhonghua, E-mail: z.zhu@uq.edu.au [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia)

    2016-01-15

    The structure of Ni/CeO{sub 2} catalyst with doping of Cr, Fe and Ta was investigated with XRD, N{sub 2} physisorption, XPS and HRTEM and the catalytic activity of the catalysts under microwave irradiation in dry reforming of methane was tested in a microwave reactor. The results show that the introduction of Cr and Ta to Ni/CeO{sub 2} can enhance the interaction between Ni and the support/promoter and inhibit the enlargement of NiO particles during the synthesis. The CH{sub 4} conversions in dry reforming on the catalysts follow the order: Ni/CeO{sub 2}<2Fe–Ni<2Ta–Ni<2Cr–Ni. The superior performance of 2Ta–Ni and 2Cr–Ni may be attributed to the locally-heated Ni particles caused by the strong microwave absorption of the in-situ grown graphene attached on them under microwave irradiation. - Highlights: • The influences of doping Cr, Fe and Ta on Ni/CeO{sub 2} were investigated. • The catalytic performances before and after doping were investigated. • The in-situ grown graphene can promote the conversion of reactants.

  17. Current-voltage characteristics of single-molecule diarylethene junctions measured with adjustable gold electrodes in solution.

    Science.gov (United States)

    Briechle, Bernd M; Kim, Youngsang; Ehrenreich, Philipp; Erbe, Artur; Sysoiev, Dmytro; Huhn, Thomas; Groth, Ulrich; Scheer, Elke

    2012-01-01

    We report on an experimental analysis of the charge transport through sulfur-free photochromic molecular junctions. The conductance of individual molecules contacted with gold electrodes and the current-voltage characteristics of these junctions are measured in a mechanically controlled break-junction system at room temperature and in liquid environment. We compare the transport properties of a series of molecules, labeled TSC, MN, and 4Py, with the same switching core but varying side-arms and end-groups designed for providing the mechanical and electrical contact to the gold electrodes. We perform a detailed analysis of the transport properties of TSC in its open and closed states. We find rather broad distributions of conductance values in both states. The analysis, based on the assumption that the current is carried by a single dominating molecular orbital, reveals distinct differences between both states. We discuss the appearance of diode-like behavior for the particular species 4Py that features end-groups, which preferentially couple to the metal electrode by physisorption. We show that the energetic position of the molecular orbital varies as a function of the transmission. Finally, we show for the species MN that the use of two cyano end-groups on each side considerably enhances the coupling strength compared to the typical behavior of a single cyano group.

  18. Current–voltage characteristics of single-molecule diarylethene junctions measured with adjustable gold electrodes in solution

    Directory of Open Access Journals (Sweden)

    Bernd M. Briechle

    2012-11-01

    Full Text Available We report on an experimental analysis of the charge transport through sulfur-free photochromic molecular junctions. The conductance of individual molecules contacted with gold electrodes and the current–voltage characteristics of these junctions are measured in a mechanically controlled break-junction system at room temperature and in liquid environment. We compare the transport properties of a series of molecules, labeled TSC, MN, and 4Py, with the same switching core but varying side-arms and end-groups designed for providing the mechanical and electrical contact to the gold electrodes. We perform a detailed analysis of the transport properties of TSC in its open and closed states. We find rather broad distributions of conductance values in both states. The analysis, based on the assumption that the current is carried by a single dominating molecular orbital, reveals distinct differences between both states. We discuss the appearance of diode-like behavior for the particular species 4Py that features end-groups, which preferentially couple to the metal electrode by physisorption. We show that the energetic position of the molecular orbital varies as a function of the transmission. Finally, we show for the species MN that the use of two cyano end-groups on each side considerably enhances the coupling strength compared to the typical behavior of a single cyano group.

  19. Adsorption of sulfur compound utilizing rice husk ash modified with niobium

    Energy Technology Data Exchange (ETDEWEB)

    Cavalcanti, Rodrigo M.; Pessoa Júnior, Wanison A.G. [Laboratório de Catálise Química e Materiais (CATAMA), Instituto de Ciências Exatas, Universidade Federal do Amazonas (UFAM), Av. Gen. Rodrigo Otávio Jordão Ramos, 6200, 69077-000 Manaus, AM (Brazil); Braga, Valdeilson S. [Laboratório de Catálise, Centro das Ciências Exatas e das Tecnologias, Universidade Federal do Oeste da Bahia, Rua Professor José Seabra de Lemos, 316, Recanto dos Pássaros, 47808-021 Barreira, BA (Brazil); Barros, Ivoneide de C.L., E-mail: iclbarros@gmail.com [Laboratório de Catálise Química e Materiais (CATAMA), Instituto de Ciências Exatas, Universidade Federal do Amazonas (UFAM), Av. Gen. Rodrigo Otávio Jordão Ramos, 6200, 69077-000 Manaus, AM (Brazil)

    2015-11-15

    Graphical abstract: - Highlights: • Adsorbents based in RHA modified with niobium were prepared by impregnation. • The impregnation modified the particle size and topology of RHA particles. • The adsorbents were applied in sulfur removal in model liquid fuels. • The larger sulfur removal (>50%) was achieved using RHA with 5 wt.% niobium oxide. • The adsorbent show great selectivity in adsorption experiments. - Abstract: Adsorbents based in rice husk ash (RHA) modified with niobium pentoxide were prepared for impregnation methods and applied in sulfur removal in liquid fuels. The solids were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen physisorption and thermal analysis; they show that there was no qualitative change in the amorphous structure of the RHA; however, the method of impregnation could modify the particle size and topology of RHA particles. The larger sulfur removal (>50%) was achieved using RHA with 5 wt.% Nb{sub 2}O{sub 5} at a dosage of 10 g L{sup −1}, after 4 h of contact with the model fuel. The kinetic study of adsorption of thiophene showed that the models of pseudo-second order and intra-particle diffusion best fit the experimental data. The adsorption experiments with the thiophenic derivatives compounds show a large selectivity of the adsorbent.

  20. Mercury removal from coal combustion flue gas by fly ash

    Energy Technology Data Exchange (ETDEWEB)

    Kuang, Junyan [Chinese Academy of Sciences, Beijing (China). Research Center for Process Pollution Control; Chinese Academy of Sciences, Beijing (China). Graduate Univ.; Xu, Wenqing; Zhu, Tingyu; Jing, Pengfei [Chinese Academy of Sciences, Beijing (China). Research Center for Process Pollution Control

    2013-07-01

    The effect of physicochemical properties on the mercury adsorption performance of three fly ash samples has been investigated. The samples were tested for mercury adsorption using a fixed-bed with a simulated gas. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy and other methods were used to characterize the samples. The results indicate that mercury adsorption on fly ash is mainly physisorption and chemisorption. Uncompleted burned carbon is an important factor for the improvement of mercury removal efficiency, especially, the C-M bond may improve the oxidation of mercury, which formed via the reaction of C and Ti, Si and other elements. The higher specific surface areas and smaller pore diameter are all beneficial for the high mercury removal efficiency. The presence of O{sub 2} plays a positive role on Hg adsorption of modified fly ash, while SO{sub 2} has double role of inhibition because of competitive adsorption and promotion to chemisorption. In addition, sample modified with FeCl{sub 3} has a great performance in Hg removal.

  1. Preparation of resveratrol-loaded nanoporous silica materials with different structures

    Energy Technology Data Exchange (ETDEWEB)

    Popova, Margarita, E-mail: mpopova@orgchem.bas.bg [Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Szegedi, Agnes [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Hungarian Academy of Sciences, 1117 Budapest, Magyar tudósok körútja 2. (Hungary); Mavrodinova, Vesselina [Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Novak Tušar, Natasa [National Institute of Chemistry, Ljubljana (Slovenia); Mihály, Judith; Klébert, Szilvia [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Hungarian Academy of Sciences, 1117 Budapest, Magyar tudósok körútja 2. (Hungary); Benbassat, Niko; Yoncheva, Krassimira [Faculty of Pharmacy, 2 Dunav Str., 1000 Sofia (Bulgaria)

    2014-11-15

    Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol.

  2. Synthesis of Li{sub 2}SiO{sub 3} at low temperature; Sintesis de Li{sub 2}SiO{sub 3} a baja temperatura

    Energy Technology Data Exchange (ETDEWEB)

    Mondragon G, G. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)

    2007-07-01

    The main objective of this work is to develop a new synthesis method to obtain one of the more studied ceramics in this field Li{sub 2}SiO{sub 3}) in a simple and economic way using different solutions (urea and ammonium hydroxide). The particular objectives are first to prepare the Li{sub 2}SiO{sub 3} ceramic, by means of the use of the reaction conventional technique in solid state at temperatures between 800 and 900 C to compare it with the one proposed in this work and this way to observe the advantages that it would gives us the new method. Later on, the same one was synthesized lithium ceramic (Li{sub 2}SiO{sub 3}) by means of the new method at low temperature (between 80 and 90 C), using silicic acid and lithium hydroxide like precursory reagents and different solutions (urea and ammonium hydroxide) for the optimization in their synthesis. Finally, it was carried out the characterization of these materials by means of X-ray diffraction (XRD), electronic microscopes (SEM and TEM), nitrogen physisorption (method BET) and thermal gravimetric analysis (TGA) to observe the differences that exist among the conventional method and the proposed method and by this way to determine the advantages of the last method. (Author)

  3. Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate

    Science.gov (United States)

    Rojas García, Elizabeth; López Medina, Ricardo; May Lozano, Marcos; Hernández Pérez, Isaías; Valero, Maria J.; Maubert Franco, Ana M.

    2014-01-01

    A Metal-Organic Framework (MOF), iron-benzenetricarboxylate (Fe(BTC)), has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC) were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R2 > 0.997) and revealed the ability of Fe(BTC) to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (−25.53 kJ·mol−1). The high recovery of the dye showed that Fe(BTC) can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes. PMID:28788289

  4. Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate

    Directory of Open Access Journals (Sweden)

    Elizabeth Rojas García

    2014-12-01

    Full Text Available A Metal-Organic Framework (MOF, iron-benzenetricarboxylate (Fe(BTC, has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R2 > 0.997 and revealed the ability of Fe(BTC to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (−25.53 kJ·mol−1. The high recovery of the dye showed that Fe(BTC can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes.

  5. Steam reforming of ethanol over nickel-tungsten catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez, I.P.; Fernandez, A.M. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Privada Xochicalco S/N, Temixco, Morelos (Mexico); Gochi-Ponce, Y. [Instituto Tecnologico de Oaxaca, Division de Estudios de Posgrado e Investigacion, Ave. Ing. Victor Bravo Ahuja, esq. Ave. Tecnologico No. 120, Col. Centro. Oaxaca, Oax (Mexico); Contreras Larios, J.L. [Universidad Autonoma Metropolitana Azcapotzalco, CBI., Energia, Av. Sn. Pablo 180, Col. Reynosa, C.P. 02200, Mexico D.F (Mexico)

    2010-11-15

    Ni-W/Al{sub 2}O{sub 3} catalysts were synthesized, characterized and tested for the steam reforming of ethanol from 300 to 600 C. Addition of Ni and W on the alumina, decreased the surface area and increased the pore volume of the mesoporous materials synthesized. The reaction products obtained were: H{sub 2}, CO{sub 2}, C{sub 2}H{sub 4}, CH{sub 4}, CO{sub 2}, CO and CH{sub 3}CHO. A promoting effect of Ni-W was observed in the conversion of ethanol to H{sub 2} from 15 to 30 wt.% Ni and 1 wt.% W. The selectivity to H{sub 2} on the alumina with Ni-W, was between 66.53 and 68.53% at 550 C, appearing some undesirable products, with low ratio of CO/CO{sub 2}. Reaction was studied on a fixed bed reactor at atmospheric pressure with an ethanol/water molar ratio of 1:4, from 300 to 600 C. The catalysts were characterized by the thermal gravimetric analysis (TGA)-Differential thermal analysis (DTA), N{sub 2} physisorption (BET and BJH methods), X-ray diffraction (XRD) and scanning electron microscopy (SEM), these techniques were used for characterization, before and after of the steam reforming. (author)

  6. Effect of Ti content in the photo catalytic behavior of Fe/TiO{sub 2}-SiO{sub 2} systems

    Energy Technology Data Exchange (ETDEWEB)

    Leon C, A.; Portillo V, N.; Hernandez P, I.; May L, M.; Gonzalez R, L.; Luna P, R. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Departamento de Ciencias Basicas, Av. San Pablo No. 180, Col. Reynosa Tamaulipas, 02200 Mexico D. F. (Mexico); Suarez P, R., E-mail: ihp@correo.azc.uam.mx [UNAM, Centro de Investigacion en Energia, 62580 Temixco, Morelos (Mexico)

    2013-10-01

    In this work we report the synthesis of Fe/TiO{sub 2}-SiO{sub 2} systems with different concentrations of TiO{sub 2} in order to determine the influence of titanium content on the structural, textural, optical properties and their photo catalytic behavior. The materials were synthesized by the sol-gel method and their modification was carried out by incipient impregnation. All samples were characterized be means of X-ray diffraction, N{sub 2} physisorption (Bet method), Dr-UV-Vis and Raman spectroscopy. The modifications of the structural and optical properties are discussed on the basis of long-range order reduction, suggesting the formation of highly dispersed TiO{sub 2} species. On the other hand, it was observed that the energy of the optical band gap decreases by introducing Fe. On the basis of these phenomena, the photo catalytic activity was measured, employing the degradation of orange II azo dye as a model reaction. (Author)

  7. Study of Catalyst, Aging Time and Surfactant Effects on Silica Inorganic Polymer Characteristics

    Directory of Open Access Journals (Sweden)

    M. Pakizeh

    2007-06-01

    Full Text Available In the present study the sol-gel method is used for synthesis of amorphous nanostructure silica polymer using tetraethoxysilane (TEOS as silicon source. This polymer can be used in manufacturing of nanoporous asymmetricmembranes. The effect of catalyst on silica particle size has been studied under acidic and basic conditions.زAcid-catalyzed reaction leads to the formation of fine particles while the base-catalyzed reaction produceslarger particles. The presence of cationic template surfactant namely cetyl pyridinium bromide (CPBزdirects the structural formation of the polymer by preventing the highly branched polymeric clusters. This will increase the effective area of the produced silica membrane. Nitrogen physisorption tests by Brunaver- Emmett-Teller (BET and Barrett-Joyner-Halenda (BJH methods revealed that the surface area of the membrane increases significantly around 5-folds when acid-catalyzed reaction is used. 29Si-NMR test is also used to study the aging time effect on the level of silica polymer branching. The results show that in acidic condition, aging time up to three weeks can still affect branching. The calcinations process in which the organic materials and CPB (surfactant are burned and released from the silica particles, is studied on template free silica materials as well as templated silica materials using TGA and DTA techniques.

  8. Functionalized mesoporous silica nanoparticles for oral delivery of budesonide

    Energy Technology Data Exchange (ETDEWEB)

    Yoncheva, K., E-mail: krassi.yoncheva@gmail.com [Department of Pharmaceutical Technology, Faculty of Pharmacy, Medical University of Sofia, 2 Dunav Str., 1000 Sofia (Bulgaria); Popova, M. [Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia (Bulgaria); Szegedi, A.; Mihaly, J. [Institute of Nanochemistry and Catalysis, Chemical Research Center, Hungarian Academy of Sciences, Pusztaszeri út. 59-67, 1025 Budapest (Hungary); Tzankov, B.; Lambov, N.; Konstantinov, S.; Tzankova, V. [Department of Pharmaceutical Technology, Faculty of Pharmacy, Medical University of Sofia, 2 Dunav Str., 1000 Sofia (Bulgaria); Pessina, F.; Valoti, M. [Dipartimento di Scienze della Vita, Universita di Siena, via Aldo Moro 2, Siena (Italy)

    2014-03-15

    Non-functionalized and amino-functionalized mesoporous silica nanoparticle were loaded with anti-inflammatory drug budesonide and additionally post-coated with bioadhesive polymer (carbopol). TEM images showed spherical shape of the nanoparticles and slightly higher polydispersity after coating with carbopol. Nitrogen physisorption and thermogravimetic analysis revealed that more efficient loading and incorporation into the pores of nanoparticles was achieved with the amino-functionalized silica carrier. Infrared spectra indicated that the post-coating of these nanoparticles with carbopol led to the formation of bond between amino groups of the functionalized carrier and carboxyl groups of carbopol. The combination of amino-functionalization of the carrier with the post-coating of the nanoparticles sustained budesonide release. Further, an in vitro model of inflammatory bowel disease showed that the cytoprotective effect of budesonide loaded in the post-coated silica nanoparticles on damaged HT-29 cells was more pronounced compared to the cytoprotection obtained with pure budesonide. -- Graphical abstract: Silica mesoporous MCM-41 particles were amino-functionalized, loaded with budesonide and post-coated with bioadhesive polymer (carbopol) in order to achieve prolonged residence of anti-inflammatory drug in GIT. Highlights: • Higher drug loading in amino-functionalized mesoporous silica. • Amino-functionalization and post-coating of the nanoparticles sustained drug release. • Achievement of higher cytoprotective effect with drug loaded into the nanoparticles.

  9. Preparation of resveratrol-loaded nanoporous silica materials with different structures

    International Nuclear Information System (INIS)

    Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

    2014-01-01

    Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol

  10. Cobalt separation present in aqueous solution using shell tamarind as bio sorbent; Separacion de cobalto presente en solucion acuosa utilizando cascara de tamarindo como biosorbente

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez L, J.

    2014-07-01

    In this work a new carbonaceous material is presented with improved adsorption properties obtained by a heart treatment about 5 min from the shell tamarind. It was found that the samples obtained carbonaceous adsorbents are effective in removing Co{sup 2+} (41 mg / g) ions in aqueous solutions. These samples were prepared from tamarind shell, urea, ammonium nitrate and water. The solution was subjected to a combustion process at different temperatures. Carbonaceous samples prepared in this manner were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (Sem) and surface area measurements by Physisorption of N{sub 2}. Changes in structure, morphology and texture were studied. The results show that this material is of great importance to the applications of adsorption of metal ions. The measurements of specific surface area (Bet) were 2.35 to 203.76 m{sup 2} g{sup -1} with pore diameters between 2.31 and 15.63 nm, indicating that the samples obtained are predominantly meso porous. The combustion process of the solution proved to be advantageous to improve the textural properties of the tamarind shell. The obtained carbonaceous material plays an important role in adsorption to remove cobalt in aqueous solutions. (Author)

  11. Titanium Dioxide Supported on Different Porous Materials as Photocatalyst for the Degradation of Methyl Green in Wastewaters

    Directory of Open Access Journals (Sweden)

    Haithem Bel Hadjltaief

    2015-01-01

    Full Text Available TiO2 nanoparticles were immobilized on two porous materials used as catalyst supports, namely, activated carbon (AC and natural clay (NC, through an impregnation process using TiO2 (P25 as precursor. The so-prepared composite materials were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, transition electron microscopy (TEM, and nitrogen physisorption, that is, Brunauer-Emmett-Teller (BET surface area determination. SEM and TEM observation evidenced that TiO2 was deposited on AC and NC surface. XRD results confirmed that TiO2 existed in a mixture of anatase and rutile phases. The specific surface area of photocatalysts decreased drastically in comparison with the original materials. The photocatalytic activity of these materials was assayed in the oxidation of Methyl Green (MG dye in aqueous medium under UV irradiation. TiO2/AC exhibited higher photocatalytic oxidation activity than TiO2 at neutral pH. Total mineralization of MG was confirmed by means of COD analysis, pointing to these materials as an efficient, cost-effective, and environment friendly alternative for water treatment.

  12. Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor

    Directory of Open Access Journals (Sweden)

    Carlos J. Lucio-Ortiz

    2013-09-01

    Full Text Available Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD, scanning electronic microscope (SEM, and N2 physisorption isotherms were also determined. The Ni/Al2O3 sample reveled agglomerated (1 μm of nanoparticles of Ni (30–80 nm however, NiO particles were also identified, probably for the low temperature during the H2 reduction treatment (350 °C, the Cu/Al2O3 sample presented agglomerates (1–1.5 μm of nanoparticles (70–150 nm, but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH3ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption.

  13. Immobilized humic substances and immobilized aggregates of humic substances as sorbent for solid phase extraction.

    Science.gov (United States)

    Erny, Guillaume L; Gonçalves, Bruna M; Esteves, Valdemar I

    2013-09-06

    In this work, humic substances (HS) immobilized, as a thin layer or as aggregates, on silica gel were tested as material for solid phase extraction. Some triazines (simazine, atrazine, therbutylazine, atrazine-desethyl-desisopropyl-2-hydroxy, ametryn and terbutryn), have been selected as test analytes due to their environmental importance and to span a large range of solubility and octanol/water partition coefficient (logP). The sorbent was obtained immobilizing a thin layer of HS via physisorption on a pre-coated silica gel with a cationic polymer (polybrene). While the sorbent could be used as it is, it was demonstrated that additional HS could be immobilized, via weak interactions, to form stable humic aggregates. However, while a higher quantity of HS could be immobilized, no significant differences were observed in the sorption parameters. This sorbent have been tested for solid phase extraction to concentrate triazines from aqueous matrixes. The sorbent demonstrated performances equivalent to commercial alternatives as a concentration factor between 50 and 200, depending on the type of triazines, was obtained. Moreover the low cost and the high flow rate of sample through the column allowed using high quantity of sorbent. The analytical procedure was tested with different matrixes including tap water, river water and estuarine water. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Hydrogen storage in carbon nanotubes.

    Science.gov (United States)

    Hirscher, M; Becher, M

    2003-01-01

    The article gives a comprehensive overview of hydrogen storage in carbon nanostructures, including experimental results and theoretical calculations. Soon after the discovery of carbon nanotubes in 1991, different research groups succeeded in filling carbon nanotubes with some elements, and, therefore, the question arose of filling carbon nanotubes with hydrogen by possibly using new effects such as nano-capillarity. Subsequently, very promising experiments claiming high hydrogen storage capacities in different carbon nanostructures initiated enormous research activity. Hydrogen storage capacities have been reported that exceed the benchmark for automotive application of 6.5 wt% set by the U.S. Department of Energy. However, the experimental data obtained with different methods for various carbon nanostructures show an extreme scatter. Classical calculations based on physisorption of hydrogen molecules could not explain the high storage capacities measured at ambient temperature, and, assuming chemisorption of hydrogen atoms, hydrogen release requires temperatures too high for technical applications. Up to now, only a few calculations and experiments indicate the possibility of an intermediate binding energy. Recently, serious doubt has arisen in relation to several key experiments, causing considerable controversy. Furthermore, high hydrogen storage capacities measured for carbon nanofibers did not survive cross-checking in different laboratories. Therefore, in light of today's knowledge, it is becoming less likely that at moderate pressures around room temperature carbon nanostructures can store the amount of hydrogen required for automotive applications.

  15. Addition of titanium as a potential catalyst for a high-capacity hydrogen storage medium (abstract only)

    International Nuclear Information System (INIS)

    Zuliani, F; Baerends, E J

    2008-01-01

    In recent years there has been increased interest in the characterization of titanium as a catalyst for high-capacity hydrogen storage materials. A first-principles study (Yildirim and Ciraci 2005 Phys. Rev. Lett. 94 175501) demonstrated that a single Ti atom coated on a single-walled nanotube (SWNT) binds up to four hydrogen molecules. The bonding was claimed to be an 'unusual combination of chemisorption and physisorption'. We report an ab initio study by means of the ADF program, which provides a complete insight into the donation/back-donation mechanism characterizing the bond between the Ti atom and the four H 2 molecules, and a full understanding of the catalytic role played by the Ti atom. In addition, we found that the same amount of adsorbed hydrogen can be stored using benzene support for Ti in place of the SWNT, due to the dominant local contribution of the hexagonal carbon ring surrounding the Ti atom. The benzene-Ti-H 2 bonding is discussed on the basis of molecular orbital interaction schemes as provided by ADF. This result advances our insight into the role of titanium as a catalyst and suggests new routes to better storage through different combinations of supports and catalysts

  16. Photo catalytic reduction of benzophenone on TiO2: Effect of preparation method and reaction conditions

    International Nuclear Information System (INIS)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I.

    2010-01-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO 2 was synthesized by means of a hydrothermal technique. TiO 2 (Degussa TiO 2 -P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp (λ= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO 2 depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO 2 was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO 2 (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO 2 -P25. (Author)

  17. α-Fe2O3 lithium battery anodes by nanocasting strategy from ordered 2D and 3D templates

    International Nuclear Information System (INIS)

    Di Lupo, F.; Gerbaldi, C.; Casino, S.; Francia, C.; Meligrana, G.; Tuel, A.; Penazzi, N.

    2014-01-01

    Highlights: • Nanosized α-Fe 2 O 3 lithium battery conversion anodes with tunable morphology. • Nanocasting technique using MCM-41 and MCM-48 silica moulds is adopted. • Textural/morphological characteristics define the electrochemical behaviour. • α-Fe 2 O 3 replica of MCM-41 exhibits stable capacity (∼300 mA h g −1 ) after 100 cycles. • α-Fe 2 O 3 replica of MCM-41 shows promising prospects as high-capacity Li-ion battery anode. - Abstract: Nanocasting strategy is here proposed as effective approach to tune structure and size of α-Fe 2 O 3 active nanoparticles as a promising anode material for Li-ion cells. MCM-41 and MCM-48 silicas, presenting hexagonal 2D and cubic 3D symmetry, respectively, and regular pore diameter of about 4 nm are selected as moulds. The structural–morphological and electrochemical characteristics are assessed by X-ray diffraction, transmission electron microscopy, N 2 physisorption at 77 K, cyclic voltammetry and galvanostatic discharge/charge cycling. It is here demonstrated that structural–morphological features change accordingly to the template used and careful control of the texture/particle characteristics is likely a fundamental variable noticeably affecting the cycling behaviour

  18. Effect of Calcination Temperatures and Mo Modification on Nanocrystalline (γ-χ-Al2O3 Catalysts for Catalytic Ethanol Dehydration

    Directory of Open Access Journals (Sweden)

    Tharmmanoon Inmanee

    2017-01-01

    Full Text Available The mixed gamma and chi crystalline phase alumina (M-Al catalysts prepared by the solvothermal method were investigated for catalytic ethanol dehydration. The effects of calcination temperatures and Mo modification were elucidated. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption, transmission electron microscopy (TEM, and NH3-temperature programmed desorption (NH3-TPD. The catalytic activity was tested for ethylene production by dehydration reaction of ethanol in gas phase at atmospheric pressure and temperature between 200°C and 400°C. It was found that the calcination temperatures and Mo modification have effects on acidity of the catalysts. The increase in calcination temperature resulted in decreased acidity, while the Mo modification on the mixed phase alumina catalyst yielded increased acidity, especially in medium to strong acids. In this study, the catalytic activity of ethanol dehydration to ethylene apparently depends on the medium to strong acid. The mixed phase alumina catalyst calcined at 600°C (M-Al-600 exhibits the complete ethanol conversion having ethylene yield of 98.8% (at 350°C and the Mo-modified catalysts promoted dehydrogenation reaction to acetaldehyde. This can be attributed to the enhancement of medium to strong acid with metal sites of catalyst.

  19. Sulphonated cobalt phthalocyanine-MCM-41: An active photocatalyst for degradation of 2,4-dichlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zanjanchi, M.A., E-mail: zanjanchi@guilan.ac.ir [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Namjoo St., Rasht 41335 (Iran, Islamic Republic of); Ebrahimian, A.; Arvand, M. [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Namjoo St., Rasht 41335 (Iran, Islamic Republic of)

    2010-03-15

    The photocatalytic activity of sulphonated cobalt phthalocyanine immobilized onto MCM-41 was investigated for decomposition of 2,4-dichlorophenol (2,4-DCP) in aqueous solutions. Immobilization of anion sulpho-cobalt phthalocyanine to the walls of MCM-41 was performed by pre-anchorage of 3-(aminopropyl)-triethoxysilane (APTES) onto MCM-41 via post-synthesis method. X-ray diffraction, nitrogen physisorption, diffuse reflectance spectroscopy, energy-dispersive X-ray and FT-IR methods were used to characterize the product. Photocatalytic efficiency of the prepared catalyst for degradation of 2,4-DCP was tested under illumination of UV-A and visible light. The results obtained reveal that the photocatalyst is very active in degradation of 2,4-DCP. The photodegradation process is completed within 3 h using a dose of 0.6 g/L of the catalyst under UV irradiation. The reactions follow a pseudo-first-order kinetics and the observed rate constant values change with 2,4-DCP concentrations. The reproducibility of the catalyst was tested. The reaction intermediates were identified by gas chromatoghraphy-mass spectrometery (GC-MS) technique.

  20. Enhanced competitive adsorption of CO2 and H2 on graphyne: A density functional theory study

    Directory of Open Access Journals (Sweden)

    Hyuk Jae Kwon

    2017-12-01

    Full Text Available Adsorption using carbon-based materials has been established to be a feasible method for separating carbon dioxide and hydrogen to mitigate the emission of carbon dioxide into the atmosphere and for the collection of fuel for energy sources, simultaneously. We carried out density functional theory calculation with dispersion correction to investigate the physisorption characteristics of carbon allotropes such as graphene and graphyne for the competitive adsorption of CO2 and H2. It is worth noting that the graphyne represented preferable adsorption energies, short bond lengths and energy charges for both gases, compared with the characteristics observed with graphene. We found that in graphyne, both the affinitive adsorption of CO2, and the competitive adsorption of CO2 and H2, took place at the hollow site between acetylene links, which do not exist in graphene. We demonstrate that in the presence of H2, the CO2 adsorption selectivity of graphyne is higher than that of graphene, because of the improved electronic properties resulting from the acetylene links.

  1. Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

    Directory of Open Access Journals (Sweden)

    Hakuba Kitagawa

    2016-07-01

    Full Text Available The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S2 with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S2 was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S2 was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S2 molecules reacted further to produce bent-S3 species as the temperature was increased. Following the thermal evolution of the S2 species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-trisulfur dication (cyclo-S32+. It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species.

  2. Increase of porosity by combining semi-carbonization and KOH activation of formaldehyde resins to prepare high surface area carbons for supercapacitor applications

    Science.gov (United States)

    Heimböckel, Ruben; Kraas, Sebastian; Hoffmann, Frank; Fröba, Michael

    2018-01-01

    A series of porous carbon samples were prepared by combining a semi-carbonization process of acidic polymerized phenol-formaldehyde resins and a following chemical activation with KOH used in different ratios to increase specific surface area, micropore content and pore sizes of the carbons which is favourable for supercapacitor applications. Samples were characterized by nitrogen physisorption, powder X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The results show that the amount of KOH, combined with the semi-carbonization step had a remarkable effect on the specific surface area (up to SBET: 3595 m2 g-1 and SDFT: 2551 m2 g-1), pore volume (0.60-2.62 cm3 g-1) and pore sizes (up to 3.5 nm). The carbons were tested as electrode materials for electrochemical double layer capacitors (EDLC) in a two electrode setup with tetraethylammonium tetrafluoroborate in acetonitrile as electrolyte. The prepared carbon material with the largest surface area, pore volume and pore sizes exhibits a high specific capacitance of 145.1 F g-1 at a current density of 1 A g-1. With a high specific energy of 31 W h kg-1 at a power density of 33028 W kg-1 and a short time relaxation constant of 0.29 s, the carbon showed high power capability as an EDLC electrode material.

  3. Incorporation of Pt, Ru and Pt-Ru nanoparticles into ordered mesoporous carbons for efficient oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Stojmenović, Marija; Momčilović, Milan; Gavrilov, Nemanja; Pašti, Igor A.; Mentus, Slavko; Jokić, Bojan; Babić, Biljana

    2015-01-01

    Ordered mesoporous carbon, volume-doped up to 3 w.% with Pt, Ru and Pt-Ru nanoparticles was synthesized by evaporation-induced self-assembly method, under acidic conditions. The content of incorporated metal was determined by EDX analysis. The X-ray diffractometry confirmed the existence of highly dispersed metallic phases in doped samples. Specific surface area was determined by N 2 -physisorption measurements to range between 452 and 545 m 2 g −1 . Raman spectroscopy of investigated materials indicated highly disordered carbon structure with crystallite sizes around 1.4 nm. In a form of thin-layer electrode on glassy carbon support, in 0.1 M KOH solution, the prepared materials displayed high activity toward oxygen reduction reaction (ORR) in alkaline media, with onset potentials more positive than −0.10 V vs. SCE. The kinetics of O 2 reduction was found to be affected by both the specific surface area and the concentration of metal dopants. The ethanol tolerance of (Pt, Ru)-doped OMCs was found to be higher than that of common Pt/C ORR catalysts. Presented study provides a new route for the synthesis of active and selective ORR catalysts in alkaline media, being competitive with, or superior to, the existing ones in terms of performance and price

  4. Enhancement of Ag-Based Plasmonic Photocatalysis in Hydrogen Production from Ammonia Borane by the Assistance of Single-Site Ti-Oxide Moieties within a Silica Framework.

    Science.gov (United States)

    Verma, Priyanka; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2017-03-13

    Ag nanoparticles (NPs) have gained great attention owing to their interesting plasmonic properties and efficient catalysis under visible-light irradiation. In this study, an Ag-based plasmonic catalyst supported on mesoporous silica with isolated and tetrahedrally coordinated single-site Ti-oxide moieties, namely, Ag/Ti-SBA-15, was designed with the purpose of utilizing the broad spectral range of solar energy. The Ti-SBA-15 support allows the deposition of small Ag NPs with a narrow size distribution. The chemical structure, morphology, and optical properties of the prepared catalyst were characterized by techniques such as UV/Vis, FT extended X-ray absorption fine structure, and X-ray photoelectron spectroscopy, field-emission SEM, TEM, and N 2 physisorption studies. The catalytic activity of Ag/Ti-SBA-15 in hydrogen production from ammonia borane by hydrolysis was significantly enhanced in comparison with Ag/SBA-15 without Ti-oxide moieties and Ag/TiO 2 /SBA-15 involving agglomerated TiO 2 , both in the dark and under light irradiation. Improved electron transfer under light irradiation caused by the creation of heterojunctions between Ag NPs and Ti-oxide moieties explains the results obtained in the present study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

    Science.gov (United States)

    Tosun, Ismail

    2012-03-01

    The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

  6. Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

    Directory of Open Access Journals (Sweden)

    İsmail Tosun

    2012-03-01

    Full Text Available The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R and four three-parameter (Redlich-Peterson (R-P, Sips, Toth and Khan isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2 of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°, enthalpy (∆H° and entropy (∆S° of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

  7. The use of Euphorbia falcata extract as eco-friendly corrosion inhibitor of carbon steel in hydrochloric acid solution

    International Nuclear Information System (INIS)

    El Bribri, A.; Tabyaoui, M.; Tabyaoui, B.; El Attari, H.; Bentiss, F.

    2013-01-01

    Euphorbia falcata L. extract (EFE) was investigated as eco-friendly corrosion inhibitor of carbon steel in 1 M HCl using gravimetric, ac impedance, polarization and scanning electron microscopy (SEM) techniques. The experimental results show that EFE is good corrosion inhibitor and the protection efficiency is increased with the EEF concentration. The results obtained from weight loss and ac impedance studies were in reasonable agreement. Impedance experimental data revealed a frequency distribution of the capacitance, simulated as constant phase element. Polarization curves indicated that EFE is a mixed inhibitor. The corrosion inhibition was assumed to occur via adsorption of EFE molecules on the metal surface. The adsorption of the E. falcata extract was well described by the Langmuir adsorption isotherm. The calculated ΔG ads o value showed that the corrosion inhibition of the carbon steel in 1 M HCl is mainly controlled by a physisorption process. - Graphical abstract: Display Omitted - Highlights: • EFE is a good eco-friendly inhibitor for the corrosion of carbon steel in 1 M HCl. • EFE acts as mixed-type inhibitor in 1 M HCl medium. • Weight loss, ac impedance and polarization methods are in reasonable agreement. • The adsorption of EFE is well described by the Langmuir adsorption isotherm

  8. Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media

    Science.gov (United States)

    Huber, Patrick

    2015-03-01

    Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

  9. Polymer Brushes: Synthesis, Characterization, Applications

    Science.gov (United States)

    Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen

    2004-09-01

    Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

  10. Promoted V2O5/TiO2 catalysts for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Godiksen, Anita

    2016-01-01

    characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, Raman, FTIR and EPR spectroscopy to investigate the properties of the catalysts. XRPD, Raman and FTIR showed that promotion with 15 wt.% HPA does not cause V2O5 to be present in crystalline form, also at a loading of 5 wt.% V2O5. Hence, use of HPAs does......The influence of varying the V2O5 content (3–6 wt.%) was studied for the selective catalytic reduction (SCR) of nitrogen oxides by ammonia on heteropoly acid (HPA)- and tungsten oxide (WO3)-promoted V2O5/TiO2 catalysts. The SCR activity and alkali deactivation resistance of HPA-promoted V2O5/TiO2...... catalysts was found to be much higher than for WO3-promoted catalysts. By increasing the vanadium content from 3 to 5 wt.% the catalysts displayed a two fold increase in activity at 225 °C and retained their initial activity after alkali doping at a molar K/V ratio of 0.181. Furthermore, the catalysts were...

  11. Mn/TiO2 and Mn–Fe/TiO2 catalysts synthesized by deposition precipitation—promising for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Jensen, Anker Degn

    2015-01-01

    Mn/TiO2and Mn–Fe/TiO2catalysts have been prepared by impregnation (IMP) and deposition-precipitation (DP) techniques and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, XPS and TGA. 25 wt% Mn0.75Fe0.25Ti-DP catalyst, prepared by deposition precipitation with ammonium carbamate (AC......) as a precipitating agent, showed superior low-temperature SCR (selective catalytic reduction) of NO with NH3. The superior catalytic activity of the 25 wt% Mn0.75Fe0.25Ti-DP catalyst is probably due to the presence of amorphous phases of manganese oxide, iron oxide, high surface area, high total acidity......, acidstrength and ease of reduction of manganese oxide and iron oxide on TiO2in addition to formation of an SCR active MnOx phase with high content of chemisorbed oxygen (Oα). The optimum catalyst might beused as tail-end SCR catalysts in, e.g., biomass-fired power plants and waste incineration plants....

  12. Hydrothermally Stable Fe–W–Ti SCR Catalysts Prepared by Deposition–Precipitation

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Mossin, Susanne

    2014-01-01

    Fe/TiO2 based catalysts were prepared by incipient wetness impregnation and deposition–precipitation (DP). The catalysts were characterized by activity measurements, N2 physisorption, X-ray powder diffraction, electron paramagnetic resonance spectroscopy, energy dispersive X-ray spectroscopy, H2......-temperature programmed reduction and NH3-temperature programmed desorption. The 3 wt% Fe–10 wt% WO3/TiO2 (3Fe–10WTi-DP) catalyst prepared by DP using ammonium carbamate as a precipitating agent was found to be the most active and hydrothermally stable with 11 vol% H2O in air at 650 °C for 3 h....... The hydrothermal stability of the catalyst can be attributed to the retained crystal structure, and mild change in acidic and redox properties of the catalyst. Furthermore, hydrothermal stability of the 3Fe–10WTi-DP catalyst is competitive with that of 3Fe–ZSM-5 and much better than 3V2O5–10WO3–TiO2 catalysts...

  13. Density functional theory study of chemical sensing on surfaces of single-layer MoS2 and graphene

    International Nuclear Information System (INIS)

    Mehmood, F.; Pachter, R.

    2014-01-01

    In this work, density functional theory (DFT) calculations have been used to investigate chemical sensing on surfaces of single-layer MoS 2 and graphene, considering the adsorption of the chemical compounds triethylamine, acetone, tetrahydrofuran, methanol, 2,4,6-trinitrotoluene, o-nitrotoluene, o-dichlorobenzene, and 1,5-dicholoropentane. Physisorption of the adsorbates on free-standing surfaces was analyzed in detail for optimized material structures, considering various possible adsorption sites. Similar adsorption characteristics for the two surface types were demonstrated, where inclusion of a correction to the DFT functional for London dispersion was shown to be important to capture interactions at the interface of molecular adsorbate and surface. Charge transfer analyses for adsorbed free-standing surfaces generally demonstrated very small effects. However, charge transfer upon inclusion of the underlying SiO 2 substrate rationalized experimental observations for some of the adsorbates considered. A larger intrinsic response for the electron-donor triethylamine adsorbed on MoS 2 as compared to graphene was demonstrated, which may assist in devising chemical sensors for improved sensitivity

  14. Density functional study of TaSin (n = 1-3, 12) clusters adsorbed to graphene surface

    International Nuclear Information System (INIS)

    Guo Ping; Zheng Lin; Zheng Jiming; Zhang Ruizhi; Yang Luna; Ren, Zhaoyu

    2011-01-01

    A plane-wave density functional theory (DFT) calculations have been performed to investigate structural and electronic properties of TaSi n (n = 1-3, 12) clusters supported by graphene surface. The resulting adsorption structures are described and discussed in terms of stability, bonding, and electron transfer between the cluster and the graphene. The TaSi n clusters on graphene surface favor their free-standing ground-state structures. Especially in the cases of the linear TaSi 2 and the planar TaSi 3 , the graphene surface may catalyze the transition of the TaSi n clusters from an isomer of lower dimensionality into the ground-state structure. The adsorption site and configuration of TaSi n on graphene surface are dominated by the interaction between Ta atom and graphene. Ta atom prefers to adsorb on the hollow site of graphene, and Si atoms tend to locate on the bridge site. Further, the electron transfer is found to proceed from the cluster to the surface for n = 1 and 2, while its direction reverses as n > 2. For the case of TaSi, chemisorption is shown to prevail over physisorption as the dominant mode of surface-adsorbate interaction by charge density analysis.

  15. NaA zeolite derived from blast furnace slag: its application for ammonium removal.

    Science.gov (United States)

    Guo, Hongwei; Tang, Lizhen; Yan, Bingji; Wan, Kang; Li, Peng

    2017-09-01

    In this paper, high value added NaA zeolite material was prepared from blast furnace (BF) slag by hydrothermal method and its adsorption behavior on the removal of ammonium ion was investigated. It was found out that the synthetic NaA cubic zeolite with smaller crystal size obtained at nSiO 2 /nAl 2 O 3 = 2 and nH 2 O/nNaOH = 20 showed better adsorption performance. The kinetics of the adsorption of ammonium ion by synthesized NaA zeolite was fitted by the pseudo-second-order kinetic model. The intra-particle diffusion modeling reveals that two mixed rate-controlling mechanisms were involved in the adsorption process. The relatively high value of activation energy of 92.3 kJ·mol -1 indicates a high impact of temperature on the adsorption rate, and the nature of ammonium adsorption is chemical reaction rather than physisorption. Based on the thermodynamics calculations, the adsorption of ammonium was found to be an endothermic, spontaneous process. The adsorption isothermal analysis showed that the Langmuir model could be well fitted and a maximum adsorption capacity of 83.3 mg·g -1 of NH 4 + was obtained. Thus, it was demonstrated that by forming low cost NaA zeolite and using it for environmental remediation, the synchronous minimization of BF slag and ammonia nitrogen contamination could be achieved.

  16. Adsorption of sulfur compound utilizing rice husk ash modified with niobium

    International Nuclear Information System (INIS)

    Cavalcanti, Rodrigo M.; Pessoa Júnior, Wanison A.G.; Braga, Valdeilson S.; Barros, Ivoneide de C.L.

    2015-01-01

    Graphical abstract: - Highlights: • Adsorbents based in RHA modified with niobium were prepared by impregnation. • The impregnation modified the particle size and topology of RHA particles. • The adsorbents were applied in sulfur removal in model liquid fuels. • The larger sulfur removal (>50%) was achieved using RHA with 5 wt.% niobium oxide. • The adsorbent show great selectivity in adsorption experiments. - Abstract: Adsorbents based in rice husk ash (RHA) modified with niobium pentoxide were prepared for impregnation methods and applied in sulfur removal in liquid fuels. The solids were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen physisorption and thermal analysis; they show that there was no qualitative change in the amorphous structure of the RHA; however, the method of impregnation could modify the particle size and topology of RHA particles. The larger sulfur removal (>50%) was achieved using RHA with 5 wt.% Nb 2 O 5 at a dosage of 10 g L −1 , after 4 h of contact with the model fuel. The kinetic study of adsorption of thiophene showed that the models of pseudo-second order and intra-particle diffusion best fit the experimental data. The adsorption experiments with the thiophenic derivatives compounds show a large selectivity of the adsorbent.

  17. Adsorptive removal of 1-naphthol from water with Zeolitic imidazolate framework-67

    Science.gov (United States)

    Yan, Xinlong; Hu, Xiaoyan; Chen, Tao; Zhang, Shiyu; Zhou, Min

    2017-08-01

    1-Naphthol is widely used as an intermediate in the plastics, dyes, fibers and rubbers production areas, leading to the increasing detection of 1-naphthol in the soil and water environment, which is of particular concern due to its acute toxicity and negative environmental impacts. Considering the high surface area and good stability of ZIFs (zeolitic imidazole frameworks) material, ZIF-67 (a representative cobalt-based ZIFs material) was synthesized and applied as an adsorbent for removal of 1-naphthol from aqueous solution. The obtained ZIF-67 was characterized by XRD, TEM, XPS, N2 physisorption and TG, and the adsorption isotherm, kinetics, and regeneration of the adsorbent were studied in detail. The adsorption of 1-naphthol on ZIF-67 followed a pseudo-second-order equation kinetics and fitted Langmuir adsorption model with a maximum adsorption capacity of 339 mg/g at 313 K, which is much higher than that of the common adsorbents reported such as activated carbon and carbon nanotubes et al. The solution pH was found to be an important factor influencing the adsorption process, which could be explained by the predominant mechanism controlling the process, i.e. electrostatic attraction. In addition, the ZIF-67 showed desirable reusability toward 1-naphthol removal from alkaline aqueous solution.

  18. Adsorption of arsenic by activated carbon, calcium alginate and their composite beads.

    Science.gov (United States)

    Hassan, A F; Abdel-Mohsen, A M; Elhadidy, H

    2014-07-01

    The present investigation deals with preparation of three different adsorbent materials namely; potassium hydroxide activated carbon based apricot stone (C), calcium alginate beads (G) and calcium alginate/activated carbon composite beads (GC) were used for the removal of arsenic. The prepared adsorbent materials were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), N2-adsorption at -196°C and point of zero charge. From the obtained results, it was found that the porosity, surface area and total pore volume of the adsorbent material C>GC>G respectively, however, the G adsorbent has more acidic function group than the other adsorbents. The influence of pH, time, temperature and initial concentration of arsenic(V) were studied and optimized. GC exhibits the maximum As(V) adsorption (66.7mg/g at 30°C). The adsorption of arsenic ions was observed to follow pseudo-second order mechanism as well as the thermodynamic parameters confirm also the endothermic spontaneous and a physisorption process. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Jet-Fuel Range Hydrocarbons from Biomass-Derived Sorbitol over Ni-HZSM-5/SBA-15 Catalyst

    Directory of Open Access Journals (Sweden)

    Yujing Weng

    2015-12-01

    Full Text Available Aromatics and cyclic-hydrocarbons are the significant components of jet fuel with high energy-density. However, conventional technologies for bio-fuel production cannot produce these products without further aromatization and isomerization. In this work, renewable liquid fuel with high content of aromatics and cyclic-hydrocarbons was obtained through aqueous catalytic conversion of biomass sorbitol over Ni-HZSM-5/SBA-15 catalyst. Texture characteristics of the catalyst were determined by physisorption of N2, which indicated its bimodal pore structures were microporous (HZSM-5, pore width: 0.56 nm and mesoporous (SBA-15, pore width: 8 nm. The surface acidity included weak and strong acid sites, predominantly Lewis type, and was further confirmed by the NH3-TPD and Py-IR analysis. The catalytic performances were tested in a fixed-bed reactor under the conditions of 593 K, WHSV of 0.75 h−1, GHSV of 2500 h−1 and 4.0 MPa of hydrogen pressure, whereby oil yield of 40.4 wt. % with aromatics and cyclic-hydrocarbons content of 80.0% was obtained.

  20. Significant enhancement in the photocatalytic activity of N, W co-doped TiO2 nanomaterials for promising environmental applications

    International Nuclear Information System (INIS)

    Thind, Sapanbir S; Wu Guosheng; Tian Min; Chen Aicheng

    2012-01-01

    In this work, a mesoporous N, W co-doped TiO 2 photocatalyst was synthesized via a one-step solution combustion method, which utilized urea as the nitrogen source and sodium tungstate as the tungsten source. The photocatalytic activity of the N, W co-doped TiO 2 photocatalyst was significantly enhanced by a facile UV pretreatment approach and was evaluated by measuring the rate of photodegradation of Rhodamine B under both UV and visible (λ > 420) light. Following the UV pretreatment, the UV photocatalytic activity of the N, W co-doped TiO 2 was doubled. In terms of visible light activity, the UV pretreatment resulted in an extraordinary >12 fold improvement. In order to gain insight into this substantial enhancement, the N, W co-doped TiO 2 photocatalysts were studied using x-ray diffraction, transmission electron microscopy, N 2 physisorption, UV–vis absorbance spectroscopy and x-ray photoelectron spectroscopy prior to and following the UV pretreatment. Our experimental results have revealed that this significant augmentation of photocatalytic activity may be attributed to several synergetic factors, including increase of the specific surface area, reduction of the band gap energy and the removal of carbon impurities. (paper)

  1. Inhibitory action of quaternary ammonium bromide on mild steel and synergistic effect with other halide ions in 0.5 M H2SO4

    Directory of Open Access Journals (Sweden)

    A. Khamis

    2014-11-01

    Full Text Available The corrosion inhibition of mild steel in 0.5 M H2SO4 solution has been investigated using electrochemical methods, X-ray diffraction (XRD and scanning electron microscope (SEM. The adsorption and inhibition action of acid corrosion of mild steel using cetyltrimethylammonium bromide (CTABr and different halides (NaCl, NaBr and NaI has shown synergetic effect. The results showed that the protection efficiency (P% has high values at considerable high concentration of CTABr. However, in the presence of the different halides, the P increases dramatically at low concentration of CTABr. Physisorption was proposed from the the values of ΔGads0. The synergism parameter (Sθ is found to be greater than unity indicating that the enhanced P% caused by the addition of the halides to the CTABr is due to a co-operative adsorption of both species. Corrosion products phases and surface morphology were studied using X-ray diffraction (XRD and scanning electron microscopy (SEM, respectively.

  2. Gold nanoparticles functionalized with angiogenin-mimicking peptides modulate cell membrane interactions.

    Science.gov (United States)

    Cucci, Lorena M; Munzone, Alessia; Naletova, Irina; Magrì, Antonio; La Mendola, Diego; Satriano, Cristina

    2018-04-16

    Angiogenin is a protein crucial in angiogenesis, and it is overexpressed in many cancers and downregulated in neurodegenerative diseases, respectively. The protein interaction with actin, through the loop encompassing the 60-68 residues, is an essential step in the cellular cytoskeleton reorganization. This, in turn, influences the cell proliferation and migration processes. In this work, hybrid nanoassemblies of gold nanoparticles with angiogenin fragments containing the 60-68 sequence were prepared and characterized in their interaction with both model membranes of supported lipid bilayers (SLBs) and cellular membranes of cancer (neuroblastoma) and normal (fibroblasts) cell lines. The comparison between physisorption and chemisorption mechanisms was performed by the parallel investigation of the 60-68 sequence and the peptide analogous containing an extra cysteine residue. Moreover, steric hindrance and charge effects were considered with a third analogous peptide sequence, conjugated with a fluorescent carboxyfluorescein (Fam) moiety. The hybrid nanobiointerface was characterized by means of ultraviolet-visible, atomic force microscopy and circular dichroism, to scrutinize plasmonic changes, nanoparticles coverage and conformational features, respectively. Lateral diffusion measurements on SLBs "perturbed" by the interaction with the gold nanoparticles-peptides point to a stronger membrane interaction in comparison with the uncoated nanoparticles. Cell viability and proliferation assays indicate a slight nanotoxicity in neuroblastoma cells and a proliferative activity in fibroblasts. The actin staining confirms different levels of interaction between the hybrid assemblies and the cell membranes.

  3. HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect

    Directory of Open Access Journals (Sweden)

    Irina V. Deliy

    2017-10-01

    Full Text Available Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO2 and ((NH42HPO4 as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis, we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis.

  4. Effect of Ni on the characteristics and hydrogenation activity of sulfide Mo/{gamma}-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Schachtl, E.; Wuttke, E.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center

    2012-07-01

    The hydrogenation of phenanthrene was explored on sulfide Mo/{gamma}-Al{sub 2}O{sub 3} catalysts promoted with increasing concentrations of Ni. The characterization of the materials was done by N{sub 2}-physisorption, X-ray diffraction, transmission electron microscopy, temperature programmed sulfidation and NO adsorption experiments. Increasing loading of Ni improves the dispersion of MoS{sub 2} species; however, at Ni/(Mo+Ni) molar ratio higher than 0.5, segregation of Ni-sulfides is observed. The presence of Ni also facilitates the sulfidation of oxidic catalyst precursors by lowering the reduction temperature of Mo species. In the sulfide catalysts, Ni changes the structure of MoS{sub 2} leading to shorter slabs with higher stacking degree than on Mo/{gamma}-Al{sub 2}O{sub 3}, and increases the concentration of coordinatively unsaturated sites. The kinetic results (increased hydrogenation rate and changed reaction network in the presence of Ni) suggest that a highly active kind of active site is created by Ni promotion. (orig.)

  5. Characterization of Catalyst Materials for Production of Aerospace Fuels

    Science.gov (United States)

    Best, Lauren M.; De La Ree, Ana B.; Hepp, Aloysius F.

    2012-01-01

    Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

  6. Multi-protein delivery by nanodiamonds promotes bone formation.

    Science.gov (United States)

    Moore, L; Gatica, M; Kim, H; Osawa, E; Ho, D

    2013-11-01

    Bone morphogenetic proteins (BMPs) are well-studied regulators of cartilage and bone development that have been Food and Drug Administration (FDA)-approved for the promotion of bone formation in certain procedures. BMPs are seeing more use in oral and maxillofacial surgeries because of recent FDA approval of InFUSE(®) for sinus augmentation and localized alveolar ridge augmentation. However, the utility of BMPs in medical and dental applications is limited by the delivery method. Currently, BMPs are delivered to the surgical site by the implantation of bulky collagen sponges. Here we evaluate the potential of detonation nanodiamonds (NDs) as a delivery vehicle for BMP-2 and basic fibroblast growth factor (bFGF). Nanodiamonds are biocompatible, 4- to 5-nm carbon nanoparticles that have previously been used to deliver a wide variety of molecules, including proteins and peptides. We find that both BMP-2 and bFGF are readily loaded onto NDs by physisorption, forming a stable colloidal solution, and are triggered to release in slightly acidic conditions. Simultaneous delivery of BMP-2 and bFGF by ND induces differentiation and proliferation in osteoblast progenitor cells. Overall, we find that NDs provide an effective injectable alternative for the delivery of BMP-2 and bFGF to promote bone formation.

  7. Adsorption of gas molecules on armchair AlN nanoribbons with a dangling bond defect by using density functional theory

    International Nuclear Information System (INIS)

    Sun, Guodong; Zhao, Peng; Zhang, Wenxue; Li, Hui; He, Cheng

    2017-01-01

    In this paper, the adsorption of gas molecules (CO, NO, O_2, CO_2, and NO_2) on armchair aluminum nitride nanoribbons (AAlNNRs) with a dangling bond defect has been investigated by density functional theory. For all the studied systems, the adsorption geometries, adsorption energies, charge transfer, and electronic structures are discussed. The adsorption energies of O_2, NO_2, and CO_2 are -1.53, -2.24, and -2.88 eV, respectively, corresponding to strong chemisorption. While for CO and NO, the adsorptions are between weak chemisorption and strong physisorption. Moreover, the magnetic property of defective AAlNNR are sensitive to the adsorption of NO_2. Therefore, based on the obtained results, AAlNNRs with a dangling bond defect is promising for using in gas sensor devices to detect NO_2. - Highlights: • The adsorption properties of gas molecules on defective AAlNNRs are performed by DFT. • The adsorption of O_2, NO_2, and CO_2 on defective AAlNNRs are strong chemisorption. • The magnetic property of defective AAlNNRs are sensitive to the adsorption of NO_2. • The defective AAlNNRs is promising in gas sensor devices to detect and capture NO_2.

  8. Adsorption characteristics of As(III) from aqueous solution on iron oxide coated cement (IOCC)

    International Nuclear Information System (INIS)

    Kundu, Sanghamitra; Gupta, A.K.

    2007-01-01

    Contamination of potable groundwater with arsenic is a serious health hazard, which calls for proper treatment before its use as drinking water. The objective of the present study is to assess the effectiveness of iron oxide coated cement (IOCC) for As(III) adsorption from aqueous solution. Batch studies were conducted to study As(III) adsorption onto IOCC at ambient temperature as a function of adsorbent dose, pH, contact time, initial arsenic concentration and temperature. Kinetics reveal that the uptake of As(III) ion is very rapid and most of fixation occurs within the first 20 min of contact. The pseudo-second order rate equation successfully described the adsorption kinetics. Langmuir, Freundlich, Redlich-Peterson (R-P), and Dubinin-Radushkevich (D-R) models were used to describe the adsorption isotherms at different initial As(III) concentrations and at 30 g l -1 fixed adsorbent dose. The maximum adsorption capacity of IOCC for As(III) determined from the Langmuir isotherm was 0.69 mg g -1 . The mean free energy of adsorption (E) calculated from the D-R isotherm was found to be 2.86 kJ mol -1 which suggests physisorption. Thermodynamic parameters indicate an exothermic nature of adsorption and a spontaneous and favourable process. The results suggest that IOCC can be suitably used for As(III) removal from aqueous solutions

  9. Effective Use of Molecular Recognition in Gas Sensing: Results from Acoustic Wave and In-Situ FTIR Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Bodenhofer, K,; Gopel, W.; Hierlemann, A.; Ricco, A.J.

    1998-12-09

    To probe directly the analyte/film interactions that characterize molecular recognition in gas sensors, we recorded changes to the in-situ surface vibrational spectra of specifically fictionalized surface acoustic wave (SAW) devices concurrently with analyte exposure and SAW measurement of the extent of sorption. Fourier-lmnsform infrared external- reflectance spectra (FTIR-ERS) were collected from operating 97-MH2 SAW delay lines during exposure to a range of analytes as they interacted with thin-film coatings previously shown to be selective: cyclodextrins for chiral recognition, Ni-camphorates for Lewis bases such as pyridine and organophosphonates, and phthalocyanines for aromatic compounds. In most cases where specific chemical interactions-metal coordination, "cage" compound inclusion, or z stacking-were expected, analyte dosing caused distinctive changes in the IR spectr~ together with anomalously large SAW sensor responses. In contrast, control experiments involving the physisorption of the same analytes by conventional organic polymers did not cause similar changes in the IR spectra, and the SAW responses were smaller. For a given conventional polymer, the partition coefficients (or SAW sensor signals) roughly followed the analyte fraction of saturation vapor pressure. These SAW/FTIR results support earlier conclusions derived from thickness-shear mode resonator data.

  10. Natural Hematite and Siderite as Heterogeneous Catalysts for an Effective Degradation of 4-Chlorophenol via Photo-Fenton Process

    Directory of Open Access Journals (Sweden)

    Haithem Bel Hadjltaief

    2018-06-01

    Full Text Available This paper describes a simple and low-cost process for the degradation of 4-Chlorophenol (4-CP from aqueous solution, using natural Tunisian Hematite (M1 and Siderite (M2. Two natural samples were collected in the outcroppings of the Djerissa mining site (Kef district, northwestern Tunisia. Both Hematite and Siderite ferrous samples were characterized using several techniques, including X-Ray Diffraction (XRD, Nitrogen Physisorption (BET, Infrared Spectroscopy (FTIR, H2-Temperature Programmed Reduction (H2-TPR, Scanning Electronic Microscopy (SEM linked with Energy Dispersive X-ray (EDS and High-Resolution Transmission Electron Microscopy (HRTEM. Textural, structural and chemical characterization confirmed the presence of Hematite and Siderite phases with a high amount of iron on the both surface materials. Their activity was evaluated in the oxidation of 4-CP in aqueous medium under heterogeneous photo-Fenton process. Siderite exhibited higher photocatalytic oxidation activity than Hematite at pH 3. The experimental results also showed that 100% conversion of 4-CP and 54% TOC removal can be achieved using Siderite as catalyst. Negligible metal leaching and catalyst reutilization without any loss of activity point towards an excellent catalytic stability for both natural catalysts.

  11. DNA origami deposition on native and passivated molybdenum disulfide substrates

    Directory of Open Access Journals (Sweden)

    Xiaoning Zhang

    2014-04-01

    Full Text Available Maintaining the structural fidelity of DNA origami structures on substrates is a prerequisite for the successful fabrication of hybrid DNA origami/semiconductor-based biomedical sensor devices. Molybdenum disulfide (MoS2 is an ideal substrate for such future sensors due to its exceptional electrical, mechanical and structural properties. In this work, we performed the first investigations into the interaction of DNA origami with the MoS2 surface. In contrast to the structure-preserving interaction of DNA origami with mica, another atomically flat surface, it was observed that DNA origami structures rapidly lose their structural integrity upon interaction with MoS2. In a further series of studies, pyrene and 1-pyrenemethylamine, were evaluated as surface modifications which might mitigate this effect. While both species were found to form adsorption layers on MoS2 via physisorption, 1-pyrenemethylamine serves as a better protective agent and preserves the structures for significantly longer times. These findings will be beneficial for the fabrication of future DNA origami/MoS2 hybrid electronic structures.

  12. Interaction of Hydrogen with MOF-5.

    Science.gov (United States)

    Bordiga, Silvia; Vitillo, Jenny G; Ricchiardi, Gabriele; Regli, Laura; Cocina, Donato; Zecchina, Adriano; Arstad, Bjørnar; Bjørgen, Morten; Hafizovic, Jasmina; Lillerud, Karl Petter

    2005-10-06

    Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.

  13. CO{sub 2} capture using some fly ash-derived carbon materials

    Energy Technology Data Exchange (ETDEWEB)

    A. Arenillas; K.M. Smith; T.C. Drage; C.E. Snape [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering

    2005-12-01

    Adsorption is considered to be one of the more promising technologies for capturing CO{sub 2} from flue gases. For post-combustion capture, the success of such an approach is however dependent on the development of an adsorbent that can operate competitively at relatively high temperatures. In this work, low cost carbon materials derived from fly ash, are presented as effective CO{sub 2} sorbents through impregnation these with organic bases, for example, polyethylenimine aided by polyethylene glycol. The results show that for samples derived from a fly ash carbon concentrate, the CO{sub 2} adsorption capacities were relatively high (up to 4.5 wt%) especially at high temperatures (75{sup o}C), where commercial active carbons relying on physi-sorption have low capacities. The addition of PEG improves the adsorption capacity and reduces the time taken for the sample to reach the equilibrium. No CO{sub 2} seems to remain after desorption, suggesting that the process is fully reversible. 24 refs., 6 figs., 2 tabs.

  14. Synthesis and application of a new carboxylated cellulose derivative. Part I: Removal of Co(2+), Cu(2+) and Ni(2+) from monocomponent spiked aqueous solution.

    Science.gov (United States)

    Teodoro, Filipe Simões; Ramos, Stela Nhandeyara do Carmo; Elias, Megg Madonyk Cota; Mageste, Aparecida Barbosa; Ferreira, Gabriel Max Dias; da Silva, Luis Henrique Mendes; Gil, Laurent Frédéric; Gurgel, Leandro Vinícius Alves

    2016-12-01

    A new carboxylated cellulose derivative (CTA) was prepared from the esterification of cellulose with 1,2,4-Benzenetricarboxylic anhydride. CTA was characterized by percent weight gain (pwg), amount of carboxylic acid groups (nCOOH), elemental analysis, FTIR, TGA, solid-state (13)C NMR, X-ray diffraction (DRX), specific surface area, pore size distribution, SEM and EDX. The best CTA synthesis condition yielded a pwg and nCOOH of 94.5% and 6.81mmolg(-1), respectively. CTA was used as an adsorbent material to remove Co(2+), Cu(2+) and Ni(2+) from monocomponent spiked aqueous solution. Adsorption studies were developed as a function of the solution pH, contact time and initial adsorbate concentration. Langmuir model better fitted the experimental adsorption data and the maximum adsorption capacities estimated by this model were 0.749, 1.487 and 1.001mmolg(-1) for Co(2+), Cu(2+) and Ni(2+), respectively. The adsorption mechanism was investigated by using isothermal titration calorimetry. The values of ΔadsH° were in the range from 5.36 to 8.09kJmol(-1), suggesting that the mechanism controlling the phenomenon is physisorption. Desorption and re-adsorption studies were also performed. Desorption and re-adsorption efficiencies were closer to 100%, allowing the recovery of both metal ions and CTA adsorbent. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

    International Nuclear Information System (INIS)

    Guo Zhen; Liu Xianbin; Ng, Siu-Choon; Chen Yuan; Yang Yanhui; Du Yu

    2010-01-01

    Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

  16. Effective immobilization of alcohol dehydrogenase on carbon nanoscaffolds for ethanol biofuel cell.

    Science.gov (United States)

    Umasankar, Yogeswaran; Adhikari, Bal-Ram; Chen, Aicheng

    2017-12-01

    An efficient approach for immobilizing alcohol dehydrogenase (ADH) while enhancing its electron transfer ability has been developed using poly(2-(trimethylamino)ethyl methacrylate) (MADQUAT) cationic polymer and carbon nanoscaffolds. The carbon nanoscaffolds were comprised of single-walled carbon nanotubes (SWCNTs) wrapped with reduced graphene oxide (rGO). The ADH entrapped within the MADQUAT that was present on the carbon nanoscaffolds exhibited a high electron exchange capability with the electrode through its cofactor β-nicotinamide adenine dinucleotide hydrate and β-nicotinamide adenine dinucleotide reduced disodium salt hydrate (NAD + /NADH) redox reaction. The advantages of the carbon nanoscaffolds used as the support matrix and the MADQUAT employed for the entrapment of ADH versus physisorption were demonstrated via cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Our experimental results showed a higher electron transfer, electrocatalytic activity, and rate constant for MADQUAT entrapped ADH on the carbon nanoscaffolds. The immobilization of ADH using both MADQUAT and carbon nanoscaffolds exhibited strong potential for the development of an efficient bio-anode for ethanol powered biofuel cells. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Adsorption Properties of Typical Lung Cancer Breath Gases on Ni-SWCNTs through Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Qianqian Wan

    2017-01-01

    Full Text Available A lot of useful information is contained in the human breath gases, which makes it an effective way to diagnose diseases by detecting the typical breath gases. This work investigated the adsorption of typical lung cancer breath gases: benzene, styrene, isoprene, and 1-hexene onto the surface of intrinsic and Ni-doped single wall carbon nanotubes through density functional theory. Calculation results show that the typical lung cancer breath gases adsorb on intrinsic single wall carbon nanotubes surface by weak physisorption. Besides, the density of states changes little before and after typical lung cancer breath gases adsorption. Compared with single wall carbon nanotubes adsorption, single Ni atom doping significantly improves its adsorption properties to typical lung cancer breath gases by decreasing adsorption distance and increasing adsorption energy and charge transfer. The density of states presents different degrees of variation during the typical lung cancer breath gases adsorption, resulting in the specific change of conductivity of gas sensing material. Based on the different adsorption properties of Ni-SWCNTs to typical lung cancer breath gases, it provides an effective way to build a portable noninvasive portable device used to evaluate and diagnose lung cancer at early stage in time.

  18. Dopamine and Caffeine Encapsulation within Boron Nitride (14,0) Nanotubes: Classical Molecular Dynamics and First Principles Calculations.

    Science.gov (United States)

    García-Toral, Dolores; González-Melchor, Minerva; Rivas-Silva, Juan F; Meneses-Juárez, Efraín; Cano-Ordaz, José; H Cocoletzi, Gregorio

    2018-06-07

    Classical molecular dynamics (MD) and density functional theory (DFT) calculations are developed to investigate the dopamine and caffeine encapsulation within boron nitride (BN) nanotubes (NT) with (14,0) chirality. Classical MD studies are done at canonical and isobaric-isothermal conditions at 298 K and 1 bar in explicit water. Results reveal that both molecules are attracted by the nanotube; however, only dopamine is able to enter the nanotube, whereas caffeine moves in its vicinity, suggesting that both species can be transported: the first by encapsulation and the second by drag. Findings are analyzed using the dielectric behavior, pair correlation functions, diffusion of the species, and energy contributions. The DFT calculations are performed according to the BLYP approach and applying the atomic base of the divided valence 6-31g(d) orbitals. The geometry optimization uses the minimum-energy criterion, accounting for the total charge neutrality and multiplicity of 1. Adsorption energies in the dopamine encapsulation indicate physisorption, which induces the highly occupied molecular orbital-lower unoccupied molecular orbital gap reduction yielding a semiconductor behavior. The charge redistribution polarizes the BNNT/dopamine and BNNT/caffeine structures. The work function decrease and the chemical potential values suggest the proper transport properties in these systems, which may allow their use in nanobiomedicine.

  19. Analysis of the THAI Iod-11 and Iod-12 tests: Advancements and limitations of ASTEC V2.0R3p1 and MELCOR V2.1.4803

    International Nuclear Information System (INIS)

    Gonfiotti, Bruno; Paci, Sandro

    2015-01-01

    Highlights: • The I 2 transport in a multi-compartment vessel was analysed. • ASTEC and MELCOR codes were employed. • Same nodalisation for the code-to-code comparison. • The I 2 concentrations were quite well simulated in ASTEC. • Numerical issues on MELCOR. - Abstract: This work is related to the application of the ASTEC V2.0R3p1 and MELCOR V2.1.4803 codes to the analysis of the THAI Iod-11 and Iod-12 containment tests characterised by an iodine release. The main scope of these two tests was to investigate the steel interaction on dry and wet surfaces, with an interaction supposed to be a two-steps process: an initial faster and reversible physisorption followed by a slower, and irreversible, chemisorption of the physisorbed I 2 . The aim of the present work is to highlight advancements and limitations of the current ASTEC and MELCOR code versions respect to the older code versions employed during the European SARNET projects. The investigation was carried out as a code-to-code comparison vs. the experimental THAI data, focusing on the evaluation of the code models treating the iodine behaviour. A similar spatial nodalisation was employed for both codes. As main result, ASTEC had shown an overall good agreement compared to the iodine related experimental data while, on contrary, MELCOR had shown poor results, probably due to unsolved numerical issues and unsatisfactory iodine modellisation

  20. First-principles study of the alkali earth metal atoms adsorption on graphene

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Minglei [School of Mechanical Engineering, Southeast University, Nanjing 211189, Jiangsu (China); Tang, Wencheng, E-mail: 101000185@seu.edu.cn [School of Mechanical Engineering, Southeast University, Nanjing 211189, Jiangsu (China); Ren, Qingqiang [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, Hunan (China); Wang, Sake [Department of Physics, Southeast University, Nanjing 210096, Jiangsu (China); JinYu [School of Materials Science and Engineering, Southeast University, Nanjing 211189, Jiangsu (China); Jiangsu Key Laboratory of Advanced Metallic Materials, Southeast University, Nanjing 211189, Jiangsu (China); Du, Yanhui [School of Mechanical Engineering, Southeast University, Nanjing 211189, Jiangsu (China); Zhang, Yajun [Department of Engineering Mechanics, School of Aeronautics and Astronautics, Zhejiang University, Hangzhou 310027, Zhejiang (China)

    2015-11-30

    Graphical abstract: - Highlights: • The adsorption of Be and Mg adatoms on graphene is physisorption. • Ca, Sr, and Ba adatoms bond ionically to graphene and the most stable adsorption site for them is hollow site. • The zero band gap semiconductor graphene becomes metallic and magnetic after the adsorption of Ca, Sr, and Ba adatoms. - Abstract: Geometries, electronic structures, and magnetic properties for alkali earth metal atoms absorbed graphene have been studied by first-principle calculations. For Be and Mg atoms, the interactions between the adatom and graphene are weak van der Waals interactions. In comparison, Ca, Sr and Ba atoms adsorption on graphene exhibits strong ionic bonding with graphene. We found that these atoms bond to graphene at the hollow site with a significant binding energy and large electron transfer. It is intriguing that these adatoms may induce important changes in both the electronic and magnetic properties of graphene. Semimetal graphene becomes metallic and magnetic due to n-type doping. Detailed analysis shows that the s orbitals of these adatoms should be responsible for the arising of the magnetic moment. We believe that our results are suitable for experimental exploration and useful for graphene-based nanoelectronic and data storage.

  1. In situ generated gas bubble-assisted modulation of the morphologies, photocatalytic, and magnetic properties of ferric oxide nanostructures synthesized by thermal decomposition of iron nitrate

    International Nuclear Information System (INIS)

    Tong Guoxiu; Guan Jianguo; Xiao Zhidong; Huang Xing; Guan Yao

    2010-01-01

    Ferric oxide (Fe 2 O 3 ) complex nanoarchitectures with high BET specific surface area, superior photocatalytic activity and modulated magnetic properties are facilely synthesized via controlled thermal decomposition of iron(III) nitrate nonahydrate. The products are characterized by X-ray diffraction, Fourier-transforming infrared spectra, field-emission scanning electron microscope, field-emission high-resolution transmission electron microscope, and nitrogen physisorption and micrometrics analyzer. The corresponding photocatalytic activity and static magnetic properties are also evaluated by measuring the photocatalytic degradation of Rhodamine B aqueous solution under visible light illumination and vibrating sample magnetometer, respectively. Simply tuning the decomposition temperature can conveniently modulate the adsorbing/desorbing behaviors of the in situ generated gases on the nucleus surfaces, and consequently the crystalline structures and morphologies of the Fe 2 O 3 complex nanoarchitectures. The as-prepared Fe 2 O 3 complex nanoarchitectures show strong crystal structure and/or morphology-dependent photocatalytic and magnetic performances. The Fe 2 O 3 complex nanoarchitectures with high specific surface area and favorable crystallization are found to be beneficial for improving the photocatalytic activity. This work not only reports a convenient and low-cost decomposition procedure and a novel formation mechanism of complex nanoarchitectures but also provides an efficient route to enhance catalytic and magnetic properties of Fe 2 O 3 .

  2. Development of label-free impedimetric platform based on new conductive polyaniline polymer and three-dimensional interdigitated electrode array for biosensor applications

    International Nuclear Information System (INIS)

    Voitechovič, E.; Bratov, A.; Abramova, N.; Razumienė, J.; Kirsanov, D.; Legin, A.; Lakshmi, D.; Piletsky, S.; Whitcombe, M.; Ivanova-Mitseva, P.K.

    2015-01-01

    Graphical abstract: Display Omitted -- Abstract: Novel label-free impedimetric platform based on a three-dimensional interdigitated electrode array (3D-IDEA) sensor and new conductive polymer as a transducer for oxidoreductases is introduced. This platform is cost-effective, simple to construct and miniaturize. Monomer of conductive polymer N-(N’,N’-diethyldithiocarbamoylethylamidoethyl) aniline (AnD) was deposited onto 3D-IDEA by chemical polymerisation. It was found that the polymer film resistance depends on the redox-potential of the solution. For the first time polyAnD was used as enzyme immobilisation matrix. Pyrroloquinolinequinone (PQQ) dependent alcohol and glucose dehydrogenases were immobilized on 3D-IDEA covered with polyAnD by two different methods. 3D-IDEA sensors with enzymes, which were immobilised by physisorption on polyAnD layer, showed specific response in the presence of 1 μM of the corresponding substrates. Obtained results revealed that PQQ dependent dehydrogenases can re-oxidize on polyAnD via direct electron transfer (DET) from enzyme active site to the polymer surface. This process can be monitored by methods of electrochemical impedance spectroscopy (EIS) and chronoamperometry. Presented study shows that EIS method gives a useful tool for research of re-oxidation process and interaction of electroactive enzymes with conducting materials giving information required to construct and develop analytical devices

  3. Hydrogen production by tailoring the brookite and Cu2O ratio of sol-gel Cu-TiO2 photocatalysts.

    Science.gov (United States)

    Hinojosa-Reyes, Mariana; Camposeco-Solís, Roberto; Zanella, Rodolfo; Rodríguez González, Vicente

    2017-10-01

    Cu-TiO 2 photocatalysts were prepared by the sol-gel method. Copper loadings from, 1.0 to 5.0 wt % were used. The materials were annealed at different temperatures (from 400 to 600 °C) to study the formation of brookite and copper ionic species. The photocatalysts were characterized by X-ray diffraction, UV-vis, Raman and XPS spectroscopies, H 2 -temperature programmed reduction (TPR), N 2 physisorption, and SEM-EDS to quantify the actual copper loadings and characterize morphology. The photocatalysts were evaluated during the hydrogen photocatalytic production using an ethanolic solution (50% v/v) under UV and visible radiation. The best hydrogen production was performed by Ti-Cu 1.0 with an overall hydrogen production that was five times higher than that obtained with photolysis. This sample had an optimal thermal treatment at 500 °C, and at this temperature, the Cu 2 O and brookite/anatase ratio boosted the photocatalytic production of hydrogen. In addition, a deactivation test was carried out for the most active sample (TiO 2 -Cu 1.0), showing unchanged H 2 production for three cycles with negligible Cu lixiviation. The activity of hydrogen-through-copper production reported in this research work is comparable with the one featured by noble metals and that reported in the literature for doped TiO 2 materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Hydrogen storage in carbon nano-materials. Elaboration, characterization and properties

    International Nuclear Information System (INIS)

    Luxembourg, D.

    2004-10-01

    This work deals with hydrogen storage for supplying fuel cells. Hydrogen storage by adsorption in carbon nano-tubes and nano-fibers is a very controversial issue because experimental results are very dispersed and adsorption mechanisms are not yet elucidated. Physi-sorption cannot explain in fact all the experimental results. All the potential adsorption sites, physical and chemical, are discussed as detailed as possible in a state of the art. Experimental works includes the steps of elaboration, characterization, and measurements of the hydrogen storage properties. Nano-fibers are grown using a CVD approach. Single wall carbon nano-tubes (SWNT) synthesis is based on the vaporization/condensation of a carbon/catalysts mixture in a reactor using a fraction of the available concentrated solar energy at the focus of the 1000 kW solar facility of IMP-CNRS at Odeillo. Several samples are produced using different synthesis catalysts (Ni, Co, Y, Ce). SWNT samples are purified using oxidative and acid treatments. Hydrogen storage properties of these materials are carefully investigated using a volumetric technique. The applied pressure is up to 6 MPa and the temperature is 253 K. Hydrogen uptake of the investigated materials are less than 1 % wt. at 253 K and 6 MPa. (author)

  5. Influence of nitrogen doping in sumanene framework toward hydrogen storage: A computational study.

    Science.gov (United States)

    Reisi-Vanani, Adel; Shamsali, Fatemeh

    2017-09-01

    Two conditions are important to obtain appropriate substances for hydrogen storage; high surface area and fitting binding energy (BE). Doping is a key strategy that improves BE. We investigated hydrogen adsorption onto twenty six nitrogen disubstituted isomers of sumanene (C 19 N 2 H 12 ) by MP2/6-311++G(d,p)//B3LYP/6-31+G(d) and M06-2X/6-31+G(d) levels of theory. Effect of nitrogen doping in different positions of sumanene was checked. To obtain better BE, basis set superposition error (BSSE) and zero point energy (ZPE) corrections were used. Anticipating of adsorption sites and extra details about adsorption process was done by molecular electrostatic potential (MEP) surfaces. Various types of density of state (DOS) diagrams such as total DOS (TDOS), projected DOS (PDOS) and overlap population DOS (OPDOS) and natural bond orbital (NBO) analysis were used to find better insight on the adsorption properties. In addition of temperature depending of the BE, HOMO-LUMO gap (HLG), dipole moment, reactivity and stability, bowl depth and natural population analysis (NPA) of the isomers were studied. A physisorption mechanism for adsorption was proposed and a trivial change was seen. Place of nitrogen atoms in sumanene frame causes to binding energy increases or decreases compared with pristine sumanene. The best and the worst isomers and category of isomers were suggested. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Electronic Structure Calculations of Hydrogen Storage in Lithium-Decorated Metal-Graphyne Framework.

    Science.gov (United States)

    Kumar, Sandeep; Dhilip Kumar, Thogluva Janardhanan

    2017-08-30

    Porous metal-graphyne framework (MGF) made up of graphyne linker decorated with lithium has been investigated for hydrogen storage. Applying density functional theory spin-polarized generalized gradient approximation with the Perdew-Burke-Ernzerhof functional containing Grimme's diffusion parameter with double numeric polarization basis set, the structural stability, and physicochemical properties have been analyzed. Each linker binds two Li atoms over the surface of the graphyne linker forming MGF-Li 8 by Dewar coordination. On saturation with hydrogen, each Li atom physisorbs three H 2 molecules resulting in MGF-Li 8 -H 24 . H 2 and Li interact by charge polarization mechanism leading to elongation in average H-H bond length indicating physisorption. Sorption energy decreases gradually from ≈0.4 to 0.20 eV on H 2 loading. Molecular dynamics simulations and computed sorption energy range indicate the high reversibility of H 2 in the MGF-Li 8 framework with the hydrogen storage capacity of 6.4 wt %. The calculated thermodynamic practical hydrogen storage at room temperature makes the Li-decorated MGF system a promising hydrogen storage material.

  7. Theoretical study of hydrogen storage in a truncated triangular pyramid molecule consisting of pyridine and benzene rings bridged by vinylene groups

    Science.gov (United States)

    Ishikawa, Shigeru; Nemoto, Tetsushi; Yamabe, Tokio

    2018-06-01

    Hydrogen storage in a truncated triangular pyramid molecule C33H21N3, which consists of three pyridine rings and one benzene ring bridged by six vinylene groups, is studied by quantum chemical methods. The molecule is derived by substituting three benzene rings in a truncated tetrahedron hydrocarbon C36H24 with pyridine rings. The optimized molecular structure under C 3v symmetry shows no imaginary vibrational modes at the B3LYP/cc-pVTZ level of theory. The hydrogen storage process is investigated based on the MP2/cc-pVTZ method. Like the structure before substitution, the C33H21N3 molecule has a cavity that stores a hydrogen molecule with a binding energy of - 140 meV. The Langmuir isotherm shows that this cavity can store hydrogen at higher temperatures and lower pressures than usual physisorption materials. The C33H21N3 molecule has a kinetic advantage over the C36H24 molecule because the former molecule has a lower barrier (+ 560 meV) for the hydrogen molecule entering the cavity compared with the latter molecule (+ 730 meV) owing to the lack of hydrogen atoms narrowing the opening.

  8. Influence of crystallite size and shape of zeolite ZSM-22 on its activity and selectivity in the catalytic cracking of n-octane

    Energy Technology Data Exchange (ETDEWEB)

    Bager, F.; Ernst, S. [Kaiserslautern Univ. (Germany). Dept. of Chemistry, Chemical Technology

    2013-11-01

    Light olefins belong to the major building blocks for the petrochemical industry, particularly for the production of polymers. It has become necessary to increase the production of light olefins specifically in the case for propene with so called 'on-purpose propene' technologies. One possible route is to increase the amount of propene that can be obtained from Fluid Catalytic Cracking (FCC) by optimizing the catalyst through introducing new additives, which offer a high selectivity to propene. Zeolite ZSM-22 samples with different crystallite sizes and morphologies have been synthesized via hydrothermal syntheses and characterized by powder X-Ray diffraction, nitrogen physisorption, atomic absorption spectroscopy, scanning electron microscopy and solid-state NMR spectroscopy. The zeolites in the Broensted-acid form have been tested as catalysts in the catalytic cracking of n-octane as a model hydrocarbon. Clear influences of the crystallite size on the deactivation behavior have been observed. Larger crystals of zeolite ZSM-22 produce an increased amount of coke deposits resulting in a faster deactivation of the catalyst. The experimental results suggest that there is probably some influence of pore diffusion on the catalytic activity of the ZSM-22 sample with the large crystallite size. However a noticeable influence on the general product distribution could not be observed. (orig.)

  9. Characterization and parametric study of mesoporous calcium titanate catalyst for transesterification of waste cooking oil into biodiesel

    International Nuclear Information System (INIS)

    Yahya, Noor Yahida; Ngadi, Norzita; Jusoh, Mazura; Halim, Noor Amirah Abdul

    2016-01-01

    Highlights: •Simple synthesis of mesoporous calcium titanate by sol-gel-hydrothermal method. •Improvement of characteristics and catalytic activity from commercial CaO. • Production of biodiesel at relatively mild reaction conditions. - Abstract: Mesoporous calcium titanate (MCT) catalyst was synthesized via a sol-gel-hydrothermal method and investigated as a catalyst for biodiesel production from waste cooking oil (WCO). Calcium was supported on titanate in order to increase their surface area, stability and consequently, improve its performance in the transesterification of WCO to biodiesel. Synthesized catalyst was characterized with powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), N_2 physisorption, Fourier transform-infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and carbon dioxide temperature-programmed desorption (CO_2-TPD). The catalyst possessed high surface area, basicity and stability than calcium oxide (CaO) catalyst. The highest biodiesel yield achieved was 80.0% in 3:1 of methanol to WCO molar ratio, 0.2 wt.% of MCT catalyst for 1 h at 65 °C. Reusability study suggested that this catalyst can be recycled for five successive runs.

  10. Density functional theory study on the interactions of l-cysteine with graphene: adsorption stability and magnetism

    International Nuclear Information System (INIS)

    Luo, Huijuan; Li, Hejun; Fu, Qiangang; Chu, Yanhui; Cao, Xiaoyu; Sun, Can; Yuan, Xiaoyan; Liu, Lei

    2013-01-01

    Understanding the interactions between graphene and biomolecules is of fundamental relevance to the area of nanobiotechnology. Herein, we take l-cysteine as the probe biomolecule and investigate its adsorption on pristine graphene and B-, N-, Al-, Ni-, Ga-, Pd-doped graphene using density functional theory calculations. Three kinds of upright adsorption configurations, via unprotonated functional groups (–SH, –NH 2 , –COOH), are considered. The calculations reveal pristine graphene physically adsorbs l-cysteine. N-doped graphene shows physisorption towards the S-end and N-end l-cysteine, and chemisorption towards the O-end radical. Strong chemisorption, with site-specific preference, occurs on Al-, Ni-, Ga- and Pd-doped graphene, accompanied by severe structural changes. Spin polarization with an unusual mirror symmetry on Ni- and Pd-doped graphene is induced by chemisorption of unprotonated l-cysteine, except for O-end adsorption on Pd-doped graphene. The magnetization arises mainly from spin polarization of the C 2p z orbital, with a minor magnetism located on Ni or Pd. The influence of van der Waals forces is also evaluated. A thorough analysis of the adsorption stability and magnetism of these systems would be beneficial to facilitate applications in graphene-based biosensing, biomolecule immobilization, magnetic bio-separation and other fields in bionanotechnology. (paper)

  11. Boron nitride ceramics from molecular precursors: synthesis, properties and applications.

    Science.gov (United States)

    Bernard, Samuel; Salameh, Chrystelle; Miele, Philippe

    2016-01-21

    Hexagonal boron nitride (h-BN) attracts considerable interest because its structure is similar to that of carbon graphite while it displays different properties which are of interest for environmental and green technologies. The polar nature of the B-N bond in sp(2)-bonded BN makes it a wide band gap insulator with different chemistry on its surface and particular physical and chemical properties such as a high thermal conductivity, a high temperature stability, a high resistance to corrosion and oxidation and a strong UV emission. It is chemically inert and nontoxic and has good environmental compatibility. h-BN also has enhanced physisorption properties due to the dipolar fields near its surface. Such properties are closely dependent on the processing method. Bottom-up approaches consist of transforming molecular precursors into non-oxide ceramics with retention of the structural units inherent to the precursor molecule. The purpose of the present review is to give an up-to-date overview on the most recent achievements in the preparation of h-BN from borazine-based molecular single-source precursors including borazine and 2,4,6-trichloroborazine through both vapor phase syntheses and methods in the liquid/solid state involving polymeric intermediates, called the Polymer-Derived Ceramics (PDCs) route. In particular, the effect of the chemistry, composition and architecture of the borazine-based precursors and derived polymers on the shaping ability as well as the properties of h-BN is particularly highlighted.

  12. α-Fe{sub 2}O{sub 3} lithium battery anodes by nanocasting strategy from ordered 2D and 3D templates

    Energy Technology Data Exchange (ETDEWEB)

    Di Lupo, F. [GAME Lab, Department of Applied Science and Technology – DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin (Italy); Gerbaldi, C., E-mail: claudio.gerbaldi@polito.it [GAME Lab, Department of Applied Science and Technology – DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin (Italy); Casino, S.; Francia, C.; Meligrana, G. [GAME Lab, Department of Applied Science and Technology – DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin (Italy); Tuel, A. [Institut de Recherches sur la Catalyse, IRC-CNRS (UPR 5401), 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); Penazzi, N. [GAME Lab, Department of Applied Science and Technology – DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin (Italy)

    2014-12-05

    Highlights: • Nanosized α-Fe{sub 2}O{sub 3} lithium battery conversion anodes with tunable morphology. • Nanocasting technique using MCM-41 and MCM-48 silica moulds is adopted. • Textural/morphological characteristics define the electrochemical behaviour. • α-Fe{sub 2}O{sub 3} replica of MCM-41 exhibits stable capacity (∼300 mA h g{sup −1}) after 100 cycles. • α-Fe{sub 2}O{sub 3} replica of MCM-41 shows promising prospects as high-capacity Li-ion battery anode. - Abstract: Nanocasting strategy is here proposed as effective approach to tune structure and size of α-Fe{sub 2}O{sub 3} active nanoparticles as a promising anode material for Li-ion cells. MCM-41 and MCM-48 silicas, presenting hexagonal 2D and cubic 3D symmetry, respectively, and regular pore diameter of about 4 nm are selected as moulds. The structural–morphological and electrochemical characteristics are assessed by X-ray diffraction, transmission electron microscopy, N{sub 2} physisorption at 77 K, cyclic voltammetry and galvanostatic discharge/charge cycling. It is here demonstrated that structural–morphological features change accordingly to the template used and careful control of the texture/particle characteristics is likely a fundamental variable noticeably affecting the cycling behaviour.

  13. Preparation and characterization of V/TiO{sub 2} nanocatalyst with magnetic nucleus of iron

    Energy Technology Data Exchange (ETDEWEB)

    Feyzi, Mostafa; Rafiee, Hamid Reza, E-mail: rafieehr@yahoo.com; Ranjbar, Shahram; Jafari, Fataneh; Safari, Banafsheh

    2013-11-15

    Graphical abstract: - Highlights: • Fe-V/TiO{sub 2} nanocatalyst is prepared. • Combination of sol–gel and wetness impregnation methods. • Facile separation of catalyst from medium by magnet. - Abstract: A magnetic composite containing V/TiO{sub 2} was prepared by combination of sol–gel and wetness impregnation methods. The effects of synthesis temperature, different weight percents of Fe supported on TiO{sub 2}, vanadium loading and the heating rate of calcination on the structure and morphology of nanocatalyst were investigated. The optimum conditions for synthesized catalyst were 40 wt.% of Fe, 15 wt.% of V and synthesis temperature equal to 30 °C. Characterization of catalyst is carried out using XRD, TGA, DSC, SEM, FTIR and N{sub 2} physisorption measurements. The magnetic character of nanocatalyst was measured using VSM, which showed the typical paramagnetic behavior of sample at room temperature with a saturation magnetization value equal to 8.283 emu/g. The nanocatalyst has a particle size about 56 nm and can easily be separated from medium by a magnet.

  14. Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

    Energy Technology Data Exchange (ETDEWEB)

    Guo Zhen; Liu Xianbin; Ng, Siu-Choon; Chen Yuan; Yang Yanhui [School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459 (Singapore); Du Yu, E-mail: du_yu@jlu.edu.cn, E-mail: yhyang@ntu.edu.sg [College of Electronic Science and Engineering, Jilin University, Changchun 130012 (China)

    2010-04-23

    Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

  15. Three dimensional analysis of nanoporous silicon particles for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Roiban, Lucian, E-mail: lucian.roiban@insa-lyon.fr [Université de Lyon, Insa-Lyon, MATEIS, UMR5510 CNRS, 7 Avenue Jean Capelle, 69621, Villeurbanne cedex (France); Koneti, Siddardha [Université de Lyon, Insa-Lyon, MATEIS, UMR5510 CNRS, 7 Avenue Jean Capelle, 69621, Villeurbanne cedex (France); Wada, Takeshi, E-mail: wada-t@imr.tohoku.ac.jp [Institute for Materials Research, Tohoku University, Sendai, Miyagi 980-8577 (Japan); Kato, Hidemi [Institute for Materials Research, Tohoku University, Sendai, Miyagi 980-8577 (Japan); Cadete Santos Aires, Francisco J. [Université de Lyon, Université Lyon1, IRCELYON, UMR5256 CNRS, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); Laboratory of Catalytic Research, National Research Tomsk State University, 36 Lenin Avenue, 634050 Tomsk (Russian Federation); Curelea, Sergiu; Epicier, Thierry; Maire, Eric [Université de Lyon, Insa-Lyon, MATEIS, UMR5510 CNRS, 7 Avenue Jean Capelle, 69621, Villeurbanne cedex (France)

    2017-02-15

    Bulk nanoporous silicon prepared by top-down method form Li-ion batteries was investigated combining different conventional technique such as nitrogen physisorption and high resolution electron microscopy with electron tomography. It was found that the Si nanorods are forming porous aggregates with a half of the volume of the particle occupied by pores. The nanorods are preferentially oriented along the main axis of the aggregate. The porosity and the lack of compaction between the aggregates provide space for the Si expansion during the lithiation process. It was found that the Si nanorods mainly expose the (111) family plane as an external faces. The size distributions of the porous and solid phases in a granule were found to be similar. The pores represent 50% of the total volume of an aggregate. The shape orientation of the particles was quantified and it was found to exhibit a narrow distribution. - Highlights: •Bulk nanoporous silicon for Li-ion batteries is studied by HRTEM and electron tomography. •The crystalline facets of Si nanorods are formed by (111) plains. •The lack of compactness between Si nanorods provides 50% of porous volume. •The Si nanorods are oriented along a preferential axis.

  16. Steam Reforming of Ethylene Glycol over Ni/Al2O3 Catalysts: Effect of the Preparation Method and Reduction Temperature

    International Nuclear Information System (INIS)

    Choi, Dong Hyuck; Park, Jung Eun; Park, Eun Duck

    2015-01-01

    The effect of preparation method on the catalytic activities of the Ni/Al 2 O 3 catalysts on steam reforming of ethylene glycol was investigated. The catalysts were prepared with various preparation methods such as an incipient wetness impregnation, wet impregnation, and coprecipitation method. In the case of coprecipitation method, various precipitants such as KOH, K 2 CO 3 , and NH 4 OH were compared. The prepared catalysts were characterized by using N 2 physisorption, inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, temperature programmed reduction, pulsed H 2 chemisorption, temperature-programmed oxidation, scanning electron microscopy, and thermogravimetric analysis. Among the catalysts reduced at 773 K, the Ni/Al 2 O 3 catalyst prepared by a coprecipitation with KOH or K 2 CO 3 as precipitants showed the best catalytic performance. The preparation method affected the particle size of Ni, reducibility of nickel oxides, catalytic performance (activity and stability), and types of coke formed during the reaction. The Ni/Al 2 O 3 catalyst prepared by a coprecipitation with KOH showed the increasing catalytic activity with an increase in the reduction temperature from 773 to 1173 K because of an increase in the reduction degree of Ni oxide species even though the particle size of Ni increased with increasing reduction temperature

  17. Investigation of the interaction of carbon dioxide fluid with internal and external single-wall carbon nanotubes by DFT

    Directory of Open Access Journals (Sweden)

    M. Oftadeh

    2011-07-01

    Full Text Available The effective parameters of (5, 0 and (5, 5 single-wall carbon nanotubes during the interaction with carbon dioxide as sensors are determined. The interaction of carbon dioxide  molecules with internal and external walls of the nanotubes is studied using Gaussian 03 coding by density functional theory (DFT at the B3LYP/6-311G level of theory. CO2 rotation around tube axles vertically and parallel to the internal and external walls has been investigated. The carbon dioxide molecule is predicted to bind only weakly to nanotubes, and the tube-molecule interactions can be identified as physisorption. CO2 adsorption is stronger on external wallsthan on internal walls, and adsorption on the external wall of (5, 0 is stronger than on the external wall of (5, 5; the adsorption energies are exothermic and equal to -0.8884 and -0.0528 kcal/mol, respectively. The rotation energy barrier for (5, 5 is lower than that for (5, 0 in all rotations, therefore in these interactions (5, 5 is more active. The energy gap significantly changes in the presence of  carbon  dioxide molecules on the inside surface of (5, 0 and the electric conductivity is affected, but no remarkable change is observed in the electronic structure of (5, 5.

  18. Effect of physisorbed molecules and an external external fields on the metallic Shockley surface state of Cu(111): A density functional theory study

    Science.gov (United States)

    Berland, Kristian; Einstein, T. L.; Hyldgaard, Per

    2012-02-01

    To manipulate the Cu(111) partially-filled Shockley surface state, we study its response to an external fieldootnotetextKB, TLE, PH; arXiv 1109:6706 E and physisorbed PAHs and quinone molecules. We use density-functional theory calculations with periodic-boundary conditions. The van der Waals density functional version vdW-DF2 accounts for the molecular adsorption. The issue that the Kohn-Sham wave functions couple to both sides of the Cu slab is handled with a decoupling scheme based on a rotation in Hilbert space. A convergence study reveals that to obtain a proper Shockley surface state, 6 Cu layers is sufficient, while 15 is optimal. We use 6 layers for the response to the molecules and 15 to external field. We find that the surface state displays isotropic dispersion (up to order k^6), free-electron like until the Fermi wave vector but with a significant quartic component beyond. The shift in band minimum and effective mass depend linearly on E, with a smaller fractional change in the latter. Charge transfer occurs beyond the outermost copper atoms, and most of the screening is due to bulk electrons. We find that the molecular physisorption increases the band minimum, with the effect the of a quinone being much stronger than the corresponding PAH.

  19. Gelatin Template Synthesis of Aluminum Oxide and/or Silicon Oxide Containing Micro/Mesopores Using the Proteic Sol-Gel Method

    Directory of Open Access Journals (Sweden)

    Amanda Sayure Kasuya de Oliveira

    2017-01-01

    Full Text Available Aluminum oxide and/or silicon oxide-based supports were synthesized by proteic sol-gel method. The characterization was performed through the analysis of TG, XRD, FTIR, SEM, and N2 physisorption. The XRD diffractograms showed an amorphous material profile. TG results indicate the total liberation of the organic and inorganic material in the calcination temperature used, occurring in different mass loss range. This piece of information was reaffirmed by the FTIR spectra, which presented characteristic bands of gelatin structure before calcinations which disappear in the spectrum of the solid after calcinations, indicating the loss of organic matter from gelatin after heat treatment. The spectra exhibited M-O stretching vibration at low wavenumbers after calcinations related to metal oxides. The acquired images by SEM suggest the obtaining of a highly porous material with very different characteristics depending on the composition of the support. The N2 isotherms indicate the presence of a micro/mesoporous oxide with interesting textural properties, particularly for the supports containing aluminum and silicon oxide. The ethanol dehydration results showed greater selectivity to diethyl ether compared to ethylene. From the reaction data, the following order of acid strength was obtained: 2Si-Al > Si-2Al > Si-Al > Al, which is related to the Si-Al ratio.

  20. Adsorptive removal of congo red and sunset yellow dyes from water systems by lady finger stem

    International Nuclear Information System (INIS)

    Abbas, A.; Murtaza, S.; Ayub, R.; Rehman, R.; Zahid, A.

    2012-01-01

    Summary: In this research work two anionic dyes, i.e. Congo Red and Sunset Yellow were removed successfully from aqueous media by Lady Finger stem in batch mode. Operational conditions optimization showed that agitation speed and particle size did not affect much in adsorption of these dyes; but contact time, pH, adsorbent dose and temperature of system effects the adsorption rate. Optimized conditions of adsorption for Congo Red dye were: 40 minute contact time, 8.0 pH, 0.5 g adsorbent dose, 40-60 microns mesh sized particles, 150 rpm agitation speed and 50 degree C temperature. Whereas for Sunset Yellow optimized conditions were: 30 minute contact time, 2.0 pH, 2.5 g adsorbent dose, 20-40 microns mesh sized particles, 50 rpm agitation speed and 30 degree C temperature. Suitability of equilibrium data was modulated with Langmuir, Freundlich and Temkin models and found that both physisorption and chemisorption processes play important role in adsorption of these dyes by Lady Finger stem. The results demonstrated that Lady Finger stem can be efficiently employed on larger scale wastewater treatment. (author)

  1. Silica Nanofibers with Immobilized Tetracycline for Wound Dressing

    Directory of Open Access Journals (Sweden)

    Irena Lovětinská-Šlamborová

    2016-01-01

    Full Text Available Local antibiotic treatment has its justification for superficial infections. The advantage of this treatment is that the antibiotic has effects on bacterial agent directly at the application site. Skin infections which are intended for the local antibiotic treatment are superficial pyoderma, some festering wounds, burns of second and third degree, infected leg ulcers, or decubitus of second and third degree. Tetracyclines are available topical antibiotics with a broad bacterial spectrum. At present, ointments containing tetracycline are also used for the treatment, which rarely can lead to skin sensitization. In this paper, a development of novel nanofibrous material with immobilized tetracycline is presented. Two different methods of immobilized tetracycline quantification onto silica nanofibers are employed. It was proven that the prevailing part of tetracycline was bound weakly by physisorption forces, while the minor part was covalently bound by NH2 groups formed by the preceding functionalization. The silica nanofibers with immobilized tetracycline are promising material for wound dressing applications due to its antibacterial activity; it was proved by tests.

  2. Teknologi Proses Pembuatan Molecular Sieve TiZA Untuk Pemekatan Asam Nitrat

    Directory of Open Access Journals (Sweden)

    Ali Nurdin

    2017-10-01

    Full Text Available Molecular sieve zeolit dapat memurnikan campuran larutan yang bersifat azeotrop yang tidak bisa dilakukan menggunakan metode distilasi biasa. Namun, masih memiliki kelemahan dalam half life time molecular sieve tersebut, khususnya stabilitas bahan apabila digunakan pada larutan yang bersifat korosif seperti larutan asam atau basa. Pada penelitian ini telah  dilakukan pembuatan molecular sieve zeolit A yang dimodifikasi  dengan penambahan 10% titanium. Molecular sieve titanium - zeolit A (TiZA dibuat dengan dengan metode hidrotermal pada temperatur 110 °C dan kalsinasi pada temperatur 500 °C. Karakterisasi dilakukan antara lain menggunakan X-ray Diffraction (XRD, Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDX dan karakterisasi pori dengan metode physisorption menggunakan nitrogen pada temperatur 44 K. Molecular sieve TiZA yang dihasilkan stabil terhadap temperatur tinggi, dan larutan asam. Modifikasi zeolit A dengan titanium telah mampu meningkatkan stabilitas molecular sieve Ti-zeolit A dalam larutan asam nitrat selama 24 jam. Distribusi ukuran pori BJH (Barret Joyner Halenda  yang sempit menggambarkan ukuran yang homogen dengan didominasi oleh mikro porus dengan diameter rata-rata sekitar 4Å. Uji coba pemurnian asam nitrat dengan menggunakan molecular sieve secara single stage dapat meningkatkan kemurnian asam nitrat dari 70% hingga 85%.

  3. Synthesis and characterizations of isolated WO{sub 4} anchored on mesoporous TiTUD-1 support

    Energy Technology Data Exchange (ETDEWEB)

    Pachamuthu, Muthusamy P. [Department of Chemistry, Bannari Amman Institute of Technology, Sathyamangalam, Erode, 638401 (India); Maheswari, Rajamanickam [Center for Environmentally Beneficial Catalysis (CEBC), The University of Kansas, Lawrence, KS, 66047 (United States); Ramanathan, Anand, E-mail: anand@ku.edu [Center for Environmentally Beneficial Catalysis (CEBC), The University of Kansas, Lawrence, KS, 66047 (United States)

    2017-04-30

    Highlights: • Incorporation of (WO{sub 4}{sup 2−}) species into amorphous mesoporous silicate TiTUD-1. • Typical TUD-1 structure with dispersed Ti{sup 4+} and WO{sub 4}{sup 2−} species. • FT Raman and XPS results evidenced the WO{sub 4}{sup 2−} species dispersion. • Catalyst with 20% W loading yields higher conversion in esterification reaction. - Abstract: The titanium incorporated mesoporous silicate TUD-1 (Si/Ti ratio 40) was synthesized by non-surfactant route, and utilized as a support for tungstate (WO{sub 4}{sup 2−}) species with variable loading (5–30 wt%). The structural and textural properties of these samples were evaluated from X-ray diffraction (XRD) and N{sub 2} physisorption studies. Diffuse reflectance UV–vis (DR UV–vis), Fourier transform infrared (FTIR), Fourier transform Raman (FT Raman) spectra evidenced the Ti{sup 4+} coordination and the formation of WO{sub 4}{sup 2−} species, further supported by X-ray photoelectron spectroscopy (XPS) studies. Scanning electron microscope–energy dispersive X-ray analysis (SEM-EDAX), High resolution transmission electron microscope (HRTEM) further support the materials morphology corroborating other characterizations. The catalytic activities of these materials were tested in the liquid phase, solvent free esterification of acetic acid with n-butanol. About 95% of acetic acid conversion resulted by these catalysts with 8 h of reaction time.

  4. Synthesis of carbon nanorods by reduction of carbon bisulfide

    International Nuclear Information System (INIS)

    Lou Zhengsong; He Minglong; Zhao Dejian; Li Zhongchun; Shang Tongming

    2010-01-01

    Research highlights: Our manuscript is a concise preliminary account of original and of significant research, which illuminates carbon nanorods and variously shaped Y-junction carbon nanorods are successfully fabricated on a large scale through a carbon bisulfide thermal reduction process. Various shaped Y-junction carbon nanorods can be used as studying the electronic and transport properties of the nano-meter carbon material. - Abstract: Carbon nanorods are synthesized at large scale by the reduction of carbon bisulfide at 600 o C. Moreover, novel Y-junction carbon nanorods are detected in the samples. The X-ray power diffraction pattern indicates that the products are hexagonal graphite. Scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and N 2 physisorption studies show that carbon nanorods predominate in the product. Based on the supercritical carbon bisulfide system, the possible growth mechanism of the carbon nanorods was discussed. This method provides a simple and cheap route to large-scale synthesis of carbon nanorods.

  5. Fabrication of polylactic acid/hydroxyapatite/graphene oxide composite and their thermal stability, hydrophobic and mechanical properties

    Directory of Open Access Journals (Sweden)

    Ming Gong

    2017-06-01

    Full Text Available A series of polylactic acid/hydroxyapatite/graphene oxide composite (PLA/HA/GO were fabricated via solution blending and casting method using N,N-dimethyl-formamide (DMF and CH2Cl2 as mutual solvents. The physicochemical properties of the resulting composites were characterized by means of FT-IR, SEM, TEM, Raman spectra, XRD and N2-physisorption. Particularly, the thermal stabilities, hydrophobic and mechanical properties of PLA/HA/GO composites were systematically investigated. The influences of GO content on thermal stabilities, hydrophobic and mechanical properties of the composites were also evaluated. The results showed that the addition of GO and HA not only improved the thermal stability of PLA, but also improved the hydrophobic property of PLA-based composites. By compared with the PLA/HA/GO composite, the tensile strength of pristine PLA is slight high. The tensile strength and hardness of PLA/HA/GO composites increased with the increase of GO content. The obtained PLA/HA/GO composite may be a promising material for load-bearing orthopedic implants.

  6. Experimental Studies on the Hydrotreatment of Kraft Lignin to Aromatics and Alkylphenolics Using Economically Viable Fe-Based Catalysts

    Science.gov (United States)

    2017-01-01

    Limonite, a low-cost iron ore, was investigated as a potential hydrotreatment catalyst for kraft lignin without the use of an external solvent (batch reactor, initial H2 pressure of 100 bar, 4 h). The best results were obtained at 450 °C resulting in 34 wt % of liquefied kraft lignin (lignin oil) on lignin intake. The composition of the lignin oil was determined in detail (elemental composition, GC-MS, GC×GC-FID, and GPC). The total GC-detectable monomeric species amounts up to 31 wt % on lignin intake, indicating that 92 wt % of the products in the lignin oil are volatile and thus of low molecular weight. The lignin oil was rich in low-molecular-weight alkylphenolics (17 wt % on lignin) and aromatics (8 wt % on lignin). Performance of the limonite catalyst was compared to other Fe-based catalysts (goethite and iron disulfide) and limonite was shown to give the highest yields of alkylphenolics and aromatics. The limonite catalyst before and after reaction was characterized using XRD, TEM, and nitrogen physisorption to determine changes in structure during reaction. Catalyst recycling tests were performed and show that the catalyst is active after reuse, despite the fact that the morphology changed and that the surface area of the catalyst particles was decreased. Our results clearly reveal that cheap limonite catalysts have the potential to be used for the depolymerization/hydrodeoxygenation of kraft lignin for the production of valuable biobased phenolics and aromatics. PMID:28413733

  7. Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

    Directory of Open Access Journals (Sweden)

    Thuan M. Huynh

    2016-11-01

    Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

  8. Catalytic Hydrodeoxygenation of Fatty Acids for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Аntonina A. Stepacheva

    2016-08-01

    Full Text Available This paper is devoted to the production of second generation biodiesel via catalytic hydrodeoxygenation of fatty acids. Pd/C catalysts with different metal loading were used. The palladium catalysts were characterized using low-temperature nitrogen physisorption and X-ray photoelectron spectroscopy. It was revealed that the most active and selective catalyst was 1%-Pd/C which allowed reaching up 97.5% of selectivity (regarding to n-heptadecane at 100% conversion of substrate. Moreover, the chosen catalyst is more preferable according to lower metal content that leads the decrease of the process cost. The analysis of the catalysts showed that 1%-Pd/C had the highest specific surface area compared with 5%-Pd/C. Copyright © 2016 BCREC GROUP. All rights reserved Received: 31st July 2015; Revised: 9th December 2015; Accepted: 30th December 2015 How to Cite: Stepacheva, A.A., Sapunov, V.N., Sulman, E.M., Nikoshvili, L.Z., Sulman, M.G., Sidorov, A.I., Demidenko, G.N., Matveeva, V.G. (2016. Catalytic Hydrodeoxygenation of Fatty Acids for Biodiesel Production. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 125-132 (doi:10.9767/bcrec.11.2.538.125-132 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.538.125-132

  9. Adsorption of carbon dioxide in porous magnesium oxides

    International Nuclear Information System (INIS)

    Gutierrez B, E.

    2016-01-01

    Mg O powders were synthesized by chemical solution combustion and treated by mechanical milling, and separately were doped with Fe and Ni. The obtained powders were characterized by the X-ray diffraction (DRX) technique, scanning electron microscopy (Sem), elementary semi-quantitative analysis (EDS), N_2 physisorption measurements and infrared spectroscopy (IR). It was studied the CO_2 adsorption capacity in the synthesized materials as a function of temperature, pressure and saturation time. The results show that the CO_2 adsorption capacities on respective materials were 0.39 mmol/g in Mg O powders synthesized by chemical solution combustion, 1.61 mmol/g in Mg O powders treated by mechanical milling during 2.5 h, 0.90 mmol/g in Mg O powders doped with Fe by milling during 2.5 h and 1.50 mmol/g for Mg O powders doped with Ni milling during 7.5 h, at 25 degrees Celsius, 1 atm and 30 min of saturation time. The results showed that the powders treated by mechanical milling are efficient for CO_2 adsorption and are an alternative of advanced materials to be used as potential adsorbent materials and contribute to reduce the global warming. (Author)

  10. Separation of toxic rhodamine B from aqueous solution using an efficient low-cost material, Azolla pinnata, by adsorption method.

    Science.gov (United States)

    Kooh, Muhammad Raziq Rahimi; Lim, Linda B L; Lim, Lee Hoon; Dahri, Muhammad Khairud

    2016-02-01

    This study investigated the potential of untreated Azolla pinnata (AP) to remove toxic rhodamine B (RB) dye. The effects of adsorbent dosage, pH, ionic strength, contact time, and concentration were studied. Experiments involving the effects of pH and ionic strength indicated that hydrophobic-hydrophobic interactions might be the dominant force of attraction for the RB-AP adsorption system. The kinetics modelling of the kinetics experiment showed that pseudo-second-order best represented the adsorption process. The Weber-Morris intraparticle diffusion model showed that intraparticle diffusion is not the rate-limiting step, while the Boyd model suggested that film diffusion might be rate-limiting. The adsorption isotherm model, Langmuir, best represented the adsorption process, and the maximum adsorption capacity was predicted to be 72.2 and 199.7 mg g(-1) at 25 and 65 °C, respectively. Thermodynamics study indicates spontaneity, endothermic and physisorption-dominant adsorption process. The adsorbents were regenerated to satisfactory level with distilled water, HNO3 and NaOH. Pre-treatment of adsorbent with oxalic acid, citric acid, NaOH, HCl and phosphoric acid was investigated but the adsorption capacity was less than the untreated AP.

  11. DFT simulation on H2 adsorption over Ni-decorated defective h-BN nanosheets

    Science.gov (United States)

    Zhou, Xuan; Chu, Wei; Zhou, Yanan; Sun, Wenjing; Xue, Ying

    2018-05-01

    Nickel doped defective h-BN nanosheets and their potential application on hydrogen storage were explored by density functional theory (DFT) calculation. Three types of defective h-BN (SW defect, VB and VN substrates) were modeled. In comparison with the SW defect, the B or N vacancy can improve the interaction between Ni atom and h-BN nanosheet strikingly. Furthermore, the Ni-doped SW defect sheet shows chemisorption on H2 molecules, and the Hsbnd H bond is partially dissociated. While on the VB sheet, Ni adatom interacts with H2 in the range of physisorption. However, the Ni-functionalized VN sheet exhibits a desirable adsorption on H2, and the corresponding energy varies from -0.40 to -0.51 eV, which is favorable for H2 adsorption and release at ambient conditions. As a result, the VN substrate is expected to a desirable support for H2 storage. Our work provides an insight into H2 storage on Ni-functionalized defective h-BN monolayer.

  12. Microstructure and Magnetic Properties of Highly Ordered SBA-15 Nanocomposites Modified with Fe2O3 and Co3O4 Nanoparticles

    Directory of Open Access Journals (Sweden)

    P. F. Wang

    2012-01-01

    Full Text Available Owing to the unique order mesopores, mesoporous SBA-15 could be used as the carrier of the magnetic nanoparticles. The magnetic nanoparticles in the frame and the mesopores lead to the exchange-coupling interaction or other interactions, which could improve the magnetic properties of SBA-15 nanocomposites. Mesoporous Fe/SBA-15 had been prepared via in situ anchoring Fe2O3 into the frame and the micropores of SBA-15 using the sol-gel and hydrothermal processes. Co3O4 nanoparticles had been impregnated into the mesopores of Fe/SBA-15 to form mesoporous Fe/SBA-15-Co3O4 nanocomposites. XRD, HRTEM, VSM, and N2 physisorption isotherms were used to characterize the mesostructure and magnetic properties of the SBA-15 nanocomposites, and all results indicated that the Fe2O3 nanoparticles presented into the frame and micropores, while the Co3O4 nanoparticles existed inside the mesopores of Fe/SBA-15. Furthermore, the magnetic properties of SBA-15 could be conveniently adjusted by the Fe2O3 and Co3O4 magnetic nanoparticles. Fe/SBA-15 exhibited ferromagnetic properties, while the impregnation of Co3O4 nanoparticles greatly improved the coercivity with a value of 1424.6 Oe, which was much higher than that of Fe/SBA-15.

  13. A low cost preparation of WO3 nanospheres film with improved thermal stability of gasochromic and its application in smart windows

    Science.gov (United States)

    Zhou, Baoyu; Feng, Wei; Gao, Guohua; Wu, Guangming; Chen, Yue; Li, Wen

    2017-11-01

    Porous WO3 nanospheres film was successfully synthesized by employing a low-cost and facile template-assisted sol-gel method. The effects of template agent (Pluronic F127) on structure, morphology and specific surface area were systematically studied by Fourier transform infrared (FTIR), x-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and N2 physisorption. It was found that F127 played a significant role in governing the morphology of WO3 sol clusters, and the optimal post-processing for ‘naked’ WO3 nanospheres film is acetone extraction and subsequent annealing treatment at 350 °C. As anticipated, the relative fast coloring/bleaching rates of WO3 nanospheres film are believed to be the results of porous microstructure and nanocrystalline, where provides much surface active position (166 m2 g-1) and shortens the proton diffusion distance. We believe that this unique approach to synthesize nanospheres structure may has beneficial effects on applications which also are based on insertion/extraction and diffusion abilities, such as supercapacitor, batteries and gas sensors.

  14. Effect of Mo-Doped Mesoporous Al-SSP Catalysts for the Catalytic Dehydration of Ethanol to Ethylene

    Directory of Open Access Journals (Sweden)

    Titinan Chanchuey

    2016-01-01

    Full Text Available The catalytic dehydration of ethanol to ethylene over the mesoporous Al-SSP and Mo-doped Al-SSP catalysts was investigated. The Al-SSP catalyst was first synthesized by the modified sol-gel method and then doped with Mo by impregnation to obtain 1% Mo/Al-SSP and 5% Mo/Al-SSP catalysts (1 and 5 wt% of Mo. The final catalysts were characterized using various techniques such as XRD, N2 physisorption, SEM/EDX, TEM, and NH3-TPD. The catalytic activity for all catalysts in gas-phase ethanol dehydration reaction was determined at temperature range of 200°C to 400°C. It was found that the most crucial factor influencing the catalytic activities appears to be the acidity. The acid property of catalysts depended on the amount of Mo loading. Increased Mo loading in Al-SSP resulted in increased weak acid sites, which enhanced the catalytic activity. Besides acidity, the high concentration of Al at surface of catalyst is also essential to obtain high activity. Based on the results, the most suitable catalyst in this study is 1% Mo/Al-SSP catalyst, which can produce ethylene yield of ca. 90% at 300°C with slight amounts of diethyl ether (DEE and acetaldehyde.

  15. A Comparative Study of Solvothermal and Sol-Gel-Derived Nanocrystalline Alumina Catalysts for Ethanol Dehydration

    Directory of Open Access Journals (Sweden)

    Mingkwan Wannaborworn

    2015-01-01

    Full Text Available The ethanol dehydration to ethylene over alumina catalysts prepared by solvothermal and sol-gel methods was investigated. Also, a commercial alumina was used for comparison purposes. The results showed that the catalytic activity depends on the properties of catalyst derived from different preparation methods and reaction temperature. The alumina synthesized by solvothermal method exhibited the highest activity. This can be attributed to the higher surface area and larger amount of acid site, especially the ratio of weak/strong acid strength as determined by N2 physisorption and NH3-TPD studies. The solvothermal-derived catalyst exhibited an excellent performance with complete ethanol conversion and 100% selectivity to ethylene at 350°C in comparison with other ones. In addition, we further studied the catalytic dehydration of alumina catalyst modified with Fe. The presence of 10 wt.% Fe decreased both conversion and ethylene selectivity. However, the acetaldehyde selectivity apparently increased. It was related to the dehydrogenation pathway that takes place on Fe species.

  16. Preparation, characterization and catalytic activity of mesoporous Ag2HPW12O40/SBA-15 and Ag2HPW12O40/TiO2 composites

    International Nuclear Information System (INIS)

    Holclajtner-Antunović, Ivanka; Bajuk-Bogdanović, Danica; Popa, Alexandru; Sasca, Viorel; Nedić Vasiljević, Bojana; Rakić, Aleksandra; Uskoković-Marković, Snežana

    2015-01-01

    The current study reports the synthesis and characterization of tungstophosphoric acid and its acid silver salt supported on mesoporous molecular sieve SBA-15 and TiO 2 . Because silver salts are partially insoluble, the SBA-15 and TiO 2 supported silver acid salts were prepared by two step sequential impregnations. The synthesized catalysts were characterized by various physicochemical methods such as Fourier transform infrared and Raman spectroscopy, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and nitrogen physisorption at −196 °C. It is observed that both active phases keep their Keggin-type structure after being supported on the supports while their specific surface area is considerably increased by deposition on mesoporous substrates. The results also indicated that the synthesized catalysts retained the morphology specific for each of the supports, while their thermal stability is increased in comparison with their active phases. The catalytic activity of the prepared catalysts was probed for the vapor phase dehydration of ethanol at 300 °C. Results revealed that all the catalysts show considerably improved catalytic activity in comparison to the bulk active phases. - Highlights: • SBA-15 and TiO 2 supported Ag 2 HPW 12 O 40 and H 3 PW 12 O 40 were prepared. • Active phases are uniformly dispersed without changing morphology of the substrates. • Composites are more thermally stable than active phases. • Composites exhibit high catalytic activity for gas phase ethanol dehydration

  17. Production of Ethylene through Ethanol Dehydration on SBA-15 Catalysts Synthesized by Sol-gel and One-step Hydrothermal Methods.

    Science.gov (United States)

    Autthanit, Chaowat; Jongsomjit, Bunjerd

    2018-02-01

    The present work deals with the catalytic performance of SBA-15 supported catalysts in the gas phase catalytic dehydration of ethanol in the temperature range of 200 to 400°C. The SBA-15 support was incorporated on a zirconium (Zr) and bimetal of zirconium and lanthanum (Zr-La) prepared by sol-gel (SG) and hydrothermal (HT) methods. The catalysts were characterized by means of N 2 physisorption, SEM/EDX, and NH 3 -TPD. The experimental results demonstrated that the Zr-La/SBA-15-HT exhibited the highest catalytic activity. Ethanol conversion and ethylene selectivity were found to increase with increased reaction temperature. The best catalytic results were achieved for Zr-La/SBA-15-HT indicating values of ethanol conversion and ethylene yield of ca. 84% and 80%, respectively at 400°C. The most important parameter influencing their catalytic properties appears to be the interaction between metal and support depending on different methods. The metal dispersion inside the siliceous matrix of SBA-15 has a direct influence on their surface acidity. Meanwhile, the performance of these SBA-15 supported catalysts in ethanol dehydration is also related with the alteration of surface acidity caused by the introduction of Zr and Zr-La.

  18. Various characteristics of Ni and Pt-Al2O3 nano catalysts prepared by microwave method to be applied in some petrochemical processes

    International Nuclear Information System (INIS)

    Gobara, H.M.; Mohamed, A.R.S.; Khalil, F.H.; El-Shall, M.S.; Hassan, S.A.

    2014-01-01

    Alumina-supported metal nano catalysts were prepared via the microwave method, by loading nano Ni particles (at 1, 3 and 5 wt %) or nano Pt particles (at 0.3, 0.6 and 0.9 wt %). Structural and adsorption features of the nano catalysts were revealed through XRD, DSC- DTA, TEM, H 2 -chemisorption and N 2 -physisorption. N 2 -adsorption-desorption isotherms of type IV were related typically to meso porous materials with H 2 class of hysteresis loops characterizing ink bottle type of pores. The well dispersed nano-sized metal particles were evidenced in the studied catalytic systems, exhibiting marked thermal stability up to 800 degree C. The catalytic performances of different catalyst samples were assessed during cyclohexane, normal hexane and ethanol conversions, using the micro-catalytic pulse technique at different operating conditions. The 5% Ni-γAl 2 O 3 sample was found to be the most active in dehydration of ethanol to produce ethylene, as well as in n -hexane cracking. However, the 1% Ni-Al 2 O 3 sample showed the highest dehydrogenation activity for selective production of benzene from cyclohexane. On the other hand, the 0.9% Pt-γAl 2 O 3 sample exhibited the highest activity in the dehydration of ethanol and in the dehydrogenation of cyclohexane. The 0.3% Pt-γAl 2 O 3 sample was the most active in the dehydrocyclization of normal hexane, as compared to the other catalyst samples under study

  19. The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

    Science.gov (United States)

    Montero, J. M.; Isaacs, M. A.; Lee, A. F.; Lynam, J. M.; Wilson, K.

    2016-04-01

    An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 - sites to OH- and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C-H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

  20. Morphology, microstructure, and magnetic properties of ordered large-pore mesoporous cadmium ferrite thin film spin glasses.

    Science.gov (United States)

    Reitz, Christian; Suchomski, Christian; Chakravadhanula, Venkata Sai Kiran; Djerdj, Igor; Jagličić, Zvonko; Brezesinski, Torsten

    2013-04-01

    Herein, we report the synthesis, microstructure, and magnetic properties of cadmium ferrite (CdFe2O4) thin films with both an ordered cubic network of 18 nm diameter pores and single-phase spinel grains averaging 13 nm in diameter. These mesoporous materials were produced through facile polymer templating of hydrated nitrate salt precursors. Both the morphology and the microstructure, including cation site occupancy and electronic bonding configuration, were analyzed in detail by electron microscopy, grazing incidence small-angle X-ray scattering, Raman and X-ray photoelectron spectroscopy, and N2-physisorption. The obtained data demonstrate that the network of pores is retained up to annealing temperatures as high as 650 °C--the onset of crystallization is at ϑ = (590 ± 10) °C. Furthermore, they show that the polymer-templated samples exhibit a "partially" inverted spinel structure with inversion parameter λ = 0.40 ± 0.02. This differs from microcrystalline CdFe2O4 which shows virtually no inversion. Magnetic susceptibility studies reveal ferrimagnetic spin coupling below 147 K and further point to the likelihood of glassy behavior at low temperature (T(f) ≈ 60 K). In addition, analysis of room temperature magnetization data indicates the presence of sub-10 nm diameter superparamagnetic clusters in an otherwise paramagnetic environment.

  1. Structural, vibrational and morphological properties of layered double hydroxides containing Ni2+, Zn2+, Al3+ and Zr4+ cations

    International Nuclear Information System (INIS)

    Bezerra, Débora M.; Rodrigues, João E.F.S.; Assaf, Elisabete M.

    2017-01-01

    Layered double hydroxides are anionic clays with formula [M II 1−x M III x (OH) 2 ] q+ [A n− ] q/n ·mH 2 O, finding possible uses as catalyst support, adsorbents and so on. In this paper, we address the phase formation of layered double hydroxides containing Ni 2+ , Zn 2+ , Al 3+ and Zr 4+ cations, namely, NiZn-Al, NiZn-AlZr and NiZn-Zr compositions obtained by the coprecipitation method. Such systems were characterized by X-ray diffraction, confirming the phase formation for NiZn-Al and NiZn-AlZr samples. Infrared and Raman spectroscopies elucidated the anion and water molecules occurrence in the interlayer. Nitrogen physisorption (BET method) determined the presence of pores and specific surface area. The isotherm shapes were Type IV, according to the IUPAC, and represent a mesoporous structure. A morphological study was performed by means of scanning and transmission electron microscopies, and particle size values of 120, 131 and 235 nm for NiZn-Al, NiZn-AlZr and NiZn-Zr, respectively, were determined. Thermogravimetric analysis of the decomposition of the systems revealed that their complete disintegration occurred at ~ 450 °C and resulted in mixed oxides.

  2. Advanced materials for solid state hydrogen storage: “Thermal engineering issues”

    International Nuclear Information System (INIS)

    Srinivasa Murthy, S.; Anil Kumar, E.

    2014-01-01

    Hydrogen has been widely recognized as the “Energy Carrier” of the future. Efficient, reliable, economical and safe storage and delivery of hydrogen form important aspects in achieving success of the “Hydrogen Economy”. Gravimetric and volumetric storage capacities become important when one considers portable and mobile applications of hydrogen. In the case of solid state hydrogen storage, the gas is reversibly embedded (by physisorption and/or chemisorption) in a solid matrix. A wide variety of materials such as intermetallics, physisorbents, complex hydrides/alanates, metal organic frameworks, etc. have been investigated as possible storage media. This paper discusses the feasibility of lithium– and sodium–aluminum hydrides with emphasis on their thermodynamic and thermo-physical properties. Drawbacks such as poor heat transfer characteristics and poor kinetics demand special attention to the thermal design of solid state storage devices. - Highlights: • Advanced materials suitable for solid state hydrogen storage are discussed. • Issues related to thermodynamic and thermo-physical properties of hydriding materials are brought out. • Hydriding and dehydriding behavior including sorption kinetics of complex hydrides with emphasis on alanates are explained

  3. Impact of potassium promoter on Cu–Fe based mixed alcohols synthesis catalyst

    International Nuclear Information System (INIS)

    Ding, Mingyue; Tu, Junling; Qiu, Minghuang; Wang, Tiejun; Ma, Longlong; Li, Yuping

    2015-01-01

    Highlights: • Adding K facilitated the immigration of bulky iron species to surface layers. • Adding potassium strengthened the interaction of Fe–K on the surface layers. • Increasing K content facilitated the formation of C 2 + OH. • A maximum in catalytic activity is obtained at 0.5 wt.% of potassium loading. - Abstract: Impacts of K promoter on microstructures of a precipitated Cu–Fe based catalyst were studied by N 2 -physisorption (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD) and hydrogen temperature-programmed desorption/reduction (H 2 -TPD/TPR). Mixed alcohols synthesis (MAS) was carried out in a fixed-bed reactor. The results indicated that incorporation of K in the Cu–Fe based catalyst decreased the surface area of the particles, whereas promoted the immigration of bulky iron species to surface layers and strengthened the interaction of surface Fe–Cu. The increase of K concentration weakened the H 2 chemisorption and restrained the reduction of both the Cu and Fe species. The catalytic activity and mixed alcohols selectivity increased accompanied with a gradually increasing K concentration, and reached the highest values as the amount of K increased to 0.5 wt.%. Subsequently, the MAS activity and selectivity C 2 + OH presented a decreasing trend. In addition, the increase of K concentration facilitated the formation of heavy hydrocarbons

  4. Ground state analytical ab initio intermolecular potential for the Cl2-water system

    International Nuclear Information System (INIS)

    Hormain, Laureline; Monnerville, Maurice; Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón

    2015-01-01

    The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl 2 molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl 2 − H 2 O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl 2 interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl 2 on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results

  5. Surface coverage and corrosion inhibition effect of Rosmarinus officinalis and zinc oxide on the electrochemical performance of low carbon steel in dilute acid solutions

    Science.gov (United States)

    Loto, Roland Tolulope

    2018-03-01

    Electrochemical analysis of the corrosion inhibition and surface protection properties of the combined admixture of Rosmarinus officinalis and zinc oxide on low carbon steel in 1 M HCl and H2SO4 solution was studied by potentiodynamic polarization, open circuit potential measurement, optical microscopy and ATR-FTIR spectroscopy. Results obtained confirmed the compound to be more effective in HCl solution, with optimal inhibition efficiencies of 93.26% in HCl and 87.7% in H2SO4 acid solutions with mixed type inhibition behavior in both acids. The compound shifts the corrosion potential values of the steel cathodically in HCl and anodically in H2SO4 signifying specific corrosion inhibition behavior without applied potential. Identified functional groups of alcohols, phenols, 1°, 2° amines, amides, carbonyls (general), esters, saturated aliphatic, carboxylic acids, ethers, aliphatic amines, alkenes, aromatics, alkyl halides and alkynes within the compound completely adsorbed onto the steel forming a protective covering. Thermodynamic calculations showed physisorption molecular interaction with the steel's surface according to Langmuir and Frumkin adsorption isotherms. Optical microscopy images of the inhibited and uninhibited steels contrast each other with steel specimens from HCl solution showing a better morphology.

  6. Influence of the precursor chemical composition on heavy metal adsorption properties of hemp (Cannabis Sativa fibers based biocarbon

    Directory of Open Access Journals (Sweden)

    Vukčević Marija M.

    2017-01-01

    Full Text Available Waste hemp (Cannabis sativa fibers were used as sustainable and renewable raw materials for production of low-cost biocarbon sorbent for heavy metals removal. Carbon precursors of different chemical composition were obtained by oxidative and alkaline treatments of hemp fibers. Influence of lignocellulosic precursor chemical composition on hemp fibers-based biocarbon (HFB characteristics was examined by BET surface area measurement, scanning electron microscopy and mass titration. It was found that lignin content and polymorphic transformation of cellulose increase the SBET of microporous HFBs, while hemicelluloses induce more homogeneous distribution of adsorption active sites. Heavy metal ions adsorption onto HFBs is primarily influenced by the amount of surface oxygen groups, while specific surface area plays a secondary role. Equilibrium data obtained for lead ions adsorption were analyzed by different nonlinear adsorption isotherms, and the best fitting model was chosen using standard deviation and Akaike information criterion (AICC. The maximum adsorption capacities of HFBs ranged from 103.1 to 116.3 mg Pb/g. Thermodynamic parameters showed that Pb2+ adsorption onto HFBs is a spontaneous and complex endothermic process, suggesting the coexistence of physisorption and chemisorption mechanisms. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172007 and Grant no. 172029

  7. Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry

    Science.gov (United States)

    Lei, Sidong; Wang, Xifan; Li, Bo; Kang, Jiahao; He, Yongmin; George, Antony; Ge, Liehui; Gong, Yongji; Dong, Pei; Jin, Zehua; Brunetto, Gustavo; Chen, Weibing; Lin, Zuan-Tao; Baines, Robert; Galvão, Douglas S.; Lou, Jun; Barrera, Enrique; Banerjee, Kaustav; Vajtai, Robert; Ajayan, Pulickel

    2016-05-01

    Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti4+ to form planar p-type [Ti4+n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B3+, Al3+ and Sn4+) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

  8. Sorption of Heterocyclic Organic Compounds to Multiwalled Carbon Nanotubes.

    Science.gov (United States)

    Metzelder, Florian; Funck, Matin; Schmidt, Torsten C

    2018-01-16

    Sorption is an important natural and technical process. Sorption coefficients are typically determined in batch experiments, but this may be challenging for weakly sorbing compounds. An alternative method enabling analysis of those compounds is column chromatography. A column packed with the sorbent is used and sorption data are determined by relating sorbate retention to that of a nonretarded tracer. In this study, column chromatography was applied for the first time to study sorption of previously hardly investigated heterocyclic organic compounds to multiwalled carbon nanotubes (MWCNTs). Sorption data for these compounds are very limited in literature, and weak sorption is expected from predictions. Deuterium oxide was used as nonretarded tracer. Sorption isotherms were well described by the Freundlich model and data showed reasonable agreement with predicted values. Sorption was exothermic and physisorption was observed. H-bonding may contribute to overall sorption, which is supported by reduced sorption with increasing ionic strength due to blocking of functional groups. Lowering pH reduced sorption of ionizable compounds, due to electrostatic repulsion at pH 3 where sorbent as well as sorbates were positively charged. Overall, column chromatography was successfully used to study sorption of heterocyclic compounds to MWCNTs and could be applied for other carbon-based sorbents.

  9. Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

    Science.gov (United States)

    Pershina, V.; Borschevsky, A.; Iliaš, M.; Türler, A.

    2014-08-01

    With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl4, MOCl2, MCl6-, and MOCl42 with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl4, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔHsub, of the Zr and Hf tetrachlorides, i.e., Zr Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl4 on a chlorinated quartz surface, formation of the MCl62- surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the "one-atom-at-a-time" gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.

  10. Screening of Lactobacillus strains for their ability to bind benzo(a)pyrene and the mechanism of the process.

    Science.gov (United States)

    Zhao, Hongfei; Zhou, Fang; Qi, Yeqiong; Dziugan, Piotr; Bai, Fengling; Walczak, Piotr; Zhang, Bolin

    2013-09-01

    In order to investigate the binding ability of Lactobacillus strains to Benzo(a)pyrene (BaP), 15 strains were analysed. L. plantarum CICC 22135 and L. pentosus CICC 23163 exhibited high efficiency in removing BaP from aqueous medium; the binding rates were 66.76% and 64.31%, respectively. This process was affected by temperature, incubation time and pH, and cell viability was not necessary for the binding ability. Additionally, both strains, especially strain CICC 23163 showed high specificity in binding BaP. The cell-BaP complexes were stable in aqueous medium. The mechanism of binding was investigated by examining the binding ability of different components of the microorganism cells. The results revealed that peptidoglycans played an important role in binding BaP and its structural integrity was required. Consequently, we proposed that the mechanism of this process was a physisorption and peptidoglycan was the main binding site. These two strains may be used for dietary detoxification in human diet and animal feed. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Measurement and analysis of adsorption isotherms of CO_2 on activated carbon

    International Nuclear Information System (INIS)

    Singh, Vinod Kumar; Anil Kumar, E.

    2016-01-01

    In the present work CO_2 adsorption isotherms of a commercially available activated carbon, Norit Darco type obtained from lignite granular material, were measured. Adsorption isotherms were measured at different temperatures 298 K, 308 K, 318 K and 338 K and over a pressure range of 0–45 bar using Sievert's type experimental setup. Experimental data of CO_2 adsorption isotherms were modelled using Langmuir and Dubinin–Astakhov (D–A) isotherm models. Based on coefficient of correlation and normalized standard deviation it was found that D–A isotherm model was well suited with the experimental data of CO_2 adsorption isotherms. The important thermodynamic properties viz., limiting heat of adsorption at zero coverage, entropy, Gibbs free energy and isosteric heat of adsorption as a function of surface coverage were evaluated using van't Hoff and Clausius–Clapeyron equations. These thermodynamic properties were indicating that CO_2 uptake by activated carbon is a physisorption phenomenon. The adsorption isotherms data and the thermodynamic parameters estimated in the present study are useful for designing of an adsorption based gas storage systems.

  12. TS-1 supported highly dispersed sub-5 nm gold nanoparticles toward direct propylene epoxidation using H2 and O2

    Science.gov (United States)

    Li, Naixu; Chen, Yong; Shen, Quanhao; Yang, Bin; Liu, Ming; Wei, Lingfei; Tian, Wei; Zhou, Jiancheng

    2018-05-01

    We report a simple and efficient method for the preparation of highly dispersed Au nanoparticles (< 5 nm) on TS-1 substrate. The synthesis relies on the use of NaBH4 as a reductant for rapid Au atom generation, as well as PVA as a capping agent confining the particle size and dispersion. The samples were characterized by N2 physisorption, inductively coupled plasma mass spectrometry, power X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, CO pulse chemisorption and thermogravimetric analysis. The size of Au particles can be controlled in the range of 3-5 nm. The supported catalyst shows both good activity and selectivity for propylene oxide (PO) generation from direct propylene epoxidation. An optimal performance with PO formation rate of 102.94 gPO h-1 kg-1cat and selectivity of 84.83% is achieved over 2.0 wt% Au/TS-1 catalyst, which is prepared by controlling PVA/Au3+ mass ratio of 1.5/1 and NaBH4/Au3+ mole ratio of 5/1. After 50 h test at 200 °C, no significant decrement of both catalytic activity and PO selectivity can be observed, indicating the excellent thermally stability of the catalyst. Furthermore, a possible reaction mechanism is described on basis of the previous researches and our experimental results.

  13. Biosynthesis of Multicomponent Nanoparticles with Extract of Mortiño (Vaccinium floribundum Kunth Berry: Application on Heavy Metals Removal from Water and Immobilization in Soils

    Directory of Open Access Journals (Sweden)

    Mayra Abril

    2018-01-01

    Full Text Available Through preparation of multicomponent nanoparticles (MCNPs using ferric chloride (FeCl3, sodium sulfate (Na2SO4, and the extract of mortiño fruit (Vaccinium floribundum Kunth, we dramatically improved the removal/immobilization of heavy metals from water and in soils. As-prepared nanoparticles were spherical measuring approximately 12 nm in diameter and contained iron oxides and iron sulfides in the crystal structure. Removal of copper and zinc from water using MCNPs showed high efficiencies (>99% at pH above 6 and a ratio of 0.5 mL of the extract:10 mL 0.5 M FeCl3·6H2O : 10 mL 0.035 M Na2SO4. The physisorption process followed by chemisorption was regarded as the removal mechanism of Cu and Zn from water. While, when MCNPs were used to treat soils contaminated with heavy metals, more than 95% of immobilization was accomplished for all metals. Nevertheless, the distribution of the metallic elements changed in the soil fractions after treatment. Results indicate that immobilization of metals after the injection of nanoparticles into soils was effective. Metals did not leach out when soils were drained with rain, drinking, and deionized water but fairly leached out under acidic water drainage.

  14. A comparative study of the corrosion inhibition of mild steel in sulphuric acid by 4,4-dimethyloxazolidine-2-thione

    International Nuclear Information System (INIS)

    Musa, Ahmed Y.; Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Daud, Abdul Razak; Takriff, Mohd Sobri; Kamarudin, Siti Kartom

    2009-01-01

    The corrosion protection of mild steel in a 2.5 M H 2 SO 4 solution by 4,4-dimethyloxazolidine-2-thione (DMT) was studied at different temperatures by measuring changes in open circuit potential (OCP), potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS). Corrosion current densities calculated from EIS data were comparable to those obtained from polarisation measurements. Results showed that DMT inhibited mild steel corrosion in a 2.5 M H 2 SO 4 solution and indicated that the inhibition efficiencies increased with the concentration of inhibitor, but decreased proportionally with temperature. Polarisation curves showed that DMT is a mixed-type inhibitor. Changes in impedance parameters suggested the adsorption of DMT on the mild steel surface, leading to the formation of protective films. The DMT adsorption on the mild steel surface followed the Langmuir adsorption isotherm. The kinetic and thermodynamic parameters for dissolution and adsorption were investigated. Comprehensive adsorption (physisorption and chemisorption) of the inhibitor molecules on the mild steel surface was suggested based on the thermodynamic adsorption parameters.

  15. BN and BN oxide nanosheets based nanosensor for paracetamol adsorption: a first principles simulation

    Directory of Open Access Journals (Sweden)

    Miguel Castro

    2014-04-01

    Full Text Available The effects that the adsorption of the paracetamol molecule produce on the structural and electronic properties of boron nitride (hBNNs; B27N27H18 and boron nitride oxide (hBNONs; B27N27H17 + O + (OH3 + COOH hexagonal symmetry nanosheets were studied by means of Density Functional Theory. The generalized gradient approximation proposed by Heyd—Scuseria—Ernzerhof ((HSEh1PBE―GGA was used in concert with 6-31G(d basis sets. Several candidate structures, 9 and 13 for the hBNNs―Paracetamol and BNONs―Paracetamol interactions, respectively, were used for the geometry optimization procedure. The results show that in the lowest energy absorption site the paracetamol molecule reaches a parallel orientation to the surface of the nanosheets, producing physisorption for hBNNs―Paracetamol and chemisorption for BNONs―Paracetamol. Besides, the adsorption process yields an increase of the polarity opening the possibility for the solubility and dispersion of these compounds. The paracetamol molecule promotes also a decrease of the reactivity parameter, which is crucial for biological applications of these systems. Referred to pristine hBNNs and BNONs, the work functions of hBNNs-Paracetamol and BNONs―Paracetamol are diminished. That is, these functionalized 2D systems yields appropriate conditions for field emission and they may be used as sensors of such pharmaceutical compound.

  16. Functionalization of PDMS modified and plasma activated two-component polyurethane coatings by surface attachment of enzymes

    International Nuclear Information System (INIS)

    Kreider, Alexej; Richter, Katharina; Sell, Stephan; Fenske, Mandus; Tornow, Christian; Stenzel, Volkmar; Grunwald, Ingo

    2013-01-01

    This article describes a new strategy for coupling the enzyme horseradish peroxidase to a two-component polyurethane (2C-PUR) coating. A stable polymer conjugate was achieved by combining the enzyme and the 2C-PUR coating which was modified with poly(dimethylsiloxane) (PDMS), located at the surface. An atmospheric pressure plasma jet system was used to convert alkyl groups from the PDMS into polar silanol functionalities. This conversion was proven by X-ray photoelectron spectroscopy and dynamic contact angle measurements. In addition, the stability of the activated 2C-PUR surface containing silanol groups was determined by measuring the contact angle as a function of time. Compared to the non-modified 2C-PUR systems the one with PDMS displayed a higher stability over a time period over 28 h. In a silanization process the coating was treated with (3-aminopropyl) trimethoxysilane and the enzyme was subsequently immobilized to the coating via the cross linker glutaraldehyde to receive new biomimetic catalytic/enzymatic functions. The chemical immobilization (chemisorption) of the enzyme to the surface showed statistically significant higher biological activity as compared to references samples without using a cross linker (physisorption). The presented technique offers the opportunity to design new and smart multifunctional surface coatings which employ biomimetic capabilities.

  17. Hydrogen as fuel carrier in PEM fuelcell for automobile applications

    Science.gov (United States)

    Sk, Mudassir Ali; Venkateswara Rao, K.; Ramana Rao, Jagirdar V.

    2015-02-01

    The present work focuses the application of nanostructured materials for storing of hydrogen in different carbon materials by physisorption method. To market a hydrogen-fuel cell vehicle as competitively as the present internal combustion engine vehicles, there is a need for materials that can store a minimum of 6.5wt% of hydrogen. Carbon materials are being heavily investigated because of their promise to offer an economical solution to the challenge of safe storage of large hydrogen quantities. Hydrogen is important as a new source of energy for automotive applications. It is clear that the key challenge in developing this technology is hydrogen storage. Combustion of fossil fuels and their overuse is at present a serious concern as it is creates severe air pollution and global environmental problems; like global warming, acid rains, ozone depletion in stratosphere etc. This necessitated the search for possible alternative sources of energy. Though there are a number of primary energy sources available, such as thermonuclear energy, solar energy, wind energy, hydropower, geothermal energy etc, in contrast to the fossil fuels in most cases, these new primary energy sources cannot be used directly and thus they must be converted into fuels, that is to say, a new energy carrier is needed. Hydrogen fuel cells are two to three times more efficient than combustion engines. As they become more widely available, they will reduce dependence on fossil fuels. In a fuel cell, hydrogen and oxygen are combined in an electrochemical reaction that produces electricity and, as a byproduct, water.

  18. A new surface catalytic model for silica-based thermal protection material for hypersonic vehicles

    Directory of Open Access Journals (Sweden)

    Li Kai

    2015-10-01

    Full Text Available Silica-based materials are widely employed in the thermal protection system for hypersonic vehicles, and the investigation of their catalytic characteristics is crucially important for accurate aerothermal heating prediction. By analyzing the disadvantages of Norman’s high and low temperature models, this paper combines the two models and proposes an eight-reaction combined surface catalytic model to describe the catalysis between oxygen and silica surface. Given proper evaluation of the parameters according to many references, the recombination coefficient obtained shows good agreement with experimental data. The catalytic mechanisms between oxygen and silica surface are then analyzed. Results show that with the increase of the wall temperature, the dominant reaction contributing to catalytic coefficient varies from Langmuir–Hinshelwood (LH recombination (TW  1350 K. The surface coverage of chemisorption areas varies evidently with the dominant reactions in the high temperature (HT range, while the surface coverage of physisorption areas varies within quite low temperature (LT range (TW < 250 K. Recommended evaluation of partial parameters is also given.

  19. Electrochemical evaluation of antibacterial drugs as environment-friendly inhibitors for corrosion of carbon steel in HCl solution

    Energy Technology Data Exchange (ETDEWEB)

    Golestani, Gh.; Shahidi, M., E-mail: shahidi1965@gmail.com; Ghazanfari, D.

    2014-07-01

    The effect of penicillin G, ampicillin and amoxicillin drugs on the corrosion behavior of carbon steel (ASTM 1015) in 1.0 mol L⁻¹ hydrochloric acid solution was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) techniques. The inhibition efficiency was found to increase with increasing inhibitor concentration. The effect of temperature on the rate of corrosion in the absence and presence of these drugs was also studied. Some thermodynamic parameters were computed from the effect of temperature on corrosion and inhibition processes. Adsorption of these inhibitors was found to obey Langmuir adsorption isotherm. There was a case of mixed mode of adsorption here but while penicillin was adsorbed mainly through chemisorption, two other drugs were adsorbed mainly through physisorption. Potentiodynamic polarization measurements indicated that the inhibitors were of mixed type. In addition, this paper suggests that the electrochemical noise (EN) technique under open circuit conditions as the truly noninvasive electrochemical method can be employed for the quantitative evaluation of corrosion inhibition. This was done by using the standard deviation of partial signal (SDPS) for calculation of the amount of noise charges at the particular interval of frequency, thereby obtaining the inhibition efficiency (IE) of an inhibitor. These IE values showed a reasonable agreement with those obtained from potentiodynamic polarization and EIS measurements.

  20. Electrochemical evaluation of antibacterial drugs as environment-friendly inhibitors for corrosion of carbon steel in HCl solution

    International Nuclear Information System (INIS)

    Golestani, Gh.; Shahidi, M.; Ghazanfari, D.

    2014-01-01

    The effect of penicillin G, ampicillin and amoxicillin drugs on the corrosion behavior of carbon steel (ASTM 1015) in 1.0 mol L −1 hydrochloric acid solution was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) techniques. The inhibition efficiency was found to increase with increasing inhibitor concentration. The effect of temperature on the rate of corrosion in the absence and presence of these drugs was also studied. Some thermodynamic parameters were computed from the effect of temperature on corrosion and inhibition processes. Adsorption of these inhibitors was found to obey Langmuir adsorption isotherm. There was a case of mixed mode of adsorption here but while penicillin was adsorbed mainly through chemisorption, two other drugs were adsorbed mainly through physisorption. Potentiodynamic polarization measurements indicated that the inhibitors were of mixed type. In addition, this paper suggests that the electrochemical noise (EN) technique under open circuit conditions as the truly noninvasive electrochemical method can be employed for the quantitative evaluation of corrosion inhibition. This was done by using the standard deviation of partial signal (SDPS) for calculation of the amount of noise charges at the particular interval of frequency, thereby obtaining the inhibition efficiency (IE) of an inhibitor. These IE values showed a reasonable agreement with those obtained from potentiodynamic polarization and EIS measurements.

  1. Removal of lead and fluoride from contaminated water using exhausted coffee grounds based bio-sorbent.

    Science.gov (United States)

    Naga Babu, A; Reddy, D Srinivasa; Kumar, G Suresh; Ravindhranath, K; Krishna Mohan, G V

    2018-07-15

    Water pollution by industrial and anthropogenic actives has become a serious threat to the environment. World Health Organization (WHO) has identified that lead and fluoride amid the environmental pollutants are most poisonous water contaminants with devastating impact on the human race. The present work proposes a study on economical bio-adsorbent based technique using exhausted coffee grounds in the removal of lead and fluoride contaminants from water. The exhausted coffee grounds gathered from industrial wastes have been acid-activated and examined for their adsorption capacity. The surface morphology and elemental characterization of pre-and-post adsorption operations by FESEM, EDX and FTIR spectral analysis confirmed the potential of the exhausted coffee ground as successful bio-sorbent. However, thermodynamic analysis confirmed the adsorption to be spontaneous physisorption with Langmuir mode of homogenous monolayer deposition. The kinetics of adsorption is well defined by pseudo second order model for both lead and fluoride. A significant quantity of lead and fluoride is removed from the synthetic contaminated water by the proposed bio-sorbent with the respective sorption capabilities of 61.6 mg/g and 9.05 mg/g. However, the developed bio-sorbent is also recyclable and is capable of removing the lead and fluoride from the domestic and industrial waste-water sources with an overall removal efficiency of about 90%. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Response of Si- and Al-doped graphenes toward HCN: A computational study

    International Nuclear Information System (INIS)

    Rastegar, Somayeh F.; Peyghan, Ali Ahmadi; Hadipour, Nasser L.

    2013-01-01

    Highlights: ► Sensitivity of Si- and Al-doped graphene (SiG and AlG) toward HCN is investigated. ► The electronic properties of AlG are significantly changed in the presence of HCN. ► It is established that AlG can be a good sensor for HCN molecule. - Abstract: Sensitivity of Si- and Al-doped graphenes (SiG and AlG) toward toxic HCN has been investigated using density functional theory (DFT) in terms of energetic, geometric and electronic properties. Optimized configurations corresponding to physisorption and, subsequently, chemisorption of HCN on each surface have been identified. It is found that HCN molecule can be adsorbed on impurity atoms with adsorption energies about −27.20 and −38.75 kcal/mol on the SiG and the AlG, respectively. By comparing to HCN adsorption on SiG, it can be inferred that molecular HCN adsorbed on AlG can induce significant change in AlG conductivity. On the basis of calculated changes in the HOMO/LUMO energy gap it is found that electronic properties of AlG are sensitive toward adsorption of HCN and the reverse is correct for SiG, suggesting that the AlG may be a promising sensor for HCN.

  3. Surface modification to improve the sorption property of U(VI) on mesoporous silica

    International Nuclear Information System (INIS)

    Lijuan Song; Yulong Wang; Lu Zhu; Bolong Guo; Suwen Chen; Wangsuo Wu

    2014-01-01

    Polyoxometalates K 7 [α-PW 11 O 39 ]·14H 2 O (PW11) modified mesoporous silica (MCM-48) with cubic structure, was prepared by impregnation and calcination methods. The modified mesoporous silica sorbent (PW11/MCM-48) was studied as a potential adsorbent for U(VI) from aqueous solutions. MCM-48 and PW11/MCM-48 were confirmed by X-ray diffraction and nitrogen physisorption techniques. The results indicate the original keggin structure of PW11 and mesoporous structure of MCM-48 are maintained after supporting PW11 on mesoporous silica MCM-48. The effects of contact time, solid-to-liquid ratio (m/V), solution pH and ionic strength on U(VI) sorption behaviors of the pure and modified mesoporous silicas were also studied. Typical sorption isotherms such as Langmuir and Freundlich isotherms were determined for sorption process. The results suggest that the sorption of U(VI) on MCM-48 or PW11/MCM-48 are strongly dependent on pH values but independent of ionic strength. The sorption capacity of PW11/MCM-48 for U(VI) is about ten times more than that of MCM-48. (author)

  4. Synthesis of ZnO-CuO/MCM-48 photocatalyst for the degradation of organic pollutions.

    Science.gov (United States)

    Duan, Yongzheng; Shen, Yulian

    2017-07-01

    The photocatalytic properties of ZnO-CuO catalysts supported on siliceous MCM-48 (Mobil Composition of Matter No. 48) for the degradation of organic pollutions such as methylene blue and salicylic acid under UV light irradiation were investigated. These catalysts were prepared by impregnation of MCM-48 with a mixed aqueous solution of copper acetate and zinc acetate. X-ray diffraction, N 2 -physisorption, high resolution transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and photoluminescence were used to characterize these samples. Results from characterizations showed that the addition of ZnO to CuO/MCM-48 could markedly improve the photocatalytic degradation properties. The enhanced photocatalytic behaviors of ZnO-CuO/MCM-48 may be due to the formation of p-n heterojunctions between ZnO and CuO, resulting in the effective separation of photogenerated electron-hole pairs. Moreover, the photocatalysts were easily recovered and reused for five cycles without considerable loss of activity.

  5. Application of B{sub 12}N{sub 12} and B{sub 12}P{sub 12} as two fullerene-like semiconductors for adsorption of halomethane: Density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Rad, Ali Shokuhi, E-mail: a.shokuhi@gmail.com [Islamic Azad University, Department of Chemical Engineering, Qaemshahr Branch (Iran, Islamic Republic of)

    2017-01-15

    We examined and discussed the interaction of two halomethanes (mono-chloromethane (MCM), and mono-fluoromethane (MFM)) with B{sub 12}N{sub 12} and B{sub 12}P{sub 12} fullerene-like nanocages as semiconductor based on density functional theory (DFT). We calculated adsorption energies and followed the changes in the electronic structure of semiconductors upon adsorption of MCM and MFM. We found that the adsorption on the B{sub 12}N{sub 12} nano-cluster is energetically more favorable compared to B{sub 12}P{sub 12} nano-cluster. Also for both systems we found higher values of adsorption energy for MFM than for MCM. We found that upon adsorption of above-mentioned species on these two fullerene-like semiconductors, the HOMO–LUMO distributions and also the gap energy for each system did not change significantly, which correspond to the physisorption process. As a result, B{sub 12}N{sub 12} is a more appropriate nano-cluster to be used as a selective sensor for halomethanes, especially for MFM.

  6. MCM-41 ordered mesoporous molecular sieves synthesis and characterization

    Directory of Open Access Journals (Sweden)

    Rogério A.A. Melo

    1999-07-01

    Full Text Available The aim of this work was to study the hydrothermal synthesis of Si and SiAlMCM-41 performed under both autogenic pressure and refluxing conditions. XRD data showed that the MCM-41 phase may be formed by both processes and that the synthesized material in the presence of Al and/or under reflux presents the hexagonally arrangement of less ordered mesopores. However, as verified by XRD and physisorption data, the order was improved with higher synthesis times. 29Si and 1H - 29Si C/P MAS NMR spectra showed that a great part of the Si atoms exists as silanol groups which originate resonance peaks at -110, -100 and -91 ppm. The presence of Al atoms may generate Si(3Si, Al and Si(2Si, 2Al environments which might be contributing to resonance peaks at -100 and -91 ppm. The 27Al MAS NMR spectrum of the as synthesized AlSiMCM-41 showed a resonance peak of tetrahedral framework aluminum close to 53 ppm and two others, one close to 14 ppm attributed to Al(H2O6+3 species and the other a weak signal close to 32 ppm attributed to pentacoordinated Al. 27Al MAS NMR spectra of the calcined sample showed a peak at 0 ppm corresponding to an hexacoordinated extra-framework aluminum formed during calcination.

  7. Ordered Mesoporous NiCeAl Containing Catalysts for Hydrogenolysis of Sorbitol to Glycols

    Science.gov (United States)

    Zhou, Zhiwei; Zhang, Jiaqi; Qin, Juan; Li, Dong; Wu, Wenliang

    2018-03-01

    Cellulose-derived sorbitol is emerging as a feasible and renewable feedstock for the production of value-added chemicals. Highly active and stable catalyst is essential for sorbitol hydrogenolysis. Ordered mesoporous M- xNi yCeAl catalysts with different loadings of nickel and cerium species were successfully synthesized via one-pot evaporation-induced self-assembly strategy (EISA) and their catalytic performance were tested in the hydrogenolysis of sorbitol. The physical chemical properties for the catalysts were characterized by XRD, N2 physisorption, H2-TPR, H2 impulse chemisorption, ICP and TEM techniques. The results showed that the ordered mesopores with uniform pore sizes can be obtained and the Ni nanoparticles around 6 nm in size were homogeneously dispersed in the mesopore channels. A little amount of cerium species introduced would be beneficial to their textural properties resulting in higher Ni dispersion, metal area and smaller size of Ni nanoparticles. The M-10Ni2CeAl catalyst with Ni and Ce loading of 10.9 and 6.3 wt % shows better catalytic performance than other catalysts, and the yield of 1,2-PG and EG can reach 56.9% at 493 K and 6 MPa pressure for 8 h after repeating reactions for 12 times without obvious deterioration of physical and chemical properties. Ordered mesoporous M-NiCeAl catalysts are active and stable in sorbitol hydrogenolysis.

  8. Precious Metals Supported on Alumina and Their Application for Catalytic Aqueous Phase Reforming of Glycerol

    Directory of Open Access Journals (Sweden)

    Kiky Corneliasari Sembiring

    2015-11-01

    Full Text Available The high cost of Pt based catalyst for aqueous phase reforming (APR reaction makes it advantageous to develop less cost of other metals for the same reaction. APR is hydrogen production process from biomass-derived source at mild condition near 500 K and firstly reported by Dumesic and co-worker. The use of hydrogen as environmentally friendly energy carrier has been massively encouraged over the last year. When hydrogen is used in fuel cell for power generation, it produces a little or no pollutants. The aim of this study is to study the effect of some precious metal catalysts for APR process. Due to investigation of metal catalysts for APR process, four precious metals (Cu, Co, Zn, Ni supported on γ-Al2O3 with 20% feeding amount have been successfully prepared by impregnation method. Those precious metals were identified as promising catalysts for APR. The catalysts were characterized by N2 physisorption at 77 K, X-Ray Diffraction (XRD and Fourier Transform-Infra Red (FT-IR. The catalytic performance was investigated at 523 K and autogenous pressure in a batch reactor with glycerol concentration of 10%. The gaseous hydrogen product was observed over the prepared catalysts by GC. It was found that performance of catalysts to yield the hydrogen product was summarized as follow Cu/γ-Al2O3 > Co/γ-Al2O3 > Zn/γ-Al2O3 > Ni/γ-Al2O3.

  9. Influence of Synthesis pH on Textural Properties of Carbon Xerogels as Supports for Pt/CXs Catalysts for Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    C. Alegre

    2012-01-01

    Full Text Available Carbon xerogels (CXs have been prepared by polycondensation of resorcinol and formaldehyde. Two synthesis pHs were studied in order to evaluate its influence on the electrochemical behaviour of Pt catalysts supported on previous carbon xerogels, synthesized by conventional impregnation method. Catalysts were also synthesized over a commercial carbon black (Vulcan-XC-72R for comparison purposes. Characterization techniques included nitrogen physisorption, scanning electron microscopy, and X-ray diffraction. Catalysts electrochemical activity towards the oxidation of carbon monoxide and methanol was studied by cyclic voltammetry and chronoamperometry to establish the effect of the carbon support on the catalysts performance. Commercial Pt/C catalyst (E-TEK was analyzed for comparison purposes. It was observed that the more developed and mesopore-enriched porous structure of the carbon xerogel synthesized at a higher initial pH resulted in an optimal utilization of the active phase and in an enhanced and promising catalytic activity in the electrooxidation of methanol, in comparison with commercial catalysts.

  10. Sodium phthalamates as corrosion inhibitors for carbon steel in aqueous hydrochloric acid solution

    International Nuclear Information System (INIS)

    Flores, Eugenio A.; Olivares, Octavio; Likhanova, Natalya V.; Dominguez-Aguilar, Marco A.; Nava, Noel; Guzman-Lucero, Diego; Corrales, Monica

    2011-01-01

    Highlights: → N-Alkyl-sodium phthalamates as corrosion inhibitors for industry in acidic medium. → Compounds behaved as mixed type inhibitors and followed Langmuir adsorption isotherm. → Efficiencies were proportional to aliphatic chain length and inhibitor concentration. → Iron complexes and chelates with phthalamates contributed to carbon steel protection. - Abstract: Three compounds of N-alkyl-sodium phthalamates were synthesized and tested as corrosion inhibitors for carbon steel in 0.5 M aqueous hydrochloric acid. Tests showed that inhibitor efficiencies were related to aliphatic chain length and dependent on concentration. N-1-n-tetradecyl-sodium phthalamate displayed moderate efficiency against uniform corrosion, 42-86% at 25 deg. C and 25-60% at 40 o C. Tests indicated that compounds behave as mixed type inhibitors where molecular adsorption on steel followed Langmuir isotherm, whereas thermodynamic suggested that a physisorption process occurred. XPS analysis confirmed film formation on surface, where Fe +2 complexes and Fe +2 chelates with phthalamates prevented steel from further corrosion.

  11. Structural analysis of platinum-palladium nanoparticles dispersed on titanium dioxide to evaluate cyclo-olefines reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Castillo, N., E-mail: necastillo@yahoo.co [Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Edificio B, 04510 Mexico DF (Mexico); Centro de Investigacion y de Estudios Avanzados del IPN, Depto. de Fisica, Av. IPN 2508, C.P. 07360, Mexico DF (Mexico); Perez, R. [Instituto de Ciencias Fisicas, Universidad Nacional Autonoma de Mexico, Campus Morelos, 62251 Cuernavaca Morelos (Mexico); Martinez-Ortiz, M.J.; Diaz-Barriga, L. [Instituto Politecnico Nacional - ESIQIE, UPALM Edif. 7, 07738 Mexico DF (Mexico); Garcia, L. [Instituto Politecnico Nacional - ESIT, UPALM, 07738 Mexico DF (Mexico); Conde-Gallardo, A. [Centro de Investigacion y de Estudios Avanzados del IPN, Depto. de Fisica, Av. IPN 2508, C.P. 07360, Mexico DF (Mexico)

    2010-04-16

    Structural and chemical properties were correlated to explain catalytic behavior of Pt-Pd/TiO{sub 2} in a cyclo-olefin reaction. Bimetallic nanoparticles supported on TiO{sub 2} were prepared by wetness impregnation techniques at different concentrations of Pt and Pd {approx}1 metallic wt%. The physicochemical properties of these metallic nanoparticles supported on TiO{sub 2} were characterized by N{sub 2} physisorption (Brunauer-Emmett-Teller-BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The relationship between chemical composition, physicochemical properties and particle size on the cyclo-olefin reaction was then studied. XRD and TEM results show that these nanoparticles are composed of Pt-Pd with FFC structure (a = 0.389-0.391 nm) supported on TiO{sub 2} (anatase-like structure), and the materials present tetragonal structure nanoparticles (a = 0.37842, b = 0.37842, c = 0.95146 nm). Samples with higher contents of platinum and particle sizes of 4.2 nm show the highest catalytic conversion in cyclo-olefins reaction. Finally, structural examinations of Pt{sub x}-Pd{sub (1-x)}/TiO{sub 2} based system was then conducted to study the effects of metals on the nanostructure of the materials.

  12. Structural analysis of platinum-palladium nanoparticles dispersed on titanium dioxide to evaluate cyclo-olefines reactivity

    International Nuclear Information System (INIS)

    Castillo, N.; Perez, R.; Martinez-Ortiz, M.J.; Diaz-Barriga, L.; Garcia, L.; Conde-Gallardo, A.

    2010-01-01

    Structural and chemical properties were correlated to explain catalytic behavior of Pt-Pd/TiO 2 in a cyclo-olefin reaction. Bimetallic nanoparticles supported on TiO 2 were prepared by wetness impregnation techniques at different concentrations of Pt and Pd ∼1 metallic wt%. The physicochemical properties of these metallic nanoparticles supported on TiO 2 were characterized by N 2 physisorption (Brunauer-Emmett-Teller-BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The relationship between chemical composition, physicochemical properties and particle size on the cyclo-olefin reaction was then studied. XRD and TEM results show that these nanoparticles are composed of Pt-Pd with FFC structure (a = 0.389-0.391 nm) supported on TiO 2 (anatase-like structure), and the materials present tetragonal structure nanoparticles (a = 0.37842, b = 0.37842, c = 0.95146 nm). Samples with higher contents of platinum and particle sizes of 4.2 nm show the highest catalytic conversion in cyclo-olefins reaction. Finally, structural examinations of Pt x -Pd (1-x) /TiO 2 based system was then conducted to study the effects of metals on the nanostructure of the materials.

  13. Application of Organophosphonic Acids by One-Step Supercritical CO2 on 1D and 2D Semiconductors: Toward Enhanced Electrical and Sensing Performances.

    Science.gov (United States)

    Bhartia, Bhavesh; Bacher, Nadav; Jayaraman, Sundaramurthy; Khatib, Salam; Song, Jing; Guo, Shifeng; Troadec, Cedric; Puniredd, Sreenivasa Reddy; Srinivasan, Madapusi Palavedu; Haick, Hossam

    2015-07-15

    Formation of dense monolayers with proven atmospheric stability using simple fabrication conditions remains a major challenge for potential applications such as (bio)sensors, solar cells, surfaces for growth of biological cells, and molecular, organic, and plastic electronics. Here, we demonstrate a single-step modification of organophosphonic acids (OPA) on 1D and 2D structures using supercritical carbon dioxide (SCCO2) as a processing medium, with high stability and significantly shorter processing times than those obtained by the conventional physisorption-chemisorption method (2.5 h vs 48-60 h).The advantages of this approach in terms of stability and atmospheric resistivity are demonstrated on various 2D materials, such as indium-tin-oxide (ITO) and 2D Si surfaces. The advantage of the reported approach on electronic and sensing devices is demonstrated by Si nanowire field effect transistors (SiNW FETs), which have shown a few orders of magnitude higher electrical and sensing performances, compared with devices obtained by conventional approaches. The compatibility of the reported approach with various materials and its simple implementation with a single reactor makes it easily scalable for various applications.

  14. Kinetic and thermodynamic studies on the adsorption of anionic surfactant on quaternary ammonium cationic cellulose.

    Science.gov (United States)

    Zhang, Yuanzhang; Shi, Wenjian; Zhou, Hualan; Fu, Xing; Chen, Xuan

    2010-06-01

    Removal of anionic surfactants from aqueous solutions by adsorption onto quaternary ammonium cationic cellulose (QACC) was investigated. The effects of solution acidity, initial concentration, adsorption time, and temperature on the adsorption of sodium dodecyl-benzene sulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfonate (SDS) were studied. The kinetic experimental data fit well with the pseudo-second-order model; the rate constant of the adsorption increased with temperature. The values of apparent activation energy for the adsorption were calculated as ranging from 10.2 to 17.4 kJ/ mol. The adsorption isotherm can be described by the Langmuir isotherm. The values of thermodynamic parameters (deltaH0, deltaS0, and deltaG0) for the adsorption indicated that this process was spontaneous and endothermic. At 318 K, the saturated adsorption capacities of QACC for SDBS, SLS, and SDS were 1.75, 1.53, and 1.39 mmol/g, respectively. The adsorption process was mainly chemisorption and partially physisorption. The results show that QACC is effective for the removal of anionic surfactants.

  15. Adsorption affinity and selectivity of 3-ureidopropyltriethoxysilane grafted oil palm empty fruit bunches towards mercury ions.

    Science.gov (United States)

    Kunjirama, Magendran; Saman, Norasikin; Johari, Khairiraihanna; Song, Shiow-Tien; Kong, Helen; Cheu, Siew-Chin; Lye, Jimmy Wei Ping; Mat, Hanapi

    2017-06-01

    This study was conducted to investigate the potential application of oil palm empty fruit branches (OPEFB) as adsorbents to remove organic methylmercurry, MeHg(II), and inorganic Hg(II) from aqueous solution. The OPEFB was functionalized with amine containing ligand namely 3-ureidopropyltriethoxysilane (UPTES) aiming for better adsorption performance towards both mercury ions. The adsorption was found to be dependent on initial pH, initial concentraton, temperatures, and contact time. The maximum adsorption capacities (Q m.exp ) of Hg(II) adsorption onto OPEFB and UPTES-OPEFB were 0.226 and 0.773 mmol/g, respectively. The Q m.exp of MeHg(II) onto OPEFB, however, was higher than UPTES-OPEFB. The adsorption kinetic data obeyed the Elovich model and the adsorption was controlled by the film-diffusion step. The calculated thermodynamic parameters indicate an endothermic adsorption process. Adsorption data analysis indicates that the adsorption mechanism may include ion-exchange, complexation, and physisorption interactions. The potential applications of adsorbents were demonstrated using oilfield produced water and natural gas condensate. The UPTES-OPEFB offered higher selectivity towards both mercury ions than OPEFB. The regenerability studies indicated that the adsorbent could be reused for multiple cycles.

  16. Efficient removal of cobalt from aqueous solution by zinc oxide nanoparticles. Kinetic and thermodynamic studies

    International Nuclear Information System (INIS)

    Khezami, L.; Modwi, A.; Taha, Kamal K.; Univ. of Bahri, Khartoum

    2017-01-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg.g -1 of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  17. Preparation and Characterization of Promoted Fe-V/SiO2 Nanocatalysts for Oxidation of Alcohols

    Directory of Open Access Journals (Sweden)

    Hamid Reza Rafiee

    2013-01-01

    Full Text Available A series of SiO2 supported iron-vanadium catalysts were prepared using sol-gel and wetness impregnation methods. This research investigates the effects of V and Cu on the structure and morphology of Fe/SiO2 catalysts. The SiO2 supported catalyst with the highest specific surface area and pore volume was obtained when it is containing 40 wt.% Fe, 15 wt.% V, and 2 wt.% Cu. Characterization of prepared catalysts was carried out by powder X-ray diffraction (XRD, scanning electron microcopy (SEM, vibrating sample magnetometry (VSM, Fourier transform infrared (FT-IR spectrometry, temperature program reduction (TPR, N2 physisorption, and thermal analysis methods such as thermal gravimetric analysis (TGA and differential scanning calorimetry (DSC. The Fe-V/SiO2 catalyst promoted with 2 wt.% of Cu exhibited typical ferromagnetic behavior at room temperature with a saturation magnetization value of 11.44 emu/g. This character of catalyst indicated great potential for application in magnetic separation technologies. The prepared catalyst was found to act as an efficient recoverable nanocatalyst for oxidation reaction of alcohols to aldehydes and ketones in aqueous media under mild condition. Moreover, the catalyst was reused five times without significant degradation in catalytic activity and performance.

  18. Influence of Ce-precursor and fuel on structure and catalytic activity of combustion synthesized Ni/CeO{sub 2} catalysts for biogas oxidative steam reforming

    Energy Technology Data Exchange (ETDEWEB)

    Vita, Antonio, E-mail: antonio.vita@itae.cnr.it; Italiano, Cristina; Fabiano, Concetto; Laganà, Massimo; Pino, Lidia

    2015-08-01

    A series of nanosized Ni/CeO{sub 2} catalysts were prepared by Solution Combustion Synthesis (SCS) varying the fuel (oxalyldihydrazide, urea, carbohydrazide and glycerol), the cerium precursor (cerium nitrate and cerium ammonium nitrate) and the nickel loading (ranging between 3.1 and 15.6 wt%). The obtained powders were characterized by X-ray Diffraction (XRD), N{sub 2}-physisorption, CO-chemisorption, Temperature Programmed Reduction (H{sub 2}-TPR) and Scanning Electron Microscopy (SEM). The catalytic activity towards the Oxy Steam Reforming (OSR) of biogas was assessed. The selected operating variables have a strong influence on the nature of combustion and, in turn, on the morphological and structural properties of the synthesized catalysts. Particularly, the use of urea allows to improve nickel dispersion, surface area, particle size and reducibility of the catalysts, affecting positively the biogas OSR performances. - Highlights: • Synthesis of Ni/CeO{sub 2} nanopowders by quick and easy solution combustion synthesis. • The fuel and precursor drive the structural and morphological properties of the catalysts. • The use of urea as fuel allows to improve nickel dispersion, surface area and particle size. • Ni/CeO{sub 2} (7.8 wt% of Ni loading) powders synthesized by urea route exhibits high performances for the biogas OSR process.

  19. First-principles study of the alkali earth metal atoms adsorption on graphene

    International Nuclear Information System (INIS)

    Sun, Minglei; Tang, Wencheng; Ren, Qingqiang; Wang, Sake; JinYu; Du, Yanhui; Zhang, Yajun

    2015-01-01

    Graphical abstract: - Highlights: • The adsorption of Be and Mg adatoms on graphene is physisorption. • Ca, Sr, and Ba adatoms bond ionically to graphene and the most stable adsorption site for them is hollow site. • The zero band gap semiconductor graphene becomes metallic and magnetic after the adsorption of Ca, Sr, and Ba adatoms. - Abstract: Geometries, electronic structures, and magnetic properties for alkali earth metal atoms absorbed graphene have been studied by first-principle calculations. For Be and Mg atoms, the interactions between the adatom and graphene are weak van der Waals interactions. In comparison, Ca, Sr and Ba atoms adsorption on graphene exhibits strong ionic bonding with graphene. We found that these atoms bond to graphene at the hollow site with a significant binding energy and large electron transfer. It is intriguing that these adatoms may induce important changes in both the electronic and magnetic properties of graphene. Semimetal graphene becomes metallic and magnetic due to n-type doping. Detailed analysis shows that the s orbitals of these adatoms should be responsible for the arising of the magnetic moment. We believe that our results are suitable for experimental exploration and useful for graphene-based nanoelectronic and data storage.

  20. Textural, structural and electrical properties of TiO2 nanoparticles using Brij 35 and P123 as surfactants

    Directory of Open Access Journals (Sweden)

    Dora Solís et al

    2008-01-01

    Full Text Available The effect of the use of the triblock copolymer Pluronic P123[(PEO20(PPO70(PEO20, Aldrich] and the non-ionic polyoxyethylene-lauryl ether Brij 35 as surfactants on the textural, structural and electrical properties of nanosized TiO2 is analyzed in this work. The as-obtained samples were thermally treated at 400 °C to eliminate the surfactant, promote dehydroxylation and crystallize the sample. The TiO2 samples were characterized by thermal analysis, N2 physisorption, x-ray diffraction analysis, micro-Raman spectroscopy and scanning electron microscopy. To evaluate the TiO2 electrical features, I–V data were obtained. The x-ray diffraction results show that in the chemical synthesis using surfactants, the crystallite size is smaller than that of the commercial sample. The Raman spectroscopy results clearly indicate that, when P123 is used, the anatase phase of TiO2 is obtained, whereas when Brij 35 is used a mixture of the anatase and brookite phases is obtained. The specific surface area and crystallite size of the TiO2 prepared as indicated above are higher and smaller, respectively, than the corresponding properties found in commercial TiO2. The I–V plot showed a nonlinear behavior of the nanosized TiO2. The samples obtained with P123 showed the best electrical conductivity.

  1. Electrochemical analysis of the corrosion inhibition effect of trypsin complex on the pitting corrosion of 420 martensitic stainless steel in 2M H2SO4 solution.

    Science.gov (United States)

    Loto, Roland Tolulope

    2018-01-01

    Inhibition effect of trypsin complex (TC) on the pitting corrosion of martensitic stainless steel (type 420) in 1M H2SO4 solution was studied with potentiodynamic polarization, open circuit potential measurement and optical microscopy. TC reduced the corrosion rate of the steel with maximum inhibition efficiency of 80.75%. Corrosion potential shifted anodically due to the electrochemical action of TC. The pitting potential increased from 1.088VAg/AgCl (3M) at 0% TC to 1.365VAg/AgCl(3M) at 4% TC. TC shifts the open circuit corrosion potential from -0.270s at 0% TC concentration to -0.255V at 5% TC. The compound completely adsorbed onto the steel according to Langmuir, Frumkin and Temkin isotherms. ATF-FTIR spectroscopy confirmed the inhibition mode to be through surface coverage. Thermodynamic calculations showed physisorption molecular interaction. Corrosion pits are present on the uninhibited 420 morphology in comparison to TC inhibited surface which slightly deteriorated.

  2. Photo catalytic reduction of benzophenone on TiO{sub 2}: Effect of preparation method and reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I., E-mail: mavalenz@ipn.m [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Laboratorio de Catalisis y Materiales, Zacatenco, 07738 Mexico D. F. (Mexico)

    2010-07-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO{sub 2} was synthesized by means of a hydrothermal technique. TiO{sub 2} (Degussa TiO{sub 2}-P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp ({lambda}= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO{sub 2} depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO{sub 2} was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO{sub 2} (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO{sub 2}-P25. (Author)

  3. Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Liu Jing, E-mail: liujing27@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China); Cheney, Marcos A. [Department of Natural Sciences, University of Maryland Eastern Shore, Princess Anne, MD 21853 (United States); Wu Fan; Li Meng [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2011-02-15

    A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg{sup 0}. The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg{sup 0} adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg{sup 0}, and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.

  4. Density Functional Investigation of Graphene Doped with Amine-Based Organic Molecules

    Directory of Open Access Journals (Sweden)

    Yeun Hee Hwang

    2015-01-01

    Full Text Available To improve the electronic properties of graphene, many doping techniques have been studied. Herein, we investigate the electronic and molecular structure of doped graphene using density functional theory, and we report the effects of amine-based benzene dopants adsorbed on graphene. Density functional theory (DFT calculations were performed to determine the role of amine-based aromatic compounds in graphene doping. These organic molecules bind to graphene through long-range interactions such as π-π interactions and C-H⋯π hydrogen bonding. We compared the electronic structures of pristine graphene and doped graphene to understand the electronic structure of doped graphene at the molecular level. Also, work functions of doped graphene were obtained from electrostatic potential calculations. A decrease in the work function was observed when the amine-based organic compounds were adsorbed onto graphene. Because these systems are based on physisorption, there was no obvious band structure change at point K at the Fermi level after doping. However, the amine-based organic dopants did change the absolute Fermi energy levels. In this study, we showed that the Fermi levels of the doped graphene were affected by the HOMO energy level of the dopants and by the intermolecular charge transfer between the adsorbed molecules and graphene.

  5. Improved Structural Design and CO2 Capture of Porous Hydroxy-Rich Polymeric Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Kidder, Michelle K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Earl, Lyndsey D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); de Almeida, Valmor F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-04-16

    Polymeric organic frameworks (POFs) are tunable and robust porous materials with potential applications for gas capture, catalysis, and separations technologies. A series of new porous POFs have been synthesized from the reaction of phloroglucinol or resorcinol derivatives with aryl aldehyde precursors. The monomers have various molecular shapes including linear, bent, trigonal, and tetrahedral geometries. Depending on the size and geometric matching of the monomers, the polymers are dominantly microporous with some mesoporous character or they are non-porous. In addition to standard spectroscopic and surface characterization, the materials were screened as adsorbents for carbon dioxide capture at low pressure (0-1 bar). The best performing material (POF 1D) has a CO2 capture capacity of 9.0 wt. % (2.04 mmol g-1) at 298 K and 1 bar which is comparable to other polymeric organic frameworks. Isosteric heats of adsorption for POF 1A, POF 2A, and POF 2B were found to be dependent on the weight percent of CO2 adsorbed: this suggests there are both chemisorptive and physisorptive components of CO2 capture by the POFs.

  6. Highly Efficient Adsorption of Copper Ions by a PVP-Reduced Graphene Oxide Based On a New Adsorptions Mechanism

    Institute of Scientific and Technical Information of China (English)

    Yongji Zhang; HuiJuan Chi; WenHui Zhang; Youyi Sun; Qing Liang; Yu Gu; Riya Jing

    2014-01-01

    Polyvinylpyrrolidone-reduced graphene oxide was prepared by modified hummers method and was used as adsorbent for removing Cu ions from wastewater. The effects of contact time and ions concentration on adsorption capacity were examined. The maximum adsorption capacity of 1689 mg/g was observed at an initial p H value of 3.5 after agitating for 10 min. It was demonstrated that polyvinylpyrrolidone-reduced graphene oxide had a huge adsorption capacity for Cu ions, which was 10 times higher than maximal value reported in previous works. The adsorption mechanism was also discussed by density functional theory. It demonstrates that Cu ions are attracted to surface of reduced graphene oxide by C atoms in reduced graphene oxide modified by polyvinylpyrrolidone through physisorption processes, which may be responsible for the higher adsorption capacity. Our results suggest that polyvinylpyrrolidone-reduced graphene oxide is an effective adsorbent for removing Cu ions in wastewater. It also provides a new way to improve the adsorption capacity of reduced graphene oxide for dealing with the heavy metal ion in wastewater.

  7. Functionalization of CoCr surfaces with cell adhesive peptides to promote HUVECs adhesion and proliferation

    Energy Technology Data Exchange (ETDEWEB)

    Castellanos, Maria Isabel, E-mail: maria.isabel.castellanos@upc.edu [Biomaterials, Biomechanics and Tissue Engineering Group, Department of Materials Science and Metallurgical Engineering, Technical University of Catalonia (UPC), ETSEIB, 08028 Barcelona (Spain); Centre for Research in Nanoengineering (CRNE), UPC, 08028 Barcelona (Spain); Mas-Moruno, Carlos, E-mail: carles.mas.moruno@upc.edu [Biomaterials, Biomechanics and Tissue Engineering Group, Department of Materials Science and Metallurgical Engineering, Technical University of Catalonia (UPC), ETSEIB, 08028 Barcelona (Spain); Centre for Research in Nanoengineering (CRNE), UPC, 08028 Barcelona (Spain); Grau, Anna, E-mail: agraugar@gmail.com [Biomaterials, Biomechanics and Tissue Engineering Group, Department of Materials Science and Metallurgical Engineering, Technical University of Catalonia (UPC), ETSEIB, 08028 Barcelona (Spain); Centre for Research in Nanoengineering (CRNE), UPC, 08028 Barcelona (Spain); Serra-Picamal, Xavier, E-mail: xserrapicamal@gmail.com [Institute for Bioengineering of Catalonia (IBEC), 08028 Barcelona (Spain); University of Barcelona and CIBER-BBN, 08036 Barcelona (Spain); Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona (Spain); Trepat, Xavier, E-mail: xtrepat@ub.edu [Institute for Bioengineering of Catalonia (IBEC), 08028 Barcelona (Spain); University of Barcelona and CIBER-BBN, 08036 Barcelona (Spain); Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona (Spain); Albericio, Fernando, E-mail: fernando.albericio@irbbarcelona.org [Department of Chemistry, University of Barcelona, CIBER-BBN, 08028 Barcelona (Spain); Joner, Michael, E-mail: michaeljoner@me.com [Department of Cardiology, Deutsches Herzzentrum München, 80636 Munich (Germany); CVPath Institute, Gaithersburg, MD 20878 (United States); and others

    2017-01-30

    Highlights: • We immobilized peptides on CoCr alloy through physisorption and covalent bonding. • Surface activation is an essential step prior to silanization to enhance peptide attachment. • Biofunctionalized surface characteristics were discussed. • RGDS, YIGSR and combination peptides display an improved HUVECs adhesion and proliferation. - Abstract: Biomimetic surface modification with peptides that have specific cell-binding moieties is a promising approach to improve endothelialization of metal-based stents. In this study, we functionalized CoCr surfaces with RGDS, REDV, YIGSR peptides and their combinations to promote endothelial cells (ECs) adhesion and proliferation. An extensive characterization of the functionalized surfaces was performed by XPS analysis, surface charge and quartz crystal microbalance with dissipation monitoring (QCM-D), which demonstrated the successful immobilization of the peptides to the surface. Cell studies demonstrated that the covalent functionalization of CoCr surfaces with an equimolar combination of RGDS and YIGSR represents the most powerful strategy to enhance the early stages of ECs adhesion and proliferation, indicating a positive synergistic effect between the two peptide motifs. Although these peptide sequences slightly increased smooth muscle cells (SMCs) adhesion, these values were ten times lower than those observed for ECs. The combination of RGDS with the REDV sequence did not show synergistic effects in promoting the adhesion or proliferation of ECs. The strategy presented in this study holds great potential to overcome clinical limitations of current metal stents by enhancing their capacity to support surface endothelialization.

  8. Adsorption Characteristics of DNA Nucleobases, Aromatic Amino Acids and Heterocyclic Molecules on Silicene and Germanene Monolayers

    KAUST Repository

    Hussain, Tanveer

    2017-09-14

    Binding of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules on two-dimensional silicene and germanene sheets have been investigated for the application of sensing of biomolecules using first principle density functional theory calculations. Binding energy range for nucleobases, amino acids and heterocyclic molecules with both the sheets have been found to be (0.43-1.16eV), (0.70-1.58eV) and (0.22-0.96eV) respectively, which along with the binding distances show that these molecules bind to both sheets by physisorption and chemisorption process. The exchange of electric charges between the monolayers and the incident molecules has been examined by means of Bader charge analysis. It has been observed that the introduction of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules alters the electronic properties of both silicene and germanene nano sheets as studied by plotting the total (TDOS) and partial (PDOS) density of states. The DOS plots reveal the variation in the band gaps of both silicene and germanene caused by the introduction of studied molecules. Based on the obtained results we suggest that both silicene and germanene monolayers in their pristine form could be useful for sensing of biomolecules.

  9. Synthesis and characterization of perovskite-type La1-yCayMn1-xB″xO3±δ nanomaterials (B″ = Ni, Fe; x = 0.2, 0.5; y = 0.4, 0.25)

    Science.gov (United States)

    Franke, Daniela; Trots, Dmytro; Vasylechko, Leonid; Vashook, Vladimir; Guth, Ulrich

    2018-02-01

    Perovskite-type nanomaterials of the compositions La1-yCayMn1-xB″xO3±δ with B'' = Ni, Fe; x = 0.2, 0.5 and y = 0.4, 0.25 were prepared using two different preparation routes (synthesis by precipitation and the PVA/sucrose method) at 500 °C-700 °C. The calcined products of the syntheses were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and physisorption measurements. The materials from the PVA/sucrose method contain particles with diameters from 33 nm to 48 nm, generate specific surface areas up to 33 m2/g and form pure compared to 45 nm-93 nm and up to 18 m2/g from precipitation method which contain a significant amount of sodium ions. The agglomeration process was analyzed for one nanomaterial (B'' = Fe, x = 0.2, y = 0.4) from the PVA/sucrose method using temperature dependent XRD showing only a slight growth (4.3%) of nanoparticles at 600 °C. The materials from the PVA/sucrose method turned out to be more suitable as electrode materials in electrochemical applications (SOFC, sensors) because of smaller particle sizes, higher specific surface areas and purity.

  10. Cavitation and pore blocking in nanoporous glasses.

    Science.gov (United States)

    Reichenbach, C; Kalies, G; Enke, D; Klank, D

    2011-09-06

    In gas adsorption studies, porous glasses are frequently referred to as model materials for highly disordered mesopore systems. Numerous works suggest that an accurate interpretation of physisorption isotherms requires a complete understanding of network effects upon adsorption and desorption, respectively. The present article deals with nitrogen and argon adsorption at different temperatures (77 and 87 K) performed on a series of novel nanoporous glasses (NPG) with different mean pore widths. NPG samples contain smaller mesopores and significantly higher microporosity than porous Vycor glass or controlled pore glass. Since the mean pore width of NPG can be tuned sensitively, the evolution of adsorption characteristics with respect to a broadening pore network can be investigated starting from the narrowest nanopore width. With an increasing mean pore width, a H2-type hysteresis develops gradually which finally transforms into a H1-type. In this connection, a transition from a cavitation-induced desorption toward desorption controlled by pore blocking can be observed. Furthermore, we find concrete hints for a pore size dependence of the relative pressure of cavitation in highly disordered pore systems. By comparing nitrogen and argon adsorption, a comprehensive insight into adsorption mechanisms in novel disordered materials is provided. © 2011 American Chemical Society

  11. Removal of lead(II ions from aqueous solutions using cashew nut shell liquid-templated thiol-silica materials

    Directory of Open Access Journals (Sweden)

    J. E. G. Mdoe

    2014-09-01

    Full Text Available A range of thiol-silica composites were prepared using cashew nut shell liquid (CNSL or one of its phenolic constituents, cardanol, as templates. The procedure involved formation of a CNSL or cardanol emulsion in a water-ethanol system into which (3-mercaptopropyl-trimethoxysilane and tetraethyl orthosilicate were simultaneously added at various ratios. The reaction mixture was aged at room temperature for 18 h followed by a Soxhlet extraction of the template and drying. The materials were characterized by diffuse reflectance Fourier transform infrared, nitrogen physisorption, scanning electron microscopy and acid titration. Results indicated that indeed the thiol-silica composites were successfully prepared, with thiol group loadings ranging from 1.6-2.5 mmol/g. The materials were tested for lead(II adsorption, and results showed that they had maximum adsorption capacities up to 66.7 mg/g, depending on the thiol group loading and type of template used in preparing the adsorbent. DOI: http://dx.doi.org/10.4314/bcse.v28i3.5

  12. Chlorinated paraffins wrapping of carbon nanotubes: A theoretical investigation

    Science.gov (United States)

    Ding, Qiuyue; Ding, Ning; Chen, Xiangfeng; Wu, Chi-Man Lawrence

    2018-04-01

    How nanomaterials interact with pollutants is the central for understanding their environmental behavior and practical application. In this work, molecular dynamics (MD) and density functional theoretical (DFT) methods were used to investigated the influence of carbon chain length, degree of chlorination, chain configuration, and chirality of chlorinated paraffin (CP) and diameter of single-walled carbon nanotubes (SWNTs) on the interaction between CPs and SWNTs. The simulation results demonstrated that CP chain length and chlorination degree played considerably important roles in determining interaction strength between SWNTs and CPs. The interaction energies increased with increasing chain length and chlorination degree. The chirality of SWNT exerted negligible influence on the interaction energy between SWNTs and CPs. On the contrary, interaction energy increased with increasing radius of SWNTs due to the surface curvatures. This result was rationalized by considering the decrease in SWNT curvature with increasing radius, which resulted in plane-like CNT wall. The negligible influence of CP chain configurations was attributed to relative flexibility of CP carbon chains, which can wrap on tubes through conformational changes with low-energy barriers. MD results indicated that CPs could adsorb on SWNT surface rapidly in aqueous environment. Charge transfer and electronic density results indicated that the interaction between CPs and SWNTs was physisorption in nature. This work provides fundamental information regarding SWNTs as sorbents for CPs extraction and adsorptive removal from environmental water system.

  13. Molecular self assembly of mixed comb-like dextran surfactant polymers for SPR virus detection.

    Science.gov (United States)

    Mai-Ngam, Katanchalee; Kiatpathomchai, Wansika; Arunrut, Narong; Sansatsadeekul, Jitlada

    2014-11-04

    The synthesis of two comb-like dextran surfactant polymers, that are different in their dextran molecular weight (MW) distribution and the presence of carboxylic groups, and their characterization are reported. A bimodal carboxylic dextran surfactant polymer consists of poly(vinyl amine) (PVAm) backbone with carboxyl higher MW dextran, non-functionalized lower MW dextran and hydrophobic hexyl branches; while a monomodal dextran surfactant polymer is PVAm grafted with non-functionalized lower MW dextran and hexyl branches. Layer formation of non-covalently attached dextran chains with bimodal MW distributions on a surface plasmon resonance (SPR) chip was investigated from the perspective of mixed physisorption of the bimodal and monomodal surfactant polymers. Separation distances between the carboxylic longer dextran side chains within the bimodal surfactant polymer and between the whole bimodal surfactant molecules on the chip surface could be well-controlled. SPR analysis of shrimp yellow head virus using our mixed surfactant chips showed dependence on synergetic adjustment of these separation distances. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Adsorption characteristics and polymerization of pyrrole on Y-zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Matsumoto, Akihiko; Kitajima, Tsutomu; Tsutsumi, Kazuo

    1999-10-26

    Conductive polymers have attracted considerable interest from the viewpoint of their electrochemical aspects and have been investigated for application in novel devices such as solid electrolyte cells and molecular electronic devices. Adsorption characteristics and polymerization of pyrrole on Y-zeolites of different cation types (NaY, HY, and CuY) have been investigated in connection with adsorption behavior, in situ IR spectroscopy, and EPR spectroscopy. Adsorption of pyrrole on NaY is physisorption giving no significant changes in IR and EPR spectra. In the adsorption on HY and CuY, the formation of pyrrole oligomers or polymers is observed. Pyrrole oligomer formed on HY is a nonconjugated one, which gives no EPR signal. In the case of CuY, EPR signal assigned to polaron of polypyrrole was observed at g = 2.008 by the pyrrole adsorption. The relationship between the amount of the spin of g = 2.008 and the adsorbed amount of pyrrole was linear even at the number of pyrrole exceeding that of Cu{sub 2+}, which suggests that the polymerization giving conjugated polypyrrole would take place on Cu{sup 2+} sites and the polypyrrole of aromatic form would be oxidized to quinoid form to give polaron on CuY surface.

  15. Comment on "Theoretical study of the dynamics of atomic hydrogen adsorbed on graphene multilayers"

    Science.gov (United States)

    Bonfanti, Matteo; Martinazzo, Rocco

    2018-03-01

    It is shown that the theoretical prediction of a transient magnetization in bilayer and multilayer graphene (M. Moaied et al., Phys. Rev. B 91, 155419 (2015), 10.1103/PhysRevB.91.155419) relies on an incorrect physical scenario for adsorption, namely, one in which H atoms adsorb barrierless on graphitic substrates and form a random adsorption pattern of monomers. Rather, according to experimental evidence, H atom sticking is an activated process, and adsorption is under kinetic control, largely ruled by a preferential sticking mechanism that leads to stable, nonmagnetic dimers at all but the smallest coverages (Theory and experiments are reconciled by reconsidering the hydrogen atom adsorption energetics with the help of van der Waals-inclusive density functional calculations that properly account for the basis set superposition error. It is shown that today van der Waals-density functional theory predicts a shallow physisorption well that nicely agrees with available experimental data and suggests that the hydrogen atom adsorption barrier in graphene is 180 meV high, within ˜5 meV accuracy.

  16. Comprehensive Study of the Impact of Steam on Polyethyleneimine on Silica for CO2 Capture

    Energy Technology Data Exchange (ETDEWEB)

    Hammache, Sonia; Hoffman, James S.; Gray, McMahan L.; Fauth, Daniel J.; Howard, Bret H.; Pennline, Henry W.

    2013-11-21

    An amine sorbent, prepared by impregnation of polyethyleneimine on silica, was tested for steam stability. The stability of the sorbent was investigated in a fixed bed reactor using multiple steam cycles of 90 vol % H2O/He at 105 °C, and the gas effluent was monitored with a mass spectrometer. CO2 uptake of sorbent was found to decrease with repeated exposure to steam. Characterization of the spent sorbent using N2 physisorption, SEM, and thermogravimetric analysis (TGA) showed that the decrease in CO2 loading can possibly be attributed to a reagglomeration of the amine in the pores of the silica. No support effect was found in this study. The commercial SiO2 used, Cariact G10, was found to be stable under the conditions used. While it was found that subjecting the sorbent to several steam cycles decreased its CO2 uptake, a continuous exposure of the sorbent to steam did not have a significant performance impact. Finally, a silanated sorbent, consisting of a mixture of PEI and aminopropyl-triethoxysilane on SiO2 support, was also investigated for steam stability. Similarly to the nonsilanated sorbent, the CO2 loading of this sorbent decreased upon steam exposure, although a mechanism for this change has not been postulated at this time.

  17. Poly (furfural-acetone as New Adsorbent for Removal of Cu(II from Aqueous Solution: Equilibrium Study

    Directory of Open Access Journals (Sweden)

    Tariq S. Najim

    2010-01-01

    Full Text Available The batch removal of Cu(II from aqueous solution using poly (furfural-acetone, (PFA as adsorbent was investigated in this study. The influences of initial Cu(II ion concentration (10 to 120 ppm, pH (4-8 and contact time have been reported. Adsorption of Cu(II is highly pH-dependent and the result indicate that the optimum pH for the removal was found to be 6. At this pH a small amount of PFA, 2 g/L, could remove as much as 97% of Cu(II from a solution of initial concentration 10 ppm. It was observed that an increase in initial concentration of Cu(II leads to decrease in percent removal of Cu(II and increase in amount of Cu(II adsorbed per unit mass of PFA. The adsorption process of Cu(II is tested with four isotherm models, Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D-R. It was found that all models were applicable and the maximum adsorption capacity was found to be 13.66 mg/g. From the isotherm constants it was confirmed that, the sorption process was physisorption.

  18. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Energy Technology Data Exchange (ETDEWEB)

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  19. Adsorption of Cr(III) from Aqueous Solution using Borax Sludge.

    Science.gov (United States)

    Senberber, Fatma Tugce; Yildirim, Meral; Mermer, Nevin Karamahmut; Derun, Emek Moroydor

    2017-09-01

    Borax sludge is the waste produced by a trommel sieve in the borax production process and is used as an adsorbent for Cr(III) removal. The effects of various parameters, including pH, initial Cr(III) concentration and contact time were investigated for batch adsorption of Cr(III). The experimental results obtained were applied to different adsorption isotherms and kinetic models. The results indicated that the Temkin isotherm (R2 = 0.9749) was most suitable to explain the adsorption characteristics of borax sludge, and the removal of Cr(III) was achieved by a physisorption process. The overall kinetic data fitted the pseudo-second order rate model (R2 = 0.9990). According to thermodynamic studies, which were carried out at different temperatures, changes in enthalpy (ΔH) and entropy (ΔS) values for Cr(III) adsorption by borax sludge were determined to be 69.395 kJ/mol and 0.276 kJ/mol K, respectively. The study implied that borax sludge could be used as an alternative adsorbent in the adsorption of Cr(III) from aqueous solutions.

  20. Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

    International Nuclear Information System (INIS)

    Kim, Yong Tae; Park, Eun Duck; Jung, Kwang Deog

    2010-01-01

    The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. γ-Al 2 O 3 , SiO 2 -Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 , AC, CeO 2 and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, N 2 -physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia (NH 3 - TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at 315 .deg. C among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/ZrO 2 and HSiW/SiO 2 -Al 2 O 3 showed the highest acrolein selectivity. In the case of HSiW/ZrO 2 , the initial catalytic activity was recovered after the removal of the accumulated carbon species at 550 .deg. C in the presence of oxygen

  1. Adsorption of caffeine on mesoporous activated carbon fibers prepared from pineapple plant leaves.

    Science.gov (United States)

    Beltrame, Karla K; Cazetta, André L; de Souza, Patrícia S C; Spessato, Lucas; Silva, Taís L; Almeida, Vitor C

    2018-01-01

    The present work reports the preparation of activated carbon fibers (ACFs) from pineapple plant leaves, and its application on caffeine (CFN) removal from aqueous solution. The preparation procedure was carried out using the H 3 PO 4 as activating agent and slow pyrolysis under N 2 atmosphere. The characterization of materials was performed from the N 2 adsorption and desorption isotherms, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, Boehm titration and pH pzc method. ACFs showed high BET surface area value (S BET = 1031m 2 g -1 ), well-developed mesoporous structure (mesopore volume of 1.27cm³ g -1 ) and pores with average diameter (D M ) of 5.87nm. Additionally, ACFs showed features of fibrous material with predominance of acid groups on its surface. Adsorption studies indicated that the pseudo-second order kinetic and Langmuir isotherm models were that best fitted to the experimental data. The monolayer adsorption capacity was found to be 155.50mgg -1 . thermodynamic studies revealed that adsorption process is spontaneous, exothermic and occurs preferably via physisorption. The pineapple leaves are an efficient precursor for preparation of ACFs, which were successful applied as adsorbent material for removal of caffeine from the aqueous solutions. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Removal of anionic azo dyes from aqueous solution by functional ionic liquid cross-linked polymer

    International Nuclear Information System (INIS)

    Gao, Hejun; Kan, Taotao; Zhao, Siyuan; Qian, Yixia; Cheng, Xiyuan; Wu, Wenli; Wang, Xiaodong; Zheng, Liqiang

    2013-01-01

    Highlights: • Equilibrium, kinetic and thermodynamic of adsorption of dyes onto PDVB-IL was investigated. • PDVB-IL has a high adsorption capacity to treat dyes solution. • Higher adsorption capacity is due to the functional groups of PDVB-IL. • Molecular structure of dyes influences the adsorption capacity. -- Abstract: A novel functional ionic liquid based cross-linked polymer (PDVB-IL) was synthesized from 1-aminoethyl-3-vinylimidazolium chloride and divinylbenzene for use as an adsorbent. The physicochemical properties of PDVB-IL were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The adsorptive capacity was investigated using anionic azo dyes of orange II, sunset yellow FCF, and amaranth as adsorbates. The maximum adsorption capacity could reach 925.09, 734.62, and 547.17 mg/g for orange II, sunset yellow FCF and amaranth at 25 °C, respectively, which are much better than most of the other adsorbents reported earlier. The effect of pH value was investigated in the range of 1–8. The result shows that a low pH value is found to favor the adsorption of those anionic azo dyes. The adsorption kinetics and isotherms are well fitted by a pseudo second-order model and Langmuir model, respectively. The adsorption process is found to be dominated by physisorption. The introduction of functional ionic liquid moieties into cross-linked poly(divinylbenzene) polymer constitutes a new and efficient kind of adsorbent

  3. Physicochemical modeling of reactive violet 5 dye adsorption on home-made cocoa shell and commercial activated carbons using the statistical physics theory

    Directory of Open Access Journals (Sweden)

    Lotfi Sellaoui

    Full Text Available Two equilibrium models based on statistical physics, i.e., monolayer model with single energy and multilayer model with saturation, were developed and employed to access the steric and energetic aspects in the adsorption of reactive violet 5 dye (RV-5 on cocoa shell activated carbon (AC and commercial activated carbon (CAC, at different temperatures (from 298 to 323 K. The results showed that the multilayer model with saturation was able to represent the adsorption system. This model assumes that the adsorption occurs by a formation of certain number of layers. The n values ranged from 1.10 to 2.98, indicating that the adsorbate molecules interacted in an inclined position on the adsorbent surface and aggregate in solution. The study of the total number of the formed layers (1 + L2 showed that the steric hindrance is the dominant factor. The description of the adsorbate–adsorbent interactions by calculation of the adsorption energy indicated that the process occurred by physisorption in nature, since the values were lower than 40 kJ mol−1. Keywords: RV-5 dye, Activated carbon, Modeling, Aggregation

  4. Surface coverage and corrosion inhibition effect of Rosmarinus officinalis and zinc oxide on the electrochemical performance of low carbon steel in dilute acid solutions

    Directory of Open Access Journals (Sweden)

    Roland Tolulope Loto

    2018-03-01

    Full Text Available Electrochemical analysis of the corrosion inhibition and surface protection properties of the combined admixture of Rosmarinus officinalis and zinc oxide on low carbon steel in 1 M HCl and H2SO4 solution was studied by potentiodynamic polarization, open circuit potential measurement, optical microscopy and ATR-FTIR spectroscopy. Results obtained confirmed the compound to be more effective in HCl solution, with optimal inhibition efficiencies of 93.26% in HCl and 87.7% in H2SO4 acid solutions with mixed type inhibition behavior in both acids. The compound shifts the corrosion potential values of the steel cathodically in HCl and anodically in H2SO4 signifying specific corrosion inhibition behavior without applied potential. Identified functional groups of alcohols, phenols, 1°, 2° amines, amides, carbonyls (general, esters, saturated aliphatic, carboxylic acids, ethers, aliphatic amines, alkenes, aromatics, alkyl halides and alkynes within the compound completely adsorbed onto the steel forming a protective covering. Thermodynamic calculations showed physisorption molecular interaction with the steel’s surface according to Langmuir and Frumkin adsorption isotherms. Optical microscopy images of the inhibited and uninhibited steels contrast each other with steel specimens from HCl solution showing a better morphology. Keywords: Corrosion, Inhibitor, Adsorption, Steel, Acid

  5. Effect of the Mg/Al Ratio on Activated Sol-Gel Hydrotalcites for Photocatalytic Degradation of 2,4,6-Trichlorophenol

    Directory of Open Access Journals (Sweden)

    Esthela Ramos-Ramírez

    2017-01-01

    Full Text Available Currently, interest has grown in finding effective solutions for the treatment of water pollution by toxic compounds. Some of the latter that have acquired importance are phenols and chlorophenols, due to their employment in the manufacture of pesticides, insecticides, cords of wood, paper industry, among others. The problem is rooted in that these compounds are very persistent in the environment because they are partially biodegradable and cannot be photodegraded directly by sunlight. Chlorophenols are extremely toxic, especially 2,4,6-trichlorophenol, which is potentially carcinogenic. In this work, Mg/Al-mixed oxide catalysts were obtained from the thermal treatment of hydrotalcite-type materials, synthesized by sol-gel method with different Mg/Al ratios. Hydrotalcites and Mg/Al-mixed oxides were physicochemically characterized by X-ray diffraction, thermal analysis (DTA and TGA, and N2 physisorption. The results were obtained on having proven the photocatalytic degradation of 2,4,6-trichlorophenol as a pollutant model by water. The catalysts obtained present the hydrotalcite phase with thermal evolution until achieving Mg/Al-mixed oxides at 500°C. The catalysts are of mesoporous materials and exhibiting large surface areas. The catalysts demonstrated good photocatalytic activity with good efficiency, reaching degradation percentages with Mg/Al = 1, 2, 4, 5, and 7 ratios of 94.2, 92.5, 86.2, 84.2, and 63.9%, respectively, until achieving mineralization.

  6. Charge transport properties of graphene: Effects of Cu-based gate electrode

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Qide [School of Physics and Optoelectronics, Xiangtan University, Xiangtan 411105 (China); Zhang, C. X., E-mail: zhangchunxiao@xtu.edu.cn; Tang, Chao, E-mail: tang-chao@xtu.edu.cn; Zhong, Jianxin [School of Physics and Optoelectronics, Xiangtan University, Xiangtan 411105 (China); Hunan Provincial Key Laboratory of Micro-Nano Energy Materials and Devices, Xiangtan University, Hunan 411105 (China); He, Chaoyu [Hunan Provincial Key Laboratory of Micro-Nano Energy Materials and Devices, Xiangtan University, Hunan 411105 (China)

    2016-07-21

    Using the first-principles nonequilibrium Green's function method, we study effects of Cu and Ni@Cu used as the Cu-based gate electrode on the charge transport of graphene in the field effect transistors (FET). We find that the transmission of graphene decreases with both Cu and Ni@Cu absorbed in the scatter region. Especially, noticeable transmission gaps are present around the Femi level. The transmission gaps are still effective, and considerable cut-off regions are found under the non-equilibrium environment. The Ni@Cu depresses the transmission of graphene more seriously than the Cu and enlarges the transmission gap in armchair direction. The effects on the charge transport are attributed to the redistribution of electronic states of graphene. Both Cu and Ni@Cu induce the localization of states, so as to block the electronic transport. The Ni@Cu transforms the interaction between graphene and gate electrode from the physisorption to the chemisorption, and then induces more localized states, so that the transmission decreases further. Our results suggest that besides being used to impose gate voltage, the Cu-based gate electrode itself will have a considerable effect on the charge transport of graphene and induces noticeable transmission gap in the FET.

  7. A study on hydrogen adsorption behaviors of open-tip carbon nanocones

    International Nuclear Information System (INIS)

    Liao Mingliang

    2012-01-01

    Hydrogen adsorption behaviors of single-walled open-tip (tip-truncated) carbon nanocones (CNCs) with apex angles of 19.2° at temperatures of 77 and 300 K were investigated by the molecular dynamics simulations. Four nanomaterials (including three CNCs with different dimensions and a reference CNT) were analyzed to examine the hydrogen adsorption behaviors and influences of cone sharpness on the behaviors of the CNCs. Physisorption of hydrogen molecules could be observed from the distribution pattern of the hydrogen molecules adsorbed on the nanomaterials. Because of the cone geometry effect, the open-tip CNCs could have larger storage weight percentage and less desorption of hydrogen molecules (caused by the temperature growth) on their outer surfaces, as compared with those of the reference CNT. The hydrogen molecules inside the CNCs and the reference CNT, however, were noted to have similar desorption behaviors owing to the confinement effects from the structures of the nanomaterials. In addition, the sharper CNC could have higher storage weight percentage but the cone sharpness does not have evident enhancement in the average adsorption energy of the CNC. Combination of confinement and repulsion effects existing near the tip region of the CNC would be responsible for the non-enhancement feature.

  8. Influence of Ce-precursor and fuel on structure and catalytic activity of combustion synthesized Ni/CeO2 catalysts for biogas oxidative steam reforming

    International Nuclear Information System (INIS)

    Vita, Antonio; Italiano, Cristina; Fabiano, Concetto; Laganà, Massimo; Pino, Lidia

    2015-01-01

    A series of nanosized Ni/CeO 2 catalysts were prepared by Solution Combustion Synthesis (SCS) varying the fuel (oxalyldihydrazide, urea, carbohydrazide and glycerol), the cerium precursor (cerium nitrate and cerium ammonium nitrate) and the nickel loading (ranging between 3.1 and 15.6 wt%). The obtained powders were characterized by X-ray Diffraction (XRD), N 2 -physisorption, CO-chemisorption, Temperature Programmed Reduction (H 2 -TPR) and Scanning Electron Microscopy (SEM). The catalytic activity towards the Oxy Steam Reforming (OSR) of biogas was assessed. The selected operating variables have a strong influence on the nature of combustion and, in turn, on the morphological and structural properties of the synthesized catalysts. Particularly, the use of urea allows to improve nickel dispersion, surface area, particle size and reducibility of the catalysts, affecting positively the biogas OSR performances. - Highlights: • Synthesis of Ni/CeO 2 nanopowders by quick and easy solution combustion synthesis. • The fuel and precursor drive the structural and morphological properties of the catalysts. • The use of urea as fuel allows to improve nickel dispersion, surface area and particle size. • Ni/CeO 2 (7.8 wt% of Ni loading) powders synthesized by urea route exhibits high performances for the biogas OSR process

  9. One-step rapid synthesis of ultrafine γ-Ga2O3 nanocrystals by microwave hydrothermal method in ammonium hydroxide medium

    Science.gov (United States)

    Cui, Lu; Wang, Hong; Xin, Baifu; Mao, Guijie

    2017-10-01

    Ultrafine nanocrystals of γ-gallium oxide (γ-Ga2O3) were rapidly synthesized via microwave hydrothermal method at 140 °C, in which Ga(NO3)3 was used as the gallium source and urea was the precipitant. The samples were characterized by X-ray diffraction (XRD), ultraviolet-visible absorption spectroscopy (UV-Vis), transmission electron microscopy (TEM), nitrogen physisorption and photoluminescence spectroscopy (PL). The crystallite size of ultrafine spinel γ-Ga2O3 was in the range from 4 to 5 nm and the optical bandgap was 4.61 eV. To improve the crystallinity, the ultrafine γ-Ga2O3 nanocrystals were calcined at 300-700 °C further. The ultrafine γ-Ga2O3 calcined at 500 °C (calcined-γ-Ga2O3) still remained the metastable γ-phase with relatively high crystallinity and the crystallite size around 5-7 nm. Photocatalytic performances of the synthesized samples were also evaluated by the degradation of rhodamine B (RhB). Results revealed that the ultrafine γ-Ga2O3 and the calcined-γ-Ga2O3 samples exhibited high photocatalytic efficiencies of 68.2 and 90.7%, respectively.

  10. Synthesis of Fe–Cu/TiO2 nanostructure and its use in construction of a sensitive and selective sensor for metformin determination

    International Nuclear Information System (INIS)

    Gholivand, Mohammad Bagher; Shamsipur, Mojtaba; Paimard, Giti; Feyzi, Mostafa; Jafari, Fataneh

    2014-01-01

    A carbon paste electrode modified with Fe-Cu/TiO 2 was prepared and used for low level determination of metformin (MET) using square wave adsorptive stripping voltammetry (SWAdSV). The Fe-Cu/TiO 2 nanoparticle was synthesized by a modified sol–gel method. The surface structure and composition of nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction analysis (XRD) and N 2 physisorption. Also, electrochemical properties of the prepared nanocomposite modified electrode were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques. Under optimized conditions, the modified electrode exhibited a linear response over the concentration range of 15 nM to 75 μM MET, with a detection limit of 3 nM. The proposed sensor exhibited a high sensitivity, good selectivity and was successfully applied for MET determination in real samples such as human urine and pharmaceutical formulations. - Highlights: • A carbon paste modified electrode for determination of MET was developed. • The synthesized Fe-Cu/TiO 2 nanocomposite was used as a modifier. • The sensor was successfully applied for MET determination in real samples. • Square wave adsorptive stripping voltammetric method was used for MET determination

  11. Gold nanoclusters confined in a supercage of Y zeolite for aerobic oxidation of HMF under mild conditions.

    Science.gov (United States)

    Cai, Jiaying; Ma, Hong; Zhang, Junjie; Song, Qi; Du, Zhongtian; Huang, Yizheng; Xu, Jie

    2013-10-11

    Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5-furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2 , CeO2 , and Mg(OH)2 ) and channel-type zeolites (ZSM-5 and H-MOR). Detailed characterizations, such as X-ray diffraction, transmission electron microscopy, N2 -physisorption, and H2 -temperature-programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Studies on Structural and Morphological Properties of Multidoped Ceria Ce0.8Nd0.0025Sm0.0025Gd0.005Dy0.095Y0.095O2-δ (x=0.2 as Solid Solutions

    Directory of Open Access Journals (Sweden)

    Marija Stojmenović

    2016-01-01

    Full Text Available The nanopowdery solid solutions of multidoped ceria Ce0.8Nd0.0025Sm0.0025Gd0.005Dy0.095Y0.095O2-δ (x=0.2 with the fluorite type crystal structure of CeO2 were synthesized for the first time. Two synthesis procedures were applied: the modified glycine-nitrate procedure (MGNP method and room temperature self-propagating reaction (SPRT method. All nanopowders were characterized by XRPD analysis, Raman spectroscopy, low temperature nitrogen physisorption, TEM, and SEM methods. According to the XRPD and Raman spectroscopy results, single phase solid solutions of fluorite structure were evidenced regardless of the number of dopants and synthesis procedure. Both XRPD and TEM were analyses evidenced nanometer particle dimensions. The SPRT method results in obtaining sample with higher specific surface area, smaller crystallite and particles sizes, and the same values of the lattice parameter in comparison to pure CeO2. Raman spectroscopy was confirmed to the oxygen vacancies introduced into the ceria lattice when Ce4+ ions were replaced with cations (dopants of lower valence state (3+, which may indicate the potential improvement of ionic conductivity. Additionally, the presence of oxygen vacancies in the lattice ceria, as well as very developed grain boundaries, gives a new possibility for potential application of obtained nanopowders in the area of room temperature ferromagnetism as spintronics.

  13. Electrochemical evaluation of inhibition efficiency of ciprofloxacin on the corrosion of copper in acid media

    Energy Technology Data Exchange (ETDEWEB)

    Thanapackiam, P. [Department of Chemistry, Coimbatore Institute of Technology, Coimbatore, Tamilnadu, 641 014 (India); Rameshkumar, Subramaniam [Department of Chemistry, Sri Vasavi College, Erode, Tamilnadu, 638 316 (India); Subramanian, S.S. [Department of Chemistry, PSG College of Technology, Coimbatore, Tamilnadu, 641 004 (India); Mallaiya, Kumaravel, E-mail: mkvteam.research@gmail.com [Department of Chemistry, PSG College of Technology, Coimbatore, Tamilnadu, 641 004 (India)

    2016-05-01

    The inhibition efficiency of ciprofloxacin on the corrosion of copper was studied in 1.0MHNO{sub 3} and 0.5MH{sub 2}SO{sub 4} solutions by electrochemical impedance spectroscopy and potentiodynamic polarization techniques. The corrosion inhibition action of ciprofloxacin was observed to be of mixed type in both the acid media, but with more of a cathodic nature. The experimental data were found to fit well with the Langmuir adsorption isotherm. The thermodynamic parameters such as adsorption equilibrium constant(K{sub ads}), free energy of adsorption(ΔG{sub ads}), activation energy(E{sub a}) and potential of zero charge(PZC) showed that the adsorption of ciprofloxacin onto copper surface involves both physisorption and chemisorption. - Highlights: • The inhibitor efficiency increases with increase in ciprofloxacin concentration. • Polarization measurements show that ciprofloxacin acts as a mixed type inhibitor. • The adsorption of the inhibitor on copper surface follows Langmuir adsorption isotherm. • The negative values of ΔG{sub ads} indicates that the adsorption is spontaneous and exothermic.

  14. Impact of H2/CO ratios on phase and performance of Mn-modified Fe-based Fischer Tropsch synthesis catalyst

    International Nuclear Information System (INIS)

    Ding, Mingyue; Yang, Yong; Li, Yongwang; Wang, Tiejun; Ma, Longlong; Wu, Chuangzhi

    2013-01-01

    Highlights: ► Decreasing H 2 /CO ratio facilitated the conversion of Fe 3 O 4 to iron carbides on the surface layers. ► The formation of surface carbonaceous species was promoted in higher CO partial pressure. ► The formation of iron carbides on the surface of Fe 3 O 4 provided the FTS active sites. ► Decreasing H 2 /CO ratio promoted the product shifting towards heavy hydrocarbons. - Abstract: Impacts of H 2 /CO ratios on both the bulky and surface compositions of an iron–manganese based catalyst were investigated by XRD, MES, N 2 -physisorption, XPS and LRS. Fischer–Tropsch (F–T) synthesis performances were studied in a slurry-phase continuously stirred tank reactor. The characterization results showed that the fresh catalyst was comprised of the hematite, which was converted firstly to Fe 3 O 4 , and then carburized to iron carbides in both the bulk and surface regions under different H 2 /CO ratios atmosphere. Pretreatment in lower H 2 /CO ratio facilitated the formation of iron carbides on the surface of magnetite and surface carbonaceous species. During the F–T synthesis reaction, the catalyst reduced in lower H 2 /CO ratio presented higher catalytic activity, which is assigned probably to the formation of more iron carbides (especially for χ-Fe 5 C 2 ) on the surface of magnetite. The increase of CO partial pressure promoted the product distribution shifting towards heavy hydrocarbons

  15. Thermodynamic analysis of combined Solid Oxide Electrolyzer and Fischer–Tropsch processes

    International Nuclear Information System (INIS)

    Stempien, Jan Pawel; Ni, Meng; Sun, Qiang; Chan, Siew Hwa

    2015-01-01

    In this paper a thermodynamic analysis and simple optimization of a combined Solid Oxide Electrolyzer Cell and Fisher–Tropsch Synthesis processes for sustainable hydrocarbons fuel production is reported. Comprehensive models are employed to describe effects of temperature, pressure, reactant composition and molar flux and flow on the system efficiency and final production distribution. The electrolyzer model was developed in-house and validated with experimental data of a typical Solid Oxide Electrolyzer. The Fischer–Tropsch Synthesis model employed lumped kinetics of syngas utilization, which includes inhibiting effect of water content and kinetics of Water–Gas Shift reaction. Product distribution model incorporated olefin re-adsorption and varying physisorption and solubility of hydrocarbons with their carbon number. The results were compared with those reported by Becker et al. with simplified analysis of such process. In the present study an opposite effect of operation at elevated pressure was observed. Proposed optimized system achieved overall efficiency of 66.67% and almost equal spread of light- (31%wt), mid-(36%wt) and heavy-hydrocarbons (33%wt). Paraffins contributed the majority of the yield. - Highlights: • Analysis of Solid Oxide Electrolyzer combined with Fisher Tropsch process. • Efficiency of converting water and carbon dioxide into synthetic fuels above 66%. • Effects of process temperature, pressure, gas flux and compositions were analyzed

  16. Selective removal mercury (Ⅱ) from aqueous solution using silica aerogel modified with 4-amino-5-methyl-1,2,4-triazole-3(4H)-thion

    Energy Technology Data Exchange (ETDEWEB)

    Tadayon, Fariba; Saber-Tehrani, Mohammad; Motahar, Shiva [Islamic Azad University, Tehran (Iran, Islamic Republic of)

    2013-03-15

    Silica aerogel surface modifications with chelating agents for adsorption/removal of metal ions have been reported in recent years. This investigation reported the preparation of silica aerogel (SA) adsorbent coupled with metal chelating ligands of 4-amino-5-methyl-1,2,4-triazole-3(4H)-thion (AMTT) and its application for selective adsorption of Hg(Ⅱ) ion. The adsorbent was characterized by Fourier transform infrared spectra (FTIR) and thermo gravimetric analysis (TGA) measurements, nitrogen physisorption and scanning electron microscope (SEM). Optimal experimental conditions including pH, temperature, adsorbent dosage and contact time have been established. Langmuir and Freundlich isotherm models were applied to analyze the experimental data. The best interpretation for the experimental data given by the Langmuir isotherm equation and the maximum adsorption capacity of the modified silica gel and silica aerogel was 142.85 and 17.24mgg⌃(-1), respectively. Thermodynamic parameters such as Gibbs free energy (ΔG{sup o}), standard enthalpy (ΔH{sup o}) and entropy change (ΔS{sup o}) were investigated. The adsorbed Hg(Ⅱ) on the SA-AMTT adsorbents could be completely eluted by 1.0M KBr solution and recycled at least four times without the loss of adsorption capacity. The results of the present investigation illustrate that modified silica aerogel with AMTT could be used as an adsorbent for the effective removal of Hg(Ⅱ) ions from aqueous solution.

  17. Ethanol-selective catalytic reduction of NO by Ag/Al2O3 catalysts: Activity and deactivation by alkali salts

    DEFF Research Database (Denmark)

    Schill, Leonhard; Putluru, Siva Sankar Reddy; Jacobsen, Casper Funk

    2012-01-01

    Ag/Al2O3 catalysts with and without potassium doping were prepared by incipient wetness impregnation and characterized by N2 physisorption, XRPD, NH3-TPD and SEM. The influence of the Ag content from 1 to 5 wt.% was investigated for the selective catalytic reduction (SCR) of NO with ethanol. The 3...... wt.% Ag/Al2O3 catalyst was found to be the most active and CO2 selective over a wide temperature window (300–500 ◦C). Addition of 500 ppm of H2 has a mild promotional effect on the activity while SO2 has a strong negative influence on the SCR activity. Furthermore, the Ag/Al2O3 ethanol-SCR catalyst......3 ethanol-SCR catalyst compared to the conventional NH3-SCR catalyst. The still low potassium resistance, in combination with the high sensitivity to SO2, seems not to make these catalysts a real option for biomass fired boilers....

  18. Dual pore-connectivity and flow-paths affect shale hydrocarbon production

    Science.gov (United States)

    Hu, Q.; Barber, T.; Zhang, Y.; Md Golam, K.

    2017-12-01

    Aided with integrated characterization approaches of droplet contact angle measurement, mercury intrusion capillary pressure, low-pressure gas physisorption, scanning electron microscopy, and small angle neutron scattering, we have systematically studied how pore connectivity and wettability are associated with mineral and organic matter phases of shales (Barnett, Bakken, Eagle Ford), as well as their influence on macroscopic fluid flow and hydrocarbon movement, from the following complementary tests: vacuum saturation with vacuum-pulling on dry shale followed with tracer introduction and high-pressure intrusion, tracer diffusion into fluid-saturated shale, fluid and tracer imbibition into partially-saturated shale, and Wood's metal intrusion followed with imaging and elemental mapping. The first three tests use tracer-bearing fluids (hydrophilic API brine and hydrophobic n-decane) fluids with a suite of wettability tracers of different sizes and reactivities developed in our laboratory. These innovative and integrated approaches indicate a Dalmatian wettability behavior at a scale of microns, limited connectivity (50-100 nm), which is linked to the steep initial decline and low overall recovery because of the limited connection of hydrocarbon molecules in the shale matrix to the stimulated fracture network.

  19. Characterization of nanoporous shales with gas sorption

    Science.gov (United States)

    Joewondo, N.; Prasad, M.

    2017-12-01

    The understanding of the fluid flow in porous media requires the knowledge of the pore system involved. Fluid flow in fine grained shales falls under different regime than transport regime in conventional reservoir due to the different average pore sizes in the two materials; the average pore diameter of conventional sandstones is on the micrometer scale, while of shales can be as small as several nanometers. Mercury intrusion porosimetry is normally used to characterize the pores of conventional reservoir, however with increasingly small pores, the injection pressure required to imbibe the pores becomes infinitely large due to surface tension. Characterization of pores can be expressed by a pore size distribution (PSD) plot, which reflects distribution of pore volume or surface area with respect to pore size. For the case of nanoporous materials, the surface area, which serves as the interface between the rock matrix and fluid, becomes increasingly large and important. Physisorption of gas has been extensively studied as a method of nanoporous solid characterization (particularly for the application of catalysis, metal organic frameworks, etc). The PSD is obtained by matching the experimental result to the calculated theoretical result (using Density Functional Theory (DFT), a quantum mechanics based modelling method for molecular scale interactions). We present the challenges and experimental result of Nitrogen and CO2 gas sorption on shales with various mineralogy and the interpreted PSD obtained by DFT method. Our result shows significant surface area contributed by the nanopores of shales, hence the importance of surface area measurements for the characterization of shales.

  20. Adsorption behavior of glycidoxypropyl-trimethoxy-silane on titanium alloy Ti-6.5Al-1Mo-1V-2Zr

    Energy Technology Data Exchange (ETDEWEB)

    Liu Jianhua; Zhan Zhongwei [School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Yu Mei, E-mail: yumei@buaa.edu.cn [School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Li Songmei [School of Materials Science and Engineering, Beihang University, Beijing 100191 (China)

    2013-01-01

    Highlights: Black-Right-Pointing-Pointer The adsorption isotherm of glycidoxypropyl-trimethoxy-silane (GTMS) on a titanium alloy was found fitting Temkin isotherm by XPS. Black-Right-Pointing-Pointer From an electrochemical point of view, the in situ adsorption process of GTMS molecules agreed with XPS results. Black-Right-Pointing-Pointer At 30 Degree-Sign C, the adsorption of GTMS molecules is spontaneous, and follows a chemisorption-based mechanism. - Abstract: The adsorption behavior of glycidoxypropyl-trimethoxy-silane (GTMS) on titanium alloy Ti-6.5Al-1Mo-1V-2Zr was investigated by using X-ray photoelectron spectroscopy (XPS), Tafel polarization test, and electrochemical impedance spectroscopy (EIS). From the XPS results, it was found that the silane coverage on the titanium surface generally increased with GTMS concentration, with a slight decrease at concentration of 0.1%. Based on the relationship between isoelectronic point (IEP) of titanium surface and the pH values of silane solutions, adsorption mechanisms at different concentrations were proposed. The surface coverage data of GTMS on titanium surface was also derived from electrochemical measurements. By linear fitting the coverage data, it revealed that the adsorption of GTMS on the titanium alloy surface at 30 Degree-Sign C was of a physisorption-based mechanism, and obeyed Langmuir adsorption isotherm. The adsorption equilibrium constant (K{sub ads}) and free energy of adsorption process ({Delta}G{sub ads}) were calculated to elaborate the mechanism of GTMS adsorption.

  1. Synthesis of Li2SiO3 at low temperature

    International Nuclear Information System (INIS)

    Mondragon G, G.

    2007-01-01

    The main objective of this work is to develop a new synthesis method to obtain one of the more studied ceramics in this field Li 2 SiO 3 ) in a simple and economic way using different solutions (urea and ammonium hydroxide). The particular objectives are first to prepare the Li 2 SiO 3 ceramic, by means of the use of the reaction conventional technique in solid state at temperatures between 800 and 900 C to compare it with the one proposed in this work and this way to observe the advantages that it would gives us the new method. Later on, the same one was synthesized lithium ceramic (Li 2 SiO 3 ) by means of the new method at low temperature (between 80 and 90 C), using silicic acid and lithium hydroxide like precursory reagents and different solutions (urea and ammonium hydroxide) for the optimization in their synthesis. Finally, it was carried out the characterization of these materials by means of X-ray diffraction (XRD), electronic microscopes (SEM and TEM), nitrogen physisorption (method BET) and thermal gravimetric analysis (TGA) to observe the differences that exist among the conventional method and the proposed method and by this way to determine the advantages of the last method. (Author)

  2. The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate).

    Science.gov (United States)

    Arellanes-Lozada, Paulina; Olivares-Xometl, Octavio; Guzmán-Lucero, Diego; Likhanova, Natalya V; Domínguez-Aguilar, Marco A; Lijanova, Irina V; Arce-Estrada, Elsa

    2014-08-07

    Compounds of poly(ionic liquid)s (PILs), derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium) (PImC 12 ), poly(1-vinyl-3-octylimidazolium) (PImC₈) and poly(1-vinyl-3-butylimidazolium) (PImC₄) hexafluorophosphate) were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1-1 M H₂SO₄) by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir's isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC 12 > PImC₈ > PImC₄) to reach 61% for PImC 12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs' partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.

  3. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    International Nuclear Information System (INIS)

    Al-Hamdani, Yasmine S.; Michaelides, Angelos; Alfè, Dario; Lilienfeld, O. Anatole von

    2014-01-01

    Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B 3 N 3 H 6 ) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy

  4. Hydrogenation of tetralin in the presence of dibenzothiophene and quinoline on Pt-Pd/SiO{sub 2}-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, O.Y.; Yu, Y.; Jentys, A.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center

    2012-07-01

    Three Pt-Pd catalysts with 0.3 and 0.5 wt.% of Pt and Pd, respectively, were supported on amorphous silica alumina with Al{sub 2}O{sub 3}:SiO{sub 2} wt.% ratios of 20:80, 30:70 and 55:45. The materials were characterized by physisorption of N{sub 2}, TEM, X-ray absorption spectroscopy and adsorption of pyridine and CO followed by IR spectroscopy. The EXAFS fitting and IR characterization showed that bimodal distributions of monometallic Pd and bimetallic Pt-Pd particles. The bimetallic particles in all catalysts have a Pt-rich core and a Pd-rich shell. However, the degree of alloying and proportion of exposed Pt increases with increasing concentration of Lewis acid sites (LAS) in the support, probably because the LAS are good anchoring sites for Pt species. The activity of the catalysts for the hydrogenation of tetralin in the presence of DBT and quinoline, and the corresponding selectivity to cis-decalin increase with the proportion of exposed Pt. Therefore, in the presence of DBT and quinoline the morphology of bimetallic clusters is the parameter determining its hydrogenation performance. (orig.)

  5. Thermodynamics of Methane Adsorption on Copper HKUST-1 at Low Pressure.

    Science.gov (United States)

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-07-02

    Metal-organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH4 adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH4-CH4 intermolecular interactions are minimized and the energetics solely reflects the CH4-MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH4 independent of coverage. This calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH4 adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH4-HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.

  6. Sodium alginate: A promising biopolymer for corrosion protection of API X60 high strength carbon steel in saline medium.

    Science.gov (United States)

    Obot, I B; Onyeachu, Ikenna B; Kumar, A Madhan

    2017-12-15

    Sodium alginate (SA), a polysaccharide biopolymer, has been studied as an effective inhibitor against the corrosion of API X60 steel in neutral 3.5% NaCl using gravimetric and electrochemical techniques (OCP, EIS and EFM). The inhibition efficiency of the SA increased with concentration but was lower at higher temperature (70°C). Electrochemical measurements showed that the SA shifted the steel corrosion potential to more positive value and reduced the kinetics of corrosion by forming an adsorbed layer which mitigated the steel surface wetting, based on contact angle measurement. SEM-EDAX was used to confirm the inhibition of SA on API X60 steel surfaces. The SA adsorbs on the steel surface through a physisorption mechanism using its carboxylate oxygen according to UV-vis and ATR-IR measurements, respectively. This phenomena result in decreased localized pitting corrosion of the API X60 steel in 3.5% NaCl solution. Theoretical results using quantum chemical calculations and Monte Carlo simulations provide further atomic level insights into the interaction of SA with steel surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Simple synthesis of nitrogen-rich polymer network and its further amination with PEI for CO2 adsorption

    Science.gov (United States)

    Yin, Fengqin; Zhuang, Linzhou; Luo, Xianyong; Chen, Shuixia

    2018-03-01

    The nitrogen-rich polymer network (MF/PAM) was synthesized through interpenetration between the molecular chains of melamine-formaldehyde resin(MF) and polyacrylamide (PAM), to which the polyethylene imine (PEI) was grafted to obtain solid amine adsorbent (MF/PAM-g-PEI). Compared with MF, the swelling capacity of MF/PAM was greatly enhanced, it could swell rapidly and directly in water. Although the interpenetration of PAM into MF may reduce the porosity of MF/PAM, the CO2 capture capacity of the solid amine adsorbents (MF/PAM-g-PEI) could still reach 2.8 mmol/g at 273 K. The adsorbents also exhibited promising adsorption kinetics and regeneration performances. The kinetics observation showed that the Avrami model could better descript the CO2 adsorption process compared with the pseudo-first-order model and pseudo-second-order model. Meanwhile, the Avrami kinetic orders (na) range from 1.21 to 1.56, displaying that the both physisorption and chemisorption exist in the adsorption process and the PEI have successfully grafted onto the polymer network, which also can be confirmed by the adsorption activation energy value. After 18 adsorption-desorption recycles, the MF/PAM-g-PEI could preserve its initial capacity without any decrease. Our work provides a new method to achieve promising solid amine adsorbents with higher adsorption capacity and better regeneration performance.

  8. Ozonation of Indigo Carmine Enhanced by Fe/Pimenta dioica L. Merrill Particles

    Directory of Open Access Journals (Sweden)

    Teresa Torres-Blancas

    2015-01-01

    Full Text Available Green synthesis of metallic particles has become an economic way to improve and protect the environment by decreasing the use of toxic chemicals and eliminating dyes. The synthesis of metal particles is gaining more importance due to its simplicity, rapid rate of synthesis of particles, and environmentally friendly. The present work aims to report a novel and environmentally friendly method for the synthesis of iron particles using deoiled Pimenta dioica L. Merrill husk as support. The indigo carmine removal efficiency by ozonation and catalyzed ozonation is also presented. Synthesized materials were characterized by N2 physisorption and scanning electron microscopy (SEM/EDS. By UV-Vis spectrophotometry the removal efficiency of indigo carmine was found to be nearly 100% after only 20 minutes of treatment under pH 3 and with a catalyst loading of 1000 mgL−1. Analytical techniques such as determination of the total organic carbon content (TOC and chemical oxygen demand (COD showed that iron particles supported on deoiled Pimenta dioica L. Merrill husk can be efficiently employed to degrade indigo carmine and achieved a partial mineralization (conversion to CO2 and H2O of the molecule. From the results can be inferred that the prepared biocomposite increases the hydroxyl radicals generation.

  9. Label-free peptide aptamer based impedimetric biosensor for highly sensitive detection of TNT with a ternary assembly layer.

    Science.gov (United States)

    Li, Yanyan; Zhao, Manru; Wang, Haiyan

    2017-11-01

    We report a label-free peptide aptamer based biosensor for highly sensitive detection of TNT which was designed with a ternary assembly layer consisting of anti-TNT peptide aptamer (peptamer), dithiothreitol (DTT), and 6-mercaptohexanol (MCH), forming Au/peptamer-DTT/MCH. A linear relationship between the change in electron transfer resistance and the logarithm of the TNT concentration from 0.44 to 18.92 pM, with a detection limit of 0.15 pM, was obtained. In comparison, the detection limit of the aptasensor with a common binary assembly layer (Au/peptamer/MCH) was 0.15 nM. The remarkable improvement in the detection limit could be ascribed to the crucial role of the ternary assembly layer, providing an OH-richer hydrophilic environment and a highly compact surface layer with minimal surface defects, reducing the non-covalent binding (physisorption) of the peptamer and non-specific adsorption of TNT onto the electrode surface, leading to high sensitivity, and which can serve as a general sensing platform for the fabrication of other biosensors.

  10. XPS Spectra Analysis of Ti2+, Ti3+ Ions and Dye Photodegradation Evaluation of Titania-Silica Mixed Oxide Nanoparticles

    Science.gov (United States)

    Chinh, Vu Duc; Broggi, Alessandra; Di Palma, Luca; Scarsella, Marco; Speranza, Giorgio; Vilardi, Giorgio; Thang, Pham Nam

    2018-04-01

    TiO2-SiO2 mixed oxides have been prepared by the sol-gel technique from tetrabutyl orthotitanate and tetraethyl orthosilicate. The prepared materials were characterized by x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, nitrogen physisorption, Fourier-transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS). The results indicate that the TiO2-SiO2 mixed oxides have a large surface area and a nanoscale size. FT-IR spectra show that Ti atoms are bonded to silica by oxygen bridging atoms in Ti-O-Si bonds. The titanium valence states in TiO2-SiO2 mixed oxides were investigated by XPS, and their spectra report the presence of Ti2+ and Ti3+ cations for high silica concentration, suggesting the formation of oxygen vacancies. The photocatalytic activity of the prepared materials has been evaluated for the photodegradation of methylene blue (MB). The mixed oxides were activated by means of a UV light source, and the concentration of MB was monitored by UV-Vis spectroscopy. The synthesized TiO2-SiO2 shows significantly higher MB removal efficiency in comparison with that of the commercial TiO2 Degussa, P25.

  11. Synthesis, Characterization, and Photocatalytic Activity of TiO2 Microspheres Functionalized with Porphyrin

    Directory of Open Access Journals (Sweden)

    Jin-Hua Cai

    2012-01-01

    Full Text Available In order to utilize visible light more efficiently in the photocatalytic reaction, TiO2 microspheres sensitized by 5-(4-allyloxyphenyl-10,15,20-tri(4-methylphenylporphyrin (APTMPP were prepared and characterized by X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, nitrogen physisorption, scanning electron microscopy (SEM, Fourier transform infrared spectroscopy (FT-IR and UV-vis diffuse reflectance spectroscopy, and so forth, The characterization results indicated that APTMPP-MPS-TiO2 was composed of the anatase crystal phase. The morphology of the composite materials was spheriform with size of 0.3–0.7 μm and the porphyrin was chemisorbed on the surface of TiO2 through a Si–O–Ti bond. The photooxidation of α-terpinene was employed as the model reaction to evaluate the photocatalytic activity of APTMPP-MPS-TiO2 microspheres under visible light. The results indicated that the photodegradation of α-terpinene was significantly enhanced in the presence of the APTMPP-MPS-TiO2 compared with the nonmodified TiO2 under visible light.

  12. The effect of supercritical isobutane regeneration on the nature of hydrocarbons deposited on a USY zeolite catalyst utilized for isobutane/butene alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar; Lucia M. Petkovic

    2004-11-01

    The chemical nature of hydrocarbons remaining on an ultrastable Y-zeolite (USY) utilized for liquid phase isobutane/butene alkylation reaction at 333 K and 1.1x107 Pa before and after supercritical isobutane regeneration (SFR) at 453 K and 1.1x107 Pa are presented. Catalyst samples were deactivated to different levels by running the alkylation reaction for different times on stream (TOS) and regenerated under flowing supercritical isobutane for 60 min. Nitrogen physisorption, temperature-programmed oxidation (TPO), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and ultraviolet-visible (UV-Vis) spectroscopy measurements suggested that the SFR process was effective in recovering catalyst surface area and micropore volume and that most coke precursors were removed from samples regenerated after short TOS, when the level of activity for trimethylpentanes (TMP) production was high. Samples that were allowed to react for longer TOS contained unsaturated hydrocarbons that, instead of being extracted by the supercritical fluid, dehydrogenated during the SFR process to produce more condensed species.

  13. Synthesis and characterization of α-, β-, and γ-Ga2o3 prepared from aqueous solutions by controlled precipitation

    Science.gov (United States)

    Li, Liandi; Wei, Wei; Behrens, Malte

    2012-07-01

    α, β and γ-Ga2O3 have been successfully obtained in an easily scalable synthesis using aqueous solution of gallium nitrate and sodium carbonate as starting materials without any surfactant and additive. α and β-Ga2O3 were obtained by calcination at 350 and 700 °С, respectively, of α-GaOOH, prepared by controlled precipitation at constant pH 6 and T = 55 °С, with 24 h of aging. Aging was necessary to fully convert the initially preciptated gel into a well-crystalline and phase-pure material. γ-Ga2O3 was obtained after calcination at 500 °С of gallia gel, synthesized at constant pH 4 and T = 25 °С, without aging. These three polymorphs have a for gallia relatively high surface area: 55 m2/g (α-Ga2O3), 23 m2/g (β-Ga2O3) and 116 m2/g (γ-Ga2O3). The combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), nitrogen physisorption and thermogravimetry (TG) was employed to characterize the samples and their formation.

  14. Adsorption of CO on the perovskite-type oxide LaCoO3

    International Nuclear Information System (INIS)

    Tascon, J.M.D.; Gonzalez Tejuca, L.

    1980-01-01

    In this work the adsorption of CO on LaCoO 3 between 113 and 773 K is studied. Low isosteric heats of adsorption in the temperature range 133-273 K, of 15 to 5 kJ/mol -1 point to physisorption. Between 573 and 648 K, the isosteric heat was 49 kJ/mol -1 , and the entropy values show that the adsorbed species has translational mobility in two dimensions. Adsorption of CO at 673 K and above caused reduction of the bulk. CO adsorption at 298 K gives rise to IR bands at 1495, 1450, 1175, 1110, 1070 and 850 cm -1 , attributed to bidentate carbonates. CO adsorption at 298 K on a surface with preadsorbed O 2 was found to be practically equal to the adsorption measured on a clean surface. On the contrary, preadsorbtion of CO 2 decreased the subsequent adsorption of CO to 1.2%. It is concluded that CO and CO 2 and adsorb on surface O 2- ions while oxygen adsorbs on surface metallic ions (Co 3+ or La 3+ ) of the La CoO 3 . (orig.) [de

  15. Biodiesel synthesis using K2CO3/Al–O–Si aerogel catalysts

    Directory of Open Access Journals (Sweden)

    IVANA LUKIĆ

    2010-06-01

    Full Text Available In this study, catalysts for fatty acid methyl esters (FAME or bio-diesel synthesis with K2CO3 as the active component on an alumina/silica support were synthesized using the sol–gel method, which was followed by drying the “dense” wet gels with supercritical carbon dioxide to obtain the aerogels. The prepared catalysts were characterized by XRD analysis, FTIR spectroscopy and N2 physisorption at 77 K, and tested in the methanolysis of sunflower oil. The effects of reaction variables, such as reaction time, temperature and methanol to oil molar ratio, on the yield of FAME were investigated. The aerogel catalysts with K2CO3 as the active component on an alumina/silica support exhibited good activity in the methanolysis of sunflower oil. The leaching of potassium when the catalyst was in contact with pure methanol under the working conditions of methanolysis was also tested in this study, indicating that it occurred only at higher temperatures, while at lower ones, it was negligible.

  16. Effect of Ni on the characteristics and hydrogenation activity of sulfide Mo/γ-Al2O3

    International Nuclear Information System (INIS)

    Schachtl, E.; Wuttke, E.; Gutierrez, O.Y.; Lercher, J.A.

    2012-01-01

    The hydrogenation of phenanthrene was explored on sulfide Mo/γ-Al 2 O 3 catalysts promoted with increasing concentrations of Ni. The characterization of the materials was done by N 2 -physisorption, X-ray diffraction, transmission electron microscopy, temperature programmed sulfidation and NO adsorption experiments. Increasing loading of Ni improves the dispersion of MoS 2 species; however, at Ni/(Mo+Ni) molar ratio higher than 0.5, segregation of Ni-sulfides is observed. The presence of Ni also facilitates the sulfidation of oxidic catalyst precursors by lowering the reduction temperature of Mo species. In the sulfide catalysts, Ni changes the structure of MoS 2 leading to shorter slabs with higher stacking degree than on Mo/γ-Al 2 O 3 , and increases the concentration of coordinatively unsaturated sites. The kinetic results (increased hydrogenation rate and changed reaction network in the presence of Ni) suggest that a highly active kind of active site is created by Ni promotion. (orig.)

  17. A facile route to glycated albumin detection.

    Science.gov (United States)

    Bohli, Nadra; Meilhac, Olivier; Rondeau, Philippe; Gueffrache, Syrine; Mora, Laurence; Abdelghani, Adnane

    2018-07-01

    In this paper we propose an easy way to detect the glycated form of human serum albumin which is biomarker for several diseases such as diabetes and Alzheimer. The detection platform is a label free impedimetric immunosensor, in which we used a monoclonal human serum albumin antibody as a bioreceptor and electrochemical impedance as a transducing method. The antibody was deposited onto a gold surface by simple physisorption technique. Bovine serum albumin was used as a blocking agent for non-specific binding interactions. Cyclic voltammetry and electrochemical impedance spectroscopy were used for the characterization of each layer. Human serum albumin was glycated at different levels with several concentrations of glucose ranging from 0 mM to 500 mM representing physiological, pathological (diabetic albumin) and suprapathological concentration of glucose. Through the calibration curves, we could clearly distinguish between two different areas related to physiological and pathological albumin glycation levels. The immunosensor displayed a linear range from 7.49% to 15.79% of glycated albumin to total albumin with a good sensitivity. Surface plasmon resonance imaging was also used to characterize the developed immunosensor. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. MgAl-Layered Double Hydroxide Solid Base Catalysts for Henry Reaction: A Green Protocol

    Directory of Open Access Journals (Sweden)

    Magda H. Abdellattif

    2018-03-01

    Full Text Available A series of MgAl-layered double hydroxide (MgAl-HT, the calcined form at 500 °C (MgAlOx, and the rehydrated one at 25 °C (MgAl-HT-RH were synthesized. Physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Surface area of the as-synthesized, calcined, and rehydrated catalysts was determined by N2 physisorption at −196 °C. CO2 temperature-programmed desorption (CO2-TPD was applied to determine the basic sites of catalysts. The catalytic test reaction was carried out using benzaldehyde and their derivatives with nitromethane and their derivatives. The Henry products (1–15 were obtained in a very good yield using MgAl-HT-RH catalyst either by conventional method at 90 °C in liquid phase or under microwave irradiation method. The mesoporous structure and basic nature of the rehydrated solid catalyst were responsible for its superior catalytic efficiency. The robust nature was determined by using the same catalyst five times, where the product % yield was almost unchanged significantly.

  19. Adsorption of heavy metals from aqueous solutions by Mg-Al-Zn mingled oxides adsorbent.

    Science.gov (United States)

    El-Sayed, Mona; Eshaq, Gh; ElMetwally, A E

    2016-10-01

    In our study, Mg-Al-Zn mingled oxides were prepared by the co-precipitation method. The structure, composition, morphology and thermal stability of the synthesized Mg-Al-Zn mingled oxides were analyzed by powder X-ray diffraction, Fourier transform infrared spectrometry, N 2 physisorption, scanning electron microscopy, differential scanning calorimetry and thermogravimetry. Batch experiments were performed to study the adsorption behavior of cobalt(II) and nickel(II) as a function of pH, contact time, initial metal ion concentration, and adsorbent dose. The maximum adsorption capacity of Mg-Al-Zn mingled oxides for cobalt and nickel metal ions was 116.7 mg g -1 , and 70.4 mg g -1 , respectively. The experimental data were analyzed using pseudo-first- and pseudo-second-order kinetic models in linear and nonlinear regression analysis. The kinetic studies showed that the adsorption process could be described by the pseudo-second-order kinetic model. Experimental equilibrium data were well represented by Langmuir and Freundlich isotherm models. Also, the maximum monolayer capacity, q max , obtained was 113.8 mg g -1 , and 79.4 mg g -1 for Co(II), and Ni(II), respectively. Our results showed that Mg-Al-Zn mingled oxides can be used as an efficient adsorbent material for removal of heavy metals from industrial wastewater samples.

  20. Development of chemically engineered porous metal oxides for phosphate removal

    International Nuclear Information System (INIS)

    Delaney, Paul; McManamon, Colm; Hanrahan, John P.; Copley, Mark P.; Holmes, Justin D.; Morris, Michael A.

    2011-01-01

    In this study, the application of ordered mesoporous silica (OMS) doped with various metal oxides (Zr, Ti, Fe and Al) were studied for the removal of (ortho) phosphate ions from water by adsorption. The materials were characterized by means of N 2 physisorption (BET), powder X-ray diffraction (PXRD) and transmission electron microscopy (TEM). The doped materials had surface areas between 600 and 700 m 2 g -1 and exhibited pore sizes of 44-64 A. Phosphate adsorption was determined by measurement of the aqueous concentration of orthophosphate using ultraviolet-visible (UV-vis) spectroscopy before and after extraction. The effects of different metal oxide loading ratios, initial concentration of phosphate solution, temperature and pH effects on the efficiency of phosphate removal were investigated. The doped mesoporous materials were effective adsorbents of orthophosphate and up to 100% removal was observed under appropriate conditions. 'Back extracting' the phosphate from the doped silica (following water treatment) was also investigated and shown to have little adverse effect on the adsorbent.

  1. Ca-Embedded C2N: an efficient adsorbent for CO2 capture.

    Science.gov (United States)

    Liu, Yuzhen; Meng, Zhaoshun; Guo, Xiaojian; Xu, Genjian; Rao, Dewei; Wang, Yuhui; Deng, Kaiming; Lu, Ruifeng

    2017-10-25

    Carbon dioxide as a greenhouse gas causes severe impacts on the environment, whereas it is also a necessary chemical feedstock that can be converted into carbon-based fuels via electrochemical reduction. To efficiently and reversibly capture CO 2 , it is important to find novel materials for a good balance between adsorption and desorption. In this study, we performed first-principles calculations and grand canonical Monte Carlo (GCMC) simulations, to systematically study metal-embedded carbon nitride (C 2 N) nanosheets for CO 2 capture. Our first-principles results indicated that Ca atoms can be uniformly trapped in the cavity center of C 2 N structure, while the transition metals (Sc, Ti, V, Cr, Mn, Fe, Co) are favorably embedded in the sites off the center of the cavity. The determined maximum number of CO 2 molecules with strong physisorption showed that Ca-embedded C 2 N monolayer is the most promising CO 2 adsorbent among all considered metal-embedded materials. Moreover, GCMC simulations revealed that at room temperature the gravimetric density for CO 2 adsorbed on Ca-embedded C 2 N reached 50 wt% at 30 bar and 23 wt% at 1 bar, higher than other layered materials, thus providing a satisfactory system for the CO 2 capture and utilization.

  2. Absorption of CO2 on Carbon-based Sensors: First-Principle Analysis

    Science.gov (United States)

    Tit, Nacir; Elezzi, Mohammed; Abdullah, Hasan; Bahlouli, Hocine; Yamani, Zain

    We present first-principle investigation of the adsorption properties of CO and CO2 molecules on both graphene and carbon nano-tubes (CNTs) in presence of metal catalysis, mainly iron (Fe). The relaxations were carried out using the self-consistent-charge density-functional tight-binding (SCC-DFTB) code in neglect of heat effects. The results show the following: (1) Defected graphene is found to have high sensitivity and high selectivity towards chemisorption of CO molecules and weak physisorption with CO2 molecules. (2) In case of CNTs, the iron ``Fe'' catalyst plays an essential role in capturing CO2 molecules. The Fe ad-atoms on the surface of CNT introduce huge density of states at Fermi level, but the capture of CO2 molecules would reduce that density and consequently reduce conductivity and increase sensitivity. Concerning the selectivity, we have studied the sensitivity versus various gas molecules (such as: O2, N2, H2, H2O, and CO). Furthermore, to assess the effect of catalysis on sensitivity, we have studied the sensitivity of other metal catalysts (such as: Ni, Co, Ti, and Sc). We found that CNT-Fe is highly sensitive and selective towards detection of CO and CO2 molecules. CNT being conductive or semiconducting does not matter much on the adsorption properties.

  3. Catalytic Activity Studies of Vanadia/Silica–Titania Catalysts in SVOC Partial Oxidation to Formaldehyde: Focus on the Catalyst Composition

    Directory of Open Access Journals (Sweden)

    Niina Koivikko

    2018-02-01

    Full Text Available In this work, silica–titania supported catalysts were prepared by a sol–gel method with various compositions. Vanadia was impregnated on SiO2-TiO2 with different loadings, and materials were investigated in the partial oxidation of methanol and methyl mercaptan to formaldehyde. The materials were characterized by using N2 physisorption, X-ray diffraction (XRD, X-ray fluorescence spectroscopy (XRF, X-ray photoelectron spectroscopy (XPS, Scanning transmission electron microscope (STEM, NH3-TPD, and Raman techniques. The activity results show the high importance of an optimized SiO2-TiO2 ratio to reach a high reactant conversion and formaldehyde yield. The characteristics of mixed oxides ensure a better dispersion of the active phase on the support and in this way increase the activity of the catalysts. The addition of vanadium pentoxide on the support lowered the optimal temperature of the reaction significantly. Increasing the vanadia loading from 1.5% to 2.5% did not result in higher formaldehyde concentration. Over the 1.5%V2O5/SiO2 + 30%TiO2 catalyst, the optimal selectivity was reached at 415 °C when the maximum formaldehyde concentration was ~1000 ppm.

  4. Theoretical maximal storage of hydrogen in zeolitic frameworks.

    Science.gov (United States)

    Vitillo, Jenny G; Ricchiardi, Gabriele; Spoto, Giuseppe; Zecchina, Adriano

    2005-12-07

    Physisorption and encapsulation of molecular hydrogen in tailored microporous materials are two of the options for hydrogen storage. Among these materials, zeolites have been widely investigated. In these materials, the attained storage capacities vary widely with structure and composition, leading to the expectation that materials with improved binding sites, together with lighter frameworks, may represent efficient storage materials. In this work, we address the problem of the determination of the maximum amount of molecular hydrogen which could, in principle, be stored in a given zeolitic framework, as limited by the size, structure and flexibility of its pore system. To this end, the progressive filling with H2 of 12 purely siliceous models of common zeolite frameworks has been simulated by means of classical molecular mechanics. By monitoring the variation of cell parameters upon progressive filling of the pores, conclusions are drawn regarding the maximum storage capacity of each framework and, more generally, on framework flexibility. The flexible non-pentasils RHO, FAU, KFI, LTA and CHA display the highest maximal capacities, ranging between 2.86-2.65 mass%, well below the targets set for automotive applications but still in an interesting range. The predicted maximal storage capacities correlate well with experimental results obtained at low temperature. The technique is easily extendable to any other microporous structure, and it can provide a method for the screening of hypothetical new materials for hydrogen storage applications.

  5. First-principles study of pollutant molecules absorbed on polymeric adsorbents using the vdW-DF2 functional

    Science.gov (United States)

    Zhu, Jinguo; Wang, Yapeng; Tian, Ting; Zhang, Qianfan

    2018-03-01

    Polymeric adsorbents have been attracting increasing attention because of their favorable structrual properties and effectiveness of solving small molecules contaminants. However, due to the absence of deep insight into the adsorption mechanism of polymeric adsorbents, researches on new polymeric adsorbents can only be carried out by repeated experiments and tests, which is extremely inefficient. Therefore, investigating the adsorption process of polymeric adsorbents, especially the mechanism of adsorbing various air pollutant molecules by materials modelling and simulation, is of great significance. Here in this work, we systematically studied the adsorption mechanism by first-principles computation with van der Waals interaction. It demonstrates that the adsorption between them was pure physisorption originating from the hydrogen bond and intermolecular forces consisting of Keesom force, Debye force and London dispersion force. The proportions of these forces varied according to different adsorption systems. The adsorption effects were determined by the polymers’ dipole moment and polarizability. The adsorption performance of some polymers with special structures was also investigated to explore their possibility as potential adsorbents. The results of our simulation can provide some guidance for developing new polymeric adsorbents with better performance.

  6. Functionalization of PDMS modified and plasma activated two-component polyurethane coatings by surface attachment of enzymes

    Energy Technology Data Exchange (ETDEWEB)

    Kreider, Alexej; Richter, Katharina; Sell, Stephan; Fenske, Mandus; Tornow, Christian; Stenzel, Volkmar [Fraunhofer Institute for Manufacturing Technology and Advanced Materials - IFAM, Wiener Strasse 12, 28359 Bremen (Germany); Grunwald, Ingo, E-mail: ingo.grunwald@ifam.fraunhofer.de [Fraunhofer Institute for Manufacturing Technology and Advanced Materials - IFAM, Wiener Strasse 12, 28359 Bremen (Germany)

    2013-05-15

    This article describes a new strategy for coupling the enzyme horseradish peroxidase to a two-component polyurethane (2C-PUR) coating. A stable polymer conjugate was achieved by combining the enzyme and the 2C-PUR coating which was modified with poly(dimethylsiloxane) (PDMS), located at the surface. An atmospheric pressure plasma jet system was used to convert alkyl groups from the PDMS into polar silanol functionalities. This conversion was proven by X-ray photoelectron spectroscopy and dynamic contact angle measurements. In addition, the stability of the activated 2C-PUR surface containing silanol groups was determined by measuring the contact angle as a function of time. Compared to the non-modified 2C-PUR systems the one with PDMS displayed a higher stability over a time period over 28 h. In a silanization process the coating was treated with (3-aminopropyl) trimethoxysilane and the enzyme was subsequently immobilized to the coating via the cross linker glutaraldehyde to receive new biomimetic catalytic/enzymatic functions. The chemical immobilization (chemisorption) of the enzyme to the surface showed statistically significant higher biological activity as compared to references samples without using a cross linker (physisorption). The presented technique offers the opportunity to design new and smart multifunctional surface coatings which employ biomimetic capabilities.

  7. A theoretical study of structural and electronic properties of pentacene/Al(100) interface.

    Science.gov (United States)

    Saranya, G; Nair, Shiny; Natarajan, V; Kolandaivel, P; Senthilkumar, K

    2012-09-01

    The first principle calculations within the framework of density functional theory have been performed for the pentacene molecule deposited on the aluminum Al(100) substrate to study the structural and electronic properties of the pentacene/Al(100) interface. The most stable configuration was found at bridge site with 45° rotation of the pentacene molecule on Al(100) surface with a vertical distance of 3.4 Å within LDA and 3.8 Å within GGA functionals. The calculated adsorption energy reveals that the adsorption of pentacene molecule on Al(100) surface is physisorption. For the stable adsorption geometry the electronic properties such as density of states (DOS), partial density of states (PDOS), Mulliken population analysis and Schottky barrier height are studied. The analysis of atomic charge, DOS and PDOS show that the charge is transferred from the Al(100) surface to pentacene molecule, and the transferred charge is about -0.05 electrons. For the adsorbed system, the calculated Schottky barrier height for hole and electron transport is 0.27 and 1.55 eV, respectively. Copyright © 2012 Elsevier Inc. All rights reserved.

  8. Noble metal (Pt or Au)-doped monolayer MoS2 as a promising adsorbent and gas-sensing material to SO2, SOF2 and SO2F2: a DFT study

    Science.gov (United States)

    Chen, Dachang; Zhang, Xiaoxing; Tang, Ju; Cui, Hao; Li, Yi

    2018-02-01

    We explored the adsorption of SO2, SOF2, and SO2F2 on Pt- or Au-doped MoS2 monolayer based on density functional theory. The adsorption energy, adsorption distance, charge transfer as well as density of states were discussed. SO2 and SOF2 exhibit strong chemical interactions with Pt-doped MoS2 based on large adsorption energy, charge transfer, and changes of electron orbitals in gas molecule. SO2 also shows obvious chemisorption on Au-doped MoS2 with apparent magnetism transfer from Au to gas molecules. The adsorption of SO2F2 on Pt-MoS2 and SOF2 on Au-MoS2 exhibits weaker chemical interactions and SO2F2 losses electrons when adsorbed on Pt-MoS2 which is different from other gas adsorption. The adsorption of SO2F2 on Au-MoS2 represents no obvious chemical interaction but physisorption. The gas-sensing properties are also evaluated based on DFT results. This work could provide prospects and application value for typical noble metal-doped MoS2 as gas-sensing materials.

  9. Core Level Spectra of Organic Molecules Adsorbed on Graphene

    Directory of Open Access Journals (Sweden)

    Abhilash Ravikumar

    2018-03-01

    Full Text Available We perform first principle calculations based on density functional theory to investigate the effect of the adsorption of core-excited organic molecules on graphene. We simulate Near Edge X-ray absorption Fine Structure (NEXAFS and X-ray Photoemission Spectroscopy (XPS at the N and C edges for two moieties: pyridine and the pyridine radical on graphene, which exemplify two different adsorption characters. The modifications of molecular and graphene energy levels due to their interplay with the core-level excitation are discussed. We find that upon physisorption of pyridine, the binding energies of graphene close to the adsorption site reduce mildly, and the NEXAFS spectra of the molecule and graphene resemble those of gas phase pyridine and pristine graphene, respectively. However, the chemisorption of the pyridine radical is found to significantly alter these core excited spectra. The C 1s binding energy of the C atom of graphene participating in chemisorption increases by ∼1 eV, and the C atoms of graphene alternate to the adsorption site show a reduction in the binding energy. Analogously, these C atoms also show strong modifications in the NEXAFS spectra. The NEXAFS spectrum of the chemisorbed molecule is also modified as a result of hybridization with and screening by graphene. We eventually explore the electronic properties and magnetism of the system as a core-level excitation is adiabatically switched on.

  10. Controlled drug release on amine functionalized spherical MCM-41

    Energy Technology Data Exchange (ETDEWEB)

    Szegedi, Agnes, E-mail: szegedi@chemres.hu [Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, 1025 Budapest, Pusztaszeri ut 59-67 (Hungary); Popova, Margarita; Goshev, Ivan [Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia (Bulgaria); Klebert, Szilvia [Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, 1025 Budapest, Pusztaszeri ut 59-67 (Hungary); Mihaly, Judit [Institute of Molecular Pharmacology, Research Centre for Natural Sciences, Hungarian Academy of Sciences, 1025 Budapest, Pusztaszeri ut 59-67 (Hungary)

    2012-10-15

    MCM-41 silica with spherical morphology and small particle sizes (100 nm) was synthesized and modified by post-synthesis method with different amounts of 3-aminopropyltriethoxysilane (APTES). A comparative study of the adsorption and release of a model drug, ibuprofen, was carried out. The modified and drug loaded mesoporous materials were characterized by XRD, TEM, N{sub 2} physisorption, elemental analysis, thermal analysis and FT-IR spectroscopy. A new method was developed for the quantitative determination of amino groups in surface modified mesoporous materials by the ninhydrin reaction. Good correlation was found between the amino content of the MCM-41 materials determined by the ninhydrin method and their ibuprofen adsorption capacity. Amino modification resulted in high degree of ibuprofen loading and slow release rate in comparison to the parent non-modified MCM-41. - Graphical abstract: Determination of surface amino groups by ninhidrin method. Highlights: Black-Right-Pointing-Pointer Spherical MCM-41 modified by different amounts of APTES was studied. Black-Right-Pointing-Pointer Ibuprofen (IBU) adsorption and release characteristics was tested. Black-Right-Pointing-Pointer The ninhydrin reaction was used for the quantitative determination of amino groups. Black-Right-Pointing-Pointer Stoichiometric amount of APTES is enough for totally covering the surface with amino groups. Black-Right-Pointing-Pointer Good correlation was found between the amino content and IBU adsorption capacity.

  11. Hydrogen adsorption on metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs)

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, E.; Chahine, R.; Benard, P.; Lafi, L.; Dorval-Douville, G.; Chandonia, P.-A. [Univ. du Quebec a Trois-Rivieres, Inst. de recherche sur l' hydrogene, Trois-Rivieres, Quebec (Canada)]. E-mail: Lyubov.Lafi@uqtr.ca

    2006-07-01

    'Full text:' In recent years, several novel carbon-based microporous materials such as single-walled carbon nanotubes (SWNTs) and metal-organic frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. Hydrogen adsorption measurements on Al-, Cr- and Zn-based metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs) are presented. The measurements were performed at temperatures ranging from 77 to 300K and pressures up to 50 atm using a volumetric approach. The maximum excess adsorption at 77K ranges from 2,8 to 3,9 wt % for the MOFs and from 1,5 to 2,5 wt % for the SWNTs. These values are reached at pressures below 40 atm. At room temperature and 40 atm, modest amounts of hydrogen are adsorbed (< 0,4 wt %). A Dubinin-Astakhov (DA) approach is used to investigate the measured adsorption isotherms and retrieve energetic and structural parameters. The adsorption enthalpy averaged over filling is found to be about 2,9 kJ/mol for the MOF-5 and about 3,6 - 4,2 kJ/mol for SWNTs. The uptake of hydrogen on SWNTs and MOF-5 appears to be due to physisorption and can be described, through the DA-model, by a traditional theory of micropore filling. (author)

  12. Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling

    International Nuclear Information System (INIS)

    Poirier, Eric; Dailly, Anne

    2009-01-01

    Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn 4 O(1,3,5-benzenetribenzoate) 2 , MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g -1 . An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid. These liquid state properties observed under supercritical conditions reveal a remarkable effect of nanoscale confinement. The entire set of adsorption isotherms can be well described using a micropore filling model. The latter is used, in particular, to determine the absolute amounts adsorbed and the adsorption enthalpy. When expressed in terms of absolute adsorption, the isotherms show considerable hydrogen storage capacities, reaching up to 125 mg g -1 at 50 K and 25 bar. The adsorption enthalpies are calculated as a function of fractional filling and range from 3 to 5 kJ mol -1 in magnitude, in accordance with physisorption. These results are discussed with respect to a similar analysis performed on another Zn-based MOF, Zn 4 O(1,4-benzenedicarboxylate) 3 , IRMOF-1, presented recently. It is found that both materials adsorb hydrogen by similar mechanisms.

  13. Direct measurement of the adsorption kinetics of 2-Mercaptobenzothiazole on a microcrystalline copper surface

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez-Cano, J. A.; Veleva, L.

    2016-05-01

    The adsorption on copper of 2-Mercaptobenzothiazole (2-MBT), a heterocyclic compound member of the tiazole family, has been investigated at different concentrations (1x10{sup -}1 to 1x10{sup -}6 M) in water, employing the Electrochemical Quartz Crystal Microbalance (EQCM). The frequency response over time was obtained for each concentration, showing a defined exponential behavior at higher concentrations (1x10{sup -}1, 1x10{sup -}2 and 1x10{sup -}3 M), which was filed to the Langmuir adsorption isotherm with a good correlation coefficients (R{sup 2}=0.91 to 0.98) Surface coverage (θ) was calculated and found to be in the order of 0.50 to 0.01 for 2-MBT high concentrations. The free energy of adsorption was ΔG{sub a}ds=-5.59 kJ mol{sup -}1, corresponding to physisorption process, probably of electrostatic nature of the interaction between 2-MBT and copper surface in aqueous solution. (Author)

  14. Comparative Study on The Photocatalytic Hydrogen Production from Methanol over Cu-, Pd-, Co- and Au-Loaded TiO2

    Directory of Open Access Journals (Sweden)

    Udani P.P.C.

    2015-09-01

    Full Text Available Photocatalytic hydrogen production from a methanol-water solution was investigated in a semi-continuous reactor over different metal-loaded TiO2 catalysts under UltraViolet (UV light irradiation. The catalysts were mainly prepared by the incipient wetness impregnation method by varying the metal weight ratio in the range of 1-10 wt%. The effects of metal loading and H2 pre-treatment on the photocatalytic activity were investigated. In addition, the activity of the catalysts was also compared with a reference Au-TiO2 catalyst from the World Gold Council (WGC. The photocatalysts were characterized by using X-Ray Diffraction (XRD and N2 physisorption before and after the activity measurements. The photocatalytic activity decreased in the order of Pd > Au > Cu > Co in the comparative study of Cu-TiO2, Co-TiO2, Au-TiO2 and Pd-TiO2. Optimum hydrogen evolution was achieved with 5 wt% Pd-TiO2 and 5 wt% Cu-TiO2.

  15. Kinetics, Equilibrium, and Thermodynamic Studies on Adsorption of Methylene Blue by Carbonized Plant Leaf Powder

    Directory of Open Access Journals (Sweden)

    V. Gunasekar

    2013-01-01

    Full Text Available Carbon synthesized from plant leaf powder was employed for the adsorption of methylene blue from aqueous effluent. Effects of pH (2, 4, 6, 8, and 9, dye concentration (50, 100, 150, and 200 mg/dm3, adsorbent dosage (0.5, 1.0, 1.5, and 2.0 g/dm3, and temperature (303, 313, and 323 K were studied. The process followed pseudo-second-order kinetics. Equilibrium data was examined with Langmuir and Freundlich isotherm models and Langmuir model was found to be the best fitting model with high R2 and low chi2 values. Langmuir monolayer adsorption capacity of the adsorbent was found to be 61.22 mg/g. From the thermodynamic analysis, ΔH, ΔG, and ΔS values for the adsorption of MB onto the plant leaf carbon were found out. From the values of free energy change, the process was found out to be feasible process. From the magnitude of ΔH, the process was found to be endothermic physisorption.

  16. Systematic Investigation of Controlled Nanostructuring of Mn 12 Single-Molecule Magnets Templated by Metal–Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Aulakh, Darpandeep [Department of Chemistry; amp, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States; Xie, Haomiao [Department of Chemistry, Texas A& amp,M University, College Station, Texas 77845, United States; Shen, Zhe [Department of Chemistry, Texas A& amp,M University, College Station, Texas 77845, United States; Harley, Alexander [Department of Chemistry; amp, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States; Zhang, Xuan [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Yakovenko, Andrey A. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States; Dunbar, Kim R. [Department of Chemistry, Texas A& amp,M University, College Station, Texas 77845, United States; Wriedt, Mario [Department of Chemistry; amp, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States

    2017-05-25

    This is the first systematic study exploring metal–organic frameworks (MOFs) as platforms for the controlled nanostructuring of molecular magnets. We report the incorporation of seven single-molecule magnets (SMMs) of general composition [Mn12O12(O2CR)16(OH2)4], with R = CF3 (1), (CH3)CCH2 (2), CH2Cl (3), CH2Br (4), CHCl2 (5), CH2But (6), and C6H5 (7), into the hexagonal channel pores of a mesoporous MOF host. The resulting nanostructured composites combine the key SMM properties with the functional properties of the MOF. Synchrotron-based powder diffraction with difference envelope density analysis, physisorption analysis (surface area and pore size distribution), and thermal analyses reveal that the well-ordered hexagonal structure of the host framework is preserved, and magnetic measurements indicate that slow relaxation of the magnetization, characteristic of the corresponding Mn12 derivative guests, occurs inside the MOF pores. Structural host–guest correlations including the bulkiness and polarity of peripheral SMM ligands are discussed as fundamental parameters influencing the global SMM@MOF loading capacities. These results demonstrate that employing MOFs as platforms for the nanostructuration of SMMs is not limited to a particular host–guest system but potentially applicable to a multitude of other molecular magnets. Such fundamental findings will assist in paving the way for the development of novel advanced spintronic devices.

  17. Ice XVII as a Novel Material for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Leonardo del Rosso

    2017-02-01

    Full Text Available Hydrogen storage is one of the most addressed issues in the green-economy field. The latest-discovered form of ice (XVII, obtained by application of an annealing treatment to a H 2 -filled ice sample in the C 0 -phase, could be inserted in the energy-storage context due to its surprising capacity of hydrogen physisorption, when exposed to even modest pressure (few mbars at temperature below 40 K, and desorption, when a thermal treatment is applied. In this work, we investigate quantitatively the adsorption properties of this simple material by means of spectroscopic and volumetric data, deriving its gravimetric and volumetric capacities as a function of the thermodynamic parameters, and calculating the usable capacity in isothermal conditions. The comparison of ice XVII with materials with a similar mechanism of hydrogen adsorption like metal-organic frameworks shows interesting performances of ice XVII in terms of hydrogen content, operating temperature and kinetics of adsorption-desorption. Any application of this material to realistic hydrogen tanks should take into account the thermodynamic limit of metastability of ice XVII, i.e., temperatures below about 130 K.

  18. Synthesis and characterization of SnO2, TiO2 and Ti0.5Sn0.5O2 nanoparticles as efficient materials for photocatalytic activity

    Science.gov (United States)

    Bargougui, R.; Pichavant, A.; Hochepied, J.-F.; Berger, M.-H.; Gadri, A.; Ammar, S.

    2016-08-01

    This work reports the synthesis of polydispersible SnO2, TiO2 and Ti0.5Sn0.5O2 nanoparticles via microwave-assisted polyol as an efficient method using diethylene glycol (DEG) and triethylene glycol (TREG) as solvent. The properties of as-prepared samples were investigated by X-ray diffractometry, transmission electron microscopy, diffuse reflectance and FTIR spectrophotometery, photoluminescence spectroscopy and N2 physisorption. The X-ray diffraction patterns of the samples were indexed on the anatase phase of TiO2 and cassiterite phase of SnO2 and Ti0.5Sn0.5O2. The TEM images show uniform isotropic morphologies with average sizes close to10 nm. The band gap is reduced for Ti0.5Sn0.5O2 and enhances visible light absorption, a shift resulting in the absorption threshold towards the visible spectral range, compared to pure titania and tin. Slight shifts to longer wavelength are attributed to the change in the acceptor's level induced by the mixture of both oxides. The evaluation of the photocatalytic activity is carried out using indigo carmine (IC) as model of chemical pollutants in UV irradiation conditions. The photocatalytic decolorization of the dye follows a pseudo-first-order kinetics and the constant apparent rate was increased with the increase of the tin oxide content up to 50%.

  19. First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

    Science.gov (United States)

    Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

    2018-06-01

    Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

  20. A first-principles study on adsorption behaviors of pristine and Li-decorated graphene sheets toward hydrazine molecules

    Science.gov (United States)

    Zeng, Huadong; Cheng, Xinlu; Wang, Wei

    2018-03-01

    The adsorption behaviors and properties of hydrazine (N2H4) molecules on pristine and Li-decorated graphene sheets were investigated by means of first-principles based on density functional theory. We systematically analyzed the optimal geometry, average binding energy, charge transfer, charge density difference and density of states of N2H4 molecules adsorbed on pristine and Li-decorated graphene sheets. It is found that the interaction between single N2H4 molecule and pristine graphene is weak physisorption with the low binding energy of -0.026 eV, suggesting that the pristine graphene sheet is insensitive to the presence of N2H4 molecule. However, it is markedly enhanced after lithium decoration with the high binding energy of -1.004 eV, verifying that the Li-decorated graphene sheet is significantly sensitive to detect N2H4 molecule. Meanwhile, the effects of the concentrations of N2H4 molecules on two different substrates were studied detailedly. For pristine graphene substrate, the average binding energy augments apparently with increasing the number of N2H4 molecules, which is mainly attributed to the van der Waals interactions and hydrogen bonds among N2H4 clusters. Li-decorated graphene sheet has still a strong affinity to N2H4 molecules despite the corresponding average binding energy emerges a contrary tendency. Overall, Li-decorated graphene sheet could be considered as a potential gas sensor in field of hydrazine molecules.

  1. Characterization of physicochemical properties of Pd/TiO{sub 2} nanostructured catalysts prepared by the photodeposition method

    Energy Technology Data Exchange (ETDEWEB)

    Camposeco, R. [Molecular Engineering Program, Instituto Mexicano del Petróleo, 07730 México, D.F. (Mexico); Department of Chemistry, UAM-A, 55534 México, D.F. (Mexico); Castillo, S., E-mail: scastill@imp.mx [Molecular Engineering Program, Instituto Mexicano del Petróleo, 07730 México, D.F. (Mexico); Department of Chemical Engineering, ESIQIE-IPN, 75876 México, D.F. (Mexico); Mejía-Centeno, Isidro; Navarrete, J.; Marín, J. [Molecular Engineering Program, Instituto Mexicano del Petróleo, 07730 México, D.F. (Mexico)

    2014-09-15

    In this work, the sol–gel and hydrothermal methods were used to synthesize TiO{sub 2}-nanostructured supports. The palladium supported on sol–gel TiO{sub 2} and on hydrothermal-method-TiO{sub 2} nanotubes was obtained by incorporating it through photodeposition. The characterization was performed by X-ray diffraction, transmission electron microscopy, N{sub 2} physisorption, pulse chemisorption, ultraviolet–visible absorption spectroscopy and X-ray photoelectron spectroscopy. Both sol–gel-palladium–TiO{sub 2} and palladium-nanotube samples showed different palladium dispersion and physicochemical properties. In the palladium-nanotube sample, high surface area (243 m{sup 2}/g), H{sub 2}Ti{sub 3}O{sub 7} stable phase, and low band gap energy (2.35 eV) were obtained. Palladium-nanotubes and palladium-TiO{sub 2}, used as reference samples, were prepared by wet impregnation. - Highlights: • The precursors of TiO{sub 2} nanotubes were synthesized by the sol–gel method. • TiO{sub 2} nanostructures showed improved textural and morphological properties. • Pd nanoparticles around 1 nm were obtained by the photodeposition method. • TiO{sub 2}-nanotube-based catalysts can be a powerful tool for facing air pollution.

  2. An investigation of the activity and stability of Pd and Pd-Zr modified Y-zeolite catalysts for the removal of PAH, CO, CH4 and NOx emissions

    International Nuclear Information System (INIS)

    Klingstedt, F.; Kalantar Neyestanaki, A.; Lindfors, L.-E.; Salmi, T.; Heikkila, T.; Laine, E.

    2003-01-01

    Pd-Y- and Pd-Zr-Y-zeolite catalysts were prepared by the ion-exchange of parent NH 3 -Y-zeolite, thermally pre-treated Y-zeolite and hydrothermally pre-treated Y-zeolite. The activity of the catalysts was studied in conversion of gas mixtures simulating the flue gases from the combustion of biofuels and natural gas driven vehicles (NGVs) at temperature ranges of 120-800C. The effect of sulphur-poisoning was examined by the addition of 5ppm SO 2 into the feed gas mixtures. High activity in the removal of the model pollutants was obtained over the fresh catalysts. De-activation was observed as a result of catalyst ageing in the reactants' flow (800C, 6h) or steam treatment (850C, 12vol.% H 2 O, 16h). The de-activation was attributed to the de-alumination as well as to the migration of Pd 2+ cations. The catalysts were characterised by XRD, SEM-EDXA, N 2 -physisorption, O 2 /SO 2 /NH 3 /naphthalene-TPD, XRF and DCP

  3. One-step synthesis of highly active Ti-containing Cr-modified MCM-48 mesoporous material and the photocatalytic performance for decomposition of H{sub 2}S under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Wang Zhen; Ci Xinbo; Dai Hongjun; Yin Lu [Department of Environmental Engineering, Zhejiang University, Hangzhou 310027 (China); Shi Huixiang, E-mail: lanyueheyu@163.com [Department of Environmental Engineering, Zhejiang University, Hangzhou 310027 (China)

    2012-08-01

    A highly photoactive Ti-containing Cr-modified MCM-48 photocatalyst (Si/Ti = 3.4, Si/Cr = 50) was prepared by a facile one-step method at room temperature. A combination of various physicochemical techniques such as X-ray diffraction (XRD), N{sub 2} physisorption, diffuse reflectance UV-vis spectra (DRS) and X-ray photoelectron spectra (XPS) were used to characterize the properties of the synthetic catalysts. The characterization and experimental results indicated that tetrahedral Ti oxide moieties as dominant Ti oxide were loaded into the mesoporous structure and there was a synergistic interaction between the Ti species anchored on the walls and the Cr ions presented in the MCM-48 framework, which was considered to be directly correlated to the photoactivity. The Ti-Cr-MCM-48 sample can remove H{sub 2}S with the efficiency of 92% under visible light, being the Cr{sup 6+} species primarily responsible for this photoactivity. A deactivation was observed as a consequence of sulfate accumulation on the surface of the catalyst and reduction of Cr{sup 6+}.

  4. Controlled drug release on amine functionalized spherical MCM-41

    International Nuclear Information System (INIS)

    Szegedi, Agnes; Popova, Margarita; Goshev, Ivan; Klébert, Szilvia; Mihály, Judit

    2012-01-01

    MCM-41 silica with spherical morphology and small particle sizes (100 nm) was synthesized and modified by post-synthesis method with different amounts of 3-aminopropyltriethoxysilane (APTES). A comparative study of the adsorption and release of a model drug, ibuprofen, was carried out. The modified and drug loaded mesoporous materials were characterized by XRD, TEM, N 2 physisorption, elemental analysis, thermal analysis and FT-IR spectroscopy. A new method was developed for the quantitative determination of amino groups in surface modified mesoporous materials by the ninhydrin reaction. Good correlation was found between the amino content of the MCM-41 materials determined by the ninhydrin method and their ibuprofen adsorption capacity. Amino modification resulted in high degree of ibuprofen loading and slow release rate in comparison to the parent non-modified MCM-41. - Graphical abstract: Determination of surface amino groups by ninhidrin method. Highlights: ► Spherical MCM-41 modified by different amounts of APTES was studied. ► Ibuprofen (IBU) adsorption and release characteristics was tested. ► The ninhydrin reaction was used for the quantitative determination of amino groups. ► Stoichiometric amount of APTES is enough for totally covering the surface with amino groups. ► Good correlation was found between the amino content and IBU adsorption capacity.

  5. Effect of amine functionalization of spherical MCM-41 and SBA-15 on controlled drug release

    International Nuclear Information System (INIS)

    Szegedi, A.; Popova, M.; Goshev, I.; Mihaly, J.

    2011-01-01

    MCM-41 and SBA-15 silica materials with spherical morphology and different particle sizes were synthesized and modified by post-synthesis method with 3-aminopropyltriethoxysilane (APTES). A comparative study of the adsorption and release of a model drug, ibuprofen, were carried out. The modified and drug loaded mesoporous materials were characterized by XRD, TEM, N 2 physisorption, thermal analysis, elemental analysis and FT-IR spectroscopy. Surface modification with amino groups resulted in high degree of ibuprofen loading and slow rate of release for MCM-41, whereas it was the opposite for SBA-15. The adsorbed drug content and the delivery rate can be predetermined by the choice of mesoporous material with the appropriate structural characteristics and surface functionality. -- Graphical Abstract: Ibuprofen delivery from the parent and amino-modified spherical MCM-41 materials with 100 nm (small) and 500 nm (large) particle sizes. Display Omitted Highlights: → Spherical type MCM-41 and SBA-15 with different particle sizes were modified by APTES. → Adsorption and release rate of ibuprofen were compared. → High degree of ibuprofen loading, slow release rate for MCM-41, the opposite for SBA-15. → MCM-41 with 100 nm particles was more stable and showed slower release rate

  6. Studies on Structural and Morphological Properties of Multidoped Ceria Ce 0.8 Nd 0.0025 Sm 0.0025 Gd 0.005 Dy 0.095 Y 0.095 O 2 - δ ( x = 0.2 ) as Solid Solutions

    KAUST Repository

    Stojmenović, Marija

    2016-04-17

    The nanopowdery solid solutions of multidoped ceria Ce0.8Nd0.0025Sm0.0025Gd0.005Dy0.095Y0.095 () with the fluorite type crystal structure of CeO2 were synthesized for the first time. Two synthesis procedures were applied: the modified glycine-nitrate procedure (MGNP method) and room temperature self-propagating reaction (SPRT method). All nanopowders were characterized by XRPD analysis, Raman spectroscopy, low temperature nitrogen physisorption, TEM, and SEM methods. According to the XRPD and Raman spectroscopy results, single phase solid solutions of fluorite structure were evidenced regardless of the number of dopants and synthesis procedure. Both XRPD and TEM were analyses evidenced nanometer particle dimensions. The SPRT method results in obtaining sample with higher specific surface area, smaller crystallite and particles sizes, and the same values of the lattice parameter in comparison to pure CeO2. Raman spectroscopy was confirmed to the oxygen vacancies introduced into the ceria lattice when Ce4+ ions were replaced with cations (dopants) of lower valence state (3+), which may indicate the potential improvement of ionic conductivity. Additionally, the presence of oxygen vacancies in the lattice ceria, as well as very developed grain boundaries, gives a new possibility for potential application of obtained nanopowders in the area of room temperature ferromagnetism as spintronics.

  7. Synthesis and characterization of hydrotalcite-hydroxyapatite material doped with carbon nanotubes and its application in catalysis of transesterification reaction

    International Nuclear Information System (INIS)

    Rodrigues, E.; Barros, T.; Pereira, C.; Almeida, O.; Brasil, H.; Reis, M.A L. dos

    2018-01-01

    The aim of this study was to synthesize and characterize hydrotalcite-hydroxyapatite (HTHAp) material doped with three different proportions (1, 5 and 15% w/w) of carbon nanotubes (NTC) in order to evaluate its potential as a heterogeneous catalyst in the soybean oil methanolysis reaction. The synthesis of the HTHAp material was performed by the co-precipitation method (10≤pH≤ 11) with ultrasonic homogenization and hydrothermal treatment at 80 °C. XRD, SEM/EDS, FT-IR, Raman, N 2 physisorption and TG/DTA were the characterization techniques performed. The sample HTHAp1NTC, doped at 1% w/w, was tested as a catalyst under two temperature conditions (180 and 240 °C), 4 h reaction time, 2.5% catalyst loading and alcohol:oil ratio of 12:1. Doping contributed to improve structural, morphological and thermal stability properties of HTHAp material. The yield results achieved 35.2% (180 °C) and 40.5% (240 °C) qualifying the HTHAp material doped with CNT as a potential catalyst in the transesterification reaction. (author)

  8. Correlation between the Microstructure of Porous Materials and the Adsorption Properties of H2 and D2

    International Nuclear Information System (INIS)

    Krkljus, Ivana Biljana

    2011-01-01

    One of the most challenging tasks toward the full implementation of the hydrogen based economy is the reversible storage of hydrogen for portable applications. Three main approaches have been investigated to store the hydrogen, storage as a compressed gas or a liquid, or through a direct chemical bond between the hydrogen atom and the material. The alternative approach, the most recently investigated, is the storage of hydrogen at cryogenic conditions. Storage by physisorption within porous adsorbents has particular advantages of complete reversibility, the fast refueling time, the low heat evolution, and above all increased safety. The nature of interaction of hydrogen, deuterium, and gas mixtures with porous adsorbents was exploited by performing thermal desorption spectroscopy (TDS) measurements. This sensitive experimental technique gives qualitative information about the different adsorption sites, which show different desorption temperatures depending on the interaction energy. After an appropriate calibration the amount of gas desorbed may be quantified. To gain a more fundamental insight into the available adsorption sites multiple TDS spectra were recorded, corresponding to different surface coverages (in the pressure range of 1 to 700 mbar), and different heating regimes. Different kind of porous adsorbents, conventional carbon-based materials and novel Metal Organic Framework Materials (MOFs), were used to investigate the hydrogen/deuterium physisorption mechanism. For carbon materials an increase in the hydrogen interaction potential was observed for adsorbents with narrow pore size. The confined geometry, where hydrogen simultaneously interacts with all the surrounding adsorbent walls, strengthens the interaction potential with the adsorbate molecule, thus, maximizing the total van der Waals force on the adsorbate. Crystalline MOFs are a new class of porous materials assembled from discrete metal centers, which act as framework nodes, and organic

  9. Evaluating the Adsorptive Capabilites of Chemsorb 1000 and Chemsorb 1425

    Science.gov (United States)

    Mejia, Oscar Alberto Monje; Surma, Jan M.; Johnsey, Marissa; Melendez, Orlando

    2014-01-01

    The removal of trace contaminants from spacecraft cabin air is necessary for crew health and comfort during long duration space exploration missions. The air revitalization technologies used in these future exploration missions will evolve from current ISS ISS State-of-Art (SOA) and is being designed and tested by the Advanced Exploration Systems (AES) Program's Atmosphere Resource Recovery and Environmental Monitoring (ARREM) project. The ARREM project is working to mature optimum atmosphere revitalization and environmental monitoring system architectures to enable exploration beyond Lower Earth Orbit (LEO). The Air Revitalization Lab at KSC is one of six NASA field centers participating in the ARREM that specializes in adsorbent and catalyst characterization with simulated spacecraft gas streams using combinations of pressure, O2 partial pressure, CO2 partial pressure, and humidity that are representative of a range of anticipated cabin atmospheric conditions and loads. On board ISS, the Trace Contaminant Control Subassembly (TCCS) provides active control of trace contaminants from the cabin atmosphere utilizing physical adsorption, thermal catalytic oxidation, and chemical adsorption processes. High molecular weight contaminants and ammonia (NH3) are removed a granular activated carbon treated with approx. 10% by weight phosphoric acid (H3PO4) (B-S Type 3032 4×6 mesh), which is expendable and is periodically refurbished. The Type 3032 granular activated carbon bed is no longer commercially available and therefore it is important to characterize the efficiency and capacity of commercially available NH3 sorbents. This paper describes the characterization of two Molecular Products LTD activated carbons: Chemsorb 1000 and Chemsorb 1425. Untreated activated carbons (e.g. Chemsorb 1000) remove contaminants by physisorption, which concentrates the contaminant within the pores of the carbon while letting air to pass through the sorbent4. Low molecular weight or polar

  10. Experimental investigation of changes in methane adsorption of bitumen-free Woodford Shale with thermal maturation induced by hydrous pyrolysis

    Science.gov (United States)

    Hu, Haiyan; Zhang, Tongwei; Wiggins-Camacho, Jaclyn D.; Ellis, Geoffrey S.; Lewan, Michael D.; Zhang, Xiayong

    2014-01-01

    This study quantifies the effects of organic-matter (OM) thermal maturity on methane (CH4) sorption, on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature Woodford Shale under five different time–temperature conditions. CH4-sorption isotherms at 35 °C, 50 °C, and 65 °C, and pressures up to 14 MPa on dry, solvent-extracted samples of the artificially matured Woodford Shale were measured. The results showed that CH4-sorption capacity, normalized to TOC, varied with thermal maturity, following the trend: maximum oil (367 °C) > oil cracking (400 °C) > maximum bitumen/early oil (333 °C) > early bitumen (300 °C) > immature stage (130 °C). The Langmuir constants for the samples at maximum-oil and oil-cracking stages are larger than the values for the bitumen-forming stages. The total pore volume, determined by N2 physisorption at 77 K, increases with increased maturation: mesopores, 2–50 nm in width, were created during the thermal conversion of organic-matter and a dramatic increase in porosity appeared when maximum-bitumen and maximum-oil generation stages were reached. A linear relationship between thermal maturity and Brunauer–Emmett–Teller (BET) surface area suggests that the observed increase in CH4-sorption capacity may be the result of mesopores produced during OM conversion. No obvious difference is observed in pore-size distribution and pore volume for samples with pores 2 physisorption at 273 K. The isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17.9 kJ mol−1 to 21.9 kJ mol−1 and from −85.4 J mol−1 K−1 to −101.8 J mol−1 K−1, respectively. These values are similar to the values of immature Woodford kerogen concentrate previously observed, but are larger than naturally matured organic-rich shales. High-temperature hydrous pyrolysis might have induced Lewis acid sites on both organic and mineral surfaces

  11. Synthesis and physico-chemical characterization of CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez E, J. M.; Silva R, R.; Garcia A, R. [Instituto Tecnologico de Ciudad Madero, Div. de Estudios de Posgrado e Investigacion, Juventino Rosas y Jesus Urueta s/n, Col. Los Mangos, 89440 Ciudad Madero, Tamaulipas (Mexico); Garcia S, L. A. [IPN, Centro Interdisciplinario de Investigaciones y de Estudios sobre Medio Ambiente y Desarrollo, 30 de Junio No. 1520, Barrio La Laguna Ticoman, 07340 Mexico D. F. (Mexico); Handy, B. E.; Cardenas G, G. [Universidad Autonoma de San Luis Potosi, CIEP, Facultad de Ciencias Quimicas, Av. Dr. Manuel Nava No. 6, Zona Universitaria, 78210 SLP, San Luis Potosi (Mexico); Cueto H, A. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Av. San Pablo No. 180, Col. Reynosa Tamaulipas, 02200 Mexico D. F. (Mexico)

    2012-07-01

    Environmentally friendly solid-acid catalysts CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} were prepared by the sol gel method varying CeO{sub 2} content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO{sub 2} and ZrO{sub 2}-SO{sub 4}{sup 2-} were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO{sub 2}-SO{sub 4}{sup 2-} was high (160 m{sup 2}/g) compared with the unmodified ZrO{sub 2} (80 m{sup 2}/g), however this area decreased with increasing the CeO{sub 2} content (37-100 m{sup 2}/g). There was no significant effect of CeO{sub 2} on the tetragonal structure of ZrO{sub 2}-SO{sub 4}{sup 2-}. The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} catalyst with the highest CeO{sub 2} content was used. (Author)

  12. Rationale for switching to nonlocal functionals in density functional theory.

    Science.gov (United States)

    Lazić, P; Atodiresei, N; Caciuc, V; Brako, R; Gumhalter, B; Blügel, S

    2012-10-24

    Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

  13. Ultrasonic and hydrothermal mediated synthesis routes for functionalized Mg-Al LDH: Comparison study on surface morphology, basic site strength, cyclic sorption efficiency and effectiveness.

    Science.gov (United States)

    Ezeh, Collins I; Tomatis, Marco; Yang, Xiaogang; He, Jun; Sun, Chenggong

    2018-01-01

    Amine functionalized layered double hydroxide (LDHs) adsorbents prepared using three different routes: co-precipitation, sono-chemical and ultrasonic-assisted high pressure hydrothermal. The prepared adsorbent samples were characterized using X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning electron microscope-Energy dispersive X-ray spectroscopy (SEM-EDX), Temperature Programmed Desorption (TPD), Brunauer-Emmett-Teller (BET), and Thermogravimetric analysis (TGA), respectively. The performance of the prepared adsorbents was tested in a controlled thermal-swing adsorption process to measure its adsorption capacity, regeneration and cyclic efficiencies subsequently. The characterisation results were compared with those obtained using the conventional preparation routes but taking into account of the impact of sonochemical and hydrothermal pre-treatment on textural properties, adsorption capacity, regeneration and cyclic efficiencies. Textural results depicts a surge in surface area of the adsorbent synthesised by hydrothermal route (311m 2 /g) from 25 to 171m 2 /g for conventional and ultrasonic routes respectively. Additionally, it has been revealed from the present study that adsorbents prepared using ultrasonic-assisted hydrothermal route exhibit a better CO 2 uptake capacity than that prepared using sonochemical and conventional routes. Thus, the ultrasonic-assisted hydrothermal treatment can effectively promote the adsorption capacity of the adsorbent. This is probably due to the decrease of moderate (M-O) and weak (OH - groups) basic sites with subsequent surge in the number of strong basic sites (O 2- ) resulting from the hydrothermal process. Moreover, the cyclic adsorption efficiency of the ultrasonic mediated process was found to be 76% compared with 60% for conventional and 53% for hydrothermal routes, respectively. According to the kinetic model analysis, adsorption mechanism is mostly dominated by physisorption before amine

  14. Adsorption of SO{sub 2} on Li atoms deposited on MgO (1 0 0) surface: DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Eid, Kh.M., E-mail: Kheid98@hotmail.com [Physics Department, Faculty of Education, Ain Shams University, Cairo 11757 (Egypt); Ammar, H.Y. [Department of Physics, Faculty of Science, Najran University, Najran 1988 (Saudi Arabia)

    2011-05-01

    The adsorption of sulfur dioxide molecule (SO{sub 2}) on Li atom deposited on the surfaces of metal oxide MgO (1 0 0) on both anionic and defect (F{sub s}-center) sites located on various geometrical defects (terrace, edge and corner) has been studied using density functional theory (DFT) in combination with embedded cluster model. The adsorption energy (E{sub ads}) of SO{sub 2} molecule (S-atom down as well as O-atom down) in different positions on both of O{sup -2} and F{sub s} sites is considered. The spin density (SD) distribution due to the presence of Li atom is discussed. The geometrical optimizations have been done for the additive materials and MgO substrate surfaces (terrace, edge and corner). The oxygen vacancy formation energies have been evaluated for MgO substrate surfaces. The ionization potential (IP) for defect free and defect containing of the MgO surfaces has been calculated. The adsorption properties of SO{sub 2} are analyzed in terms of the E{sub ads}, the electron donation (basicity), the elongation of S-O bond length and the atomic charges on adsorbed materials. The presence of the Li atom increases the catalytic effect of the anionic O{sup -2} site of MgO substrate surfaces (converted from physisorption to chemisorption). On the other hand, the presence of the Li atom decreases the catalytic effect of the F{sub s}-site of MgO substrate surfaces. Generally, the SO{sub 2} molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F{sub s}-center.

  15. Inexpensive sol-gel synthesis of multiwalled carbon nanotube-TiO{sub 2} hybrids for high performance antibacterial materials

    Energy Technology Data Exchange (ETDEWEB)

    Abbas, Nadir; Shao, Godlisten N. [Department of Fusion Chemical Engineering, Hanyang University, 1271 Sa 3-dong, Sangnok-gu, Ansan-si, Gyeonggi-do 426-791 (Korea, Republic of); Haider, M. Salman [Department of Civil and Environmental System Engineering, Hanyang University, 1271 Sa 3-dong, Sangnok-gu, Ansan-si, Gyeonggi-do 426-791 (Korea, Republic of); Imran, Syed Muhammad; Park, Sung Soo; Jeon, Sun-Jeong [Department of Fusion Chemical Engineering, Hanyang University, 1271 Sa 3-dong, Sangnok-gu, Ansan-si, Gyeonggi-do 426-791 (Korea, Republic of); Kim, Hee Taik, E-mail: khtaik@hanyang.ac.kr [Department of Fusion Chemical Engineering, Hanyang University, 1271 Sa 3-dong, Sangnok-gu, Ansan-si, Gyeonggi-do 426-791 (Korea, Republic of)

    2016-11-01

    This study reports an inexpensive sol-gel method to synthesize TiO{sub 2}-CNT hybrid materials. Synthesized TiO{sub 2}-CNT materials show strong antibacterial activity in the absence of light. Cheap TiO{sub 2} source TiOCl{sub 2} is used during synthesis in the absence of high temperatures, high pressures and organic solvents. TiO{sub 2}-CNT materials with 0, 2, 5, 10, 15 and 20 wt% of CNT were synthesized and compared for antibacterial activity, surface area, porosity, crystalline structure, chemical state, and HaCaT cell proliferation. The antibacterial strength of hybrid materials increased significantly with the increase in CNT loading amount, and the TiO{sub 2}-CNT samples with a CNT loading of 10 wt% or more nearly removed all of the E.coli bacteria. HaCaT cell proliferation studies of synthesized hybrid materials illustrated that prepared TiO{sub 2}-CNT systems exhibit minimum cytotoxicity. The characteristics of prepared materials were analyzed by means of XRD, FTIR, Raman spectroscopy, XPS, TEM, and nitrogen gas physisorption studies, compared and discussed. - Highlights: • An inexpensive scheme of preparing TiO{sub 2}-CNT hybrids is presented. • Significant increase in the antibacterial properties of TiO{sub 2} in absence of light • Effects of CNT addition on the physicochemical properties of hybrids are studied. • Antibacterial activity increases with increase in CNT content. • Hybrids show no toxicity towards HaCaT skin cell line.

  16. Processing and characterization of diatom nanoparticles and microparticles as potential source of silicon for bone tissue engineering

    Energy Technology Data Exchange (ETDEWEB)

    Le, Thi Duy Hanh [Department of Industrial Engineering, University of Trento, Trento (Italy); BIOtech Research Center and European Institute of Excellence on Tissue Engineering and Regenerative Medicine, Trento (Italy); Bonani, Walter [Department of Industrial Engineering, University of Trento, Trento (Italy); BIOtech Research Center and European Institute of Excellence on Tissue Engineering and Regenerative Medicine, Trento (Italy); Interuniversity Consortium for Science and Technology of Materials, Trento Research Unit, Trento (Italy); Speranza, Giorgio [Center for Materials and Microsystems, PAM-SE, Fondazione Bruno Kessler, Trento (Italy); Sglavo, Vincenzo; Ceccato, Riccardo [Department of Industrial Engineering, University of Trento, Trento (Italy); Maniglio, Devid; Motta, Antonella [Department of Industrial Engineering, University of Trento, Trento (Italy); BIOtech Research Center and European Institute of Excellence on Tissue Engineering and Regenerative Medicine, Trento (Italy); Interuniversity Consortium for Science and Technology of Materials, Trento Research Unit, Trento (Italy); Migliaresi, Claudio, E-mail: claudio.migliaresi@unitn.it [Department of Industrial Engineering, University of Trento, Trento (Italy); BIOtech Research Center and European Institute of Excellence on Tissue Engineering and Regenerative Medicine, Trento (Italy); Interuniversity Consortium for Science and Technology of Materials, Trento Research Unit, Trento (Italy)

    2016-02-01

    Silicon plays an important role in bone formation and maintenance, improving osteoblast cell function and inducing mineralization. Often, bone deformation and long bone abnormalities have been associated with silica/silicon deficiency. Diatomite, a natural deposit of diatom skeleton, is a cheap and abundant source of biogenic silica. The aim of the present study is to validate the potential of diatom particles derived from diatom skeletons as silicon-donor materials for bone tissue engineering applications. Raw diatomite (RD) and calcined diatomite (CD) powders were purified by acid treatments, and diatom microparticles (MPs) and nanoparticles (NPs) were produced by fragmentation of purified diatoms under alkaline conditions. The influence of processing on the surface chemical composition of purified diatomites was evaluated by X-ray photoelectron spectroscopy (XPS). Diatoms NPs were also characterized in terms of morphology and size distribution by transmission electron microscopy (TEM) and Dynamic light scattering (DLS), while diatom MPs morphology was analyzed by scanning electron microscopy (SEM). Surface area and microporosity of the diatom particles were evaluated by nitrogen physisorption methods. Release of silicon ions from diatom-derived particles was demonstrated using inductively coupled plasma optical emission spectrometry (ICP/OES); furthermore, silicon release kinetic was found to be influenced by diatomite purification method and particle size. Diatom-derived microparticles (MPs) and nanoparticles (NPs) showed limited or no cytotoxic effect in vitro depending on the administration conditions. - Highlights: • Diatomite is a natural source of silica and has a potential as silicon-donor for bone regenerative applications. • Diatom particles derived from purified diatom skeletons were prepared by fragmentation under extreme alkaline condition. • Dissolution of diatom particles derived from diatom skeletons in DI water depend on purification method

  17. Photocatalytic decomposition of N2O over TiO2/g-C3N4 photocatalysts heterojunction

    Science.gov (United States)

    Kočí, K.; Reli, M.; Troppová, I.; Šihor, M.; Kupková, J.; Kustrowski, P.; Praus, P.

    2017-02-01

    TiO2/g-C3N4 photocatalysts with the various TiO2/g-C3N4 weight ratios from 1:2 to 1:6 were fabricated by mechanical mixing in water suspension followed by calcination. Pure TiO2 was prepared by thermal hydrolysis and pure g-C3N4 was prepared from commercial melamine by thermal annealing at 620 °C. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, Raman spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, photoelectrochemical measurements and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic decomposition of nitrous oxide under UVC (λ = 254 nm), UVA (λ = 365 nm) and Vis (λ > 400 nm) irradiation. The TiO2/g-C3N4 nanocomposites showed moderate improvement compared to pure g-C3N4 but pure TiO2 proved to be a better photocatalyst under UVC irradiation. However, under UVA irradiation conditions, the photocatalytic activity of TiO2/g-C3N4 (1:2) nanocomposite exhibited an increase compared to pure TiO2. Nevertheless, further increase of g-C3N4 amount leads/led to a decrease in reactivity. These results are suggesting the nanocomposite with the optimal weight ratio of TiO2 and g-C3N4 have shifted absorption edge energy towards longer wavelengths and decreased the recombination rate of charge carriers compared to pure g-C3N4. This is probably due to the generation of heterojunction on the TiO2/g-C3N4 interface.

  18. Structural, morphological and catalytic characterization of neutral Ag salt of 12-tungstophosphoric acid: Influence of preparation conditions

    Energy Technology Data Exchange (ETDEWEB)

    Holclajtner-Antunović, Ivanka; Bajuk-Bogdanović, Danica [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade (Serbia); Popa, Alexandru [Institute of Chemistry Timişoara, Bl. Mihail Viteazul 24, 300223 Timişoara (Romania); Nedić Vasiljević, Bojana [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade (Serbia); Krstić, Jugoslav [Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, 11001 Belgrade (Serbia); Mentus, Slavko [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade (Serbia); Uskoković-Marković, Snežana, E-mail: snezaum@pharmacy.bg.ac.rs [Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, 11221 Belgrade (Serbia)

    2015-02-15

    Graphical abstract: - Highlights: • Preparation conditions influence to self-assembly of nanocrystallites of Ag{sub 3}PW{sub 12}O{sub 40}. • Ag{sub 3}PW{sub 12}O{sub 40} obtained by filtration is microporous, Ag{sub 3}PW{sub 12}O{sub 40} obtained by evaporation is non-porous. • Thermal properties of Ag{sub 3}PW{sub 12}O{sub 40}, H{sub 3}PW{sub 12}O{sub 40} and its soluble salts are similar. - Abstract: The objective of this study is the structural and morphological characterization of the Ag{sub 3}PW{sub 12}O{sub 40} salts (AgWPA) of 12-tungstophosphoric acid (WPA) obtained under different preparation conditions and testing of their acid catalytic activity in dehydration of ethanol. The structure, morphology and physicochemical characteristics were determined by Fourier transform infrared (FT-IR) and Raman spectroscopy, X-ray diffraction (XRD), nitrogen physisorption at −196 °C, scanning electron microscopy (SEM) and differential thermal (DTA) and thermogravimetric analysis (TGA). It is shown that the preparation process has a significant influence on the morphological properties of the obtained materials which may be explained by the supposed mechanism of the formation of nanocrystallite′s aggregates with more or less epitaxial connection. Neutral AgWPA obtained by filtration from supernatant forms porous aggregates of a symmetric dodecahedral shape, having average sizes about 2 μm. This sample shows higher specific area in comparison with the salt obtained by evaporation due to the higher micropore volume, while mesopore volumes are the same for both salts. Thus conversion of ethanol and selectivities of the main products, ethylene and diethyl ether, are almost the same and constant for both prepared salts, while their values are changed over the reaction time for the parent WPA acid.

  19. Diclofenac degradation by heterogeneous photocatalysis with Fe3O4/Ti x O y /activated carbon fiber composite synthesized by ultrasound irradiation

    Science.gov (United States)

    Moreno-Valencia, E. I.; Paredes-Carrera, S. P.; Sánchez-Ochoa, J. C.; Flores-Valle, S. O.; Avendaño-Gómez, J. R.

    2017-11-01

    In this work, a photocatalytic system to degrade diclofenac was developed using a composite Fe3O4/Ti x O y on an activated carbon fiber. Diclofenac is widely used as an anti-inflammatory compound worldwide and it is constantly being added as waste in the environment (Heberer 2002 J. Hydrol. 266 175-89), exceeding the permissible maximum concentration in the wastewater (GEO-3 2002 Programa de las Naciones Unidas para el Medio Ambiente; Golet et al 2003 Environ. Sci. Technol. 37 3243-9 Oviedo et al 2010 Environ. Toxicol. Pharmacol. 29 9-43 Le-Minh et al 2010 Water Res. 44 4295-323 Legrini et al 1993 Chem. Rev. 1093 671-98). The composite was synthesized by sol-gel technique with and without ultrasound irradiation (Singh and Nakate 2014 J. Nanopart. 2014 326747). The solids were deposited by ultrasound irradiation on active carbon fiber in order to optimize the diclofenac degradation. The solids were characterized by x-ray diffraction (XRD), nitrogen physisorption (BET), and scanning electron microscopy with EDS microanalysis (SEM-EDS). The crystal size was calculated with the Debye-Scherrer equation, and the band gap values by the diffuse reflectance method. The evaluation process was studied by UV-vis spectroscopy (Rizzoa et al 2009 Water Res. 43 979-88). It was found that in this synthesis method (ultrasound), textural properties such as porosity, specific surface area and morphology depend on the ultrasound irradiation. The proposed system, Fe3O4/titanium oxide hydrate showed better degradation profile than TiO2 anatase phase; the increase of diclofenac degradation was attributed to the textural properties of the composite, it avoids the filtering process since the separation can be achieved by magnetizing and/or decantation.

  20. Covalent electron transfer chemistry of graphene with diazonium salts.

    Science.gov (United States)

    Paulus, Geraldine L C; Wang, Qing Hua; Strano, Michael S

    2013-01-15

    Graphene is an atomically thin, two-dimensional allotrope of carbon with exceptionally high carrier mobilities, thermal conductivity, and mechanical strength. From a chemist's perspective, graphene can be regarded as a large polycyclic aromatic molecule and as a surface without a bulk contribution. Consequently, chemistries typically performed on organic molecules and surfaces have been used as starting points for the chemical functionalization of graphene. The motivations for chemical modification of graphene include changing its doping level, opening an electronic band gap, charge storage, chemical and biological sensing, making new composite materials, and the scale-up of solution-processable graphene. In this Account, we focus on graphene functionalization via electron transfer chemistries, in particular via reactions with aryl diazonium salts. Because electron transfer chemistries depend on the Fermi energy of graphene and the density of states of the reagents, the resulting reaction rate depends on the number of graphene layers, edge states, defects, atomic structure, and the electrostatic environment. We limit our Account to focus on pristine graphene over graphene oxide, because free electrons in the latter are already bound to oxygen-containing functionalities and the resulting chemistries are dominated by localized reactivity and defects. We describe the reaction mechanism of diazonium functionalization of graphene and show that the reaction conditions determine the relative degrees of chemisorption and physisorption, which allows for controlled modulation of the electronic properties of graphene. Finally we discuss different applications for graphene modified by this chemistry, including as an additive in polymer matrices, as biosensors when coupled with cells and biomolecules, and as catalysts when combined with nanoparticles.