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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. 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.)

  3. Elastic Analysis of Physisorption-Induced Substrate Deformation

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ji-Qiao; PAN Xia-Hui; YU Shou-Wen; FENG Xi-Qiao

    2008-01-01

    Physisorption may cause a dimple on a deformable solid surface due to adsorbate-substrate interaction.The interactive force between the adsorbate and the crystal atoms depends on their distances,which may change with substrate deformation.This feature of displacement-dependence indicates that the equilibrium problem is a force-deformation coupled nonlinear procedure.In the present study,a continuum mechanics model,in which the force is considered as a function of the displacement field of the medium,is presented to calculate the physisorption-inducad deformation in a semi-infinite elastic medium.It is found that the nonlinear effect due to force-deformation coupling should be taken in consideration in the adsorbate-substrate interaction analysis.

  4. Size dependent pore size distribution of shales by gas physisorption

    Science.gov (United States)

    Roshan, Hamid; Andersen, Martin S.; Yu, Lu; Masoumi, Hossein; Arandian, Hamid

    2017-04-01

    Gas physisorption, in particular nitrogen adsorption-desorption, is a traditional technique for characterization of geomaterials including the organic rich shales. The low pressure nitrogen is used together with adsorption-desorption physical models to study the pore size distribution (PSD) and porosity of the porous samples. The samples are usually crushed to a certain fragment size to measure these properties however there is not yet a consistent standard size proposed for sample crushing. Crushing significantly increases the surface area of the fragments e.g. the created surface area is differentiated from that of pores using BET technique. In this study, we show that the smaller fragment sizes lead to higher cumulative pore volume and smaller pore diameters. It is also shown that some of the micro-pores are left unaccounted because of the correction of the external surface area. In order to illustrate this, the nitrogen physisorption is first conducted on the identical organic rich shale samples with different sizes: 20-25, 45-50 and 63-71 µm. We then show that such effects are not only a function of pore structure changes induced by crushing, but is linked to the inability of the physical models in differentiating between the external surface area (BET) and micro-pores for different crushing sizes at relatively low nitrogen pressure. We also discuss models currently used in nano-technology such as t-method to address this issue and their advantages and shortcoming for shale rock characterization.

  5. Modeling the physisorption of bisphenol A on graphene and graphene oxide.

    Science.gov (United States)

    Cortés-Arriagada, Diego; Sanhueza, Luis; Santander-Nelli, Mireya

    2013-09-01

    The physisorption of bisphenol A (BPA) on pristine and oxidized graphene was studied theoretically via calculations performed at the PBE-D3 level (including dispersion force corrections). Three stable conformations of BPA on graphene were found. A lying-down configuration was energetically favored because the presence of π-π stacking and dispersion forces increased interactions. In addition, the adsorption of BPA on the edges of graphene oxide was enhanced when adsorption occurred on carboxyl and carbonyl groups, whereas the adsorption strength decreased when adsorption occurred on hydroxyl groups. The highest physisorption strength was obtained on the surface of graphene oxide due to the presence of π-π stacking and dispersion forces (which provided the greatest contribution to the adsorption energy) as well as hydrogen bonds (which provided a smaller contribution), indicating that oxidized graphene is a better candidate than pristine graphene for BPA removal. On the other hand, an increase in electrophilicity was observed after the physisorption of BPA in all systems (with respect to graphene and BPA in their isolated forms), with the adsorbent acting as the electron acceptor. Finally, molecular dynamics simulations performed using the PM6 Hamiltonian showed that the adsorption of BPA on graphene is stable.

  6. Physisorption of DNA molecules on chemically modified single-walled carbon nanotubes with and without sonication.

    Science.gov (United States)

    Umemura, Kazuo; Ishibashi, Yu; Oura, Shusuke

    2016-09-01

    We investigated the physisorption phenomenon of single-stranded DNA (ssDNA) molecules onto two types of commercially available chemically functionalized single-walled carbon nanotubes (SWNTs) by atomic force microscopy (AFM) and agarose gel electrophoresis. We found that DNA molecules can adsorb on the water-soluble SWNT surfaces without sonication, although sonication treatment has been used for hybridization of DNA and SWNTs in many previous studies. Using our method, damage of DNA molecules by sonication can be avoided. On the other hand, the amount of DNA molecules adsorbed on SWNT surfaces increased when the samples were sonicated. This fact suggests that the sonication is effective not only at debundling of SWNTs, but also at assisting DNA adsorption. Furthermore, DNA adsorption was affected by the types of functionalized SWNTs. In the case of SWNTs functionalized with polyethylene glycol (PEG-SWNT), physisorption of ssDNA molecules was confirmed only by agarose-gel electrophoresis. In contrast, amino-terminated SWNTs (NH2-SWNTs) showed a change in the height distribution profile based on AFM observations. These results suggest that DNA molecules tended to adsorb to NH2-SWNT surfaces, although DNA molecules can also adsorb on PEG-SWNT surfaces. Our results revealed fundamental information for developing nanobiodevices using hybrids of DNA and SWNTs.

  7. Broad-range modulation of light emission in two-dimensional semiconductors by molecular physisorption gating.

    Science.gov (United States)

    Tongay, Sefaattin; Zhou, Jian; Ataca, Can; Liu, Jonathan; Kang, Jeong Seuk; Matthews, Tyler S; You, Long; Li, Jingbo; Grossman, Jeffrey C; Wu, Junqiao

    2013-06-12

    In the monolayer limit, transition metal dichalcogenides become direct-bandgap, light-emitting semiconductors. The quantum yield of light emission is low and extremely sensitive to the substrate used, while the underlying physics remains elusive. In this work, we report over 100 times modulation of light emission efficiency of these two-dimensional semiconductors by physical adsorption of O2 and/or H2O molecules, while inert gases do not cause such effect. The O2 and/or H2O pressure acts quantitatively as an instantaneously reversible "molecular gating" force, providing orders of magnitude broader control of carrier density and light emission than conventional electric field gating. Physi-sorbed O2 and/or H2O molecules electronically deplete n-type materials such as MoS2 and MoSe2, which weakens electrostatic screening that would otherwise destabilize excitons, leading to the drastic enhancement in photoluminescence. In p-type materials such as WSe2, the molecular physisorption results in the opposite effect. Unique and universal in two-dimensional semiconductors, the effect offers a new mechanism for modulating electronic interactions and implementing optical devices.

  8. Frequency-dependent dielectric function of semiconductors with application to physisorption

    Science.gov (United States)

    Zheng, Fan; Tao, Jianmin; Rappe, Andrew M.

    2017-01-01

    The dielectric function is one of the most important quantities that describes the electrical and optical properties of solids. Accurate modeling of the frequency-dependent dielectric function has great significance in the study of the long-range van der Waals (vdW) interaction for solids and adsorption. In this work we calculate the frequency-dependent dielectric functions of semiconductors and insulators using the G W method with and without exciton effects, as well as efficient semilocal density functional theory (DFT), and compare these calculations with a model frequency-dependent dielectric function. We find that for semiconductors with moderate band gaps, the model dielectric functions, G W values, and DFT calculations all agree well with each other. However, for insulators with strong exciton effects, the model dielectric functions have a better agreement with accurate G W values than the DFT calculations, particularly in high-frequency region. To understand this, we repeat the DFT calculations with scissors correction, by shifting the DFT Kohn-Sham energy levels to match the experimental band gap. We find that scissors correction only moderately improves the DFT dielectric function in the low-frequency region. Based on the dielectric functions calculated with different methods, we make a comparative study by applying these dielectric functions to calculate the vdW coefficients (C3 and C5) for adsorption of rare-gas atoms on a variety of surfaces. We find that the vdW coefficients obtained with the nearly free electron gas-based model dielectric function agree quite well with those obtained from the G W dielectric function, in particular for adsorption on semiconductors, leading to an overall error of less than 7% for C3 and 5% for C5. This demonstrates the reliability of the model dielectric function for the study of physisorption.

  9. Arsenite Regulates Prolongation of Glycan Residues of Membrane Glycoprotein: A Pivotal Study via Wax Physisorption Kinetics and FTIR Imaging

    Directory of Open Access Journals (Sweden)

    Chih-Hung Lee

    2016-03-01

    Full Text Available Arsenic exposure results in several human cancers, including those of the skin, lung, and bladder. As skin cancers are the most common form, epidermal keratinocytes (KC are the main target of arsenic exposure. The mechanisms by which arsenic induces carcinogenesis remains unclear, but aberrant cell proliferation and dysregulated energy homeostasis play a significant role. Protein glycosylation is involved in many key physiological processes, including cell proliferation and differentiation. To evaluate whether arsenite exposure affected protein glycosylation, the alteration of chain length of glycan residues in arsenite treated skin cells was estimated. Herein we demonstrated that the protein glycosylation was adenosine triphosphate (ATP-dependent and regulated by arsenite exposure by using Fourier transform infrared (FTIR reflectance spectroscopy, synchrotron-radiation-based FTIR (SR-FTIR microspectroscopy, and wax physisorption kinetics coupled with focal-plane-array-based FTIR (WPK-FPA-FTIR imaging. We were able to estimate the relative length of surface protein-linked glycan residues on arsenite-treated skin cells, including primary KC and two skin cancer cell lines, HSC-1 and HaCaT cells. Differential physisorption of wax adsorbents adhered to long-chain (elongated type and short-chain (regular type glycan residues of glycoprotein of skin cell samples treated with various concentration of arsenite was measured. The physisorption ratio of beeswax remain/n-pentacosane remain for KC cells was increased during arsenite exposure. Interestingly, this increase was reversed after oligomycin (an ATP synthase inhibitor pretreatment, suggesting the chain length of protein-linked glycan residues is likely ATP-dependent. This is the first study to demonstrate the elongation and termination of surface protein-linked glycan residues using WPK-FPA-FTIR imaging in eukaryotes. Herein the result may provide a scientific basis to target surface protein

  10. Arsenite Regulates Prolongation of Glycan Residues of Membrane Glycoprotein: A Pivotal Study via Wax Physisorption Kinetics and FTIR Imaging.

    Science.gov (United States)

    Lee, Chih-Hung; Hsu, Chia-Yen; Huang, Pei-Yu; Chen, Ching-Iue; Lee, Yao-Chang; Yu, Hsin-Su

    2016-03-22

    Arsenic exposure results in several human cancers, including those of the skin, lung, and bladder. As skin cancers are the most common form, epidermal keratinocytes (KC) are the main target of arsenic exposure. The mechanisms by which arsenic induces carcinogenesis remains unclear, but aberrant cell proliferation and dysregulated energy homeostasis play a significant role. Protein glycosylation is involved in many key physiological processes, including cell proliferation and differentiation. To evaluate whether arsenite exposure affected protein glycosylation, the alteration of chain length of glycan residues in arsenite treated skin cells was estimated. Herein we demonstrated that the protein glycosylation was adenosine triphosphate (ATP)-dependent and regulated by arsenite exposure by using Fourier transform infrared (FTIR) reflectance spectroscopy, synchrotron-radiation-based FTIR (SR-FTIR) microspectroscopy, and wax physisorption kinetics coupled with focal-plane-array-based FTIR (WPK-FPA-FTIR) imaging. We were able to estimate the relative length of surface protein-linked glycan residues on arsenite-treated skin cells, including primary KC and two skin cancer cell lines, HSC-1 and HaCaT cells. Differential physisorption of wax adsorbents adhered to long-chain (elongated type) and short-chain (regular type) glycan residues of glycoprotein of skin cell samples treated with various concentration of arsenite was measured. The physisorption ratio of beeswax remain/n-pentacosane remain for KC cells was increased during arsenite exposure. Interestingly, this increase was reversed after oligomycin (an ATP synthase inhibitor) pretreatment, suggesting the chain length of protein-linked glycan residues is likely ATP-dependent. This is the first study to demonstrate the elongation and termination of surface protein-linked glycan residues using WPK-FPA-FTIR imaging in eukaryotes. Herein the result may provide a scientific basis to target surface protein-linked glycan

  11. 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

  12. Physisorption of ammonia on AISI 304L stainless steel at different surface temperature under high vacuum conditions

    Directory of Open Access Journals (Sweden)

    A. de Castro

    2016-12-01

    Full Text Available The physisorption of ammonia molecules (sticking on the walls of a stainless steel pipe (AISI 304L has been studied at different wall temperatures (323-473K. The total amount of ammonia that is retained on the walls, once equilibrium is reached, has been measured by differentially-pumped mass spectrometry in gas exposure laboratory experiments. The results show ammonia retentions in the range of μg/cm2 resulting in a multilayer adsorption with lower amounts of stuck ammonia at higher temperatures of the stainless steel surface. The sticking coefficient follows an exponential decay evolution with time. The activation energy of the process has been estimated by an Arrhenius fit, assuming that the characteristic time for this decay is inversely proportional to the kinetic adsorption constant. A value of 0.15eV per ammonia molecule has been obtained, being in agreement with nominal values for the physisorption of small molecules or atoms (CO, N2, Ar… that can be found in the specialized literature. The implication of these results in the possible extrapolation to the ITER vacuum system under nitrogen seeded plasma operation is also addressed.

  13. Effect of van der Waals interactions on the chemisorption and physisorption of phenol and phenoxy on metal surfaces

    Science.gov (United States)

    Peköz, Rengin; Donadio, Davide

    2016-09-01

    The adsorption of phenol and phenoxy on the (111) surface of Au and Pt has been investigated by density functional theory calculations with the conventional PBE functional and three different non-local van der Waals (vdW) exchange and correlation functionals. It is found that both phenol and phenoxy on Au(111) are physisorbed. In contrast, phenol on Pt(111) presents an adsorption energy profile with a stable chemisorption state and a weakly metastable physisorbed precursor. While the use of vdW functionals is essential to determine the correct binding energy of both chemisorption and physisorption states, the relative stability and existence of an energy barrier between them depend on the semi-local approximations in the functionals. The first dissociation mechanism of phenol, yielding phenoxy and atomic hydrogen, has been also investigated, and the reaction and activation energies of the resulting phenoxy on the flat surfaces of Au and Pt were discussed.

  14. Doping effect on the adsorption of NH3 molecule onto graphene quantum dot: From the physisorption to the chemisorption

    Science.gov (United States)

    Seyed-Talebi, Seyedeh Mozhgan; Beheshtian, J.; Neek-amal, M.

    2013-09-01

    The adsorption of ammonia molecule onto a graphene hexagonal flake, aluminum (Al) and boron (B) doped graphene flakes (graphene quantum dots, GQDs) are investigated using density functional theory. We found that NH3 molecule is absorbed to the hollow site through the physisorption mechanism without altering the electronic properties of GQD. However, the adsorption energy of NH3 molecule onto the Al- and B-doped GQDs increases with respect GQD resulting chemisorption. The adsorption of NH3 onto the Al-doped and B-doped GQDs makes graphene locally buckled, i.e., B- doped and Al-doped GQDs are not planar. The adsorption mechanism onto a GQD is different than that of graphene. This study reveals important features of the edge passivation and doping effects of the adsorption mechanism of external molecules onto the graphene quantum dots.

  15. Physisorption of Ar, Kr, CH4, and N2 on 304 stainless steel at very low pressures.

    Science.gov (United States)

    Troy, M.; Wightman, J. P.

    1971-01-01

    Determination of physisorption isotherms of these gases on stainless steel by pressure change measurements in very low pressure cryogenic baths where a steel nipple was brought in contact with the test gas at 77 to 90 K in a sealed constant-volume system. The position of the nipple in the gas was changed in such a manner that gas adsorption on a 47.5 sq cm area of the steel surface could be measured. The Dubinin-Radushkevich (DR) equation (1947) was used for an empirical description of isotherms at different temperatures. The mean adsorption energies calculated from the DR plots were 1290, 1545, 1490 and 1903 cal/mol for Ar, Kr, CH4 and N2, respectively, being about 10% higher than the corresponding values on Pyrex.

  16. Physisorption-induced electron scattering on the surface of carbon-metal core-shell nanowire arrays for hydrogen sensing

    Science.gov (United States)

    Yick, S.; Yajadda, M. M. A.; Bendavid, A.; Han, Z. J.; Ostrikov, K.

    2013-06-01

    Palladium is sputtered on multi-walled carbon nanotube forests to form carbon-metal core-shell nanowire arrays. These hybrid nanostructures exhibited resistive responses when exposed to hydrogen with an excellent baseline recovery at room temperature. The magnitude of the response is shown to be tuneable by an applied voltage. Unlike the charge-transfer mechanism commonly attributed to Pd nanoparticle-decorated carbon nanotubes, this demonstrates that the hydrogen response mechanism of the multi-walled carbon nanotube-Pd core-shell nanostructure is due to the increase in electron scattering induced by physisorption of hydrogen. These hybrid core-shell nanostructures are promising for gas detection in hydrogen storage applications.

  17. Physisorption of Nucleic Acid Bases on Boron Nitride Nanotubes: A new class of Hybrid Nano-Bio Materials

    CERN Document Server

    Mukhopadhyay, Saikat; Scheicher, Ralph H; Pandey, Ravindra; Karna, Shashi P

    2009-01-01

    We investigate the adsorption of the nucleic acid bases, adenine (A), guanine (G), cytosine (C), thymine (T) and uracil (U) on the outer wall of a high curvature semiconducting single-walled boron nitride nanotube (BNNT) by first principles density functional theory calculations. The calculated binding energy shows the order: G>A~C~T~U implying that the interaction strength of the (high-curvature) BNNT with the nucleobases, G being an exception, is nearly the same. A higher binding energy for the G-BNNT conjugate appears to result from a stronger hybridization of the molecular orbitals of G and BNNT, since the charge transfer involved in the physisorption process is insignificant. A smaller energy gap predicted for the G-BNNT conjugate relative to that of the pristine BNNT may be useful in application of this class of biofunctional materials to the design of the next generation sensing devices.

  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. The effect of concentration of H$_2$ physisorption on the current–voltage characteristic of armchair BN nanotubes in CNT–BNNT–CNT set

    Indian Academy of Sciences (India)

    R AZIMIRAD; A H BAYANI; S SAFA

    2016-10-01

    In this research, we have studied physisorption of hydrogen molecules on armchair boron nitride (BN) nanotube (3,3) using density functional methods and its effect on the current–voltage ($I–V$) characteristic of the nanotube as a function of concentration using Green’s function techniques. The adsorption geometries and energies, charge transfer and electron transport are calculated. It is found that H$_2$ physisorption can suppress the $I–V$ characteristic of the BN nanotube, but it has no effect on the band gap of the nanotube. As the H$_2$concentration increases, under the same applied bias voltage, the current through the BN nanotube first increases and then begins to decline. The current–voltage characteristic indicates that H$_2$ molecules can be detected by aBN-based sensor.

  2. PHYSISORPTION OF WATER ON SiO2-TiO2-Al2O3 FILMS STUDIED BY IMPEDANCE SPECTROSCOPY

    Directory of Open Access Journals (Sweden)

    Alfonz Plsko

    2015-06-01

    Full Text Available The influence of film composition and surface roughness on process of physisorption of water on SiO2-TiO2-Al2O3 films prepared by sol-gel method was studied by impedance spectroscopy. The composition of prepared films, expressed by SiO2:TiO2:Al2O3 ratio, was in the range of following molar ratio: 0:0.95:0.05; 0.32:0.63:0.05; 0.475:0.475:0.05; 0.63:0.32:0.05; 0.95:0:0.05. Complex impedance spectra of thin film sensor for various relative humidities were measured in the range of 0.13 - 97.7 % and the frequency range was 1 kHz to 1 MHz. Measured dependences of complex impedance on frequency were processed by complex nonlinear least squares method. Serial connection with different counts of -(R/C-, -(R/CPE- and -R- equivalent circuits was used to analyse obtained spectra. The equivalent circuits were associated with physisorption of water, space charge polarization regions, and bulk or surface conductivity of the films. The dependencies presence of the relaxation processes on the value of relative humidity is used to analyse the process of water physisorption and determine composition influence, too.

  3. 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.

  4. 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

    Energy Technology Data Exchange (ETDEWEB)

    Shokri, Masood; Beiraghi, Asadollah [Faculty of Chemistry, Kharazmi University, Tehran (Iran, Islamic Republic of); Seidi, Shahram, E-mail: s.seidi@kntu.ac.ir [Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran (Iran, Islamic Republic of)

    2015-08-19

    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{sup −1} lithium bis (trifluoromethylsulfonyl) imide aqueous solution, Li[NTf{sub 2}], was added into the sample solution containing 100 μL of 1.0 mol L{sup −1} 1,3-(propyl-1,3-diyl) bis (3-methylimidazolium) chloride, [pbmim]Cl{sub 2}, to form a water immiscible ionic liquid, [pbmim][NTf{sub 2}]{sub 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{sub 3}O{sub 4} magnetic nanoparticles (MNPs) were added into the sample solution to collect the fine droplets of [pbmim][NTf{sub 2}]{sub 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{sup −1}. Good linearity was obtained in the range of 2.5–150 μg L{sup −1} with determination coefficient (r{sup 2}) of 0.9921. Relative standard deviation (RSD%) for seven repeated measurements at the concentration of 10 μg L{sup −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

  5. Ion photon-stimulated desorption as a tool to monitor the physisorption to chemisorption transition of benzene on Si(111) 7 x 7

    CERN Document Server

    Carbone, M; Casaletto, M P; Zanoni, R; Besnard-Ramage, M J; Comtet, G; Dujardin, G; Hellner, L

    2003-01-01

    We investigated the use of ion photodesorption as a tool to monitor the transition from the physisorbed to the chemisorbed state on a surface. The adsorption of benzene on Si(111) 7 x 7 in the temperature range 40-300 K is chosen as a prototype. The D sup + ion photodesorption yield was monitored as a function of temperature at various benzene exposures. Comparative measurements of the C 1s photoelectron yield in the same temperature range enable the physisorbed to chemisorbed state transition to be distinguished from that of the multilayer to the chemisorbed state. We find the onset at 110 K in the first case, and at 130-140 K in the second case. These results demonstrate that ion photodesorption is a potentially interesting method to identify physisorption to chemisorption transitions of adsorbed molecules on surfaces. (letter to the editor)

  6. 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

  7. 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

    Directory of Open Access Journals (Sweden)

    Ashis Tripathy

    2016-07-01

    Full Text Available 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.

  8. Searching for DFT-based methods that include dispersion interactions to calculate the physisorption of H2 on benzene and graphene

    Science.gov (United States)

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

    2017-06-01

    Simulations of the hydrogen storage capacities of nanoporous carbons require an accurate treatment of the interaction of the hydrogen molecule with the graphite-like surfaces of the carbon pores, which is dominated by the dispersion forces. These interactions are described accurately by high level quantum chemistry methods, like the Coupled Cluster method with single and double excitations and a non-iterative correction for triple excitations (CCSD(T)), but those methods are computationally very expensive for large systems and for massive simulations. Density functional theory (DFT)-based methods that include dispersion interactions at different levels of complexity are less accurate, but computationally less expensive. In order to find DFT-methods that include dispersion interactions to calculate the physisorption of H2 on benzene and graphene, with a reasonable compromise between accuracy and computational cost, CCSD(T), Møller-Plesset second-order perturbation theory method, and several DFT-methods have been used to calculate the interaction energy curves of H2 on benzene and graphene. DFT calculations are compared with CCSD(T) calculations, in the case of H2 on benzene, and with experimental data, in the case of H2 on graphene. Among the DFT methods studied, the B97D, RVV10, and PBE+DCACP methods yield interaction energy curves of H2-benzene in remarkable agreement with the interaction energy curve obtained with the CCSD(T) method. With regards to graphene, the rev-vdW-DF2, PBE-XDM, PBE-D2, and RVV10 methods yield adsorption energies of the lowest level of H2 on graphene, very close to the experimental data.

  9. Hydrogen physisorption on metal-organic framework linkers and metalated linkers: a computational study of the factors that control binding strength.

    Science.gov (United States)

    Tsivion, Ehud; Long, Jeffrey R; Head-Gordon, Martin

    2014-12-24

    In order for hydrogen gas to be used as a fuel, it must be stored in sufficient quantity on board the vehicle. Efforts are being made to increase the hydrogen storage capabilities of metal-organic frameworks (MOFs) by introducing unsaturated metal sites into their linking element(s), as hydrogen adsorption centers. In order to devise successful hydrogen storage strategies there is a need for a fundamental understanding of the weak and elusive hydrogen physisorption interaction. Here we report our findings from the investigation of the weak intermolecular interactions of adsorbed hydrogen molecules on MOF-linkers by using cluster models. Since physical interactions such as dispersion and polarization have a major contribution to attraction energy, our approach is to analyze the adsorption interaction using energy decomposition analysis (EDA) that distinguishes the contribution of the physical interactions from the charge-transfer (CT) "chemical" interaction. Surprisingly, it is found that CT from the adsorbent to the σ*(H2) orbital is present in all studied complexes and can contribute up to approximately -2 kJ/mol to the interaction. When metal ions are present, donation from the σ(H2) → metal Rydberg-like orbital, along with the adsorbent → σ*(H2) contribution, can contribute from -2 to -10 kJ/mol, depending on the coordination mode. To reach a sufficient adsorption enthalpy for practical usage, the hydrogen molecule must be substantially polarized. Ultimately, the ability of the metalated linker to polarize the hydrogen molecule is highly dependent on the geometry of the metal ion coordination site where a strong electrostatic dipole or quadrupole moment is required.

  10. 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.

  11. Page 1 CALCULATION OF PHYSISORPTION ENERGIES OF ...

    African Journals Online (AJOL)

    o-Fe:Os (I) SURFACE USING A CRYSTAL FIELD CLUSTER MODEL. A. Uzairu' and G.F.S. ... and quantum mechanically in the literature. A good. Summary of the ... the metal ion with the nearest anion neighbours as ligands is a natural cluster ...

  12. MARTINI Model for Physisorption of Organic Molecules on Graphite

    NARCIS (Netherlands)

    Gobbo, Cristian; Beurroies, Isabelle; de Ridder, David; Eelkema, Rienk; Marrink, Siewert J.; De Feyter, Steven; van Esch, Jan H.; de Vries, Alex H.

    2013-01-01

    An extension to the MARTINI coarse-grained model is presented to describe the adsorption of organic molecules on graphite surfaces. The model allows the study of the dynamics of the preferential adsorption of long-chain organic molecules from solvent and the formation of ordered structures on the su

  13. Hydrogen storage by physisorption on Metal Organic Frameworks

    Science.gov (United States)

    Dailly, Anne

    2008-03-01

    Cryo-adsorption systems based on materials with high specific surface areas have the main advantage that they can store and release hydrogen with fast kinetics and high reversibility over multiples cycles. Recently Metal Organic Frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. These crystallographically well organized hybrid solids resulting from the three dimensional connection of inorganic clusters using organic linkers show the largest specific surface areas of all known crystalline solids. The determination of the relationships between physical properties (chemistry, structure, surface area ) of the MOFs and their hydrogen storage behavior is a key step in the characterization of these materials, if they are to be designed for hydrogen storage applications. Excess hydrogen sorption measurements for different MOFs will be presented. We show that maximum hydrogen uptake at high pressure and 77K does not always scale with the specific surface area. A linear correlation trend only apply within a class of specific materials and breaks down when the surface area measurement does not represent the surface sites that are available to H2. The influence of pore size and shape will also be discussed by comparing several MOFs with different structure types. The hydrogen adsorption and binding energy at low pressure are strongly dependent on the metal ions and the pore size.

  14. Physisorption of SDS in a Hydrocarbon Nanoporous Polymer

    DEFF Research Database (Denmark)

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

    2010-01-01

    as diffusion-controlled dynamics. Both the specific equilibrium loading and the final SDS adsorption reached plateau values at concentrations above 6.8 m M. The infiltration of SDS into the nanoporous film was mainly followed by gravimetry and for a few samples confirmed by X-ray photoelectron spectroscopy...

  15. High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane

    Science.gov (United States)

    Usvyat, Denis

    2015-09-01

    A multilevel hierarchical ab initio protocol for calculating adsorption on non-conducting surfaces is presented. It employs fully periodic treatment, which reaches local Møller-Plesset perturbation theory of second order (MP2) with correction for the basis set incompleteness via the local F12 technique. Post-MP2 corrections are calculated using finite clusters. That includes the coupled cluster treatment in the local and canonical frameworks (up to perturbative quadruples) and correlated core (with MP2). Using this protocol, the potential surface of hydrogen molecules adsorbed on graphane was computed. According to the calculations, hydrogen molecules are adsorbed on graphane in a perpendicular to the surface orientation with the minimum of the potential surface of around -3.6 kJ/mol located at the distance of 3.85 Å between the bond center of the hydrogen molecule and the mid-plane of graphane. The adsorption sites along the path from the downward-pointing carbon to the ring center of the graphane are energetically virtually equally preferable, which can enable nearly free translations of hydrogen molecules along these paths. Consequently, the hydrogen molecules on graphane most likely form a non-commensurate monolayer. The analysis of the remaining errors reveals a very high accuracy of the computed potential surface with an error bar of a few tenths of a kJ/mol. The obtained results are a high-precision benchmark for further theoretical and experimental studies of hydrogen molecules interacting with graphane.

  16. Physisorption of hydroxide ions from aqueous solution to a hydrophobic surface

    NARCIS (Netherlands)

    Zangi, R; Engberts, JBFN

    2005-01-01

    We present results from detailed molecular dynamics simulations revealing a counterintuitive spontaneous physical adsorption of hydroxide ions at a water/hydrophobic interface. The driving force for the migration of the hydroxide ions from the aqueous phase is the preferential orientation of the

  17. Cooperative Chemisorption-Induced Physisorption of CO2 Molecules by Metal-Organic Chains.

    Science.gov (United States)

    Feng, Min; Petek, Hrvoje; Shi, Yongliang; Sun, Hao; Zhao, Jin; Calaza, Florencia; Sterrer, Martin; Freund, Hans-Joachim

    2015-12-22

    Effective CO2 capture and reduction can be achieved through a molecular scale understanding of interaction of CO2 molecules with chemically active sites and the cooperative effects they induce in functional materials. Self-assembled arrays of parallel chains composed of Au adatoms connected by 1,4-phenylene diisocyanide (PDI) linkers decorating Au surfaces exhibit self-catalyzed CO2 capture leading to large scale surface restructuring at 77 K (ACS Nano 2014, 8, 8644-8652). We explore the cooperative interactions among CO2 molecules, Au-PDI chains and Au substrates that are responsible for the self-catalyzed capture by low temperature scanning tunneling microscopy (LT-STM), X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRAS), temperature-programmed desorption (TPD), and dispersion corrected density functional theory (DFT). Decorating Au surfaces with Au-PDI chains gives the interfacial metal-organic polymer characteristics of both a homogeneous and heterogeneous catalyst. Au-PDI chains activate the normally inert Au surfaces by promoting CO2 chemisorption at the Au adatom sites even at surface supported Au-PDI chains provide a platform for investigating the physical and chemical interactions involved in CO2 capture and reduction.

  18. Oxygen-molecule spin-nanotubes constructed by physisorption into a nanoporous medium

    Science.gov (United States)

    Mito, Masaki; Shinto, Noritoshi; Komorida, Yuki; Tajiri, Takayuki; Deguchi, Hiroyuki; Takagi, Seishi; Kohiki, Shigemi

    2008-08-01

    We succeeded in controlling gas-liquid-solid transitions and in constructing “spin-nanotubes (SNTs)” based on antiferromagnetic correlations by physisorbing oxygen molecules (O2) into the nanosize pores of a mesoporous medium MCM-41 while also manipulating the adsorption quantity. The phase diagram of O2 physisorbed into MCM-41 presents many common characteristics with that of O2 layers physisorbed on graphite substrates. In the present case, experimental verification of the antiferromagnetic square lattice in the liquid phase of the monolayer proved the formation of O2 SNTs. The present O2 SNT is an experimental example of the successful construction of SNT.

  19. Physisorption on flat surfaces and inside square wells: a transfer matrix study

    Science.gov (United States)

    Cheng, E.; Banavar, J. R.; Cole, M. W.; Toigo, F.

    1992-01-01

    Calculations are performed with the transfer matrix method to predict adsorption on a flat surface and on a pore-like well on the surface. In the flat case, temperature-dependent deviation from the Frenkel-Halsey-Hill theory is seen. For numerical reasons the calculations are done for a two-dimensional "world".

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

    Science.gov (United States)

    2013-09-01

    during a gas-surface collision, and Rc is a critical value of Reff. For a given incident translational energy Etr , Reff is estimated from the one...dimensional (1D) approximation Etr εLJ ≈ ( r0 Reff )12 − 2 ( r0 Reff )6 , (7) where εLJ is the Lennard-Jones (LJ) well-depth parameter for the interaction...tr > Etr . This phenomenon is termed super-elastic scattering, and describes the case where the gas molecule picks up thermal energy from the surface

  1. High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane

    Energy Technology Data Exchange (ETDEWEB)

    Usvyat, Denis, E-mail: denis.usvyat@chemie.uni-regensburg.de [Institute for Physical and Theoretical Chemistry, Universität Regensburg, Universitätsstrasse 31, D-93040 Regensburg (Germany)

    2015-09-14

    A multilevel hierarchical ab initio protocol for calculating adsorption on non-conducting surfaces is presented. It employs fully periodic treatment, which reaches local Møller-Plesset perturbation theory of second order (MP2) with correction for the basis set incompleteness via the local F12 technique. Post-MP2 corrections are calculated using finite clusters. That includes the coupled cluster treatment in the local and canonical frameworks (up to perturbative quadruples) and correlated core (with MP2). Using this protocol, the potential surface of hydrogen molecules adsorbed on graphane was computed. According to the calculations, hydrogen molecules are adsorbed on graphane in a perpendicular to the surface orientation with the minimum of the potential surface of around −3.6 kJ/mol located at the distance of 3.85 Å between the bond center of the hydrogen molecule and the mid-plane of graphane. The adsorption sites along the path from the downward-pointing carbon to the ring center of the graphane are energetically virtually equally preferable, which can enable nearly free translations of hydrogen molecules along these paths. Consequently, the hydrogen molecules on graphane most likely form a non-commensurate monolayer. The analysis of the remaining errors reveals a very high accuracy of the computed potential surface with an error bar of a few tenths of a kJ/mol. The obtained results are a high-precision benchmark for further theoretical and experimental studies of hydrogen molecules interacting with graphane.

  2. On the strength of the hydrogen-carbon interaction as deduced from physisorption.

    Science.gov (United States)

    Nguyen, T X; Bae, J-S; Wang, Y; Bhatia, S K

    2009-04-21

    We deduce a new value for the potential well depth for the C-H2 interaction on the basis of experimental validations of isotherms of H2 and D2 predicted using independently characterized microstructural parameters. We use two carbons, one an activated carbon fiber whose structure has been recently characterized by us (Nguyen, T. X.; cohaut, N.; Bae, J.-S.; Bhatia, S. K. Langmuir 2008, 24, 7912) using hybrid reverse Monte Carlo simulation (HRMC) and the other the commercial Takeda 3A carbon molecular sieve whose pore size distribution is determined here from the 273 K CO2 adsorption isotherm. The conventional grand canonical Monte Carlo simulation technique incorporating a semiclassical Feynman and Hibbs (FH) potential approximation (FHGCMC) as well as path integral Monte Carlo calculations is employed to determine theoretical adsorption isotherms. It is found that curvature enhances the well depth for the LJ C-H2 interaction by a factor of 1.134 over that for a flat graphite surface, consistent with our recent study (Nguyen, T. X.; cohaut, N.; Bae, J.-S.; Bhatia, S. K. Langmuir 2008, 24, 7912). A value of the C-C well depth of 37.26 K, used for estimating the C-H2 well depth in conjunction with the Berthelot rules, with the Steele C-C well depth used for interaction with heavier gases (Ar, CO2 and CH4), leads to excellent agreement with experimental isotherms in all cases.

  3. Endohedral nitrogen storage in carbon fullerene structures: Physisorption to chemisorption transition with increasing gas pressure

    Science.gov (United States)

    Barajas-Barraza, R. E.; Guirado-López, R. A.

    2009-06-01

    We present extensive pseudopotential density functional theory (DFT) calculations in order to analyze the structural properties and chemical reactivity of nitrogen molecules confined in spheroidal (C82) and tubelike (C110) carbon fullerene structures. For a small number of encapsulated nitrogens, the N2 species exist in a nonbonded state within the cavities and form well defined molecular conformations such as linear chains, zigzag arrays, as well as both spheroidal and tubular configurations. However, with increasing the number of stored molecules, the interaction among the confined nitrogens as well as between the N2 species and the fullerene wall is not always mainly repulsive. Actually, at high densities of the encapsulated gas, we found both adsorption of N2 to the inner carbon surface together with the formation of (N2)m molecular clusters. Total energy DFT calculations reveal that the shape of the interaction potential of a test molecule moving within the carbon cavities strongly varies with the number and proximity of the coadsorbed N2 from being purely repulsive to having short-range attractive contributions close to the inner wall. In particular, the latter are always found when a group of closely spaced nitrogens is located near the carbon cage (a fact that will naturally occur at high densities of the encapsulated gas), inducing the formation of covalent bonds between the N2 and the fullerene network. Interestingly, in some cases, the previous nitrogen adsorption to the inner surface is reversible by reducing the gas pressure. The calculated average density of states of our considered carbon compounds reveals the appearance of well defined features that clearly reflect the occurring structural changes and modifications in the adsorption properties in the systems. Our results clearly underline the crucial role played by confinement effects on the reactivity of our endohedral compounds, define this kind of materials as nonideal nanocontainers for high density nitrogen storage applications, and must be taken into account when analyzing the diffusion properties of the encapsulated species.

  4. 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.

  5. Organic semiconductor/gold interface interactions: from physisorption on planar surfaces to chemical reactions with metal nanoparticles.

    Science.gov (United States)

    Ligorio, Giovanni; Nardi, Marco Vittorio; Christodoulou, Christos; Koch, Norbert

    2015-08-24

    The interaction of gold nanoparticles (AuNPs) with prototypical organic semiconductors used in optoelectronics, namely, tris(8-hydroxyquinoline)aluminium (Alq3 ) and 4,4-bis[N-(1-naphthyl)-N-phenylamino]diphenyl (α-NPD), is investigated in situ by X-ray photoelectron spectroscopy (XPS). These AuNPs-on-molecule experiments are compared with the reversed molecule-on-Au cases. The molecules-on-Au systems show only weak interactions, and the evolution of the XP spectra is dominated by final-state effects. In contrast, in the AuNPs-on-molecules cases, both initial-state effects and final-state effects occur. Spectral features arising for both molecules and metal indicate charge transfer and the formation of organometallic complexes (initial-state effects). The energy shift in the metal emission underlines the size-induced nanometric nature of the molecule/Au interaction (final-state effects). Consequently, the chemical interaction between metals and organic semiconductors likely depends strongly on the deposition sequence in general.

  6. 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.

  7. A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO2 Removal and Air Capture Using Physisorption.

    Science.gov (United States)

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

    2016-07-27

    The development of functional solid-state materials for carbon capture at low carbon dioxide (CO2) concentrations, namely, from confined spaces (CO2-selective NbOFFIVE-1-Ni exhibits the highest CO2 gravimetric and volumetric uptake (ca. 1.3 mmol/g and 51.4 cm(3) (STP) cm(-3)) for a physical adsorbent at 400 ppm of CO2 and 298 K. Practically, NbOFFIVE-1-Ni offers 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 conventional physical adsorbents but considerably lower than 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 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 notable hydrolytic stability positions NbOFFIVE-1-Ni as the new benchmark adsorbent for direct air capture and CO2 removal from confined spaces.

  8. Aqueous Foams Stabilized by Hydrophilic Silica Nanoparticles via In-Situ Physisorption of Nonionic TX100 Surfactant

    Directory of Open Access Journals (Sweden)

    Suriatie Yusuf

    2013-01-01

    Full Text Available This paper present the study of aqueous CO foam prepared 2 by a mixtures hydrophilic silica nanoparticles and non-ionic Triton X100, TX100, surfactant. The synergistic effects of the mixture on stabilizing the CO2 foam were inferred into few key parameters namely; particles and surfactant concentration, adsorption of surfactant onto the particles via surface tension and adsorption isotherm, foam lifetime and, the size of the bubbles produced. It was found that the adsorption behaviour of TX100 on silica surface exhibit a particular characteristics depend on the concentration of silica, high total surface area available leads to high adsorptionof surfactant molecules. The synergetic performance of silica/TX100 in stabilizing foam can be observed at low (0.01% and intermediate (0.1% concentration of TX100. Lower concentration required low silica concentration while the intermediate concentration required high silica fraction in the dispersion to stabilize the foam.

  9. 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.

  10. Physisorption of Nucleobases on C(9,1) and C(6,5) Single-Wall Carbon Nanotubes: A Density Functional Theory Study

    Science.gov (United States)

    Akdim, Brahim; Pachter, Ruth

    2009-03-01

    Selective enrichment of single-wall carbon nanotubes (SWCNTs) of a specific chirality by single-stranded DNA sequences has been shown experimentally by Zheng et al. [JACS 2007, 129, 6084], where a larger enrichment of C(6,5) as compared to C(9,1), which are SWCNTs of the same diameter but different chirality, was demonstrated with alternating guanine and thymine (GT) bases. In this work, we report density functional (DFT) calculations of (G) and (T) nucleobase adsorption on C(6,5) and C(9,1) SWCNTs, in order to gain an understanding of the selective sorting, specifically regarding adsorption characteristics, interface energetics, and electronic structures, as dependent on the tube chirality, also including specifically an empirical dispersion correction in the DFT functional.

  11. 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

    2016-03-01

    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.

  12. A unified single-event microkinetic model for alkane hydroconversion in different aggregation states on Pt/H-USY-zeolites.

    Science.gov (United States)

    Laxmi Narasimhan, C S; Thybaut, Joris W; Martens, Johan A; Jacobs, Pierre A; Denayer, Joeri F; Marin, Guy B

    2006-04-06

    A single-event microkinetic model for the catalytic hydroconversion of hydrocarbons on Pt/H-US-Y bifunctional zeolite catalysts developed for low-pressure vapor phase conditions was extended to cover high-pressure vapor phase and liquid phase conditions. The effect of the density of the bulk hydrocarbon phase on the physisorption as well as on the protonation steps of the reaction network was accounted for explicitly and can be interpreted in terms of "compression" of the hydrocarbon sorbate inside the zeolite pores and "solvation" of the catalyst framework by the dense bulk hydrocarbon phase. The bulk phase density effect on the physisorbed state is described via a single excess free enthalpy of physisorption. A dense bulk hydrocarbon phase destabilizes the sorbate molecules inside the catalyst pores. An expression of the excess free enthalpy of physisorption involving the fugacity coefficient and a zeolite dependent factor allows description of physisorption data. Typical excess free enthalpy values are in the range 1.5-5.1 kJ mol(-1) increasing with carbon number in the series of C5-C16 alkanes. At high-pressure vapor phase and liquid phase conditions, the excess standard protonation enthalpy is estimated at -7.8 kJ mol(-1) leading to relatively more stable carbenium ions at dense bulk phase conditions. As a result of the excess physisorption and protonation properties, the lightest hydrocarbons in mixtures are more competitive at dense phase conditions and their conversion is enhanced compared to low-density conditions.

  13. Alkali resistant Cu/zeolite deNOx catalysts for flue gas cleaning in biomass fired applications

    DEFF Research Database (Denmark)

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

    2011-01-01

    Cu/zeolite catalysts have been prepared by wet impregnation and characterized by N2 physisorption, EPR, H2-TPR and NH3-TPD methods. The Cu content was varied to optimize the loading as well as surface acidity. Optimized Cu/zeolite catalysts showed high surface acidity and excellent activity...

  14. 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.

  15. 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...

  16. Chemisorbed and physisorbed structures for 1,10-phenanthroline and dipyrido[3,2-a : 2 ',3 '-c]phenazine on au(111)

    DEFF Research Database (Denmark)

    Cafe, P.F.; Larsen, Allan G.; Yang, W.R.

    2007-01-01

    Scanning tunneling microscopy (STM) images of 1,10-phenanthroline (PHEN) and dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) on Au(111) are recorded using both in situ and ex situ techniques. The images of PHEN depict regimes of physisorption and chemisorption, whereas DPPZ is only physisorbed. All physi...

  17. Mesopore formation in zeolite H-SSZ-13 by desilication with NaOH

    NARCIS (Netherlands)

    Sommer, L.; Mores, D.; Svelle, S.; Stöcker, M; Weckhuysen, B.M.; Olsbye, U.

    2013-01-01

    A zeolite H-SSZ-13 material with CHA topology and a Si/Al ratio of 14 was treated with sodium hydroxide solutions of various concentrations. The post synthesis treatment led to desilication of the framework accompanied by mesopore formation. N2-physisorption measurements showed that the mesopore vol

  18. Effect of Peptization on Densification and Phase-Transformation Behavior of Sol–Gel-Derived Nanostructured Titania

    NARCIS (Netherlands)

    Kumar, Krishnankutty-Nair P.; Kumar, Jalajakumari; Keizer, Klaas

    1994-01-01

    Porosity reduction, packing, pore-size distribution, and anatase to rutile phase transformation behavior of nanostructured titania ceramics prepared from both peptized and unpeptized sols were studied and compared using XRD, DSC, and nitrogen-gas physisorption techniques. Precursor gels prepared fro

  19. Textural stability of titania–alumina composite membranes

    NARCIS (Netherlands)

    Kumar, Krishnankutty-Nair P.; Keizer, Klaas; Burggraaf, Anthonie J.

    1993-01-01

    Textural evolution (porosity reduction, pore and crystallite growth) in titania–alumina composite membranes has been studied using thermal analysis, X-ray diffraction, field emission scanning electron microscopy and N2 physisorption techniques. The presence of alumina in the membranes improved the t

  20. Adsorption of $^4$He on a single C$_{60}$

    OpenAIRE

    Szybisz, Leszek; Urrutia, Ignacio

    2003-01-01

    The adsorption of $^4$He inside and outside a single fullerene C$_{60}$ is studied. A physisorption potential is proposed. The energetics and structural features of C$_{60}$-$^4$He$_N$ clusters are investigated. Particular attention is paid to the growth of the highly pronounced layered density profile. The evolution towards bulk liquid and surface thickness at the free interface are discussed.

  1. Adsorption of 4He on a Single C60

    Science.gov (United States)

    Szybisz, L.; Urrutia, I.

    2004-01-01

    The adsorption of $^4$He inside and outside a single fullerene C$_{60}$ is studied. A physisorption potential is proposed. The energetics and structural features of C$_{60}$-$^4$He$_N$ clusters are investigated. Particular attention is paid to the growth of the highly pronounced layered density profile. The evolution towards bulk liquid and surface thickness at the free interface are discussed.

  2. Magnetically separable nanocomposites with photocatalytic activity under visible light for the selective transformation of biomass-derived platform molecules

    Science.gov (United States)

    Novel magnetically separable TiO2-guanidine-(Ni,Co)Fe2O4 nanomaterials were prepared and characterised by a series of techniques including XRD, SEM, TEM, N2 physisorption as well as XPS and subsequently tested for their photocatalytic activities in the selective transformation of...

  3. 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...

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

    NARCIS (Netherlands)

    Sripathi, V.G.P.; Mojet, B.L.; Nijmeijer, A.; Benes, N.E.

    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 significa

  5. 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

  6. 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...

  7. Ultra Thin Film Characterization of the Organic Rectifier Project

    Science.gov (United States)

    1991-05-05

    coating by the oleophobic method 𔃼 ito a monofunctionalized TCNQ acceptor. prepared in high y ield. hsdrox\\sl-coated electrode ". As discussed above...Bigelow oleophobic (BO) film-casting technique [29-321. The forces binding an LB or BO monolayer to the substrate are usually weak physisorptive or

  8. 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...

  9. 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/Vis...

  10. 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-.......Relative SCR activity of catalysts at 450 °C....

  11. 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 s......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...

  12. Corrosion inhibition of 6061 Al-15 vol. pct. SiC(p) composite and its base alloy in a mixture of sulphuric acid and hydrochloric acid by 4-(N,N-dimethyl amino) benzaldehyde thiosemicarbazone

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Geetha Mable [Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Srinivasnagar 575 025, Mangalore, Karnataka (India); Nayak, Jagannath [Department of Metallurgical and Materials Engineering, National Institute of Technology Karnataka, Surathkal, Srinivasnagar 575 025, Karnataka (India); Shetty, A. Nityananda, E-mail: nityashreya@gmail.com [Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Srinivasnagar 575 025, Mangalore, Karnataka (India)

    2011-02-15

    Research highlights: {yields} Corrosion inhibition of Al-SiC composite. {yields} DMABT as corrosion inhibitor. {yields} Inhibition through physisorption of DMABT. - Abstract: The corrosion inhibition characteristics of 4-(N,N-dimethylamino) benzaldehyde thiosemicarbazone (DMABT) on the corrosion behavior of 6061 Al-15 vol. pct. SiC(p) composite and its base alloy were studied at different temperatures in acid mixture medium containing varying concentrations of hydrochloric acid and sulphuric acid using Tafel extrapolation technique and ac impedance spectroscopy (EIS). The effect of inhibitor concentration, temperature and concentration of the acid mixture media on the inhibitor action was investigated. It was found that inhibition efficiencies increase with the increase in inhibitor concentration, but decrease with the increase in temperature and with the increase in concentration of the acid media. Thermodynamic parameters for dissolution process were determined. The adsorption of DMABT on both the composite and base alloy was found to be through physisorption obeying Freundlich adsorption isotherm.

  13. 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.

  14. Stepwise isotherms and phase transitions in physisorbed films

    Science.gov (United States)

    Thorny, André; Duval, Xavier

    1994-01-01

    The present paper outlines the evolution during the last thirty years of research in the field of physisorption of gases on solids with a homogeneous surface. It relates this evolution as lived by some researchers of a physical chemistry laboratory whose objective was not originally to study physisorption as such, but to use it as a method to determine the specific surface area of solids participating in gas reactions. Consequently, the aim is not to give a complete review even of only those results obtained from adsorption isotherms, but simply to recall the way which led to the discovery of several of the most typical adsorption phenomena, i.e.: "gas-liquid-solid" and "commensurate-incommensurate" 2D transitions, 2D polymorphism, wetting transitions and specific behaviour of mixed films.

  15. Vanadia supported on zeolites for SCR of NO by ammonia

    DEFF Research Database (Denmark)

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

    2010-01-01

    Vanadia supported on zeolites were prepared and characterized by N-2 physisorption, FTIR. XRPD, and NH3-TPD methods. The influence of the Si/Al ratio on the total surface acidity of the catalysts as well as the optimum V2O5 content were studied and compared with the catalytic activity in the sele......Vanadia supported on zeolites were prepared and characterized by N-2 physisorption, FTIR. XRPD, and NH3-TPD methods. The influence of the Si/Al ratio on the total surface acidity of the catalysts as well as the optimum V2O5 content were studied and compared with the catalytic activity......, acidity and micropore structure of the support. Apparently the support hosted the potassium oxide on the acid sites, thereby protecting the active vanadium species from poisoning. Zeolite based catalysts might therefore prove useful for SCR of NO in alkali-containing flue gases from, e.g. biomass fired...

  16. Revealing the multi-bonding state between hydrogen and graphene-supported Ti clusters

    CERN Document Server

    Takahashi, Keisuke; Omori, Kengo; Mashoff, Torge; Convertino, Domenica; Miseikis, Vaidotas; Coletti, Camilla; Tozzini, Valentina; Heun, Stefan

    2016-01-01

    Hydrogen adsorption on graphene-supported metal clusters has brought much controversy due to the complex nature of the bonding between hydrogen and metal clusters. The bond types of hydrogen and graphene-supported Ti clusters are experimentally and theoretically investigated. Transmission electron microscopy shows that Ti clusters of nanometer-size are formed on graphene. Thermal desorption spectroscopy captures three hydrogen desorption peaks from hydrogenated graphene-supported Ti clusters. First principle calculations also found three types of interaction: Two types of bonds with different partial ionic character and physisorption. The physical origin for this rests on the charge state of the Ti clusters: when Ti clusters are neutral, H2 is dissociated, and H forms bonds with the Ti cluster. On the other hand, H2 is adsorbed in molecular form on positively charged Ti clusters, resulting in physisorption. Thus, this work clarifies the bonding mechanisms of hydrogen on graphene-supported Ti clusters.

  17. Effect of incorporation manner of Zr promoter on precipitated ironbased catalysts for Fischer-Tropsch synthesis

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hao-jian; MA Hong-fang; ZHANG Hai-tao; YING Wei-yong; FANG Ding-ye

    2012-01-01

    The promotional effects of Zr on the structure,reduction,carburization and catalytic behavior of precipitated iron-based Fischer-Tropsch synthesis (FTS) catalysts were investigated.The catalysts were characterized by N2 physisorption,temperature-programmed reduction (TPR),and M(o)ssbauer effect spectroscopy (MES) techniques.As revealed by N2 physisorption,Zr decreased the BET surface area and pore volume of the catalyst.The results of TPR and MES show that Zr suppresses the reduction and carburization of Fe catalysts because of the interaction between Fe and Zr.The FTS reaction results indicate that Zr decreases the FTS activity of Fe catalysts but improves the catalysts' stability.In addition,Zr promoter restraines the formation of light hydrocarbons (methane and C2~C4) and shifts the production distribution to the heavy hydrocarbons.

  18. 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)

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

    KAUST Repository

    Pham, Tony T.

    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. Separation of CO2/CH4 mixtures in the mesoporous MIL-100(Cr) MOF : experimental and modelling approaches

    OpenAIRE

    Hamon, L.; Heymans, Nicolas; Llewellyn, P. L.; Guillerm, V.; Ghoufi, Aziz; Vaesen, Sébastien; Maurin, Guillaume; Serre, Christian; De Weireld, Guy; Pirngruber, Gerhard

    2012-01-01

    International audience; Carbon dioxide is the main undesirable compound present in raw natural gas and biogas. Physisorption based adsorption processes such as pressure swing adsorption (PSA) are one of the solutions to selectively adsorb CO(2) from CH(4). Some hybrid crystalline porous materials that belong to the family of metal-organic frameworks (MOFs) show larger CO(2) adsorption capacity compared to the usual industrial adsorbents, such as zeolites and most activated carbons, which make...

  1. MnFe/Al2O3 Catalyst Synthesized by Deposition Precipitation for Low-Temperature Selective Catalytic Reduction of NO with NH3

    DEFF Research Database (Denmark)

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

    2015-01-01

    Mn-Fe/Al2O3 and Mn-Fe/TiO2 catalysts have been prepared by impregnation (IMP) and deposition precipitation (DP) and characterized with several techniques including: XRDP, N2-physisorption, NH3-TPD, H2-TPR, TGA and XPS. 40 wt% Mn0.75Fe0.25/Al2O3 prepared with ammonia carbamate as precipitating agent...

  2. 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

  3. A quantitative method to discriminate between non-specific and specific lectin-glycan interactions on silicon-modified surfaces.

    Science.gov (United States)

    Yang, Jie; Siriwardena, Aloysius; Boukherroub, Rabah; Ozanam, François; Szunerits, Sabine; Gouget-Laemmel, Anne Chantal

    2016-02-15

    Essential to the success of any surface-based carbohydrate biochip technology is that interactions of the particular interface with the target protein be reliable and reproducible and not susceptible to unwanted nonspecific adsorption events. This condition is particularly important when the technology is intended for the evaluation of low-affinity interactions such as those typically encountered between lectins and their monomeric glycan ligands. In this paper, we describe the fabrication of glycan (mannoside and lactoside) monolayers immobilized on hydrogenated crystalline silicon (111) surfaces. An efficient conjugation protocol featuring a key "click"-based coupling step has been developed which ensures the obtention of interfaces with controlled glycan density. The adsorption behavior of these newly developed interfaces with the lectins, Lens culinaris and Peanut agglutinin, has been probed using quantitative IR-ATR and the data interpreted using various isothermal models. The analysis reveals that protein physisorption to the interface is more prevalent than specific chemisorption for the majority of washing protocols investigated. Physisorption can be greatly suppressed through application of a strong surfactinated rinse. The coexistence of chemisorption and physisorption processes is further demonstrated by quantification of the amounts of adsorbed proteins distributed on the surface, in correlation with the results obtained by atomic force microscopy (AFM). Taken together, the data demonstrates that the nonspecific adsorption of proteins to these glycan-terminated surfaces can be effectively eliminated through the proper control of the chemical structure of the surface monolayer combined with the implementation of an appropriate surface-rinse protocol.

  4. Theoretical study on the initial reaction mechanisms of ansa-metallocene zirconium precursor on hydroxylated Si(1 0 0) surface.

    Science.gov (United States)

    Zhou, Guangfen; Ren, Jie; Zhang, Shaowen

    2016-05-01

    The initial reaction mechanisms for depositing ZrO2 thin films using ansa-metallocene zirconium (Cp2CMe2)ZrMe2 precursor were studied by density functional theory (DFT) calculations. The (Cp2CMe2)ZrMe2 precursor could be absorbed on the hydroxylated Si(1 0 0) surface via physisorption. Possible reaction pathways of (Cp2CMe2)ZrMe2 were proposed. For each reaction, the activation energies and reaction energies were compared, and stationary points along the reaction pathways were shown. In addition, the influence of dispersion effects on the reactions was evaluated by non-local dispersion corrected DFT calculations.

  5. Synthesis and characterization of simultaneously-impregnated Co-Mo-P on Al-MCM41. Effect of support precursors

    OpenAIRE

    Agileo Hernández; José Escobar; José G. Pacheco; José A. De Los Reyes; María C. Barrera

    2004-01-01

    Al-MCM-41 (SiO2/Al2O3=200) materials from various Al and Si sources were synthesized. The calcined solids (823 K) were characterized by N2 physisorption, X-ray diffraction and surface acidity measurements. The sample from tetraethyl orthosilicate-Al(SO4)3 had decreased surface area (836 m2/g) and pore volume (0.88 cm3/g), meanwhile the lowest amount of Al3+ incorporated into the MCM41 walls was registered when SiO2-boehmite was used as precursor. Co, Mo and P (~3, ~12.5 and ~1.6 weight %, res...

  6. Preparación y caracterización de óxidos mixtos nanoestructurados soportados sobre MgO

    Directory of Open Access Journals (Sweden)

    Jairo Rondón

    2010-05-01

    Full Text Available Mixed oxide catalysts of Co, Ni, Cu and Mn supported on MgO were synthesized using two different methods to obtain nanoparticles: the combustion method with urea and the sol-gel modified with citric acid. Different techniques were used to determine their physicochemical properties. X-ray diffraction (XRD, the N2 physisorption by BET method, the temperature programmed reduction (TPR-H2, scanning electron microscopy (SEM and energy dispersive X-ray (EDX. The results show particle sizes between 5 and 31nm in diameter for solid preparations. Co and Mn show changes in their oxidation states.

  7. 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.

  8. 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.

  9. Magnesium nanocrystals embedded in a metal-organic framework: hybrid hydrogen storage with synergistic effect on physi- and chemisorption.

    Science.gov (United States)

    Lim, Dae-Woon; Yoon, Ji Woong; Ryu, Keun Yong; Suh, Myunghyun Paik

    2012-09-24

    Hexagonal-disk-shaped magnesium nanocrystals (MgNCs) are fabricated within a porous metal-organic framework (MOF, see picture). The MgNCs@MOF stores hydrogen by both physi- and chemisorptions, exhibiting synergistic effects to decrease the isosteric heat of H(2) physisorption compared with that of pristine MOF, and decrease the H(2) chemisorption/desorption temperatures by 200 K compared with those of bare Mg powder. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Substantial enhancement in the anticorrosivity of AA6061 by Doxycycline hydrochloride drug

    Directory of Open Access Journals (Sweden)

    Mudigere Krishnegowda Pavithra

    2015-08-01

    Full Text Available The significant anticorrosive property of the antibiotic drug doxycycline hydrochloride (DCH was investigated by electrochemical techniques such as potentiodynamic polarization, electrochemical impedance and chronoamperometric techniques. DCH inhibited the pitting corrosion of aluminium alloy 6061 (AA6061 in 3.5% NaCl media with 90% efficiency. The adsorption of DCH on AA6061 conform Langmuir isotherm by means of physisorption.  Quantum chemical calculations were evaluated to ascertain the active sites of DCH molecule responsible for adsorption and to support the experimental findings.

  11. Outstanding inhibitive effect of colchicine on aluminium alloy 6061 corrosion

    Directory of Open Access Journals (Sweden)

    Mudigere Krishnegowda Pavithra

    2015-12-01

    Full Text Available The corrosion protection ability of colchicine (CC on Aluminium alloy 6061 (AA6061 in 3.5% NaCl medium was examined by potentiodynamic polarization, electrochemical impedance, and chronoamperometric techniques. About 99 % of protection efficiency was achieved by 2 mM concentration of CC in 3.5% NaCl solution.The adsorption of CC on AA6061 surface obeys Langmuir isotherm by following both physisorption and chemisorption mechanism. Variation in the surface morphology of inhibited and uninhibited metal samples was examined by scanning electron microscopy. 

  12. On the mechanism of reactive adsorption of dibenzothiophene on organic waste derived carbons

    Science.gov (United States)

    Ania, C. O.; Parra, J. B.; Arenillas, A.; Rubiera, F.; Bandosz, T. J.; Pis, J. J.

    2007-04-01

    The mechanism of reactive adsorption of dibenzothiophene (DBT) on a series of modified carbons derived from the recycled PET was investigated. The influence of the oxygen functionalities of the adsorbent on the DBT adsorption capacity was explored. The results revealed that adsorption of DBT on activated carbons is governed by two types of contributions: physisorption on the microporous network of the carbons and chemisorption. Introduction of surface acidic groups enhanced the performance of the carbons as a result of their specific interactions with DBT. The nature of the acidic groups is a decisive factor in the selectivity of the reactive adsorption process.

  13. 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

    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...

  14. Analysis of CuInSe2: Electron and ion beam effects

    Science.gov (United States)

    Kazmerski, L. L.; Burnham, N. A.; Swartzlander, A. B.; Nelson, A. J.; Asher, S. E.

    The effects of electron and ion beams used in the analysis of CuInSe2 surfaces are examined. Potential changes in the surface chemistry-including oxidation, desorption and preferential species removal-under a range of incident probe conditions are investigated for possible artifactural information generation. Emphasis is placed on the relationships between beam conditions and oxygen chemisorption and physisorption, since oxygen treatments of devices utilizing this semiconductor are critial to performance. Single crystals and polycrystalline thin films are analyzed and compared to establish the beam-induced phenomena.

  15. Electron beam effects in the analysis of compound semiconductors and devices

    Energy Technology Data Exchange (ETDEWEB)

    Kazmerski, L.L.; Burnham, N.A.; Swartzlander, A.B.; Nelson, A.J.; Asher, S.E.

    1987-09-01

    The effects of electron beams on the analysis of CuInSe/sub 2/ surfaces are examined in this paper. Potential changes in the surface chemistry: including oxidation and desorption: under a range of incident probe conditions, are investigated for possible artifactual information generation. Emphasis is placed on the relationships between beam conditions and oxygen chemisorption and physisorption, since oxygen treatments of devices utilizing this semiconductor are critical to performance. Single crystals and polycrystalline thin films are analyzed and compared to establish the beam-induced phenomena.

  16. 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....

  17. Creation of surface defects on carbon nanofibers by steam treatment

    Institute of Scientific and Technical Information of China (English)

    Zhengfeng; Shao; Min; Pang; Wei; Xia; Martin; Muhler; Changhai; Liang

    2013-01-01

    A direct strategy for the creation of defects on carbon nanofibers (CNFs) has been developed by steam treatment.Nitrogen physisorption,XRD,Raman spectra,SEM and TEM analyses proved the existence of the new defects on CNFs.BET surface area of CNFs after steam treatment was enhanced from 20 to 378 m2/g.Pd catalysts supported on CNFs were also prepared by colloidal deposition method.The different activity of Pd/CNFs catalysts in the partial hydrogenation of phenylacetylene further demonstrated the diverse surfaces of CNFs could be formed by steam treatment.

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

    Science.gov (United States)

    Fediai, Artem; Ryndyk, Dmitry A.; Seifert, Gotthard; Mothes, Sven; Schroter, Michael; Claus, Martin; Cuniberti, Gianaurelio

    2016-09-01

    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.

  19. Effect of H-vacancy defect on the adsorption of CO and NO on graphane: A DFT study

    Science.gov (United States)

    Zhou, Qingxiao; Ju, Weiwei; Yong, Yongliang; Su, Xiangying; Li, Xiaohong; Fu, Zhibing; Wang, Chaoyang

    2017-10-01

    We investigated the adsorption of CO and NO molecules on hydrogenated graphene (graphane) monolayer using density functional theory (DFT) calculations. The geometry, adsorption stability, and electronic properties of CO and NO molecules absorbed on pure and H-vacancy defected graphane sheet were performed. The calculated results suggested that the small adsorption energy indicated the adsorption of CO and NO molecules on pure graphane were physisorption. However, the presence of H-vacancy improved the reactivity of graphane and the adsorption on H-vacnacy defected graphane changed to chemisorption. The adsorption also induced obvious change into the band gaps, which can be seen as signal to detect the CO and NO gas.

  20. 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......)-TPD. Due to the high-surface area anatase particles, loading of 20 wt% vanadia could be obtained without exceeding monolayer coverage of V(2)O(5). This resulted in unprecedented high deNO(x) SCR activity corresponding to a factor of two compared to an industrial reference and to other V(2)O(5)/TiO(2...

  1. Basics and applications of cryopumps

    CERN Document Server

    Day, C

    2007-01-01

    This report introduces the wide field of cryogenic pumping, from commercial cryogen-free refrigerator cryopumps to very special, tailor-made cryopumps. It starts with a short historic overview of the field of cryopumping. Then, the principles of cryogenic pumping via sublimation/condensation and physisorption are introduced, and we illustrate how they are exploited to derive a design for a usable cryopump. In the third part, typical characteristics of cryosorption pumps are discussed. The report finishes with a few examples of applications.

  2. Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

    Directory of Open Access Journals (Sweden)

    M. C. Leuenberger

    2015-08-01

    Full Text Available It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i physisorption and (ii chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−1 compared to chemisorption ranging from 100 to 1000 kJ mol−1. Furthermore, chemisorption forms only monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws, however, it can be influenced by hysteresis effects. In the present experiment we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. We proved the pressure effect on physisorption for CO2, CH4 and H2O by decanting one steel and two aluminium cylinders completely. The CO2 results for both cylinders are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, adsorption on aluminium (2 and H2O was about 10 times less than on steel (2 amounts adsorbed (5.8 × 1019 CO2 molecules corresponds to about the five-fold monolayer adsorption indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH4 and for CO. However, the latter dependence requires further attention since it was only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2 ranging from 0.0014 to 0.0184 ppm °C−1 for steel cylinders and −0.0002 to −0.0003 ppm °C−1 for aluminium cylinders. The reversed temperature dependence for aluminium cylinders

  3. Interaction of atomic hydrogen with anthracene and polyacene from density functional theory

    Science.gov (United States)

    Ferullo, Ricardo M.; Castellani, Norberto J.; Belelli, Patricia G.

    2016-03-01

    The interaction of atomic hydrogen with two linear polycyclic aromatic hydrocarbons (PAHs), anthracene and polyacene (the polymer of benzene), was studied within the density functional theory (DFT). Using a proper dispersion-corrected method (DFT-D) the preferential physisorption sites were explored. The activation barrier for the bond formation between a peripheral C and the incoming H was calculated to be 58.5 and 34.1 meV with pure DFT on anthracene and polyacene at its antiferromagnetic ground state, respectively. DFT-D, although improves the description of the physisorbed state, tends to underestimate the chemisorption barriers due an artifact arising from the dispersion correction.

  4. 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.

  5. CARACTERIZAÇÃO E ATIVIDADE CATALÍTICA DE K2CO3/AL2O3 NA TRANSESTERIFICAÇÃO DO ÓLEO DE GIRASSOL COM AQUECIMENTO CONVENCIONAL E MICRO-ONDAS

    Directory of Open Access Journals (Sweden)

    Paola E. Gama

    2015-02-01

    Full Text Available Commercial and synthetic mesoporous aluminas impregnated with potassium carbonate were characterized by X-ray diffraction (XRD, nitrogen physisorption, infrared spectroscopy and 27Al MAS NMR. The activities in the transesterification reaction of sunflower oil with methanol for biodiesel production were evaluated. 27Al MAS NMR spectra evidenced the presence of AlIV and AlVI in the samples, and also of AlV sites in the mesoporous synthesized alumina, which disappeared after impregnation with potassium salt followed by calcination. All aluminas containing potassium were active for biodiesel production from sunflower seed oil, with high conversions by both conventional heating and microwave irradiation.

  6. Inhibitory Action of Artemisia annua Extracts and Artemisinin on the Corrosion of Mild Steel in H2SO4 Solution

    Directory of Open Access Journals (Sweden)

    P. C. Okafor

    2012-01-01

    Full Text Available The action of ethanol (EEAA, acid (AEAA, and toluene (TEAA extracts from Artemisia annua and Artemisinin (ATS on mild steel corrosion in H2SO4 solutions was investigated using gravimetric and gasometric techniques. The extracts and ATS functioned as good inhibitors, and their inhibition efficiencies (%IE followed the trend: EEAA > AEAA > TEAA > ATS. %IE increased with increase in inhibitors concentration and decreased with increase in temperature. The enhanced %IE values of the extracts were attributed to synergistic effect of the components of the plant extracts with ATS. The adsorption of the inhibitors was consistent with Langmuir isotherm. Physisorption is proposed as the mechanism of inhibition.

  7. Adsorption and Inhibitive Properties of Triazolo- pyrimidine Derivatives in Acid Corrosion of Mild Steel

    Directory of Open Access Journals (Sweden)

    K. Parameswari

    2011-01-01

    Full Text Available Inhibitive and adsorption properties of synthesized triazolo- pryimidine derivatives (P1, P2 & P3 for the corrosion of mild steel was investigated using weight loss and electrochemical methods. Inhibition efficiency increased as the concentration of the inhibitor increased but decreased with increase in temperature. The triazolopyrimidines were found to act as adsorption inhibitors for the corrosion of mild steel. The adsorption mechanism of the triazolopyrimidine was found to be physisorption, spontaneous and exothermic. Also the adsorption followed Langmuir adsorption isotherm. polarisation studies showed that the inhibitors behave as cathodic type.

  8. A solvent evaporation route towards fabrication of hierarchically porous ZSM-11 with highly accessible mesopores

    DEFF Research Database (Denmark)

    Song, Wen; Liu, Zhiting; Liu, Liping;

    2015-01-01

    in dry gel has been found to undergo an orientated attachment growth mechanism whereby hexadecyltrimethoxysilane directs the formation of auxiliary mesopores and inhibits the fusion of primary nucleates. Measurements such as XRD, SEM, TEM, N2-physisorption, and TEM for an inverse replica of Pt derived...... from hierarchical ZSM-11 have been conducted to characterize the textural properties of the material. Ammonia temperature-programmed-desorption (NH3-TPD) measurements and infrared spectra using probe molecules such as pyridine (Py-IR) and 2,4,6-collidine (Coll-IR) have been collected to investigate...

  9. Comparison of Two Preparation Methods on Catalytic Activity and Selectivity of Ru-Mo/HZSM5 for Methane Dehydroaromatization

    Directory of Open Access Journals (Sweden)

    Lucia M. Petkovic

    2014-01-01

    Full Text Available Catalytic performance of Mo/HZSM5 and Ru-Mo/HZSM5 catalysts prepared by vaporization-deposition of molybdenum trioxide and impregnation with ammonium heptamolybdate was analyzed in terms of catalyst activity and selectivity, nitrogen physisorption analyses, temperature-programmed oxidation of carbonaceous residues, and temperature-programmed reduction. Vaporization-deposition rendered the catalyst more selective to ethylene and coke than the catalyst prepared by impregnation. This result was assigned to lower interaction of molybdenum carbide with the zeolite acidic sites.

  10. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    OpenAIRE

    V.Viditha, M.Venkateswer Rao, K.Srilatha11, V.Himabindu, Anjaneyulu Yerramilli

    2013-01-01

    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 pap...

  11. A Covalent Organic Framework that Exceeds the DOE 2015 Volumetric Target for H2 Uptake at 298 K.

    Science.gov (United States)

    Mendoza-Cortes, Jose L; Goddard, William A; Furukawa, Hiroyasu; Yaghi, Omar M

    2012-09-20

    Physisorption in porous materials is a promising approach for meeting H2 storage requirements for the transportation industry, because it is both fully reversible and fast at mild conditions. However, most current candidates lead to H2 binding energies that are too weak (leading to volumetric capacity at 298 K of MOF-200 and MOF-177, are predicted to store 7.6 g/L (0.54 wt % excess) and 9.6 g/L (0.87 wt % excess), respectively, at 298 K and 100 bar compared with 60 g/L (4.2 wt % excess) for COF-301-PdCl2.

  12. 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.

  13. 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.

  14. Electronic Properties of Hydrogen Storage Materials with Photon-in/Photon-out Soft-X-Ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Jinghua

    2008-09-22

    The applications of resonant soft X-ray emission spectroscopy on a variety of carbon systems have yielded characteristic fingerprints. With high-resolution monochromatized synchrotron radiation excitation, resonant inelastic X-ray scattering has emerged as a new source of information about electronic structure and excitation dynamics. Photon-in/photon-out soft-X-ray spectroscopy is used to study the electronic properties of fundamental materials, nanostructure, and complex hydrides and will offer potential in-depth understanding of chemisorption and/or physisorption mechanisms of hydrogen adsorption/desorption capacity and kinetics.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Morphological phase diagrams of C60 and C70 films on graphite

    Science.gov (United States)

    Sato, Kazuma; Tanaka, Tomoyasu; Akaike, Kouki; Kanai, Kaname

    2017-10-01

    The morphologies of C60 and C70 fullerene films vacuum-deposited onto graphite at various deposition rates and grown at several temperatures were investigated using atomic force microscopy. These fullerene films on graphite are model systems of physisorption of organic molecules that likely exhibit little chemical interaction with the graphite's surface. The morphologies of C60 and C70 films grown on graphite can be understood well from growth models previously reported. Comparison of the morphological phase diagrams obtained for C60 and C70 indicate that the diffusion properties of the adsorbed molecule are key in determining the morphology of the obtained film. The low diffusion rate of C70 resulted in various film morphologies for all deposition conditions tested. Also, the obtained phase diagrams can be understood by the results of fractal dimension analysis on the C60 and C70 islands. The fundamental understanding of film growth obtained using these ideal physisorption systems will aid in understanding film growth by other molecular adsorption systems.

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

    Science.gov (United States)

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

    2017-07-01

    In this paper, a novel mesoporous sulfated zirconium (M-ZrO2/SO42-) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N2-physisorption and TEM characterization techniques indicated that M-ZrO2/SO42- possessed distinct mesostructure with big specific surface area (133.5 m2 g-1), large pore volume (0.18 cm3 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, N2-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO42-, improved the textural properties of prepared materials. In addition, the NH3-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO2/SO42- even evacuated at 400 °C. Furthermore, the M-ZrO2/SO42- was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  1. Chemisorption-induced n-doping of MoS{sub 2} by oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Long; Wang, Ying; Wu, Yihong, E-mail: elewuyh@nus.edu.sg [Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore, Singapore 117583 (Singapore); Shen, Lei, E-mail: shenlei@nus.edu.sg [Engineering Science Program, Faculty of Engineering, National University of Singapore, Singapore, Singapore 117579 (Singapore)

    2016-02-08

    Both chemisorption and physisorption affect the electronic properties of two-dimensional materials, such as MoS{sub 2}, but it remains a challenge to probe their respective roles experimentally. Through repeated in-situ electrical measurements of few-layer MoS{sub 2} field-effect transistors in an ultrahigh vacuum system with well-controlled oxygen partial pressure (6 × 10{sup −8} mbar–3 × 10{sup −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{sub 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{sub 2}, which lowers the conduction band edge locally and makes the MoS{sub 2} channel more n-type-like as compared to the as-fabricated devices.

  2. Hg0 removal from flue gas over different zeolites modified by FeCl3.

    Science.gov (United States)

    Qi, Hao; Xu, Wenqing; Wang, Jian; Tong, Li; Zhu, Tingyu

    2015-02-01

    The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg0) into oxidized mercury (Hg2+). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl3-HZSM-5 was mainly in the form of mercuric chloride (HgCl2), while on FeCl3-NaX and FeCl3-NaA it was mainly mercuric oxide (HgO).

  3. Adsorptive removal of α-endosulfan from water by hydrophobic zeolites. An isothermal study.

    Science.gov (United States)

    Yonli, Arsène H; Batonneau-Gener, Isabelle; Koulidiati, Jean

    2012-02-15

    This paper deals with the removal of α-endosulfan from water over HY and steamed HBEA zeolites. Experiments were performed to understand the adsorption mechanisms of α-endosulfan on zeolites and to determine the most efficient adsorbent for the purification of water contaminated by this pesticide. The experiments exhibit that α-endosulfan was adsorbed in the micropores. In the case of HY zeolites an adsorption of α-endosulfan molecules on BrØnsted sites was pointed out, due to a preferential water adsorption in mesopores. Moreover a physisorption of α-endosulfan occurred in micropores. For steamed HBEA zeolites physisorption in micropores was pointed out as the adsorption mode. For both types of zeolites a decrease of the adsorption capacities was noticed when the acidity of zeolites increased. There was also a linear relation between the adsorption capacities of α-endosulfan and the hydrophobicity (HI) of the samples and by determining the values of HI for a type of zeolite it was possible to deduce the uptake of α-endosulfan. The HY(40) sample was the most efficient for the removal of α-endosulfan from water because of preferential adsorption of water molecules in mesopores and lower acidity. For this sample the adsorption capacity for α-endosulfan was about 833.33 mg/g where for the most effective HBEA sample (St700(3)) the adsorption capacity was about 793.65 mg/g.

  4. Density Functional Theory with Modified Dispersion Correction for Metals Applied to Self-Assembled Monolayers of Thiols on Au(111

    Directory of Open Access Journals (Sweden)

    M. P. Andersson

    2013-01-01

    Full Text Available Using sound physical principles we modify the DFT-D2 atom pairwise semiempirical dispersion correction to density functional theory to work for metallic systems and in particular self-assembled monolayers of thiols on gold surfaces. We test our approximation for two functionals PBE-D and revPBE-D for lattice parameters and cohesive energies for Ni, Pd, Pt, Cu, Ag, and Au, adsorption energies of CO on (111 surfaces of Pd, Pt, Cu, Ag, and Au, and adsorption energy of benzene on Ag(111 and Au(111. Agreement with experimental data is substantially improved. We apply the method to self-assembled monolayers of alkanethiols on Au(111 and find reasonable agreement for PBE-D and revPBE-D for both physisorption of n-alkanethiols as well as dissociative chemisorption of dimethyl disulfide as an Au-adatom-dithiolate complex. By modifying the C6 coefficient for Au, we obtain quantitative agreement for physisorption and chemisorption for both PBE-D and revPBE-D using the same set of parameters. Our results confirm that inclusion of dispersion forces is crucial for any quantitative analysis of the thiol and thiolate bonds to the gold surface using quantum chemical calculations.

  5. 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.

  6. Adsorption of Orange II dye in aqueous solution onto surfactant-coated zeolite: characterization, kinetic and thermodynamic studies.

    Science.gov (United States)

    Jin, Xiaoying; Yu, Bing; Chen, Zuliang; Arocena, Joselito M; Thring, Ronald W

    2014-12-01

    Adsorption of anionic dye - Orange II - in aqueous solution onto hexadecyltrimethylammonium bromide (HDTMA)-coated zeolite (HCZ) reached 38.96mg/g compared with 8.13mg/g onto natural zeolite. Fourier Transform Infrared (FTIR), scanning electronic microscopy (SEM) and X-ray powder diffraction (XRD) data showed that HDTMA-coated zeolite developed surficial positive charges. The adsorption reaction fits the Freundlich isotherm (R(2)=0.93) and the value of 1/n was less than unity (=0.81) and suggest a multi-layer physi-sorption process. The kinetics of the adsorption is a pseudo-second-order model. The activation energy (Ea) of the reaction is +35.70kJ/mol to further support a physi-sorption process while the ΔH(o) (+82.79kJ/mol) is characteristic for an endothermic reaction. The ΔG(o) values of -2.33, -0.98 and -0.37kJ/mol at 25°C, 30°C and 35°C, respectively implied that the adsorption reaction was feasible and thermodynamically spontaneous. We proposed that both electrostatic interactions and partitioning process are involved in the adsorption mechanisms of Orange II dye onto HCZ. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. Theoretical assessment of graphene-metal contacts.

    Science.gov (United States)

    Janthon, Patanachai; Viñes, Francesc; Kozlov, Sergey M; Limtrakul, Jumras; Illas, Francesc

    2013-06-28

    Graphene-metal contacts have emerged as systems of paramount importance in the synthesis of high-quality and large-size patches of graphene and as vital components of nanotechnological devices. Herein, we study the accuracy of several density functional theory methods using van der Waals functionals or dispersive forces corrections when describing the attachment of graphene on Ni(111). Two different experimentally observed chemisorption states, top-fcc and bridge-top, were put under examination, together with the hcp-fcc physisorption state. Calculated geometric, energetic, and electronic properties were compared to experimental data. From the calculations, one finds that (i) predictions made by different methodologies differ significantly and (ii) optB86b-vdW functional and Grimme dispersion correction seem to provide the best balanced description of stability of physisorption and chemisorption states, the attachment strength of the latter on Ni(111) surface, the graphene-Ni(111) separation, and the bandstructure of chemisorbed graphene. The collation suggests that accurate and affordable theoretical studies on technologies based on graphene-metal contacts are already at hand.

  8. 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.

  9. 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.

  10. Quarterly Technical Progress Report - Investigation of Syngas Interaction in Alcohol Synthesis Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Murty A. Akundi

    1998-11-10

    This report presents the work done on " Investigation of Syngas Interaction in Alcohol Synthesis Catalysts" during the last quarter. The major activity during this period is on FTIR absorption studies of Co/Cr catalysts using CO as a probe molecule. Transition metals cobalt and copper play significant roles in the conversion of syngas (CO + H2 ) to liquid fuels. With a view to examine the nature of interaction between CO and metal, the FTIR spectra of CO adsorbed on Co-Cr2 O3 composites were investigated. The results indicate that as cobalt loading increases, the intensity of the CO adsorption bands increase and several vibrational modes seem to be promoted. Heat treatment of the sample revealed two distinct processes of adsorption. Bands due to physisorption disappeared while bands due to chemisorption not only increased in intensity but persisted even after desorption. It seems that the physisorption process is more active when the catalyst is fresh and is hindered when carbidic/carbonyl formations occur on the metal surfaces.

  11. Kinetics, thermodynamics and mechanistic studies of carbofuran removal using biochars from tea waste and rice husks.

    Science.gov (United States)

    Vithanage, Meththika; Mayakaduwa, S S; Herath, Indika; Ok, Yong Sik; Mohan, Dinesh

    2016-05-01

    This study reports the thermodynamic application and non-linear kinetic models in order to postulate the mechanisms and compare the carbofuran adsorption behavior onto rice husk and tea waste derived biochars. Locally available rice husk and infused tea waste biochars were produced at 700 °C. Biochars were characterized by using proximate, ultimate and surface characterization methods. Batch experiments were conducted at 25, 35, and 45 °C for a series of carbofuran solutions ranging from 5 to 100 mg L(-1) with a biochar dose of 1 g L(-1) at pH 5.0 with acetate buffer. Molar O/C ratios indicated that rice husk biochar (RHBC700) is more hydrophilic than tea waste biochar (TWBC700). Negative ΔG (Gibbs free energy change) values indicated the feasibility of carbofuran adsorption on biochar. Increasing ΔG values with the rise in temperature indicated high favorability at higher temperatures for both RHBC and TWBC. Enthalpy values suggested the involvement of physisorption type interactions. Kinetic data modeling exhibited contribution of both physisorption, via pore diffusion, π*-π electron donor-acceptor interaction, H-bonding, and van der Waals dispersion forces and chemisorption via chemical bonding with phenolic, and amine groups. Equilibrium adsorption capacities of RHBC and TWBC determined by pseudo second order kinetic model were 25.2 and 10.2 mg g(-1), respectively.

  12. Improving the quality of patchouli oil by adsorption process using surfactant modified of natural zeolite

    Science.gov (United States)

    Kuntari, Purbaningtias, Tri Esti; Wiyantoko, Bayu; Kurniawati, Puji; Prasetyoko, Didik; Suprapto

    2017-03-01

    This research concerns with the development of natural material i.e. natural zeolite. Natural zeolite were modified by surfactant treatment. Material modification has been done using cetyltrimethyllammonium bromide as cationic surfactant for mesopore template. The physicochemical characters of natural material modified and unmodified was investigated by using XRD, FTIR, nitrogen physisorption, and SEM-EDX. The XRD was used to show crystallinity structure of natural material modified and unmodified. Surfactant treatment caused decreasing crystallinity of natural zeolite. The FTIR spectra showed characteristic peaks for natural zeolite modified and unmodified, the bands around 3400-3500 cm-1 and 1635-1641 cm-1 correspond to adsorbed water and bands around finger print area were characteristic for silica and alumina. Meanwhile physisorption nitrogen profiles gave information that the pore modification by surfactant. The morphologies of natural material modified and unmodified as well as chemical composition of the particles were shown by SEM-EDX. The usage of modified material decrease acidity number into 19.47% than unmodified material, which is 7,62%. The GC analysis showed that percentage of patchouli alcohol increases and new peaks were not identified indicated there was not any reaction appeared.

  13. Removal of Chromium from Aqueous Solution Using Modified Pomegranate Peel:Mechanistic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Tariq S. Najim

    2009-01-01

    Full Text Available Modified pomegranate peel (MPGP and formaldehyde modified pomegranate peel (FMPGP were prepared and used as adsorbent for removal of Cr(VI ions from aqueous solution using batch process. The temperature variation study of adsorption on both adsorbents revealed that the adsorption process is endothermic, from the positive values of ∆H˚. These values lie in the range of physisorption. The negative values of ∆G˚ show the adsorption is favorable and spontaneous. On the other hand, these negative values increases with increase in temperature on both adsorbents, which indicate that the adsorption is preferable at higher temperatures. ∆S˚ values showed that the process is accompanied by increase in disorder and randomness at the solid solution interface due to the reorientation of water molecules and Cr(VI ions around the adsorbent surface. The endothermic nature of the adsorption was also confirmed from the positive values of activation energy, Ea, the low values of Ea confirm the physisorption mechanism of adsorption. The sticking probability, S*, of Cr(VI ion on surface of both adsorbents showed that the adsorption is preferable due to low values of S* (0< S* < 1 , but S* values are lower for FMPGP indicating that the adsorption on FMPGP is more preferable .

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

    Energy Technology Data Exchange (ETDEWEB)

    Leino, Ewelina; Kumar, Narendra; Mäki-Arvela, Päivi; Aho, Atte [Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, 20500 Turku/Åbo (Finland); Kordás, Krisztián [Chemical–Biological Centre, Department of Chemistry, Technical Chemistry, Umeå University, SE-90187 Umeå (Sweden); Laboratory of Microelectronics and Materials Physics, EMPART Research Group of Infotech Oulu, University of Oulu, PL 4500, 90014 Oulu (Finland); Leino, Anne-Riikka [Laboratory of Microelectronics and Materials Physics, EMPART Research Group of Infotech Oulu, University of Oulu, PL 4500, 90014 Oulu (Finland); Shchukarev, Andrey [Chemical–Biological Centre, Department of Chemistry, Technical Chemistry, Umeå University, SE-90187 Umeå (Sweden); Murzin, Dmitry Yu., E-mail: dmurzin@abo.fi [Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, 20500 Turku/Åbo (Finland); Mikkola, Jyri-Pekka [Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, 20500 Turku/Åbo (Finland); Chemical–Biological Centre, Department of Chemistry, Technical Chemistry, Umeå University, SE-90187 Umeå (Sweden)

    2013-12-16

    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{sub 2} properties was discussed. Moreover, the comparison of CeO{sub 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{sub 2}. Significant variations in physico-chemical properties of CeO{sub 2} by varying the preparation conditions were observed. Furthermore, the catalytic performances of CeO{sub 2} catalysts were compared in the synthesis of diethyl carbonate starting from ethanol and CO{sub 2} using butylene oxide as a dehydrating agent. The dependence of CeO{sub 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{sub 2}.

  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. 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

  17. 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

  18. Structural and electronic properties of single-walled carbon nanotubes adsorbed with 1-pyrenebutanoic acid, succinimidyl ester

    Institute of Scientific and Technical Information of China (English)

    FAN WenJie; ZHANG RuiQin

    2008-01-01

    The adsorption of a 1-pyrenebutanoic acid, succinimidyl ester (PSE) interacting with metallic armchair (n, n) carbon nanotubes (CNTs) (n=3-13)was investigated by using a density-functional tight-binding method with an empirical van der Waals force correction. In this study of large systems involving weak interactions, our calculations showed that the pyrene ring of PSE could be spontaneously absorbed onto the CNTs surface through π-π stacking at the physisorption distances. Increasing of the CNTs diameter leads to a higher adsorption energy. After adsorption of PSE on its sidewall, the geometric and electronic structures of CNTs are basically undamaged. CNTs contribute to the main peak of the elec-tron excitation procedure in the UV/vis spectrum, with a slight red shift after adsorption of PSE.

  19. Ti-Si composite oxide-supported cobalt catalysts for CO2 hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Jakrapan Janlamool; Piyasan Praserthdam; Bunjerd Jongsomjit

    2011-01-01

    In the present work,different silica-based supported cobalt (Co) catalysts were synthesized and used for CO2 hydrogenation for methanation.Different supports,such as SSP,MCM-41,TiSSP and TiMCM were used to prepare Co catalysts with 20 wt% Co loading.The supports and catalysts were characterized by means of N2 physisorption,XRD,SEM/EDX,XPS,TPR and CO chemisorption.It is found that after calcination of catalysts,Ti is present in the form of anatase.The introduction of Ti plays important roles in the properties of Co catalysts by.(i) facilitating the reduction of Co oxides species which are strongly interacted with support,(ii) preventing the formation of silicate compounds,and (iii) inhibiting the RWGS reaction.Based on CO2 hydrogenation,the CoTiMCM catalyst exhibites the highest activity and stability.

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

    Science.gov (United States)

    Mandal, Abhishek; Singh, Neera; Nain, Lata

    2017-07-05

    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 KF values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values 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.

  1. 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.

  2. Single-walled carbon nanotube sensors for monitoring partial discharge induced dissociation of SF6.

    Science.gov (United States)

    Jung, Sehun; Choi, Jaeboong; Kim, Youngjin; Lee, Jongchul; Chang, Yongmoo; Baik, Seunghyun

    2009-12-01

    We proposed to use a miniature single-walled carbon nanotube (SWNT) sensor, fabricated by alternating current dielectrophoresis, to detect dissociated and oxidized sulfur hexafluoride (SF6) gas species generated by partial discharge (PD) activity in a concealed chamber such as gas-insulated switchgear (GIS). The SWNT sensor did not react with pure SF6 gas but sensitively responded to the dissociated and oxidized SF6 species. Also, the SWNT sensor could be regenerated by purging with fresh air since the transduction was based on the physisorption of analytes. Therefore, the SWNT sensor is a promising device for the detection of the dissociated and oxidized SF6 species and for the monitoring of the PD activity inside GIS.

  3. Investigation of a Solution-Processable, Nonspecific Surface Modifier for Low Cost, High Work Function Electrodes.

    Science.gov (United States)

    Hinckley, Allison C; Wang, Congcong; Pfattner, Raphael; Kong, Desheng; Zhou, Yan; Ecker, Ben; Gao, Yongli; Bao, Zhenan

    2016-08-03

    We demonstrate the ability of the highly fluorinated, chemically inert copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) to significantly increase the work function of a variety of common electrode materials. The work function change is hypothesized to occur via physisorption of the polymer layer and formation of a surface dipole at the polymer/conductor interface. When incorporated into organic solar cells, an interlayer of PVDF-HFP at an Ag anode increases the open circuit voltage by 0.4 eV and improves device power conversion efficiency by approximately an order of magnitude relative to Ag alone. Solution-processable in air, PVDF-HFP thin films provide one possible route toward achieving low cost, nonreactive, high work function electrodes.

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

    KAUST Repository

    Jilili, Jiwuer

    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.

  5. Calibration of Surface Plasmon Resonance Imager for Biochemical Detection

    Directory of Open Access Journals (Sweden)

    T. Ktari

    2012-01-01

    Full Text Available We present a new Surface Plasmon Resonance imager (SPRi based on immobilized T4-phage for bacteria detection. First, we present the sensitivity of the SPR imager towards refractive index variation for biosensor application. The SPR imager can be calibrated versus different percentage of triethylene glycol mixture in ultrapure water. The system can be used as a refractometer with sensitivity below 5×10−5 in the range of 1.33300–1.34360. Second, bacteriophage (T4-phage can be physisorbed on gold microarray spots for bacteria detection. The kinetic physisorption of different concentrations of T4-phages can be observed in real time. Finally, two types of bacteria such as E. coli (gram negative and Lactobacillus (gram positive were used for positive and negative tests. The results show a selectivity of T4-phage toward E. coli with a detection limit below 104 CFU/mL and with good reproducibility.

  6. Design Principles of Inert Substrates for Exploiting Gold Clusters’ Intrinsic Catalytic Reactivity

    Science.gov (United States)

    Gao, Wang; Ting Cui, Ting; Fu Zhu, Yong; Wen, Zi; Zhao, Ming; Chen Li, Jian; Jiang, Qing

    2015-10-01

    Ultralow stability of gold clusters prohibits the understanding of their intrinsic reactivity (that is vital for revealing the origin of gold’s catalytic properties). Using density functional theory including many-body dispersion method, we aim to ascertain effective ways in exploiting gold clusters’ intrinsic reactivity on carbon nanotubes (CNTs). We find that the many body van der Waals interactions are essential for gold clusters’ reactivity on CNTs and even for O2 activation on these supported clusters. Furthermore, curvature and dopant of CNTs are found to qualitatively change the balance between physisorption and chemisorption for gold clusters on CNTs, determining the clusters’ morphology, charge states, stability, and reactivity, which rationalize the experimental findings. Remarkably, N doped small curvature CNTs, which effectively stabilize gold clusters and retain their inherent geometric/electronic structures, can be promising candidates for exploiting gold clusters’ intrinsic reactivity.

  7. Structural and electronic properties of single-walled carbon nanotubes adsorbed with 1-pyrenebutanoic acid,succinimidyl ester

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The adsorption of a 1-pyrenebutanoic acid, succinimidyl ester (PSE) interacting with metallic armchair (n, n) carbon nanotubes (CNTs) (n= 3-13) was investigated by using a density-functional tight-binding method with an empirical van der Waals force correction. In this study of large systems involving weak interactions, our calculations showed that the pyrene ring of PSE could be spontaneously absorbed onto the CNTs surface through π-π stacking at the physisorption distances. Increasing of the CNTs diameter leads to a higher adsorption energy. After adsorption of PSE on its sidewall, the geometric and electronic structures of CNTs are basically undamaged. CNTs contribute to the main peak of the electron excitation procedure in the UV/vis spectrum, with a slight red shift after adsorption of PSE.

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

    Science.gov (United States)

    Jiwuer, Jilili; Abdurahman, Ayjamal; Gülseren, Oğuz; Schwingenschlögl, Udo

    2015-03-01

    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 (GGA) a non-binding state, whereas the local density approximation (LDA) predicts reasonable binding energies. The results coincide after inclusion of van der Waals (vdW) 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. Research reported in this publication was supported by the King Abdullah University of Science and Technology (KAUST).

  9. NiMo/Al{sub 2}O{sub 3}-MgO (x) catalysts. The effect of the prolonged exposure to ambient air on the textural and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Solis, D.; Klimova, T.; Ramirez, J. [Departamento de Ingenieria Quimica, Facultad de Quimica, UNAM. Cd. Universitaria,, Coyoacan (Mexico); Cortez, T. [Instituto Mexicano del Petroleo, Tratamiento de Crudo Maya, Eje central Lazaro Cardenas 152, Col. San Bartolo Atepehuacan, C.P. (Mexico)

    2004-11-24

    In the search to obtain stable catalysts for selective elimination of sulfur from gasoline, maintaining octane number, NiMo catalysts supported on Al-Mg mixed oxides were prepared by the sol-gel method and evaluated after 6-month storage in contact with ambient air, the results were compared with the freshly prepared samples. Both, freshly prepared and aged samples were characterized by nitrogen physisorption measurements (S{sub BET}), infrared spectroscopy (FT-IR) and X-ray powder diffraction (XRD) and high-resolution electron microscopy (HREM), they were tested in the thiophene hydrodesulfurization reaction.The results indicate that the incorporation of small amounts of magnesia (5mol%) into the alumina support, leads to the catalyst with low hydrogenation function and appropriate stability during prolonged contact with ambient conditions.

  10. NOx abatement in the exhaust of lean-burn natural gas engines over Ag-supported γ-Al2O3 catalysts

    Science.gov (United States)

    Azizi, Y.; Kambolis, A.; Boréave, A.; Giroir-Fendler, A.; Retailleau-Mevel, L.; Guiot, B.; Marchand, O.; Walter, M.; Desse, M.-L.; Marchin, L.; Vernoux, P.

    2016-04-01

    A series of Ag catalysts supported on γ-Al2O3, including two different γ-Al2O3 supports and various Ag loadings (2-8 wt.%), was prepared, characterized (SEM, TEM, BET, physisorption, TPR, NH3-TPD) and tested for the selective catalytic reduction of NOx by CH4 for lean-burn natural gas engines exhausts. The catalysts containing 2 wt.% Ag supported on γ-Al2O3 were found to be most efficient for the NOx reduction into N2 with a maximal conversion of 23% at 650 °C. This activity was clearly linked with the ability of the catalyst to concomitantly produce CO, via the methane steam reforming, and NO2. The presence of small AgOx nanoparticles seems to be crucial for the methane activation and NOx reduction.

  11. Preparation, structural characterization and catalytic properties of Co/CeO2 catalysts for the steam reforming of ethanol and hydrogen production

    Science.gov (United States)

    Lovón, Adriana S. P.; Lovón-Quintana, Juan J.; Almerindo, Gizelle I.; Valença, Gustavo P.; Bernardi, Maria I. B.; Araújo, Vinícius D.; Rodrigues, Thenner S.; Robles-Dutenhefner, Patrícia A.; Fajardo, Humberto V.

    2012-10-01

    In this paper, Co/CeO2 catalysts, with different cobalt contents were prepared by the polymeric precursor method and were evaluated for the steam reforming of ethanol. The catalysts were characterized by N2 physisorption (BET method), X-ray diffraction (XRD), UV-visible diffuse reflectance, temperature programmed reduction analysis (TPR) and field emission scanning electron microscopy (FEG-SEM). It was observed that the catalytic behavior could be influenced by the experimental conditions and the nature of the catalyst employed. Physical-chemical characterizations revealed that the cobalt content of the catalyst influences the metal-support interaction which results in distinct catalyst performances. The catalyst with the highest cobalt content showed the best performance among the catalysts tested, exhibiting complete ethanol conversion, hydrogen selectivity close to 66% and good stability at a reaction temperature of 600 °C.

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

    Science.gov (United States)

    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 N2-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/SiO2 catalyst showed an enhanced activity, C5+ selectivity and catalytic stability as compared to the conventional thermal calcined Co/SiO2 catalyst.

  13. Mechanism of lead (Pb2+) adsorption on natural clinoptilolite%天然斜发沸石吸附铅(Pb2+)机理

    Institute of Scientific and Technical Information of China (English)

    邵卫云; 易文涛; 周永潮; 张萍

    2015-01-01

    Desorption experiment of lead (Pb2+ ) was designed to investigate the process and leading mechanism in different stages of lead adsorption on natural clinoptilolite .Clinoptilolite samples were put into lead solutions of high and low initial mass concentrations .NaCl and HNO3 were applied for desorption test on clinoptilolite samples of different sorption stages .It is found that Pb2+ is absorbed by clinoptilolite by two main mechanisms :ion exchange and physisorption , and physisorption plays a leading role in absorption process .Ion exchange occurs mainly on the surface of clinoptilolite and reaches equilibrium in short time .Ion exchange capacity is hardly influenced by the initial mass concentration of lead solution . Moreover ,the percentage of ion exchange is higher in lead solution of low initial mass concentration .On the other hand ,physisorption process occurs mostly on the surface of clinoptilolite in lead solution of low mass concentration and reaches equilibrium quickly . While , the proportion of Pb2+ absorbed by physisorption in the lead solution of high mass concentration is higher ,w hich costs a long time to reach equilibrium .In addition ,a fraction of Pb2+ cannot be desorbed due to its strong bonds with clinoptilolite .%为了探讨沸石对Pb2+的吸附过程以及不同阶段的主导吸附机制,设计铅离子脱附实验。将沸石分别置于高质量浓度和低质量浓度的铅溶液中,并将不同吸附程度的沸石取样后进行NaCl和 HNO3脱附实验。实验发现:天然斜发沸石对P b2+的吸附机理主要包括离子交换和物理吸附,其中物理吸附占主导作用。离子交换主要发生在沸石外表面,在短时间内达到平衡,其交换量几乎不受铅溶液初始质量浓度的影响,并且低质量浓度铅溶液中的离子交换所占百分比更高。在低质量浓度的铅溶液中,物理吸附主要发生在沸石外表面,达到平衡所需时间较短;在高质量浓

  14. The effects of aging on the dynamic adsorption of hazardous organic vapors on impregnated activated carbon.

    Science.gov (United States)

    Amitay-Rosen, Tal; Leibman, Amir; Nir, Ido; Zaltsman, Amalia; Kaplan, Doron

    2015-01-01

    The effects of an eight-year natural aging of ASC impregnated activated carbon on the adsorption capacity and breakthrough times of model organic vapors and of the nerve agent sarin were investigated. Aging delayed methanol breakthrough from dry air on pre-dried carbon, but shortened the breakthrough time of both methanol and hexane under relative humidity (RH) of 30-85% on pre-humidified carbon. Aging also shortened the breakthrough time of the less volatile model compound 2-methoxyethanol, especially under RH of 60-85%. Aging significantly reduced the protection capacity against sarin at RH of 85%. The effects of aging on physisorption are attributed to enhanced hydrogen-bonding capability and strength of the interaction between water and adsorption sites on the carbon surface.

  15. Energy storage device including a redox-enhanced electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. A theoretical study on the interaction of amphetamine and single-walled carbon nanotubes

    Science.gov (United States)

    Hafizi, Hamid; Najafi Chermahini, Alireza; Mohammadnezhad, Gholamhossein; Teimouri, Abbas

    2015-02-01

    The adsorption of 1-phenyl-2-aminopropane (amphetamine) on the (4,4), (5,5), (6,6), and (7,7) single-walled carbon nanotubes (SWCNTs) has been theoretically investigated. The molecule has been located in different modes including parallel, perpendicular, and oblique on the outer surface of carbon nanotubes. The physisorption of amphetamine onto SWCNT sidewall is thermodynamically favored; as a consequence, it modulates the electronic properties of pristine nanotube in the vicinity of Fermi region. The adsorption energies for the parallel and oblique modes found in the range of -1.13 to -1.88 and -1.27 to -2.01 kcal/mol, respectively. Projected density of states (PDOS) and frontier orbital analysis in the vicinity of Fermi level region suggest the electronic states to be contributed from SWCNT rather than amphetamine molecule.

  17. Engineering nanomaterial surfaces for biomedical applications.

    Science.gov (United States)

    Wang, Xin; Liu, Li-Hong; Ramström, Olof; Yan, Mingdi

    2009-10-01

    Nanomaterials, possessing unique physical and chemical properties, have attracted much interest and generated wide varieties of applications. Recent investigations of functionalized nanomaterials have expanded into the biological area, providing a versatile platform in biomedical applications such as biomolecular sensing, biological imaging, drug delivery and disease therapy. Bio-functions and bio-compatibility of nanomaterials are realized by introducing synthetic ligands or natural biomolecules onto nanomaterials, and combining ligand-receptor biological interactions with intrinsic nanomaterial properties. Common strategies of engineering nanomaterial surfaces involve physisorption or chemisorption of desired ligands. We developed a photochemically initiated surface coupling chemistry, bringing versatility and simplicity to nanomaterial functionalization. The method was applied to attach underivatized carbohydrates efficiently on gold and iron oxide nanoparticles, and the resulting glyconanoparticles were successfully used as a sensitive biosensing system probing specific interactions between carbohydrates and proteins as well as bacteria.

  18. Solid sorbents for removal of carbon dioxide from gas streams at low temperatures

    Science.gov (United States)

    Sirwardane, Ranjani V.

    2005-06-21

    New low-cost CO.sub.2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO.sub.2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35.degree. C.

  19. 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.

  20. 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).

  1. Ni/Al2O3 catalysts for syngas methanation: Effect of Mn promoter

    Institute of Scientific and Technical Information of China (English)

    Anmin Zhao; Weiyong Ying; Haitao Zhang; Hongfang Ma; Dingye Fang

    2012-01-01

    Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method.The catalysts were characterized by N2 physisorption,XRD,TPR,SEM and TEM.Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor.It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume,but decrease NiO crystallite size,leading to higher activity and stability.The effects of reaction temperature,pressure and weight hourly space velocity (WHSV) on carbon oxides conversion and CH4 formation rate were also studied.High carbon oxides conversion,CH4 selectivity and formation rate were achieved at the reaction temperature range of 280-300 ℃.

  2. 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.

  3. Preparing bioactive surface of polystyrene with hydrophobin for trypsin immobilization

    Science.gov (United States)

    Niu, Baolong; Li, Bingzhang; Wang, Huifang; Guo, Ruijie; Liang, HaiXia; Qiao, Mingqiang; Li, Wenfeng

    2016-05-01

    A simple and reliable enzyme immobilization technique which can retain their catalytic activity for a long time is interest in many technologies. Here, the trypsin was immobilized by physisorption on polystyrene (PS) surface coated with a class I hydrophobin recombinant HGFI (rHGFI). X-ray photoelectron spectroscopy and water-contact-angle measurements demonstrated that the hydrophobicity of the PS could be well improved by rHGFI modification, and the self-assembled rHGFI showed an admirable stability on the hydrophobic PS surface against hot SDS rinsing. The enzyme activity assay illustrated that the capacity of rHGFI could enable it to well intermediate trypsin on PS surface and allow its immobilization lasting in an active form. The results obtained in this work show a way that surface modification with rHGFI should be an easy and feasible strategy for applications of enzyme-based catalytic surfaces in biosensing.

  4. 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.

  5. Controlled drug release on amine functionalized spherical MCM-41

    Science.gov (United States)

    Szegedi, Agnes; Popova, Margarita; Goshev, Ivan; Klébert, Szilvia; Mihály, Judit

    2012-10-01

    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, N2 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.

  6. Effect of amine functionalization of spherical MCM-41 and SBA-15 on controlled drug release

    Science.gov (United States)

    Szegedi, A.; Popova, M.; Goshev, I.; Mihály, J.

    2011-05-01

    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.

  7. Preliminary measurement results of biotinylated BSA detection of a low cost optical cavity based biosensor using differential detection

    Science.gov (United States)

    Cowles, Peter; Joy, Cody; Bujana, Antonio; Rho, DongGee; Kim, Seunghyun

    2016-03-01

    We report an optical cavity based biosensor using a novel differential detection method for point-of-care applications. Two laser diodes allow for multiplexing capability along with the ability to enhance the responsivity using differential detection. The laser wavelengths are chosen so that the optical intensities of two lasers change monotonically with opposite slopes upon the adsorption of desired biomarkers. The cavity width, PMMA thickness, and silver thickness have been optimized to achieve a large change in scaled differential value. We chose biotinylated BSA detection with Avidin as a receptor molecule to demonstrate the proposed design. Avidin is attached directly to the PMMA layer by physisorption. Then, biotinylated BSA is introduced to the sample and the intensities of the laser diodes are measured by a sCMOS camera. A change in the scaled differential value will correlate to the binding of biotinylated BSA. In this presentation, we will discuss simulation results, fabrication procedures, and preliminary measurement results.

  8. Perlite as a potential support for nickel catalyst in the process of sunflower oil hydrogenation

    Science.gov (United States)

    Radonjić, V.; Krstić, J.; Lončarević, D.; Jovanović, D.; Vukelić, N.; Stanković, M.; Nikolova, D.; Gabrovska, M.

    2015-12-01

    Investigation was conducted in order to elucidate the possibility of using perlite as support for preparation of nickel based precursor catalyst, potentially applicable in vegetable oil hydrogenation process. On three differently prepared expanded perlite, nickel catalyst precursors with identical Ni/SiO2 = 1.1 and Ni/Mg = 10/1 ratios were synthesized by precipitation-deposition method. Different techniques, SEM micrography, He-pycnometry, calcimetry, Hg-porosimetry, N2-physisorption, H2-chemisorption and temperature programmed reduction, were used for characterization of obtained samples. Determining the precursor texture, morphology and reducibility shows a successfully deposited nickel phase on perlite support with promising properties for vegetable oil hydrogenation. Chosen precursor was reduced and passivated in paraffin oil and the obtained catalyst showed significant catalytic activity in the test of sunflower oil hydrogenation.

  9. Hovering and Twirling of Tethered Molecules by Confinement between Surfaces.

    Science.gov (United States)

    Rios, Laura; Lee, Joonhee; Tallarida, Nicholas; Apkarian, V Ara

    2016-07-07

    Through STM images, we show that azobenzene-terminated alkanethiols hover and twirl when confined between the Ag tip and Au(111) substrate of an STM junction. In contrast with mechanisms of activation used to drive molecular rotors, twirling is induced by the effective elimination of lateral corrugation in the energy landscape when molecules hover by their van der Waals attraction to the approaching tip. While in the stationary state the benzenes of the head group lie flat with an inter-ring separation of 7.5 Å, they stand on-edge as the molecule twirls and their separation contracts to 5.2 Å, close to the value of the free molecule. The captured images of motion allow the characterization of physisorption potentials.

  10. 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.

  11. Bee Wax Propolis Extract as Eco-Friendly Corrosion Inhibitors for 304SS in Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Femiana Gapsari

    2015-01-01

    Full Text Available The inhibition properties of bee wax propolis (BWP extract on the 304SS in 0.5 M sulfuric acid were conducted using potentiodynamic polarization, EIS, and XRD. Quercetin (2-(3.4-dihydroxy phenyl-3.5.7-trihydroxy-4H-chromen-4-one was identified as the main compound in the BWP extract based on FTIR and HPLC analysis. The results showed that the inhibitor could retard the corrosion rate of 304SS in 0.5 M sulfuric acid which reached 97.29% and 91.42% at 2000 ppm based on potentiodynamic polarization and EIS measurement, respectively. The inhibition efficiency decreased with increasing temperature. The inhibition mechanism of BWP extract on the 304SS was physisorption and obeyed Temkin adsorption isotherm equation. The thin protective layer on the 304SS surface was confirmed by XRD.

  12. Periodic mesoporous organosilica (PMO) materials with uniform spherical core-shell structure.

    Science.gov (United States)

    Haffer, Stefanie; Tiemann, Michael; Fröba, Michael

    2010-09-10

    We report the synthesis of monodisperse, spherical periodic mesoporous organosilica (PMO) materials. The particles have diameters between about 350 and 550 nm. They exhibit a regular core-shell structure with a solid, non-porous silica core and a mesoporous PMO shell with a thickness of approximately 75 nm and uniform pores of about 1.7 nm. The synthesis of the core and the shell is carried out in a one-pot, two-stage synthesis and can be accomplished at temperatures between 25 and 100 °C. Higher synthesis temperatures lead to substantial shrinking of the solid core, generating an empty void between core and shell. This leads to interesting cavitation phenomena in the nitrogen physisorption analysis at 77.4 K.

  13. Significant role of ultramicropores on capacitive properties of polypyrrole-based carbons

    Science.gov (United States)

    Wu, Xiaozhong; Zhang, Yan; Cai, Tonghui; Li, Xiao; Xing, Wei; Yan, Zifeng

    2017-03-01

    N-doped carbon was synthesized by carbonization of polypyrrole at 700 °C and further reduced by hydrogen under the same temperature. Pore-structure and surface elemental analyses show that both carbons have a low apparent specific surface area (by nitrogen sorption analysis) and there is a decrease of nitrogen content when th e original carbon was reduced by hydrogen. However, electrochemical measurements such as cyclic voltammetry and galvanostatic charge-discharge indicate that there is no correlation between nitrogen content and specific capacitance. Further detailed pore-structure characterization was performed by carbon dioxide physisorption analysis, which reveals that there are many ultramicropores in both carbons. Those ultramicropores are not available to nitrogen molecule but carbon dioxide and electrolyte ions, thus playing a dominant role on the energy storage process.

  14. {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.

  15. Adsorption measurements of argon, neon, krypton, nitrogen, and methane on activated carbon up to 650 MPa

    Energy Technology Data Exchange (ETDEWEB)

    Malbrunot, P.; Vidal, D.; Vermesse, J. (Centre Universitaire Paris-Nord, Villetaneuse (France)); Chahine, R.; Bose, T.K. (Universite du Quebec a Trois-Rivieres, Quebec (Canada))

    1992-02-01

    The physisorption of argon, krypton, neon, nitrogen, and methane on GAC activated carbon has been measured in the above critical region by a dielectric method. The measurements were done at room temperature and at pressures up to 650 MPa corresponding to reduced densities of up to 3.25. With the exception of nitrogen, all the measured excess adsorption isotherms show a similar behavior. They exhibit a maximum followed by a downward straight line intercepting the bulk density axis at around the liquid density of the adsorbate in the normal liquid range. The surface excess adsorption isotherms are well represented over the entire density range by Fischer's three-parameter integral equation. The results are also characterized in terms of the critical parameters and the reduced variables of the adsorbates. 21 refs., 2 figs., 3 tabs.

  16. 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.)

  17. Balance between physical and chemical interactions of second-row diatomic molecules with graphene sheet

    Science.gov (United States)

    Rahali, Seyfeddine; Belhocine, Youghourta; Touzeau, Jeremy; Tangour, Bahoueddine; Maurel, François; Seydou, Mahamadou

    2017-02-01

    We present a computational investigation of adsorption on graphene concerning the second-row diatomic molecules (Li2, B2, C2, O2, N2 and F2). The adsorption energies and the nature of the interaction between guest molecules and graphene, in both periodic and non-periodic approaches, were evaluated using dispersion-corrected density functional theory calculations (DFT/PBE-D3). A periodic graphene model, used to tune the coverage, is compared with a cluster model in which the graphene sheet is represented by coronene. The results of both energetic and electronic state analyses reveal a variety of adsorption processes. While B2 and C2 adsorb in a bridge position in order to establish two covalent bonds with the surface, O2 and N2 are clearly physisorbed in positions parallel to the surface. Li2 and F2 show intermediate behavior, with strong physisorption accompanied by charge transfer.

  18. 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

    . The activities of the composite materials in the selective catalytic reduction (SCR) of NO with NH3 were measured at temperatures of up to 200 °C and in the presence of 20 vol. % H2O. Presence of Fe can increase the surface area, enhance the redox properties, increase the number of surface acid sites, increase......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...

  19. The characterization and activity of F-doped vanadia/titania for the selective catalytic reduction of NO with NH3 at low temperatures.

    Science.gov (United States)

    Li, Yuntao; Zhong, Qin

    2009-12-30

    A F-doped vanadia/titania catalyst has been developed by partly substituting the lattice oxygen of the catalyst with fluorine, using NH(4)F as a precursor. The aim of this novel design was to promote the activity of a catalyst with low vanadia loading in the low-temperature selective catalytic reduction of NO with NH(3). Analysis by N(2) physisorption, XPS, ICP, XRD, ESR and PL spectra showed that fluorine doping facilitated the formation of V(4+) and Ti(3+) ions mainly by charge compensation, promoted the distribution of vanadium on the catalyst surface, and increased the amount of surface superoxide ions. The catalytic activity of NO removal was promoted by F-doping. And the catalyst with [F]/[Ti]=1.35 x 10(-2) showed the highest NO removal efficiency in SCR reaction at low temperatures.

  20. [Bioactive films for biomaterial coating and intended for tissue engineering: new original methods?].

    Science.gov (United States)

    Schaaf, P; Voegel, J C

    2002-04-01

    Numerous functionalized biomaterials aimed to induce specific cellular or tissular responses have been developed in the last decade. They result often from a specific treatment of the interface of the material. Techniques like physisorption, covalent binding or deposition of a Langmuir-Blodgett film have been employed to modify surface properties. We describe here a novel approach based upon an alternated adsorption of polyelectrolytes (polyanions or polycations) leading to the build-up of a film. These films can be functionalized through protein insertion (ligands) or by covalent peptide bindings able to interact with cellular receptors. Combined with a high affinity for calcium or phosphate complexing properties such functionalized architectures could constitute an original way to favour osseointegration.

  1. CeO2-TiO2 as a visible light active catalyst for the photoreduction of CO2 to methanol

    Institute of Scientific and Technical Information of China (English)

    Hamidah Abdullah; Maksudur R Khan; Manoj Pudukudy; Zahira Yaakob; Nur Aminatulmimi Ismail

    2015-01-01

    The performance of CeO2-TiO2 photocatalyst for the photocatalytic reduction of CO2 into methanol was studied under visi-ble light irradiation. The as-prepared catalysts were characterized for their structural, textural and optical properties using X-ray dif-fraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), nitrogen phy-sisorption analysis, UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The characterization results indicated that the presence of CeO2 stabilized the anatase phase of TiO2, decreased its crystallite size, increased the surface area, reduced the band gap energy and lowered the rate of electron-hole pair recombination. The CeO2-TiO2 photocatalyst showed an increased methanol yield of 18.6 µmol/g under visible light irradiation, compared to the bare TiO2 (6.0 µmol/g).

  2. Metal–Organic Frameworks as Platforms for the Controlled Nanostructuring of Single-Molecule Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Aulakh, Darpandeep; Pyser, Joshua B.; Zhang, Xuan; Yakovenko, Andrey A.; Dunbar, Kim R.; Wriedt, Mario

    2015-07-29

    The prototypical SMM molecule [Mn12O12(O2CCH3)16(OH2)4] was incorporated under mild conditions into a highly porous metal-organic framework (MOF) matrix as a proof of principle for controlled nanostructuring of SMMs. Four independent experiments revealed that the SMM clusters were successfully loaded in the MOF pores, namely synchrotron-based powder diffraction, physisorption analysis, and in-depth magnetic and thermal analyses. The results provide incontrovertible evidence that the magnetic composite, SMM@MOF, combines key SMM properties with the functional properties of MOFs. Most importantly, the incorporated SMMs exhibit a significant enhanced thermal stability with SMM loading advantageously occurring at the periphery of the bulk MOF crystals with only a single SMM molecule isolated in the transverse direction of the pores.

  3. Chiral hybrid inorganic-organic materials: synthesis, characterization, and application in stereoselective organocatalytic cycloadditions.

    Science.gov (United States)

    Puglisi, Alessandra; Benaglia, Maurizio; Annunziata, Rita; Chiroli, Valerio; Porta, Riccardo; Gervasini, Antonella

    2013-11-15

    The synthesis of chiral imidazolidinones on mesoporous silica nanoparticles, exploiting two different anchoring sites and two different linkers, is reported. Catalysts 1-4 were prepared starting from l-phenylalanine or l-tyrosine methyl esters and supporting the imidazolidinone onto silica by grafting protocols or azide-alkyne copper(I)-catalyzed cycloaddition. The four catalysts were fully characterized by solid-state NMR, N2 physisorption, SEM, and TGA in order to provide structural assessments, including an evaluation of surface areas, pore dimensions, and catalyst loading. They were used in organocatalyzed Diels-Alder cycloadditions between cyclopentadiene and different aldehydes, affording results comparable to those obtained with the nonsupported catalyst (up to 91% yield and 92% ee in the model reaction between cyclopentadiene and cinnamic aldehyde). The catalysts were recovered from the reaction mixture by simple filtration or centrifugation. The most active catalyst was recycled two times with some loss of catalytic efficiency and a small erosion of ee.

  4. Solid Sorbents for Removal of Carbon Dioxide from Gas Streams at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Sirwardane, Ranjani V.

    2005-06-21

    New low-cost CO2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35 degrees C.

  5. Tribology in Gaseous Hydrogen

    Science.gov (United States)

    Sawae, Yoshinori; Sugimura, Joich

    Hydrogen is expected as a clean and renewable energy carrier for future environment-friendly society. Many machine elements in hydrogen energy systems should be operating within hydrogen gas and tribological behavior, such as friction and wear, of bearings and seals are affected by the hydrogen environment through some interactions between material surfaces and gaseous hydrogen, i.e., physisorption of hydrogen molecules and following chemisorptions of dissociated atoms on metal surfaces, formation of metal hydride and reduction of metal oxide layer by hydrogen atoms diffused into bulk. Therefore, friction and wear characteristics of tribomaterials in the hydrogen environment should be appropriately understood to establish a design guideline for reliable hydrogen utilizing systems. This paper reviews the current knowledge about the effect of hydrogen on friction and wear of materials, and then describes our recent progress of hydrogen research in the tribology field.

  6. Estudo de catalisadores de níquel suportados em cinza de casca de arroz na reforma de metano com dióxido de carbono visando a produção de hidrogênio e gás de síntese

    Directory of Open Access Journals (Sweden)

    Karine Zanoteli

    2014-01-01

    Full Text Available Rice husk ash (RHA is used as a silica source for several purposes, among them to obtain metal catalysts, as was done in this work. The catalysts were characterized by chemisorption, physisorption, thermal analyses (TG, DSC, X-ray diffraction, X-ray fluorescence, temperature-programmed reduction and scanning electron microscopy. The catalysts synthesized with different Ni loadings supported on RHA were applied to the reaction of dry reforming of methane. The reaction was tested at three temperatures of catalytic reduction (500, 600 and 700 ºC. All synthesized catalysts were active for the studied reaction, with different H2/CO ratios achieved according to degree of metallic dispersion.

  7. Inlfuence of the Alkali Treatment of HZSM-5 Zeolite on Catalytic Performance of PtSn-Based Catalyst for Propane Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    Huang Li; Zhou Shijian; Zhou Yuming; Zhang Yiwei; Xu Jun; Wang Li

    2013-01-01

    The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2-physisorption, and NH3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical prop-erties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger external surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.

  8. 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.

  9. 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.

  10. Characterization and catalytic properties of mesoporous CuO/SBA-16 prepared by different impregnation methods

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    CuO/SBA-16 catalysts were prepared by two different routes - the conventional impregnation method and the modified impregnation method with pH adjustment.These catalysts were characterized by X-ray diffraction (XRD),atomic absorption spectrometry (AAS),N2 physisorption and hydrogen temperature programmed reduction (H2-TPR) measurements which reveal that the cubic cagelike (Im3m) pore structure of the parent SBA-16 molecule sieves was well maintained throughout the synthesis.After introduction of Cu,a different CuO dispersion exists on these catalysts.The CuO/SBA-16 prepared by modified impregnation method has a single highly dispersed CuO which is considered as a highly efficient species for hydroxylation of phenol with H2O2.CuO/SBA-16 prepared by the conventional impregnation method shows the presence of bulk CuO species which is undesirable for this reaction.

  11. Thermally modified bentonite clay for copper removal; Argila bentonita modificada termicamente para remocao de cobre

    Energy Technology Data Exchange (ETDEWEB)

    Bertagnolli, C.; Kleinübing, S.J.; Silva, M.G.C., E-mail: meuris@feq.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Faculdade de Engenharia Quimica. Laboratorio de Engenharia Ambiental

    2011-07-01

    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{sub 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)

  12. Effect of piezoelectric material on hydrogen adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xuan [Department of Materials Science and Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, MI, 49931 (United States); Civil and Environmental Engineering School, University of Science and Technology Beijing, 30 Xueyuan Road, Haidian District, Beijing, 100083 (China); Hwang, Jiann-Yang; Shi, Shangzhao; Sun, Xiang; Zhang, Zheng [Department of Materials Science and Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, MI, 49931 (United States)

    2010-09-15

    In hydrogen storage applications, the primary issue for physisorption of hydrogen onto solid-state materials is the weak interaction force between hydrogen molecules and the adsorbents. It is found that enhanced adsorption can be obtained under an external electric field, because it appears the electric field increases the hydrogen adsorption energy. Experiments were carried out to determine hydrogen adsorption on activated carbon using the piezoelectric material PMN-PT as the charge supplier under hydrogen pressure. Results indicate that more than 20% hydrogen adsorption enhancement was obtained. Parameters related to hydrogen adsorption enhancement include the amount of the charge and temperature. Higher voltage and lower temperature promote the increase of adsorption capacity but room temperature results are very encouraging. (author)

  13. 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.

  14. 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.

  15. ALOE-VERA GEL AS POTENTIAL CORROSION INHIBITOR FOR CONCRETE STEEL REINFORCEMENT

    Directory of Open Access Journals (Sweden)

    Héctor Herrera-Hernández

    2015-09-01

    Full Text Available In this work a GEL extracted from ALOE VERA leaves has been electrochemically studied as a possible corrosion inhibitor for concrete steel rebar. The corrosion resistance was evaluated by Electrochemical Impedance Spectroscopy (EIS measurements in hydrochloric acid solution (1M HCl as a function of GEL-inhibitor addition, uninhibited measurements were also discussed. The impedance results revealed that after addition of different GEL-extract proportion, the corrosion process of the steel exposed to acidic solution is remarkably inhibited, and it was also determined that the molecules of the GEL-extract follow a physisorption mechanism on the metal surface according to the Langmuir isotherm model with and adsorption standard free energy of about G°ads 14.17 kJ/mol. In this sense, the GEL extracted from ALOE-VERA leaves behaved as a mixed-type inhibitor.

  16. Characterization of Brazilian Bentonite Organoclays as sorbents of petroleum-derived fuels

    Directory of Open Access Journals (Sweden)

    Caroline Bertagnolli

    2012-04-01

    Full Text Available This work focused on preparing and characterizing Brazilian bentonite clay through the use of quaternary ammonium salt so as to apply it as a sorbent for petroleum-derived fuels. Bentonite clay was organophilizated by the intercalation of quaternary ammonium salts such as cetyl-pyridinium chloride and benzalkonium chloride. The resulting materials were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, N2 physisorption and infrared spectroscopy techniques. The clay similarity with petroleum-derived fuels, gasoline and diesel oil were defined by sorption and swelling tests. The increase in basal spacing and the appearance of absorption bands related to the CH2 and CH3 groups confirm the efficiency of Brazilian organoclays. Removal percentages between 50 and 60 for benzene, toluene and xylene indicate the potential of organoclay in the remediation of areas contaminated by petroleum-derived fuels.

  17. Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations.

    Science.gov (United States)

    Brandt, Erik G; Agosta, Lorenzo; Lyubartsev, Alexander P

    2016-07-21

    Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.

  18. Decoration of gold nanoparticles with cysteine in solution: reactive molecular dynamics simulations.

    Science.gov (United States)

    Monti, Susanna; Carravetta, Vincenzo; Ågren, Hans

    2016-07-14

    The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption.

  19. 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.

  20. Catalytic Chemical Vapor Deposition Synthesis of Carbon Aerogels of High-Surface Area and Porosity

    Directory of Open Access Journals (Sweden)

    Armando Peña

    2012-01-01

    Full Text Available In this work carbon aerogels were synthesized by catalytic chemical vapor deposition method (CCVD. Ferrocene were employed as a source both of catalytic material (Fe and of carbon. Gaseous hydrogen and argon were used as reductant and carrier gas, respectively. The products of reaction were collected over alumina. The morphology and textural properties of the soot produced in the reaction chamber were investigated using Scanning Electron Microscopy, High-Resolution Transmission Electron Microscopy, X-ray photoelectron spectroscopy, and N2 physisorption (BET and BHJ methods. After the evaluation of the porous structure of the synthesized products, 780 ± 20 m2/g of SBET and 0.55 ± 0.02 cm3/g of VBJH were found. The presence of iron carbide and the partial oxidation of carbon nanostructures were revealed by XPS.

  1. Design of Improved Metal-Organic Framework (MOF H2 Adsorbents

    Directory of Open Access Journals (Sweden)

    Hiroshi Sakai

    2011-12-01

    Full Text Available We attempted synthesis of the hydrogen adsorption material suitable for the fuel cell vehicles (FCEVs. The designed and synthesized Cu2(3,5-Pyridinedicarboxylate2 (=Cu2PDC2 metal complex showed an extremely high volumetric uptake density for a physisorption material, even though the specific surface area was only about 1,000 m2 g−1. Factors for high uptake properties are considered to be the increased adsorption sites per unit area, the increased adsorption energy, and the optimized design of pore shapes. High hydrogen uptake on volumetric basis is especially effective for FCEV because the tank volume is reduced. It is expected that property prediction using computational simulation and sophisticated analysis at the micro and nano levels will become an indispensable tool in the design of functional materials.

  2. Effect of pore size and surface chemistry of porous silica on CO2 adsorption

    Directory of Open Access Journals (Sweden)

    Thongthai Witoon

    2012-09-01

    Full Text Available In the present study, porous silica synthesized using sodium silicate as a low-cost raw material was selected as a CO2sorbent. The effects of pore size and amount of silanol content on CO2 adsorption capacity were investigated. The physicalproperties and surface chemistry (silanol content of the porous silica products were characterized by means of N2-physisorption, Fourier transform infrared spectroscopy and thermogravimetric analysis technique. The pore size of the poroussilica materials did not affect the equilibrium CO2 capacity; however the porous silica with large pore size could enhance thediffusion of CO2. The amount of silanol content was found to be a key factor for the CO2 adsorption capacity. A greater CO2adsorption capacity would be obtained with an increase of the silanol concentration on the surface of the porous silicamaterials.

  3. Methylbenzenes on graphene

    CERN Document Server

    Borck, Øyvind

    2016-01-01

    We present a theory study of the physisorption of the series of methylbenzenes (toluene, xylene and mesitylene), as well as benzene, on graphene. This is relevant for the basic understanding of graphene used as a material for sensors and as an idealized model for the carbon in active carbon filters. The molecules are studied in a number of positions and orientations relative graphene, using density functional theory with the van der Waals functional vdW-DF. We focus on the vdW-DF1 and vdW-DF-cx functionals, and find that the binding energy of the molecules on graphene grows linearly with the number of methyl groups, at the rate of 0.09 eV per added methyl group.

  4. Nanodevices for generating power from molecules and batteryless sensing

    Science.gov (United States)

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

    2014-07-15

    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. Comparative theoretical study of adsorption of lithium polysulfides (Li2Sx) on pristine and defective graphene

    Science.gov (United States)

    Jand, Sara Panahian; Chen, Yanxin; Kaghazchi, Payam

    2016-03-01

    Adsorption of Li2Sx on pristine and defective (Stone-Wales (SW) and vacancy) graphene is studied using density functional theory. Results show that the interaction between Li2Sx and graphene is dominated by dispersion interaction (physisorption), which depends on the size of molecule as well as the existence and type of defect sites on graphene. We find that single Li2Sx molecules interact only slightly stronger to the SW sites than to the defect-free sites, but they interact very strongly with single-vacant defects. In the later cases, the vacant site catches one S atom from the Li2Sx molecule, leading to the formation of a Li2Sx-1 molecule, which adsorbs weakly on the created S-doped graphene. This study suggests that defect sites can not improve the ability of graphene to catch lithium polysulfides in Li-S batteries.

  6. Fiber endface Fabry-Perot vapor microsensors fabricated by multiphoton polymerization technique

    Science.gov (United States)

    Melissinaki, Vasileia; Konidakis, Ioannis; Farsari, Maria; Pissadakis, Savros

    2015-03-01

    Three different designs of Fabry-Perot optical sensing microresonators fabricated by direct laser writing on the endface of a standard telecom fiber using a zirconium-silicon, organic-inorganic hybrid photosensitive material, are demonstrated. These endface optical fiber sensing probes are used for the detection of common organic alcohols and chlorinated solvents vapors. The devices operate in the spectral region lying between 1440 nm and 1660 nm, while the spectra recorded in reflection mode correlate to refractive index or absorption changes due to different vapors trapped inside the microcavities. A sensitivity of 1503nm/RIU, for a concentration of 4ppm ethanol vapors was succeeded. The microresonator sensing probe is explained in terms of standard physisorption and molecule packing mechanisms of organic vapors onto porous surfaces.

  7. Porous Azo-Bridged Porphyrin-Phthalocyanine Network with High Iodine Capture Capability.

    Science.gov (United States)

    Li, Hui; Ding, Xuesong; Han, Bao-Hang

    2016-08-08

    We report a highly efficient iodine adsorbent achieved by rational design of a porous azo-bridged porphyrin-phthalocyanine network (AzoPPN), which was synthesized by a catalyst-free coupling reaction between free-base 5,10,15,20-tetrakis(4-nitrophenyl)-porphyrin and nickel tetraaminophthlocyanine. AzoPPN has a permanent porous structure and plenty of porphyrin and phthalocyanine units in the skeleton as effective sorption sites. It displays excellent adsorption of iodine vapor up to 290 wt. % and also shows remarkable capability as adsorbent for iodine in solution. This strategy of combining physisorption with chemisorption in one adsorbent will pave the way for the development of new materials for iodine capture. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. Template-assisted hydrothermally obtained titania-ceria composites and their application as catalysts in ethyl acetate oxidation and methanol decomposition with a potential for sustainable environment protection

    Science.gov (United States)

    Tsoncheva, Tanya; Mileva, Alexandra; Issa, Gloria; Dimitrov, Momtchil; Kovacheva, Daniela; Henych, Jiří; Scotti, Nicola; Kormunda, Martin; Atanasova, Genoveva; Štengl, Vaclav

    2017-02-01

    High surface area mesoporous ceria-titania binary materials with high Lewis acidity and improved reduction properties were synthesized using template assisted hydrothermal technique. The obtained materials were characterized by low temperature nitrogen physisorption, XRD, SEM, TEM, Raman, UV-vis, XPS, FTIR, FTIR of adsorbed pyridine and thermo-programmed reduction with hydrogen. Their catalytic activity was tested in total oxidation of ethyl acetate and methanol decomposition to CO and hydrogen with a potential application in VOCs elimination and alternative fuels, respectively. The structural changes in the binary materials, which could be tuned by the variation in the Ce/Ti ratio and the temperature of hydrothermal treatment, provoked significant changes in their textural, surface and redox properties, which is in close relation to the catalytic activity and selectivity in various catalytic processes. The intimate contact between the individual oxides results in the formation of different catalytic active sites and their role in the studied catalytic reactions was discussed in details.

  10. Studies on Thermodynamic Properties of Adsorption of Theophylline by Phenolic Resin Adsorbents

    Institute of Scientific and Technical Information of China (English)

    WANG Zhong; SHI Zuo-qing; SHI Rong-fu; FAN Yun-ge; YAN Yi-Zhong

    2004-01-01

    In the present work, the equilibrium adsorption of theophylline was studied by phenolic resin adsorbents: JDW-2(made by ourselves) and Duolite S-761 within a temperature range of 303-323 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of theophylline on the two adsorbents, the exponents n>1 indicate that they are favorable to the adsorptions; the negative values of all the isosteric adsorption enthalpies for the theophylline indicate the exothermic process of the adsorption, while the range(10-40 kJ/mol) of their magnitudes manifests the physisorption process; other thermodynamic properties, the free energy changes and the entropy change associated with adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation.

  11. Corrosion Inhibition Performance of Triazole Derivatives on Copper-Nickel Alloy in 3.5 wt.% NaCl Solution

    Science.gov (United States)

    Jiang, B.; Jiang, S. L.; Liu, X.; Ma, A. L.; Zheng, Y. G.

    2015-12-01

    This study investigates the performance of three triazole derivatives with different molecular structures as corrosion inhibitors for the copper-nickel alloy CuNi 90/10 in 3.5 wt.% NaCl solution. Inhibition behavior was systematically determined through electrochemical measurements, scanning electron microscopy, energy-dispersive spectroscopy, and Fourier transform infrared spectroscopy. In addition, adsorption behavior and the inhibition mechanism were investigated via quantum chemical calculation and molecular dynamic simulation. Experimental results indicate that the three inhibitors with triazole rings and heteroatoms exhibited excellent corrosion inhibition capabilities on the copper-nickel alloy surface through physisorption and chemisorption. In particular, 3-amino-5-mercapto-1,2,4-triazole showed the best inhibition capability according to the concentration ranges considered in the experiments. The results of quantum chemical calculation agreed with the experimental findings.

  12. 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)

  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...... 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......-type single crystals could be crystallized from fluoride media by a newly developed procedure presented here. Thus, we here present the only known route to mesoporous BEA-type single crystals, since crystallization of this framework structure from basic media is known to give only nanosized crystals...

  14. Decyl glucoside as a corrosion inhibitor for magnesium-air battery

    Science.gov (United States)

    Deyab, M. A.

    2016-09-01

    In this research, the effects of decyl glucoside (DG) on the corrosion inhibition and battery performance of Mg-air battery have been investigated. Chemical and electrochemical techniques have been used to evaluate the corrosion rate and inhibitor efficiency. Mg surface has been characterized with scanning electron microscopy (SEM) and infrared spectroscopy (FTIR). A significant reduction in the corrosion rate of Mg in battery electrolyte (3.5% NaCl solution) has been observed in the presence of DG surfactant. Maximum inhibition efficiency (>94%) is achieved at critical micelle concentration of DG surfactant (CMC = 2.5 mM). The presence of DG surfactant increases the activation energy of the corrosion reaction. Physisorption mechanism has been suggested for the inhibition action of DG surfactant. The Mg-air battery containing DG surfactant offers higher operating voltage, discharge capacity and anodic utilization than in its absence.

  15. 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.

  16. Ambient carbon dioxide capture by different dimensional AlN nanostructures: A comparative DFT study

    Science.gov (United States)

    Esrafili, Mehdi D.; Nurazar, Roghaye; Nematollahi, Parisa

    2016-08-01

    Strong binding of an isolated carbon dioxide molecule over three different aluminium nitride (AlN) nanostructures (nanocage, nanotube and nanosheet) is verified using density functional calculations. Equilibrium geometries, electronic properties, adsorption energies and thermodynamic stability of each adsorbed configuration are also identified. Optimized configurations are shown at least one corresponding physisorption and chemisorption of CO2 molecule over different AlN nanostructures. Also, the effect of chirality on the adsorption of CO2 molecule is studied over two different finite-sized zigzag (6,0) and armchair (4,4) AlN nanotubes. It is found that the electronic properties of the Al12N12 nanocage are more sensitive to the CO2 molecule than other AlN nanostructures. This indicates the significant potential of Al12N12 nanocage toward the CO2 adsorption, fixation and catalytic applications in contrast to other AlN nanostructures.

  17. Adsorption kinetics and thermodynamics of acid Bordeaux B from aqueous solution by graphene oxide/PAMAMs.

    Science.gov (United States)

    Zhang, Fan; He, Shengfu; Zhang, Chen; Peng, Zhiyuan

    2015-01-01

    Graphene oxide/polyamidoamines dendrimers (GO/PAMAMs) composites were synthesized via modifying GO with 2.0 G PAMAM. The adsorption behavior of the GO/PAMAMs for acid Bordeaux B (ABB) was studied and the effects of media pH, adsorption time and initial ABB concentration on adsorption capacity of the adsorbent were investigated. The optimum pH value of the adsorption of ABB onto GO/PAMAMs was 2.5. The maximum adsorption capacity increased from 325.78 to 520.83 mg/g with the increase in temperature from 298 to 328 K. The equilibrium data followed the Langmuir isotherm model better than the Freundlich model. The kinetic study illustrated that the adsorption of ABB onto GO/PAMAMs fit the pseudo-second-order model. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process.

  18. Catalyzed oxidative degradation of methyl orange over Au catalyst prepared by ionic liquid-polymer modified silica

    Science.gov (United States)

    Wang, Y.; Guo, J. S.

    2015-07-01

    A new type of hybrid material was prepared by grafting an ionic liquid monomer, 1-(p-vinylbenzyl)-3-methylimidazolium chloride, on the surface of the porous silica which was synthesized via sodium silicate hydrolysis. The as-synthesized products were characterized by scanning electron microscope, nitrogen physisorption experiment, thermogravimetric analysis and Fourier transform infrared spectra. A catalyst with Au was prepared using the hybrid material as carrier. The experimental results show that the catalyst exhibits a better catalytic effect of hydrogen peroxide on the degradation of methyl orange. The reason may be that the metal component of the catalyst facilitated the dissociation of hydrogen peroxide to produce abundant highly active free radicals which can rapidly ruin the structure of methyl orange molecules in water. Finally, a probable catalytic degradation mechanism based on diffusion was discussed.

  19. Metallacarboranes: Towards promising hydrogen storage metal organic framework

    Science.gov (United States)

    Singh, Abhishek; Sadrzadeh, Arta; Yakobson, Boris

    2011-03-01

    Using first principles calculations we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms bind hydrogen via Kubas interaction. The average binding energy of ~ 0.3 eV/H favorably lies within the reversible adsorption range The Sc and Ti are found to be the optimum metal atoms maximizing the number of stored H2 molecules. Depending upon the structure, metallacarboranes can adsorb up to 8 wt% of hydrogen, which exceeds DOE goal for 2015. Being integral part of the cage, TMs do not suffer from the aggregation problem. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks (MOF), thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption. A. K. Singh, A. Sadrzadeh, and B. I. Yakobson, Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks, JACS 132,14126 (2010).

  20. Separation of ethanol/water azeotrope using compound starch-based adsorbents.

    Science.gov (United States)

    Wang, Yanhong; Gong, Chunmei; Sun, Jinsheng; Gao, Hong; Zheng, Shuai; Xu, Shimin

    2010-08-01

    Comparing breakthrough cures of five starch-based materials experimentally prepared for ethanol dehydration, a compound adsorptive agent ZSG-1 was formulated with high adsorption capacity, low energy and material cost. The selective water adsorption was conducted in a fixed-bed absorber packed with ZSG-1 to find the optimum conditions yielding 99.7 wt% anhydrous ethanol with high efficiency. The adsorption kinetics is well described by Bohart-Adams equation. The adsorption heat, Delta H(abs), was calculated to be -3.16 x 10(4)J mol(-1) from retention data by inverse gas chromatography. Results suggested that water entrapment in ZSG-1 is a exothermic and physisorption process. Also, ZSG-1 is recyclable for on-site multiple-use and then adapt for upstream fermentation process after saturation, avoiding pollution through disposal.

  1. Electronic properties of organic/metal interfaces

    CERN Document Server

    Koch, N

    2000-01-01

    Conjugated organic materials are the promising class of materials for the application in new electronic and opto-electronic devices. The successful realization of highly efficient organic light emitting devices with oligomers and polymers as active electroluminescent layers has lead to a large number of investigations on such systems, the key point being to find means of increasing efficiency and performance of the devices. Intrinsically present in light emitting devices are interfaces, and it appears that the structural and electronic properties of those are of uttermost importance for the device quality. In the present work, ultraviolet and X-ray photoelectron spectroscopy, plus related surface sensitive experimental methods, were used to investigate the electronic properties of interfaces between conjugated organic materials (based on para-phenylene) and various metals. The observed interactions between the two different kinds of materials ranged from physisorption (aluminum and samarium), to the formation...

  2. Radioactive Iodine (I-129) Gas Adsorption by Using Bismuth-Embedded SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jae Hwan; Cho, Yong-Jun; Park, Jang Jin; Ahn, Do-Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Yim, Man-Sung [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)

    2015-05-15

    The efficient capture of the long-lived I-129, released as off-gas from nuclear fuel reprocessing, have been of significant concern in the waste management field. In this study, bismuth-embedded SBA-15 mesoporous silica was firstly applied for iodine capture and storage. SBA-15 was functionalized with thiol (-SH) groups, followed by bismuth adsorption with Bi-S bonding, which was thermally treated to form Bi{sub 2}S{sub 3} within SBA-15. The bismuth-embedded SBA-15s demonstrated high iodine loading capacities with 540 mg-I/g-sorbent maximally, which benefitted from the high surface area and porosity of SBA-15 as well as the formation of thermodynamically stable BiI{sub 3} compound. Iodine physisorption could effectively be suppressed due to the large pores present in SBA-15, resulting in chemisorption as a main mechanism for iodine confinement.

  3. 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...... were studied and compared with the catalytic activity for the selective catalytic reduction (SCR) of NO with ammonia. The SCR activities and acidity values of heteropoly acid promoted catalysts were found to be much higher than unpromoted catalysts. The influence of potassium poisons on the SCR...

  4. 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.

  5. First-principles studies of HF molecule adsorption on intrinsic graphene and Al-doped graphene

    Science.gov (United States)

    Sun, Yuanyuan; Chen, Li; Zhang, Feiwu; Li, Daoyong; Pan, Hongzhe; Ye, Jun

    2010-10-01

    In the search for a high-sensitivity sensor for HF gas, the adsorption of HF molecules on both intrinsic and Al-doped graphene sheets is studied by first-principles calculations. We find that the adsorption mechanisms of HF molecules are different for intrinsic graphene and Al-doped graphene. Al-doped graphene has higher adsorption energy and shorter connecting distance to the HF molecule than intrinsic graphene. The calculated net electron transfers, electronic density difference images and densities of states give evidence that the adsorption of HF molecules on Al-doped graphene is by chemisorption, while there is weak physisorption on intrinsic graphene. Therefore, Al-doped graphene can be expected to have applications as a novel sensor for the detection of HF gas. The HF molecules adsorbed on Al-doped graphene material can be reactivated by applying an external electric field of 0.013 a.u.

  6. Monitoring adsorption-induced switching by (129)Xe NMR spectroscopy in a new metal-organic framework Ni(2)(2,6-ndc)(2)(dabco).

    Science.gov (United States)

    Klein, Nicole; Herzog, Christin; Sabo, Michal; Senkovska, Irena; Getzschmann, Jürgen; Paasch, Silvia; Lohe, Martin R; Brunner, Eike; Kaskel, Stefan

    2010-10-07

    The synthesis and structure of a new flexible metal-organic framework Ni(2)(2,6-ndc)(2)(dabco) (DUT-8(Ni), DUT = Dresden University of Technology, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane) as well as its characterization by gas adsorption and (129)Xe NMR spectroscopy is described. The compound shows reversible structural transformation without loss of crystallinity upon solvent removal and physisorption of several gases. Xenon adsorption studies combined with (129)Xe NMR spectroscopy turn out to be favorable methods for the detection and characterization of the so-called "gate-pressure" effect in this novel MOF material. The linewidth and chemical shift of the (129)Xe NMR signal are shown to be very sensitive parameters for the detection of this structural transition from a narrow pore system with low porosity to a wide pore state. The transition and threshold temperature is clearly detected.

  7. Engineering Nanomaterial Surfaces for Biomedical Applications

    Science.gov (United States)

    Wang, Xin; Liu, Li-Hong; Ramström, Olof; Yan, Mingdi

    2014-01-01

    Nanomaterials, possessing unique physical and chemical properties, have attracted much interest and generated wide varieties of applications. Recent investigations of functionalized nanomaterials have expanded into the biological area, providing a versatile platform in biomedical applications such as biomolecular sensing, biological imaging, drug delivery and disease therapy. Bio-functions and bio-compatibility of nanomaterials are realized by introducing synthetic ligands or natural biomolecules onto nanomaterials, and combining ligand-receptor biological interactions with intrinsic nanomaterial properties. Common strategies of engineering nanomaterial surfaces involve physisorption or chemisorption of desired ligands. We developed a photochemically initiated surface coupling chemistry, bringing versatility and simplicity to nanomaterial functionalization. The method was applied to attach underivatized carbohydrates efficiently on gold and iron oxide nanoparticles, and the resulting glyconanoparticles were successfully used as a sensitive biosensing system probing specific interactions between carbohydrates and proteins as well as bacteria. PMID:19596820

  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. Thermodynamic Stability and Structure of Oxidized Cu(110) Surfaces: The Critical Role of non-Local Interactions

    Science.gov (United States)

    Bamidele, Joseph; Brndiar, Jan; Stich, Ivan; Kantorovitch, Lev

    2013-03-01

    Thermodynamic stability of oxidized Cu(110) surface is studied using DFT techniques. At high oxygen exposures standard techniques predict more phases to be quasi-isoenergetic, whereas experiments observe only the c(6 × 2) phase at high oxygen exposures clearly indicating this phase to be the ground-state separated by considerable energy differences from other candidates. We show that this surface system is stabilized by a delicate coexistence and balance of chemi- and physi-sorption. Agreement with experiments is only achieved if the van der Waals interaction between the surface templates is accounted for in DFT thermodynamics. Moreover, van der Waals stabilization of the surface structure is anticipated to be a general feature present also in the cases of other related surfaces.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. 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.

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

    Science.gov (United States)

    Li, Wei; Feng, Zhilin; Dai, Enwen; Xu, Jie; Bai, Gang

    2016-11-09

    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.

  13. Watching adsorption and electron beam induced decomposition on the model system Mo(CO){sub 6}/Cu(1 1 1) by X-ray absorption and photoemission spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Paufert, Pierre, E-mail: pierre.paufert@u-bourgogne.fr [ICB, UMR 6303 CNRS-Université de Bourgogne, BP 47870, 21078 Dijon cedex (France); Fonda, Emiliano [Synchrotron SOLEIL, BP48, St Aubin, 91192 Gif sur Yvette cedex (France); Li, Zheshen [ISA, University of Aarhus, Ny Munkegade, DK-8000 Aarhus C (Denmark); Domenichini, Bruno, E-mail: bruno.domenichini@u-bourgogne.fr [ICB, UMR 6303 CNRS-Université de Bourgogne, BP 47870, 21078 Dijon cedex (France); Bourgeois, Sylvie [ICB, UMR 6303 CNRS-Université de Bourgogne, BP 47870, 21078 Dijon cedex (France)

    2013-11-01

    An in-depth study of the first steps of electron beam assisted growth of Mo from molybdenum hexacarbonyl on Cu(1 1 1) has been carried out exploiting the complementarity of X-ray photoemission and X-ray absorption spectroscopies. Frank van der Merwe (2D) growth mode has been observed for the completion of the two first monolayers of adsorbed molecules through a simple physisorption process. Irradiation of the Mo(CO){sub 6} deposit by 1 keV electron beam induces a modification of molybdenum coordination, the average number of C-neighbors decreasing from 6 to 3. Decomposed molecules remain on the surface after annealing at 520 K and organize themselves, the molybdenum atoms moving in Cu(1 1 1) surface fcc hollow sites. After annealing at 670 K, metallic molybdenum growth begins, if the total amount of adsorbed Mo atoms exceeds 1.2 monolayers.

  14. Watching adsorption and electron beam induced decomposition on the model system Mo(CO)6/Cu(1 1 1) by X-ray absorption and photoemission spectroscopies

    Science.gov (United States)

    Paufert, Pierre; Fonda, Emiliano; Li, Zheshen; Domenichini, Bruno; Bourgeois, Sylvie

    2013-11-01

    An in-depth study of the first steps of electron beam assisted growth of Mo from molybdenum hexacarbonyl on Cu(1 1 1) has been carried out exploiting the complementarity of X-ray photoemission and X-ray absorption spectroscopies. Frank van der Merwe (2D) growth mode has been observed for the completion of the two first monolayers of adsorbed molecules through a simple physisorption process. Irradiation of the Mo(CO)6 deposit by 1 keV electron beam induces a modification of molybdenum coordination, the average number of C-neighbors decreasing from 6 to 3. Decomposed molecules remain on the surface after annealing at 520 K and organize themselves, the molybdenum atoms moving in Cu(1 1 1) surface fcc hollow sites. After annealing at 670 K, metallic molybdenum growth begins, if the total amount of adsorbed Mo atoms exceeds 1.2 monolayers.

  15. Electronic inhomogeneities in graphene: the role of the substrate interaction and chemical doping

    Directory of Open Access Journals (Sweden)

    G. Rubio-Bollinger

    2012-09-01

    Full Text Available We probe the local inhomogeneities of the electronicproperties of graphene at the nanoscale usingscanning probe microscopy techniques. First, wefocus on the study of the electronic inhomogeneitiescaused by the graphene-substrate interaction ingraphene samples exfoliated on silicon oxide. Wefind that charged impurities, present in the graphenesubstrateinterface, perturb the carrier densitysignificantly and alter the electronic properties ofgraphene. This finding helps to understand theobserved device-to-device variation typically observedin graphene-based electronic devices. Second, weprobe the effect of chemical modification in theelectronic properties of graphene, grown by chemicalvapour deposition on nickel. We find that both thechemisorption of hydrogen and the physisorption ofporphyrin molecules strongly depress theconductance at low bias indicating the opening of abandgap in graphene, paving the way towards thechemical engineering of the electronic properties ofgraphene.

  16. Fenton-like degradation of Bisphenol A catalyzed by mesoporous Cu/TUD-1

    Science.gov (United States)

    Pachamuthu, Muthusamy P.; Karthikeyan, Sekar; Maheswari, Rajamanickam; Lee, Adam F.; Ramanathan, Anand

    2017-01-01

    A family of copper oxide catalysts with loadings spanning 1-5 wt% were dispersed on a three dimensional, mesoporous TUD-1 silica through a hydrothermal, surfactant-free route employing tetraethylene glycol as a structure-directing agent. Their bulk and surface properties were characterized by N2 physisorption, XRD, DRUVS, EPR, TEM and Raman spectroscopy, confirming the expected mesoporous wormhole/foam support morphology and presence of well-dispersed CuO nanoparticles (∼5-20 nm). The catalytic performance of Cu/TUD-1 was evaluated as heterogeneous Fenton-like catalysts for Bisphenol A (BPA) oxidative degradation in the presence of H2O2 as a function of [H2O2], and CuO loading. Up to 90.4% of 100 ppm BPA removal was achieved over 2.5 wt% Cu/TUD-1 within 180 min, with negligible Cu leaching into the treated water.

  17. Steam reforming of glycerol into hydrogen over nano-size Ni-based hydrotalcite-like catalysts.

    Science.gov (United States)

    Hur, Eun; Moon, Dong Ju

    2011-08-01

    Steam reforming (SR) of glycerol for the production of hydrogen was investigated over the nano-sized Ni-based catalysts. The Ni-based catalysts were prepared by solid phase crystallization and impregnation methods, and characterized by N2 physisorption, CO chemisorption, XRD, SEM, and TEM techniques. The Ni/gamma-Al2O3 catalyst showed higher conversion and H2 selectivity. However, it was slowly deactivated due to the carbon formation on the surface of catalyst and the sintering. It was found that the Ni based hydrotalcite-like catalyst (spc-Ni/MgAl) showed higher catalytic activity to prevent carbon formation than Ni/gamma-Al2O3 catalyst in the SR of glycerol.

  18. Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production.

    Science.gov (United States)

    Cho, Su Hyun; Moon, Dong Ju

    2011-08-01

    Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production was carried out at 225 degrees C, 23 bar and LHSV = 4 h(-1). The Ni-based catalyst was prepared by an incipient wetness impregnation method. The catalysts before and after the reaction were characterized by N2 physisorption, CO chemisorption, XRD, TPR, SEM and TEM techniques. It was found that Ni(20 wt%)-Co(3 wt%)/gamma-Al2O3 catalyst showed higher glycerol conversion and hydrogen selectivity than Ni(20 wt%)/gamma-Al2O3 catalyst. There are no major changes in Ni particles after the reaction over Ni-Co/gamma-Al2O3 catalyst. The results suggest that the Ni-Co/gamma-Al2O3 catalyst can be applied to the hydrogen production system using APR of glycerol.

  19. Hydrogen storage in Li-doped metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Himsl, D.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2010-12-30

    Porous Metal-Organic Frameworks have been considered as potential materials for solid state hydrogen storage in recent times. In this context their properties like high permanent porosity, large surface area and the ease of chemical modification due their modular assembly are highly attractive. Unfortunately these materials suffer from low physisorption interaction energies with hydrogen and consequently the need for low adsorption temperatures (77 K) to achieve sufficient hydrogen loadings. One possible approach to overcome the outlined problem is the introduction of unsaturated metal sites within the interior MOF surface to strengthen the adsorbate-adsorbent interaction. We established the functionalization with lithiumalkoxide groups via a post-synthetic transformation of pendant hydroxyl groups with a suitable lithium base. Our results show a significant increase of the isosteric heat of adsorption for hydrogen within the lithium-containing material, thus showing that our approach is a promising strategy to make hydrogen storage in Metal-Organic Frameworks more efficient. (orig.)

  20. Simulation of Initial Stages of the Methanol to Gasoline Process in Acidic Zeolites

    Science.gov (United States)

    Stich, I.; Hytha, M.; Gale, J. D.; Terakura, K.; Payne, M. C.

    2000-03-01

    Methanol to gasoline process is one of the most studied applications of zeolites in current commercial production. This complex process involves: (1) initial adsorption of methanol in the zeolite, (2) activation of the adsorbed methanol molecules, (3) formation of the first intermediates (dimethyl ether (DME)), (4) formation of the first -C-C- bonds. Extensive studies of the stages (1)-(3) have been performed using the method of ab initio molecular dynamics (within DFT in the GGA approximation) and the method of thermodynamic integration to compute the free energy profile for formation of the first intermediate. We find that the initial adsorption (physisorption vs. chemisorption) depends on the adsorption conditions such as zeolite framework and methanol loading. Under certain combination of these conditions the chemisorbed species undergo activation. The activated species are very susceptible to nucleophilic attack to form DME. The computed free energy profile shows that this reaction is entropically controlled with significant differences between the total and free energy profiles.

  1. Use of Citric Acid in Synthesizing a Highly Dispersed Copper Catalyst for Selective Hydrogenolysis%采用柠檬酸合成高分散铜催化剂用于选择氢解反应

    Institute of Scientific and Technical Information of China (English)

    Ming-Hoong LOOI; Shuk-Tong LEE; Sharifah Bee ABD-HAMID

    2008-01-01

    A highly dispersed Cu catalyst supported on silica was prepared by an incipient wetness impregnation method with citric acid. The synthesis was studied by nitrogen physisorption, X-ray diffraction, and temperature-programmed reduction by comparing with a reference prepared without citric acid. The catalyst precursor obtained after impregnation was X-ray amorphous. The precursor was readily transformed to crystalline CuO upon calcination. The CuO particles were of uniform size in a highly dispersed state and can be reduced to Cu at a lower temperature. The activity of the Cu catalyst obtained was an order of magnitude higher than that of the reference for the hydrogenolysis of methyl laurate to dodecanol.

  2. Changing the adsorption capacity of coal-based honeycomb monoliths for pollutant removal from liquid streams by controlling their porosity

    Energy Technology Data Exchange (ETDEWEB)

    Gatica, Jose M.; Harti, Sanae [Departamento C.M., I.M. y Quimica Inorganica, Universidad de Cadiz, Puerto Real 11510 (Spain); Vidal, Hilario, E-mail: hilario.vidal@uca.es [Departamento C.M., I.M. y Quimica Inorganica, Universidad de Cadiz, Puerto Real 11510 (Spain)

    2010-09-15

    Coal-based honeycomb monoliths extruded using methods developed for ceramic materials have been used to retain methylene blue and p-nitrophenol from aqueous solutions. The influence of the filters' thermal treatment on their textural properties and performance as adsorbents was examined. Characterization by N{sub 2} physisorption, mercury porosimetry and scanning electron microscopy along with adsorption tests under dynamic conditions suggest that, depending on the pollutant and its initial concentration, it can be more convenient to previously submit the monoliths to a simple carbonization or to an additional activation, with or without preoxidation, as a consequence of their different resulting pore structures. Infrared spectroscopy indicates that their different adsorption behaviour seems not to be related to differences in their surface chemical groups. In addition, axial crushing tests show that the monoliths have an acceptable mechanical resistance for the application investigated.

  3. Influence of the aluminium impregnation [ Al(NO33] in the beta zeolite over its acidity

    Directory of Open Access Journals (Sweden)

    Francisco José Sánchez Castellanos

    2010-04-01

    Full Text Available Beta zeolite was impregnated with [ Al(NO33], increasing the aluminium content in increments of 0.05% from 0.00% to 0.25%. A parallel treatment with 0.05% sulphuric acid was also performed; in both cases, methanol was used as solvent (disperse phase. Cation exchange capacity (CEC, ammonia chemisorption, infrared spectroscopy (FIT-IR, scanning electronic microscopy (SEM, X-Ray powder diffraction (XRD, atomic absorption spectroscopy (AAS, titration with sodium hydroxide and nitrogen physisorption at 77K were used to carry out the physical and chemical characterization of the catalysts. Futhermore, the catalysts were employed in the esterification of ethanol with acetic acid, to quantify the effect of aluminium impregnation over the beta zeolite.

  4. Industrial surfaces behaviour related to the adsorption and desorption of hydrogen at cryogenic temperature [in LHC vacuum system

    CERN Document Server

    Moulard, G; Saitô, Y

    2001-01-01

    The determination of the hydrogen adsorption capacity on different industrial surfaces has been carried out by measuring isothermal adsorption. First results show that the adsorption capacity is mainly determined by surface porosity. Therefore, the samples may be classified into two categories: smooth and porous surfaces. Thermal desorption spectra reveal two adsorption energy levels for hydrogen physisorbed on porous materials, but only a single one on smooth samples. The value of the lowest energy level seems to be independent of the substrate nature. The physisorption process studied at low coverage, well below a monolayer, shows that these two levels are not well defined but an energy distribution exists for each of them. The influences of the isotherm temperature and an annealing at 7 K of an adsorbed monolayer on hydrogen adsorption capacity have been studied. (16 refs).

  5. Investigation of Hydrogen Adsorption on Single Wall Carbon Nanotubes

    Science.gov (United States)

    Nam, Sang-Hun; Jeong, Seong Hun; Lee, Soon-Bo; Boo, Jin-Hyo

    We have investigated adsorption and desorption condition of atomic hydrogen on single-walled nanotubes (SWCNTs) using ultraviolet photoelectron spectroscopy (UPS) and thermal desorption spectroscopy (TDS). The SWCNTs were made by the high pressure carbon monoxide (HiPCO) method. In our results, we observe from UPS data absorptive states reduce with increasing hydrogen doses and a new peak is developed near 8.6 eV and other points. But this peak is gradually diminished with pumping time. The TDS data show two characteristic peaks at 640 and 790K. By comparing with density functional calculations, we propose these peaks to be related to the presence of atomic hydrogen. Therefore, we can know that there are two adsorption sites on SWCNTs. Also we observed physisorption and chemisorption site by pumping time. We note that the UPS data are fully recoverable after hydrogen desorption at 1200K.

  6. Impact of the carbonisation temperature on the activation of carbon fibres and their application for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Kunowsky, M. [Departamento de Quimica Inorganica, Universidad de Alicante, Apartado de Correos 99, E-03080 Alicante (Spain); CNRS LIMHPUPR1311, Universite Paris 13, 99 Av. J.B. Clement, 93430 Villetaneuse (France); Weinberger, B.; Lamari Darkrim, F. [CNRS LIMHPUPR1311, Universite Paris 13, 99 Av. J.B. Clement, 93430 Villetaneuse (France); Suarez-Garcia, F.; Cazorla-Amoros, D.; Linares-Solano, A. [Departamento de Quimica Inorganica, Universidad de Alicante, Apartado de Correos 99, E-03080 Alicante (Spain)

    2008-06-15

    Porous materials are gaining interest due to their potential for storing hydrogen via physisorption. In the present work, two carbon fibres, carbonised at 973 and 1273 K, have been chemically activated with KOH and NaOH, in order to obtain materials with optimised characteristics for hydrogen storage application. Highly microporous activated carbon fibres were obtained from both precursors, especially from the fibre carbonised at the lower carbonisation temperature, remarking its importance on its subsequent activation process. As activation agent, KOH is more effective for developing the narrow microporosity, and higher yields are obtained. H{sub 2} adsorption isotherms were measured at 298 K for pressures up to 20 MPa, and at 77 K up to 4 MPa. The maximum excess adsorption of hydrogen reached 1 wt% at 298 K and 3.8 wt% at 77 K. The total volumetric storage capacity is of 17 g/l at 298 K, and 32 g/l at 77 K. (author)

  7. Effect of Carbon Supported Pt Catalysts on Selective Hydrogenation of Cinnamaldehyde

    Directory of Open Access Journals (Sweden)

    Qing Han

    2016-01-01

    Full Text Available Selective hydrogenation of cinnamaldehyde (CAL to cinnamyl alcohol (COL is of both fundamental and industrial interest. It is of great significance to evaluate the possible differences between different supports arising from metal dispersion and electronic effects, in terms of activity and selectivity. Herein, Pt catalysts on different carbon supports including carbon nanotubes (CNTs and reduced graphene oxides (RGO were developed by a simple wet impregnation method. The resultant catalysts were well characterized by XRD, Raman, N2 physisorption, TEM, and XPS analysis. Applied in the hydrogenation of cinnamaldehyde, 3.5 wt% Pt/CNT shows much higher selectivity towards cinnamyl alcohol (62% than 3.5 wt% Pt/RGO@SiO2 (48%. The enhanced activity can be ascribed to the high graphitization degree of CNTs and high density of dispersed Pt electron cloud.

  8. The Synergistic Effect of Anionic Surfactant on Adsorption Enhancement of the Carotenoids Extract using Mesoporous Hydroxyapatite Nanoparticles

    Directory of Open Access Journals (Sweden)

    Supalak Kongsri

    2015-09-01

    Full Text Available Fish hydroxyapatite (FHAp was prepared from fish scale waste by alkaline heat treatment. The obtained nanoparticles (21 nm of FHAp with high crystallinity (89.5% were used as biocompatible adsorbent for an adsorption of plant carotenoids extract. For optimum conditions of batch adsorption study, experimental parameters including pH of solution, adsorbent dosage, an initial concentration of carotenoids, amount of sodium dodecyl sulfate (SDS, contact time and temperature were investigated in details. From the results, the carotenoids adsorption of the FHAp was drastically enhanced in the presence of SDS through their hydrophobic interactions between the carotenoids and the cationic element FHAp via the anionic head of SDS by electrostatic and ion-exchange interactions and surface complexation. The adsorption behaviors fitted well by pseudo-second order kinetic model and Freundlich adsorption isotherm. Thermodynamic data demonstrated that the adsorption behaviors of the carotenoids on the hydroxyapatite nanoparticles were spontaneously endothermic and physisorption process.

  9. Synthesis and mechanistic study of in situ halogen/nitrogen dual-doping in graphene tailored by stepwise pyrolysis of ionic liquids

    Science.gov (United States)

    Park, Ok-Kyung; Kim, Hyun Joo; Hwang, Jun Yeon; Lee, Dong Su; Koo, Jahyun; Lee, Hoonkyung; Yu, Jong-Sung; Ku, Bon-Cheol; Lee, Jae Kwan

    2015-03-01

    New halogen/nitrogen dual-doped graphenes (X/N-G) with thermally tunable doping levels are synthesized via the thermal reduction of graphite oxide (GO) with stepwise-pyrolyzed ionic liquids. The doping process of halogen and nitrogen into the graphene lattice proceeds via substitutional or covalent bonding through the physisorption or chemisorption of in situ pyrolyzed dopant precursors. The doping process is performed by heating to 300-400 °C of ionic liquid, and the chemically assisted reduction of GO is facilitated by ionic iodine, resulting in I/N-G materials possessing about three and two orders of magnitude higher conductivity (˜22 200 S m-1) and charge carrier density (˜1021 cm-3), compared to those of thermally reduced GO. The thermally tunable doping levels of halogen in X/N-G significantly increase the conductivity of doped graphene to ˜27 800 S m-1.

  10. Chemisorption of NO on Pt-decorated graphene as modified nanostructure media: A first principles study

    Science.gov (United States)

    Rad, Ali Shokuhi; Abedini, Ehsan

    2016-01-01

    We used density functional theory calculations (DFT) to search the potential of pristine as well as Pt-decorated graphene sheets as adsorbent/gas sensors for NO by considering the electronic properties of NO on these two surfaces. We found much higher adsorption energy, higher charge transfer, lower connecting distance, and higher orbital hybridizing of NO gas molecule on Pt-decorated graphene than pristine graphene. We used orbital analysis including density of states as well as frontier molecular orbital study for NO-surface systems because of more understanding of the kind of interaction. Our results reveal physisorption of NO on pristine graphene with adsorption energy of -24 kJ mol-1while in contrast much higher adsorption energy of -199 kJ mol-1 is achieved upon adsorption of NO on Pt-decorated graphene which is in the range of chemisorption.

  11. Adsorption mechanism of malachite green onto activated phosphate rock: a kinetics and theoretical study

    Directory of Open Access Journals (Sweden)

    LABIDI Nouar Sofiane

    2016-08-01

    Full Text Available Adsorption kinetics of malachite green onto Algerian activated phosphate rock was studied for better removal of the dye from wastewater. The prepared sorbent displayed à good surface area of 42.2 m²/g. The adsorption process appeared to be of physisorption nature and it took less than 60 min to get equilibrium whereas the kinetics indicated that the adsorption is likely a second order reaction which is further proved with the high R2 value. The intraparticle diffusion model confirms an adsorption mechanism limited on two steps, i.e., (1 surface adsorption, and (2 pore diffusion with a diffusion parameter of Di=10-18 cm2 s-1. Besides, semi-empirical theoretical calculations provide a new insight into adsorption mechanism as a principle of hydrogen bonding and ionic interaction.

  12. Graphene nanodevices for DNA sequencing

    Science.gov (United States)

    Heerema, Stephanie J.; Dekker, Cees

    2016-02-01

    Fast, cheap, and reliable DNA sequencing could be one of the most disruptive innovations of this decade, as it will pave the way for personalized medicine. In pursuit of such technology, a variety of nanotechnology-based approaches have been explored and established, including sequencing with nanopores. Owing to its unique structure and properties, graphene provides interesting opportunities for the development of a new sequencing technology. In recent years, a wide range of creative ideas for graphene sequencers have been theoretically proposed and the first experimental demonstrations have begun to appear. Here, we review the different approaches to using graphene nanodevices for DNA sequencing, which involve DNA passing through graphene nanopores, nanogaps, and nanoribbons, and the physisorption of DNA on graphene nanostructures. We discuss the advantages and problems of each of these key techniques, and provide a perspective on the use of graphene in future DNA sequencing technology.

  13. Incorporation of metals (Pt-Ni-Ru) in the zeolite ZSM-5 through ion exchange competitive: synthesis and characterization; Incorporacao de metais (Pt-Ni-Ru) na zeolita ZSM-5 atraves da troca ionica competitiva: sintese e caracterizacao

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, A.S.; Rodrigues, M.G.F., E-mail: antusiasb@hotmail.com [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Departamento de Engenharia Quimica; Grau, J.M. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE/FIQ/UNL-CONICET), Santa Fe (Argentina)

    2012-07-01

    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)

  14. 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....

  15. 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.

  16. 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)

  17. Formation of pyridine N-oxides using mesoporous titanium silicalite-1

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Abildstrøm, Jacob Oskar; Perez-Ferreras, Susana

    2014-01-01

    Mesoporous titanium silicalite-1 (TS-1) prepared by carbon-templating is significantly more active than conventional TS-1 for the oxidation of pyridine derivatives using aqueous hydrogen peroxide as oxidant. The catalytic activity is increased by the system of mesopores that helps to overcome...... the configurational diffusion limitations within the microporous catalyst. The use of a carbon-template for generation of secondary porosity is more effective than desilication. The desilicated catalyst is slightly more active than conventional TS-1, probably due to a decrease of the mean diffusion path length....... In contrast, carbon-templated mesopores provides an efficient transport throughout the zeolite, thus preventing deactivation due to product confinement. All catalysts were characterised by X-ray powder diffraction, scanning electron microscopy, UV-Vis spectroscopy and nitrogen physisorption. The results...

  18. 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.

  19. Study to improve the quality of a Mexican straight run gasoil over NiMo/{gamma}-Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dominguez-Crespo, M.A. [Instituto Politecnico Nacional, Departamento de Metalurgia y Materiales, A.P. 75-876, 07300 Mexico D.F. (Mexico)]. E-mail: adcrespo2000@yahoo.com.mx; Diaz-Garcia, L. [Instituto Mexicano del Petroleo, Avenida Eje Central Lazaro Cardenas No. 152, Col. San Bartolo Atepehuacan, 07730 Mexico D.F. (Mexico); Arce-Estrada, E.M. [Instituto Politecnico Nacional, Departamento de Metalurgia y Materiales, A.P. 75-876, 07300 Mexico D.F. (Mexico); Torres-Huerta, A.M. [Instituto Politecnico Nacional, Departamento de Metalurgia y Materiales, A.P. 75-876, 07300 Mexico D.F. (Mexico); Cortez de la Paz, M.T. [Instituto Mexicano del Petroleo, Avenida Eje Central Lazaro Cardenas No. 152, Col. San Bartolo Atepehuacan, 07730 Mexico D.F. (Mexico)

    2006-11-30

    Four NiMo catalyst supported on Al{sub 2}O{sub 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.

  20. Reinforced photocatalytic reduction of CO2 to CO by a ternary metal oxide NiCo2O4.

    Science.gov (United States)

    Wang, Zhaoyu; Jiang, Min; Qin, Jiani; Zhou, Han; Ding, Zhengxin

    2015-06-28

    The work reported herein was the facile preparation of uniform urchin-like NiCo2O4 microspheres, and their use as an efficient and stable cocatalyst for photocatalytic CO2 reduction catalysis. A combined solvothermal-calcination strategy was applied to synthesize the NiCo2O4 material that was systematically characterized by physical and chemical measurements (e.g. SEM, TEM, XRD, XPS, EDX, elemental mapping and N2 physisorption analysis). By cooperation with a visible light photosensitizer, the NiCo2O4 material effectively promoted the deoxygenative reduction of CO2 to CO by more than twenty times under mild reaction conditions. The carbon origin of CO evolution was validated by (13)CO2 isotope tracer experiments. Various reaction parameters were examined and optimized, and a possible reaction mechanism was proposed. Furthermore, the stability and reusability of NiCo2O4 cocatalysts were firmly confirmed.

  1. Application of Polyaniline Nano Composite for the Adsorption of Acid Dye from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    J.Raffiea Baseri

    2012-01-01

    Full Text Available In this research, Polyaniline coated sawdust (Polyaniline nano composite was synthesized via direct chemical polymerization and used as an adsorbent for the removal of acid dye (Acid Violet 49 from aqueous solutions. The effect of some important parameters such as pH, initial concentration of dye, contact time and temperature on the removal efficiency was investigated in batch adsorption system. The adsorption capacity of PAC was high (96.84 % at a pH of 3-4. The experimental data fitted well for pseudo second order model. Langmuir model is more appropriate to explain the nature of adsorption with high correlation coefficient. The Energy of activation from arrehenius plot suggested that the adsorption of AV49 onto PAC involves physisorption mechanism.

  2. Alkali treated Foumanat tea waste as an efficient adsorbent for methylene blue adsorption from aqueous solution

    Directory of Open Access Journals (Sweden)

    Azadeh Ebrahimian Pirbazari

    2014-08-01

    Full Text Available The adsorption of methylene blue (MB from aqueous solution by alkali treated Foumanat tea waste (ATFTW from agriculture biomass was investigated. The adsorbent was characterized by Scanning Electron Microscopy (SEM, Fourier Transform-Infrared Spectroscopy (FT-IR and nitrogen physisorption. FTIR results showed complexation and ion exchange appear to be the principle mechanism for MB adsorption. The adsorption isotherm data were fitted to Langmuir, Sips, Redlich-Peterson and Freundlich equations, and the Langmuir adsorption capacity, Qmax was found to be 461 mgg−1. It was found that the adsorption of MB increases by increasing temperature from 303 to 323 K and the process is endothermic in nature. The removal of MB by ATFTW followed pseudo-second order reaction kinetics based on Lagergren equations. Mechanism studies indicated that the adsorption of MB on the ATFTW was mainly governed by external mass transport where particle diffusion was the rate limiting step.

  3. Silver and oxygen: Transition from clusters to nanoparticles

    Science.gov (United States)

    Schmidt, Martin; Bréchignac, Catherine

    2016-03-01

    By varying the sizes of isolated and charged silver particles, we may observe a wide range of reactions from weak molecular-oxygen physisorption to strong oxygen chemisorption. The global electron configuration dominates the stability of the silver-oxygen complexes. Our experimental studies at 77 K show a cluster regime below 40 free valence electrons in the system. Here each atom of silver added to the complex cause strong alternations of the oxygen binding by quantum effects. Bigger silver-oxygen complexes show smoother size dependence. As is rather typical for nanoparticles, the quantum effects are here less important, while the system size still matters. The electrostatic interaction between the charge state of the nanoparticle and the charge transfer of the reaction accounts for the general trends observed at silver, as it is in related oxygen-metal complexes.

  4. Optimizing the crystallinity and acidity of H-SAPO-34 by fluoride for synthesizing Cu/SAPO-34 NH3-SCR catalyst.

    Science.gov (United States)

    Ma, Jing; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Ma, Yue

    2016-03-01

    A series of H-SAPO-34 zeolites were synthesized by a hydrothermal method in fluoride media. The as-synthesized H-SAPO-34 zeolites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, temperature-programmed desorption of NH3 (NH3-TPD) and nuclear magnetic resonance (NMR) measurements. The results showed that a certain concentration of F(-) anions promoted the nucleation and crystallization of H-SAPO-34. The H-SAPO-34 synthesized in the fluoride media showed high crystallinity, uniform particle size distribution, large specific surface area and pore volume, and enhanced acidity. Therefore, Cu/SAPO-34 based on the fluoride-assisted zeolite showed a broadened temperature window for the selective catalytic reduction of NO by NH3 (NH3-SCR) reaction due to the enhanced acidity of the zeolite and the improved dispersion of copper species.

  5. Hydroxyethyl cellulose as efficient organic inhibitor of zinc-carbon battery corrosion in ammonium chloride solution: Electrochemical and surface morphology studies

    Science.gov (United States)

    Deyab, M. A.

    2015-04-01

    Hydroxyethyl cellulose (HEC) has been investigated as corrosion inhibitor for zinc-carbon battery by polarization and electrochemical impedance spectroscopy (EIS) measurements. The obtained results show that the maximum inhibition efficiency by HEC in 26% NH4Cl solution at 300 ppm and 298 K is 92.07%. Tafel polarization studies reveal that HEC acts as an efficient mixed inhibitor. The corrosion rate is suppressed by the adsorption of HEC on the zinc surface. HEC adsorption obeys the Langmuir isotherm and the thermodynamic parameters Kads and Δ Gadso have been also calculated and discussed. Both physisorption and chemisorption may occur on the zinc surface. Surface characterization investigation using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) is used to ascertain the nature of the protective film.

  6. Decoration of gold nanoparticles with cysteine in solution: reactive molecular dynamics simulations

    Science.gov (United States)

    Monti, Susanna; Carravetta, Vincenzo; Ågren, Hans

    2016-06-01

    The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption.The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption. Electronic supplementary information (ESI) available: Different views of the AuNP surface coverage. Distance map describing the position of each molecule in relation to the others on the AuNP (alpha carbon distances). See DOI: 10.1039/C

  7. A stand-alone mesoporous crystal structure model from in situ X-ray diffraction: nitrogen adsorption on 3D cagelike mesoporous silica SBA-16.

    Science.gov (United States)

    Miyasaka, Keiichi; Hano, Hiroko; Kubota, Yoshiki; Lin, Yangzheng; Ryoo, Ryong; Takata, Masaki; Kitagawa, Susumu; Neimark, Alexander V; Terasaki, Osamu

    2012-08-13

    We present a modeling scheme to analyze cagelike silica mesoporous crystals based on in situ X-ray diffraction (XRD) data collected during gas adsorption-desorption (physisorption) processes. Nitrogen physisorption on a silica mesoporous crystal of SBA-16 was directly monitored by using synchrotron in situ powder XRD measurements conducted at SPring-8. SBA-16 is a well-ordered mesoporous silica in which three-dimensional interconnected cagelike primary mesopores are located at the body-centered cubic lattice points. In addition, the surrounding silica matrix contains random microporous and mesoporous intrawall porosities that are significantly influential to the diffusion properties, and thus important to be quantified for this media. The in situ XRD data exhibits seven Bragg reflections throughout the measurements, and the present method allows one to obtain the maximal and stand-alone information about the pore structure (for example, the mesopore size, the matrix density, the intrawall porosity, and pore surface roughness) together with the nitrogen film evolution in the primary mesopores and the intrawall pore-filling in the silica matrix. We furthermore observe a macroscopic amount of nitrogen adsorbed assuming the density of the fluid, and confirm that the XRD "isotherm" recalculated from the analysis result is consistent with the conventional nitrogen isotherm on a semi-quantitative level; however, these results suggest that the intrawall pores would have a greater contribution to the adsorption than considered based on the conventional isotherm analyses. The present method is readily extendable to any ordered mesopores wrapped by the wall matrix containing a certain intrawall porosity.

  8. A comparative study of CeO2-Al2O3 support prepared with different methods and its application on MoO3/CeO2-Al2O3 catalyst for sulfur-resistant methanation

    Science.gov (United States)

    Jiang, Minhong; Wang, Baowei; Yao, Yuqin; Li, Zhenhua; Ma, Xinbin; Qin, Shaodong; Sun, Qi

    2013-11-01

    The CeO2-Al2O3 supports prepared with impregnation (IM), deposition precipitation (DP), and solution combustion (SC) methods for MoO3/CeO2-Al2O3 catalyst were investigated in the sulfur-resistant methanation. The supports and catalysts were characterized by N2-physisorption, transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (RS), and temperature-programmed reduction (TPR). The N2-physisorption results indicated that the DP method was favorable for obtaining better textural properties. The TEM and RS results suggested that there is a CeO2 layer on the surface of the support prepared with DP method. This CeO2 layer not only prevented the interaction between MoO3 and γ-Al2O3 to form Al2(MoO4)3 species, but also improved the dispersion of MoO3 in the catalyst. Accordingly, the catalysts whose supports were prepared with DP method exhibited the best catalytic activity. The catalysts whose supports were prepared with SC method had the worst catalytic activity. This was caused by the formation of Al2(MoO4)3 and crystalline MoO3. Additionally, the CeO2 layer resulted in the instability of catalysts in reaction process. The increasing of calcination temperature of supports reduced the catalytic activity of all catalysts. The decrease extent of the catalysts whose supports were prepared with DP method was the lowest as the CeO2 layer prevented the interaction between MoO3 and γ-Al2O3.

  9. Hydrogen storage on metal oxide model clusters using density-functional methods and reliable van der Waals corrections.

    Science.gov (United States)

    Gebhardt, Julian; Viñes, Francesc; Bleiziffer, Patrick; Hieringer, Wolfgang; Görling, Andreas

    2014-03-21

    We investigate the capability of low-coordinated sites on small model clusters to act as active centers for hydrogen storage. A set of small magic clusters with the formula (XY)6 (X = Mg, Ba, Be, Zn, Cd, Na, Li, B and Y = O, Se, S, F, I, N) and a "drumlike" hexagonal shape showing a low coordination number of three was screened. Oxide clusters turned out to be the most promising candidates for hydrogen storage. For these ionic compounds we explored the suitability of different van der Waals (vdW) corrections to density-functional calculations by comparing the respective H2 physisorption profile to highly accurate CCSD(T) (Coupled Cluster Singles Doubles with perturbative Triples) calculations. The Grimme D3 vdW correction in combination with the Perdew-Burke-Ernzerhof exchange-correlation functional was found to be the best approach compared to CCSD(T) hydrogen physisorption profiles and is, therefore, suited to study these and other light metal oxide systems. H2 adsorption on sites of oxide model clusters is found to meet the adsorption energy criteria for H2 storage, with bond strengths ranging from 0.15 to 0.21 eV. Energy profiles and estimates of kinetic constants for the H2 splitting reaction reveal that H2 is likely to be adsorbed molecularly on sites of (MgO)6, (BaO)6, and (BeO)6 clusters, suggesting a rapid H2 uptake/release at operating temperatures and moderate pressures. The small mass of beryllium and magnesium makes such systems appealing for meeting the gravimetric criterion for H2 storage.

  10. Facile control of intra-fiber porosity and inter-fiber voids in electrospun fibers for selective adsorption

    Science.gov (United States)

    Lin, Jinyou; Tian, Feng; Shang, Yanwei; Wang, Fujun; Ding, Bin; Yu, Jianyong

    2012-08-01

    We report a facile method to control intra-fiber porosity via varying the relative humidity and inter-fiber voids through the blending of two different polymeric fibers via multi-nozzles spinning of electrospun fibers for selective adsorption of oil from water.We report a facile method to control intra-fiber porosity via varying the relative humidity and inter-fiber voids through the blending of two different polymeric fibers via multi-nozzles spinning of electrospun fibers for selective adsorption of oil from water. Electronic supplementary information (ESI) available: FE-SEM images, nitrogen physisorption isotherms, differential pore volume vs. pore width, SAXS 2D scattering patterns and SAXS curves of PS (Mw = 208 000 g mol-1) fibrous mats formed at different RH (Fig. S1). Iron element distribution of a single fiber (Fig. S2). A schematic diagram to show the multi-nozzles electrospinning (Fig. S3). FE-SEM images of as-prepared fibrous mats formed with various PS/PU nozzle ratios (Fig. S4). Nitrogen physisorption isotherms, SSA, and water contact angles of as-prepared fibrous mats formed with various PS/PU nozzle ratios (Fig. S5 and S6). Hydrophobicity-oleophilicity of an as-spun fibrous mat (Fig. S7). Typical tensile stress-strain curves of various PS fibrous mats with the addition of PU fibers formed from a 50 wt% PU resin (Fig. S8). Surface characterization of as-prepared fibers (Table S1). Tensile properties of the fibrous mats (Tables S2 and S3). See DOI: 10.1039/c2nr31515g

  11. 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.

  12. Review of Kelvin's Equation and Its Modification in Characterization of Mesoporous Materials%用于测定介孔的Kelvin方程及其修正述评

    Institute of Scientific and Technical Information of China (English)

    张颖; 阎子峰; 胡喜军

    2006-01-01

    Physical and mathematical models as well as calculation methods of nitrogen bed on porous media have been introduced to evaluate the structural parameters of mesoporous materials. Kelvin's equation is a link between the relative adsorbate pressure, the mean pore radius, and pore capillarity on the basis of macroscopic capillary condensation. However, Kelvin's equation has been identified that it underestimates the calculated pore size of a material especially in the boundary of pore size which is between 2 and 4 nm.Various modifications on Kelvin's equation were mentioned in order to develop a new model to improve the accuracy of pore size calculation. The problems on conventional mathematical models were analyzed and discussed. A number of calculation methods on physisorption and pore size, especially fundamental theories of physisorption, basis of models and their deficiencies are reviewed. It can provide guidance on developing a modified Kelvin's equation for pore size calculation.%介绍了物理吸附法评价介孔材料孔结构参数的理论基础、孔介质模型及吸附质对测量结果准确性的影响因素.讨论了Kelvin公式,以及从不同方面对Kelvin公式进行的修正,并以此为基础,评述采用物理吸附法测定介孔材料各种孔结构测试方法,着重探讨物理吸附法的理论基础、模型建立及其不足之处,分析和探讨介孔材料孔结构表征中存在的问题及原因,为建立新的理论模型探讨思路与可能.

  13. Study on the adsorption properties of O{sub 3}, SO{sub 2}, and SO{sub 3} on B-doped graphene using DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Rad, Ali Shokuhi, E-mail: a.shokuhi@gmail.com [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Shabestari, Sahand Sadeghi [Department of Chemical Engineering, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Mohseni, Soheil; Aghouzi, Samaneh Alijantabar [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of)

    2016-05-15

    We investigated the structure, adsorption, electronic states, and charge transfer of O{sub 3}, SO{sub 2} and SO{sub 3} molecules on the surface of a B-doped graphene using density functional theory (DFT). We found weak physisorption of SO{sub 2} (−10.9 kJ/mole, using B3LYP-D) and SO{sub 3} (−15.7 kJ/mole, using B3LYP-D) on the surface of B-doped graphene while there is strong chemisorption for O{sub 3} (−96.3 kJ/mole, using B3LYP-D ) on this surface. Our results suggest the potential of B-doped graphene as a selective sensor/adsorbent for O{sub 3} molecule. We noticed some change in hybridizing of boron from sp{sup 2} to sp{sup 3} upon adsorption of O{sub 3} which cases transformation of the adsorbent from 2D to 3D. - Graphical abstract: The electronic property of B-doped graphene is responsible to highly adsorption of O{sub 3} molecules while the adsorption of SO{sub 2} and SO{sub 3} molecules on this surface exhibits only a weak interaction. - Highlights: • B-doped graphene clearly is n-type semiconductor. • High negatively charge of C-atoms neighboring the boron dopant. • Chemisorption of O{sub 3} and physisorption of SO{sub 2} and SO{sub 3} on the surface of B-doped graphene.

  14. 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)

  15. 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

  16. Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations

    Science.gov (United States)

    Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P.

    2016-07-01

    Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity. Electronic supplementary information (ESI) available: Simulation data on equilibration of energies and structures (root-mean-square-deviations and

  17. 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.

  18. Development and investigation of novel nanostructures and complex hydrides for hydrogen storage

    Science.gov (United States)

    Niemann, Michael Ulrich

    2009-12-01

    Over the past few years, the need for a clean and renewable fuel has sharply risen. This is due to increasing fossil fuel costs and the desire to limit or eliminate harmful byproducts which are created during the burning of these fuels. Hydrogen is the most abundant element in the universe and can be used in either fuel cells or traditional internal combustion engines to produce energy with no harmful emissions. One of the main obstacles facing the implementation of a hydrogen economy is its storage. Classical methods of storage involve either high and unsafe pressures or liquid storage involving a large amount of energy. Two alternative hydrogen storage methods are investigated---physisorption, which is the weak chemical bonding to a material, as well as chemisorption, which is a strong chemical bond of hydrogen to a host material. Polyaniline, a conducting polymer, is investigated in both its bulk form as well as in nanostructured forms, more precisely nanofibers and nanospheres, to store hydrogen via physisorption. It is found the bulk form of polyaniline can store only approximately 0.5wt.% hydrogen, which is far short of the 6wt.% required for practical applications. Nanofibers and nanospheres, however, have been developed, which can store between 4wt.% and 10wt.% of hydrogen at room temperature with varying kinetics. A new complex metal hydride comprised of LiBH4, LiNH 2 and MgH2 has been developed to store hydrogen via chemisorption. While the parent compounds require high temperatures and suffer of slow kinetics for hydrogen sorption, the work performed as part of this dissertation shows that optimized processing conditions reduce the hydrogen release temperature from 250°C to approximately 150°C, while the addition of nano sized materials has been found to increase the kinetics of hydrogen sorption as well as further decrease the hydrogen release temperature, making this one of the first viable hydrogen storage materials available. This is the first time

  19. Incorporation of precious metal nanoparticles into various aerogels by different supercritical deposition methods

    Science.gov (United States)

    Saquing, Carl D.

    2005-11-01

    observed strong precursor-substrate interaction was corroborated by thermo-gravimetric analyses and N2 physisorption. Transmission electron microscopy, x-ray diffraction, H2 and CO chemisorption and N2 physisorption were employed to demonstrate the homogeneity of particle dispersion, to determine the morphology, range and variation in particle size within the solid matrices and to fully identify the resultant particles as Pt and Ru metals. (Abstract shortened by UMI.)

  20. Influence of Preparation Methods on Catalytic Performance of Double Mesoporous Co-Based Catalysts for Fischer-Tropsch Synthesis%制备方法对双介孔钴基催化剂结构及其费-托反应性能的影响

    Institute of Scientific and Technical Information of China (English)

    王俊刚; 孙予罕; 李德宝; 侯博; 贾丽涛; 贾利宏; 孙志强; 刘斌; 郭金刚; 任润厚

    2011-01-01

    A series of cobalt-based catalyst samples supported on double mesoporous MCM-41 for Fischer-Tropsch synthesis (FTS) were prepared using three methods, incipient-wetness impregnation (IWI), vapor-induced hydrolysis (VIH), and excessive impregnation (EI). The catalyst samples were characterized by N2 physisorption, X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR) and Raman spectroscopy. The N2 physisorption results showed that the samples prepared by IWI and VIH retained the double mesoporous character. and the cobalt particles were mainly located in the pore. The FTS results showed that the reducibility and dispersion of active species of the samples prepared by IWI and EI were very high. The catalyst prepared by IWI had the smallest Co3O4 crystallite size and the highest dispersion and showed higher FTS activity, lower CH4 selectivity and higher C5+ selectivity.%以双介孔分布MCM-41分子筛为载体,采用等体积浸渍、氨水气相诱导水解和过量浸渍法制备了费-托合成钴摹催化剂,并考察了它们的孔结构、活性物种分布及费-托合成催化性能.结粜表明,采用等体积浸渍法和氨水气相诱导水解法制备的催化剂都保持了较好的双介孔特性,Co颗粒人部分位于分子筛的孔道内部.过量浸渍法和等体积浸渍法制备的催化剂上Co物种的还原度和分散度均较高,尤其后者上Co分散度更高,因而具有较低的CH4选择性和较高的C5+选择性.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  6. Thermodynamics and Kinetics of Cadmium Ion Adsorption onto Lignite-derived Amendments

    Directory of Open Access Journals (Sweden)

    BAO Xiu-li

    2017-06-01

    Full Text Available Adsorption kinetics and thermodynamics of cadmium onto lignite-derived humic acid and lignite-derived active carbon were investigated by batch experiments under different temperatures. The adsorption thermodynamic isotherms were fitted using Langmuir, Freundlich and Temkin models, the adsorption kinetics were fitted to pseudo-first-order, pseudo-second-order, Elovich, fractional power and intraparticle diffusion models. Thermodynamic studies showed that Temkin model displayed the most suitable model to describe adsorption of cadmium onto raw lignite, extracted humic acid and active carbon. Thermodynamic parameters indicated the adsorption process were spontaneous, favourable, and endothermic physical adsorption in nature. The equilibrium adsorption capacity of cadmium obtained from the Langmiur model for humic acid, lignite and active carbon was 36.14~44.09, 29.63~38.20 mg·g-1 and 21.04~30.34 mg·g-1 respectively in the temperature range of 294.55~313.15 K, adsorption capacity magnitudes increased with a rise of temperature, indicating more feasible adsorption at high temperature. Adsorption kinetics parameters showed that the pseudo-second-order model was better than the pseudo-first-order, Elovich, fractional power and the intraparticle diffusion models, this indicated that cadmium adsorption might be a physisorption associated with chemisorption process. According to the adsorption characteristics of kinetics, thermodynamics parameters such as change in free energy(△G, change in enthalpy(△H, and change in entropy(△S, it was concluded that the adsorption process of cadmium onto these different adsorbents were spontaneous, endothermic, simultaneous physisorption and accompanied by chemisorption or alternatively physicochemical process. Adsorbents of humic acid had the great adsorption capacity and adsorption intensity. Temkin isotherm model and pseudo-second-order model could be the suitable models with good fitting for describing the

  7. Fundamental studies of H{sub 2} interaction with MAl{sub 3} clusters [M = Li, Sc, Ti, Zr

    Energy Technology Data Exchange (ETDEWEB)

    Samolia, Madhu; Dhilip Kumar, T.J., E-mail: dhilip@iitrpr.ac.in

    2014-03-05

    Highlights: • A first-principles calculation on H{sub 2} interaction and saturation on stable MAl{sub 3} clusters [M = Li, Sc, Ti, Zr] is performed. • Transition metals have negative electron charge density while Al atom has positive in MAl{sub 3} from NBO charge analysis. • H{sub 2} undergoes dissociative chemisorption on the M atop site resulting in M–H–Al bridge bond. • H{sub 2} saturation on M atop site results initially chemisorption and then physisorption with 3-centered Kubas interaction. • External electric field applied on TiAl{sub 3}H{sub 4} leads to more polarization, H{sub 2} bond elongation and increased adsorption energy. -- Abstract: Complex metal hydride is a promising hydrogen storage material for automobile applications due to its reversible storage capacity. The presence of transition metal halide is found to improve significantly the kinetics of H{sub 2} adsorption and desorption processes. Experimental studies have indicated the formation of distorted MAl{sub 3} phase where M = Sc, Ti, Zr. In this study, a first-principles density functional study has been performed to investigate the hydrogen interaction and saturation on stable tetrahedral MAl{sub 3} clusters [M = Li, Sc, Ti, and Zr] by employing spin-polarized hybrid and non-local density functionals. On saturation, the first H{sub 2} molecule undergoes chemisorption in the transition metals while further loading results in physisorption with the Kubas-type H{sub 2} interaction. Activation energy barrier for the H{sub 2} dissociation over the cluster is calculated to be ∼0.2 eV for the transition metals. Effect of external electric field on the MAl{sub 3}H{sub 4} cluster with molecular H{sub 2} is studied which leads to polarization of physisorbed H{sub 2} and the cluster. The results offer an explanation for catalysts role in improving the kinetics of H{sub 2} sorption process in complex metal hydrides.

  8. A first-principles study of hydrogen interaction and saturation on ScAl{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Samolia, Madhu [Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar 140001 (India); Dhilip Kumar, T.J., E-mail: dhilip@iitrpr.ac.in [Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar 140001 (India)

    2013-03-05

    Graphical abstract: Electrostatic potential superimposed on electron density of H{sub 2}, Al{sub 4} and ScAI{sub 3}. Highlights: ► A first principles calculation on hydrogen interaction and saturation on stable ScAl{sub 3} cluster is performed. ► Sc atom has higher negative charge electron density over Al atom in ScAl{sub 3} from natural bond orbital charge analysis. ► H{sub 2} undergoes dissociative chemisorption on the Sc atop site resulting in Sc–H–AI bridge bond. ► H{sub 2} saturation on Sc site results initially in chemisorption and then physisorption with the maximum loading of 6 molecules resulting in stable ScAl{sub 3}H{sub 12} structure. -- Abstract: Complex metal hydrides are promising hydrogen storage material for mobile applications. The presence of scandium catalysts in complex metal hydrides is found to improve significantly the kinetics of H{sub 2} adsorption and desorption. The exact role of these additives is not completely understood. NMR studies suggests the presence of distorted ScAl{sub 3} phase which is attributed to the enhancement of reversible uptake and release rates of H{sub 2}. In this study, we have investigated the hydrogen interaction and saturation on stable ScAl{sub 3} cluster at various sites using the density functional theory by employing unrestricted B3LYP/6-311++G(d,p) and the GGA-PW91/DNP methods. From natural bond orbital charge analysis and electrostatic potential superimposed on electron density plots, ScAl{sub 3} is found to be more polarized and Sc atom in ScAl{sub 3} cluster has higher negative charge and electron density over Al atoms. H{sub 2} undergoes dissociative chemisorption on the Sc atop site in ScAl{sub 3} resulting in Sc–H–Al bridge structure. The hydrogen saturation is studied by sequential H{sub 2} adsorption on ScAl{sub 3} cluster. In the Sc site, the first H{sub 2} molecule undergoes dissociative chemisorption and further addition results in H{sub 2} physisorption with the maximum loading

  9. 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

  10. Immobilization of paracetamol and benzocaine pro-drug derivatives as long-range self-organized monolayers on graphite.

    Science.gov (United States)

    Popoff, Alexandre; Fichou, Denis

    2008-05-01

    We show here by means of scanning tunneling microscopy (STM) at the liquid/solid interface that paracetamol and benzocaine molecules bearing a long aliphatic chain can be immobilized on highly oriented pyrolitic graphite (HOPG) as perfectly ordered two-dimensional domains extending over several hundreds of nanometers. In both cases, high-resolution STM images reveal that compounds 1 and 2 self-assemble into parallel lamellae having a head-to-head arrangement. The paracetamol heads of 1 are in a zigzag position with entangled n-dodecyloxy side chains while benzocaine heads of compound 2 are perfectly aligned as a double row and have their palmitic side chains on either sides of the head alignment. We attribute the very long-range ordering of these two pro-drug derivatives on HOPG to the combined effects of intermolecular H-bonding on one side and Van der Waals interactions between aliphatic side chains and graphite on the other side. The 2D immobilization of pro-drug derivatives via a non-destructive physisorption mechanism could prove to be useful for applications such as drug delivery if it can be realized on a biocompatible substrate.

  11. Adsorption of phosphorus in sediment re-suspension under sudden expansion flow conditions

    Institute of Scientific and Technical Information of China (English)

    LIANG Wen; WANG Ze; JIAO Zeng-xiang; WAN Jun

    2013-01-01

    Based on the study of hydraulic characteristics of the sudden expansion water flow of an annular flume,this paper determines the vertical velocity distribution and the turbulence intensity distribution in the mainstream and the recirculation regions to analyze the basic features of this flow field.The adsorption of the phosphorus in the sediment is studied by adding the bacteriostatic agent.The results show that the flow speed in the mainstream region is higher than that in the recirculation region.However,the turbulence intensity in the recirculation region increases more than that in the mainstream region.The adsorption of the phosphorus in the sediment includes the physisorption and the biosorption,and the former is stronger than the latter.With the biosorption in the phosphorus removal process,the phosphorus released by the sediment is mainly completed by the poly-P bacteria in the anaerobic condition.The adsorption of the phosphorus in the sediment in the mainstream region of a sudden expansion water flow is strong and stable,whereas the adsorption in the sediment in the recirculation region is largely fluctuated.

  12. 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.

  13. 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.

  14. Plane-wave pseudopotential implementation and performance of SCAN meta-GGA exchange-correlation functional for extended systems

    Science.gov (United States)

    Yao, Yi; Kanai, Yosuke

    2017-06-01

    We present the implementation and performance of the strongly constrained and appropriately normed, SCAN, meta-GGA exchange-correlation (XC) approximation in the planewave-pseudopotential (PW-PP) formalism using the Troullier-Martins pseudopotential scheme. We studied its performance by applying the PW-PP implementation to several practical applications of interest in condensed matter sciences: (a) crystalline silicon and germanium, (b) martensitic phase transition energetics of phosphorene, and (c) a single water molecule physisorption on a graphene sheet. Given the much-improved accuracy over the GGA functionals and its relatively low computational cost compared to hybrid XC functionals, the SCAN functional is highly promising for various practical applications of density functional theory calculations for condensed matter systems. At same time, the SCAN meta-GGA functional appears to require more careful attention to numerical details. The meta-GGA functional shows more significant dependence on the fast Fourier transform grid, which is used for evaluating the XC potential in real space in the PW-PP formalism, than other more conventional GGA functionals do. Additionally, using pseudopotentials that are generated at a different/lower level of XC approximation could introduce noticeable errors in calculating some properties such as phase transition energetics.

  15. 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

  16. 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.

  17. Curvature-dependent adsorption of water inside and outside armchair carbon nanotubes

    CERN Document Server

    Lei, Shulai; Schmidt, Burkhard; Paulus, Beate

    2016-01-01

    The curvature dependence of the physisorption properties of a water molecule inside and outside an armchair carbon nanotube (CNTs) is investigated by an incremental density-fitting local coupled cluster treatment with single and double excitations and perturbative triples (DF-LCCSD(T)) study. Our results show that a water molecule outside and inside (n, n) CNTs (n=4, 5, 6, 7, 8, 10) is stabilized by electron correlation. The adsorption energy of water inside CNTs decreases quickly with the decrease of curvature (increase of radius) and the configuration with the oxygen pointing towards the CNT wall is the most stable one. However, when the water molecule is adsorbed outside the CNT, the adsorption energy varies only slightly with the curvature and the configuration with hydrogens pointing towards the CNT wall is the most stable one. We also use the DF-LCCSD(T) results to parametrize Lennard-Jones (LJ) force fields for the interaction of water both with the inner and outer sides of CNTs and with graphene repre...

  18. Synthesis of Ethanol from Syngas over Rh/MCM-41 Catalyst: Effect of Water on Product Selectivity

    Directory of Open Access Journals (Sweden)

    Luis Lopez

    2015-10-01

    Full Text Available The thermochemical processing of biomass is an alternative route for the manufacture of fuel-grade ethanol, in which the catalytic conversion of syngas to ethanol is a key step. The search for novel catalyst formulations, active sites and types of support is of current interest. In this work, the catalytic performance of an Rh/MCM-41 catalyst has been evaluated and compared with a typical Rh/SiO2 catalyst. They have been compared at identical reaction conditions (280 °C and 20 bar, at low syngas conversion (2.8% and at same metal dispersion (H/Rh = 22%. Under these conditions, the catalysts showed different product selectivities. The differences have been attributed to the concentration of water vapor in the pores of Rh/MCM-41. The concentration of water vapor could promote the water-gas-shift-reaction generating some extra carbon dioxide and hydrogen, which in turn can induce side reactions and change the product selectivity. The extra hydrogen generated could facilitate the hydrogenation of a C2-oxygenated intermediate to ethanol, thus resulting in a higher ethanol selectivity over the Rh/MCM-41 catalyst as compared to the typical Rh/SiO2 catalyst; 24% and 8%, respectively. The catalysts have been characterized, before and after reaction, by N2-physisorption, X-ray photoelectron spectroscopy, X-ray diffraction, H2-chemisorption, transmission electron microscopy and temperature programmed reduction.

  19. 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.

  20. Simple benzene derivatives adsorption on defective single-walled carbon nanotubes: a first-principles van der Waals density functional study.

    Science.gov (United States)

    Ganji, Masoud Darvish; Mohseni, Maryam; Bakhshandeh, Anahita

    2013-03-01

    We have investigated the interaction between open-ended zig-zag single-walled carbon nanotube (SWCNT) and a few benzene derivatives using the first-principles van der Waals density functional (vdW-DF) method, involving full geometry optimization. Such sp (2)-like materials are typically investigated using conventional DFT methods, which significantly underestimate non-local dispersion forces (vdW interactions), therefore affecting interactions between respected molecules. Here, we considered the vdW forces for the interacting molecules that originate from the interacting π electrons of the two systems. The -0.54 eV adsorption energy reveals that the interaction of benzene with the side wall of the SWCNT is typical of the strong physisorption and comparable with the experimental value for benzene adsorption onto the graphene sheet. It was found that aromatics are physisorbed on the sidewall of perfect SWCNTs, as well as at the edge site of the defective nanotube. Analysis of the electronic structures shows that no orbital hybridization between aromatics and nanotubes occurs in the adsorption process. The results are relevant in order to identify the potential applications of noncovalent functionalized systems.

  1. Interaction between alkyl radicals and single wall carbon nanotubes.

    Science.gov (United States)

    Denis, Pablo A

    2012-06-30

    The addition of primary, secondary, and tertiary alkyl radicals to single wall carbon nanotubes (SWCNTs) was studied by means of dispersion corrected density functional theory. The PBE, B97-D, M06-L, and M06-2X functionals were used. Consideration of Van der Waals interactions is essential to obtain accurate addition energies. In effect, the enthalpy changes at 298 K, for the addition of methyl, ethyl, isopropyl, and tert-butyl radicals onto a (5,5) SWCNT are: -25.7, -25.1, -22.4, and -16.6 kcal/mol, at the M06-2X level, respectively, whereas at PBE/6-31G* level they are significantly lower: -25.0, -19.0, -16.7, and -5.0 kcal/mol respectively. Although the binding energies are small, the attached alkyl radicals are expected to be stable because of the large desorption barriers. The importance of nonbonded interactions was more noticeable as we moved from primary to tertiary alkyl radicals. Indeed, for the tert-butyl radical, physisorption onto the (11,0) SWCNT is preferred rather than chemisorption. The bond dissociation energies determined for alkyl radicals and SWCNT follow the trend suggested by the consideration of radical stabilization energies. However, they are in disagreement with some degrees of functionalization observed in recent experiments. This discrepancy would stem from the fact that for some HiPco nanotubes, nonbonded interactions with alkyl radicals are stronger than covalent bonds.

  2. Adsorption of TCDD molecule onto CNTs and BNNTs: Ab initio van der Waals density-functional study

    Science.gov (United States)

    Darvish Ganji, M.; Alinezhad, H.; Soleymani, E.; Tajbakhsh, M.

    2015-03-01

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCCD) is one of the most dangerous compounds that infect the environment and hence its removal is crucial for safety in human life. In this work, we have investigated the interaction of TCDD with boron nitride nanotubes (BNNTs) and carbon nanotubes (CNTs) by using the density functional theory (DFT) calculations. Our first-principles results have been validated by experiment and also other theoretical values for the similar system. The adsorption energies for TCDD molecule on the BNNTs and CNT are calculated. It was found that TCDD adsorption ability of BNNT is slightly stronger than that of CNT and TCDD molecule prefers to be adsorbed on BNNTs with molecular axis parallel to the tube axis. The results obtained indicate that TCDD is weakly bound to the outer surface of all the considered nanotubes and the obtained adsorption energy values and binding distance are typical for the physisorption. We also evaluated the influence of curvature and introduced defects on the TCDD adsorption ability of BNNTs. Furthermore, we have analyzed the electronic structure and charge population for the energetically most favorable complexes and the results indicate that no significant hybridization between the respective orbitals of the two entities was accomplished.

  3. Corrosion inhibition efficiency and surface activity of benzothiazol-3-ium cationic Schiff base derivatives in hydrochloric acid

    Energy Technology Data Exchange (ETDEWEB)

    Negm, N.A., E-mail: nabelnegm@hotmail.co [Petrochemicals Department, Egyptian Petroleum Research Institute, Nasr City, Cairo (Egypt); Elkholy, Y.M.; Zahran, M.K. [Chemistry Department, Faculty of Science, Helwan University, Helwan (Egypt); Tawfik, S.M. [Petrochemicals Department, Egyptian Petroleum Research Institute, Nasr City, Cairo (Egypt)

    2010-10-15

    Research highlights: {yields} Benzothiazolium inhibitors show high corrosion inhibition for carbon steel. {yields} Weight loss and corrosion rates decrease by increasing inhibitor dose. {yields} Inhibition mechanism suggested as physisorption mechanism supported by adsorption free energy values. {yields} The adsorption of the inhibitors obeys Langmuir isotherm. {yields} Side chains have ascending order on the corrosion inhibition of the different inhibitors. - Abstract: Two series of cationic Schiff base surfactants namely: 2-(benzylideneamino)-3-(2-oxo-2-alkoxyethyl)-1,3-benzothiazol-3-ium bromide and 2-[(4-methoxybenzylidene)amino]-3-(2-oxo-2-alkoxyethyl)-1, 3-benzothiazol-3-ium bromide were prepared and confirmed using elemental analysis, FTIR, and {sup 1}H NMR spectra. The surface activity of the synthesized Schiff bases showed their tendency towards adsorption at the interfaces. The prepared compounds were evaluated as corrosion inhibitors for carbon steel in 0.5 M HCl solution using gravimetric and polarization measurements. By fitting the gravimetric data, some thermodynamic and kinetic parameters were estimated. The adsorption of the inhibitors on the carbon steel surface obeyed Langmuir adsorption isotherm and had a physical mechanism. Polarization measurements showed that the synthesized inhibitors act as mixed inhibitors for carbon steel in the acidic media. The results of the corrosion inhibition using two different methods showed narrow differences in the obtained values between the two methods within 5%.

  4. Pyrolysis of Phenethyl Phenyl Ether Tethered in Mesoporous Silica. Effects of Confinement and Surface Spacer Molecules on Product Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Kidder, Michelle [ORNL; Chaffe, Alan [Monash University, Australia; Nguyen, M [Monash University, Australia; Buchanan III, A C [ORNL

    2011-01-01

    There has been expanding interest in exploring porous metal oxides as a confining environment for organic molecules resulting in altered chemical and physical properties including chemical transformations. In this paper, we examine the pyrolysis behavior of phenethyl phenyl ether (PPE) confined in mesoporous silica by covalent tethers to the pore walls as a function of tether density and the presence of co-tethered surface spacer molecules of varying structure (biphenyl, naphthyl, octyl, and hexadecyl). The PPE pyrolysis product selectivity, which is determined by two competitive free-radical pathways cycling through the two aliphatic radical intermediates (PhCH CH2OPh and PhCH2CH OPh), is shown to be dramatically different from that measured in the liquid phase as well as for PPE tethered to the exterior surface of nonporous silica nanoparticles. Tailoring the pore surface with spacer molecules further alters the selectivity such that the PPE reaction channel involving a molecular rearrangement (O-C phenyl shift in PhCH2CH OPh), which accounts for 25 % of the products in the liquid phase, can be virtually eliminated under pore confinement conditions. The origin of this change in selectivity is discussed in the context of steric constraints on the rearrangement path, confinement effects, pore surface curvature, and hydrogen bonding of PPE with residual surface silanols supplemented by nitrogen physisorption data and molecular dynamics simulations.

  5. Gold-TiO2-Nickel catalysts for low temperature-driven CO oxidation reaction

    Science.gov (United States)

    Hinojosa-Reyes, Mariana; Zanella, Rodolfo; Maturano-Rojas, Viridiana; Rodríguez-González, Vicente

    2016-04-01

    Nickel-doped-TiO2 catalysts were prepared by the sol-gel method and surface modified with gold nanoparticles (AuNPs) by the urea-deposition-precipitation technique. The as-synthesized catalysts were characterized by X-ray diffraction, Raman and XPS spectroscopies, N2 physisorption, STEM-HAADF microscopy and TPR hydrogen consumption. The Au/TiO2-Ni catalysts were evaluated catalytically performing CO oxidation reactions. The catalyst with nickel content of 1 wt. % (Au/TiO2-Ni 1) showed the highest CO conversion with respect to the high-nickel-content or bare/commercial TiO2 at 0 °C. In situ DRIFTS showed a strong participation of both nickel due to the presence of surface-nickel-metallic nanoparticles formed during the CO adsorption process at reaction temperatures above 200 °C, and surface-bridged-nickel-CO species. A minor deactivation rate was observed for the Au/TiO2-Ni 1 catalyst in comparison with the Au/TiO2 one. The oxygen vacancies that were created on the sol-gel-doped TiO2 improved the catalytic behavior during the performance of CO oxidation reactions, and inhibited the AuNP sintering.

  6. Effect of Metal-Support Interactions in Ni/Al2O3 Catalysts with Low Metal Loading for Methane Dry Reforming

    Energy Technology Data Exchange (ETDEWEB)

    Ewbank, Jessica L.; Kovarik, Libor; Diallo, Fatoumata Z.; Sievers, Carsten

    2015-03-01

    Types of nickel sites as a function of preparation method have received much attention in the literature. In this work, two preparation methods, controlled adsorption and dry impregnation, are implemented to explore the effect of preparation method on catalytic nickel centers. For controlled adsorption, optimal synthesis conditions are identified using point of zero charge measurements, pH-precipitation experiments, and adsorption isotherms to prepare a catalyst with a high dispersion and strong metal support interactions. Metal support interactions influence the types of nickel sites formed. Thus, comparison of catalysts that differ primarily in metal support interactions, strong metal support interaction (controlled adsorption) and weak metal support interactions (dry impregnation), is of great interest. It is confirmed through characterization techniques; N2 physisorption, H2 chemisorption, temperature programmed reduction (TPR), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS) that the types of nickel sites formed are indeed strongly dependent on preparation method. Methane dry reforming reactivity studies are used to demonstrate the successful application of these catalysts and further probe the types of active centers present. Combustion analysis and XPS of spent catalysts reveal different amounts and nature of carbonaceous deposits as a function of the synthesis method.

  7. n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts

    Science.gov (United States)

    Thoa Dao, Thi Kim; Loc Luu, Cam

    2015-09-01

    A series of Pd/HZSM-5 catalysts modified by various metallic species, including Co, Ni, Fe, Re, and Cu, was prepared by sequential impregnation. Contents of Pd and second metals in modified catalysts were 0.8 and 1.0 wt%, respectively. Physico-chemical characteristics of catalysts were investigated by nitrogen physi-sorption (BET), x-ray diffraction (XRD), transmission electron microscopy (TEM), ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR) and hydrogen pulse chemisorption (HPC). Coke formation was studied by the method of thermogravimetric analysis (TGA). The activities of catalysts in n-hexane isomerization were studied in a micro-flow reactor under atmospheric pressure at 250 °C, and molar ratio of H2: n-hexane of 5.92. It was found that Co, Ni, Fe, and Re additives exhibited geometric and electronic effects toward Pd/HZSM-5 catalyst, leading to an enhancement of its activity and stability. On the contrary, Cu additive caused Pd/HZSM-5 to become poorer in activity and stability.

  8. Effects of preparation method on the performance of Ni/Al(2)O(3) catalysts for hydrogen production by bio-oil steam reforming.

    Science.gov (United States)

    Li, Xinbao; Wang, Shurong; Cai, Qinjie; Zhu, Lingjun; Yin, Qianqian; Luo, Zhongyang

    2012-09-01

    Steam reforming of bio-oil derived from the fast pyrolysis of biomass is an economic and renewable process for hydrogen production. The main objective of the present work has been to investigate the effects of the preparation method of Ni/Al(2)O(3) catalysts on their performance in hydrogen production by bio-oil steam reforming. The Ni/Al(2)O(3) catalysts were prepared by impregnation, co-precipitation, and sol-gel methods. XRD, XPS, H(2)-TPR, SEM, TEM, TG, and N(2) physisorption measurements were performed to characterize the texture and structure of the catalysts obtained after calcination and after their subsequent use. Ethanol and bio-oil model compound were selected for steam reforming to evaluate the catalyst performance. The catalyst prepared by the co-precipitation method was found to display better performance than the other two. Under the optimized reaction conditions, an ethanol conversion of 99% and a H(2) yield of 88% were obtained.

  9. Preparation of platinum-iridium nanoparticles on titania nanotubes by MOCVD and their catalytic evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Colindres, S. Capula [National Polytechnic Institute, Department of Metallurgical Eng., Mexico 07300 D.F., AP 75-874 (Mexico); Garcia, J.R. Vargas, E-mail: rvargasga@ipn.m [National Polytechnic Institute, Department of Metallurgical Eng., Mexico 07300 D.F., AP 75-874 (Mexico); Antonio, J.A. Toledo; Chavez, C. Angeles [Petroleum Mexican Institute, Eje Central Lazaro Cardenas No.152, Mexico 07730 D.F. (Mexico)

    2009-08-26

    Pt based catalysts are commonly used in several industrial processes involving hydrogenation and dehydrogenation reactions. New deposition methods as well as support materials are being investigated to generate new catalysts with superior catalytic activity. In this work, platinum-iridium (Pt-Ir) nanoparticles of about 5 nm in size were supported on titania (TiO{sub 2}) nanotubes by metal organic chemical vapor deposition (MOCVD). The TiO{sub 2} nanotubes were prepared by an alkali hydrothermal method using sodium hydroxide solution at 100 deg. C, during 64.8 ks. Pt-Ir nanoparticles were obtained by controlling the MOCVD conditions at 400 deg. C and 66.6 kPa. Textural properties and particle size were investigated by nitrogen physisorption (BET method), X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. Catalytic activity was measured in cyclohexene disproportion as the test molecule for hydrogenation/dehydrogenation reactions. The TiO{sub 2} nanotubes exhibit a considerable high surface area of about 425,000 m{sup 2}/kg, however, after calcination at 400 deg. C their nanotubular morphology was partially transformed. In spite of this change, the 5 nm Pt-Ir nanoparticles supported on TiO{sub 2} nanotubes were more active in the cyclohexene disproportion reaction than conventional Pt-Ir/alumina catalysts in the whole range of temperatures investigated (50-250 deg. C). Hydrogenation reactions (high selectivity to cyclohexane) predominate at temperatures below 150 deg. C.

  10. Surface area and volume measurements of volcanic ash particles using micro-computed tomography (micro-CT): A comparison with scanning electron microscope (SEM) stereoscopic imaging and geometric considerations

    Science.gov (United States)

    Ersoy, Orkun; Şen, Erdal; Aydar, Erkan; Tatar, İlkan; Çelik, H. Hamdi

    2010-10-01

    Volcanic ash particles are important components of explosive eruptions, and their surface textures are the subject of intense research. Characterization of ash surfaces is crucial for understanding the physics of volcanic plumes, remote sensing measurements of ash and aerosols, interfacial processes, modelling transportation and deposition of tephra and characterizing eruptive styles. A number of different methods have been used over the years to arrive at surface area estimates. The more common methods include estimates based on geometric considerations (geometric surface area) and physisorption of gas molecules on the surface of interest (physical surface area). In this study, micro computed tomography (micro-CT), which is a non-destructive method providing three-dimensional data, enabled the measurement of surface area and volume of individual ash particles. Results were compared with the values obtained from SEM stereoscopic imaging and geometric considerations. Surface area estimates of micro-CT and SEM stereoscopic imaging are similar, with surface area/volume ratios (SA/V) of 0.0368 and 0.0467, respectively. Ash particle surface textures show a large deviation from that of simple geometric forms, and an approximation both to spheres and ellipsoids do not seem adequate for the representation of ash surface. SEM stereoscopic and/or micro-CT imaging are here suggested as good candidate techniques for the characterization of textures on macro-pore regions of ash particles.

  11. 氨改性的介孔二氧化硅的直接合成和CO2吸附%Direct Synthesis of Amine-functionalized Mesoporous Silica for CO2 Adsorption

    Institute of Scientific and Technical Information of China (English)

    胡智辉; 张东辉; 王纪孝

    2011-01-01

    Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the S-N+-I- mechanism and applied to CO2 adsorption at room temperature.With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the performance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pressure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol·g-1 and 0.03 mmol·g-1, respectively, indicating high separation coefficient of CO2/N2.

  12. 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.

  13. 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.

  14. Hydrogenolysis of Glycerol to 1,2-Propanediol Over Clay Based Catalysts.

    Science.gov (United States)

    Lee, Sang-Yong; Jung, Jae-Sun; Yang, Eun-Hyeok; Lee, Kwan-Young; Moon, Dong Ju

    2015-11-01

    1,2-propanediol (1,2-PDO) is one of the promising product among the valuable products derived from glycerol and it can be obtained by the catalytic hydrogenolysis of glycerol. Copper-supported clay-based catalysts were prepared with different pore sizes using various ratios of kaolin, Mg, and Al by coprecipitation and applied in the selective hydrogenolysis of glycerol to 1,2-PDO. In recent research, variations of pore volume and pore size could affect the diffusion of reagents within the catalyst due to the collision between reagents or pore wall and reagents. It changes selectivities of each product in hydrogenolysis of glycerol reaction. The physico-chemical properties of the catalysts were analyzed by XRD, N2 physisorption, TPR, CO2-TPD, SEM, and a mercury porosimeter. The Cu/TALCITE 4 catalyst showed 98% 1,2-PDO selectivity with 65% glycerol conversion under the optimized condition of 190 degrees C, 25 bar, and 20 wt% glycerol aqueous solution. It was found that the basic strength and meso-macro pore structure of the catalysts play an important role in glycerol conversion and 1,2-PDO selectivity.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Effect of vacuum impregnation on the performance of Co/SiO2 Fischer-Tropsch catalyst

    Institute of Scientific and Technical Information of China (English)

    Xiaofeng Zhou; Qingling Chen; Yuewu Tao; Huixin Weng

    2011-01-01

    Two silica-supported cobalt catalysts were prepared by incipient wetness impregnation under atmospheric and vacuum conditions.N2 physisorption,H2 chemisorption,XRD,SEM,TEM,XPS and H2-TPR were used to characterize the catalysts.The results showed that the impregnation methods had an effect on the size,dispersion and reducibility of cobalt particles.Under vacuum conditions,cobalt-containing steeping liquor could penetrate into the inner pores of silica support and more bivalent cobalt oxides were formed in the Co3O4 crystallites.Furthermore,cobalt precursors were rarely inclined to agglomerate and the smaller cobalt particles were uniform on the support,which led to the higher activity of the Co/SiO2 (B) catalyst than the normal one under the reaction conditions of 483-523 K,1-2 MPa,gas hourly space velocity of 500-1000 h-1 and molar ratio of H2/CO =0.5-2.0.

  20. Hydrogen storage on nitrogen induced defects in palladium-decorated graphene: A first-principles study

    Science.gov (United States)

    Ma, Ling; Zhang, Jian-Min; Xu, Ke-Wei

    2014-02-01

    The structure and hydrogen storage behavior of Pd-decorated nitrogen-doped graphene are investigated using the first principals based on density functional theory (DFT) calculations. Among the three types of defective structures, it is found that Pd-decorated graphene with pyridinic and pyrrolic N-doped defects are more stable and exhibit hydrogen uptake ability up to three H2 per Pd atom. A single H2 or two H2 are molecularly chemisorbed on the Pd atom, where the stretched Hsbnd H bond is relaxed but not dissociated. The binding mechanism of H2 molecule is attributed to hybridization of the 4d orbitals of Pd with the σ orbitals of H2 (so-called Kubas interaction). Out of two adsorbed H2, the first and second H2 are still chemisorbed molecularly, the nature of bonding is very weak physisorption for the third adsorbed H2. Double-side Pd-decorated graphene with pyridinic and pyrrolic N defects can theoretically reach a gravimetric capacity of 1.99 wt.% hydrogen, which is very close to the recent experimental finding.

  1. Kinetics of alkali-based photocathode degradation

    Science.gov (United States)

    Pavlenko, Vitaly; Liu, Fangze; Hoffbauer, Mark A.; Moody, Nathan A.; Batista, Enrique R.

    2016-11-01

    We report on a kinetic model that describes the degradation of the quantum efficiency (QE) of Cs3Sb and negative electron affinity (NEA) GaAs photocathodes under UHV conditions. In addition to the generally accepted irreversible chemical change of a photocathode's surface due to reactions with residual gases, such as O2, CO2, and H2O, the model incorporates an intermediate reversible physisorption step, similar to Langmuir adsorption. This intermediate step is needed to satisfactorily describe the strongly non-exponential QE degradation curves for two distinctly different classes of photocathodes -surface-activated and "bulk," indicating that in both systems the QE degradation results from surface damage. The recovery of the QE upon improvement of vacuum conditions is also accurately predicted by this model with three parameters (rates of gas adsorption, desorption, and irreversible chemical reaction with the surface) comprising metrics to better characterize the lifetime of the cathodes, instead of time-pressure exposure expressed in Langmuir units.

  2. Kinetics of alkali-based photocathode degradation

    Directory of Open Access Journals (Sweden)

    Vitaly Pavlenko

    2016-11-01

    Full Text Available We report on a kinetic model that describes the degradation of the quantum efficiency (QE of Cs3Sb and negative electron affinity (NEA GaAs photocathodes under UHV conditions. In addition to the generally accepted irreversible chemical change of a photocathode’s surface due to reactions with residual gases, such as O2, CO2, and H2O, the model incorporates an intermediate reversible physisorption step, similar to Langmuir adsorption. This intermediate step is needed to satisfactorily describe the strongly non-exponential QE degradation curves for two distinctly different classes of photocathodes –surface-activated and “bulk,” indicating that in both systems the QE degradation results from surface damage. The recovery of the QE upon improvement of vacuum conditions is also accurately predicted by this model with three parameters (rates of gas adsorption, desorption, and irreversible chemical reaction with the surface comprising metrics to better characterize the lifetime of the cathodes, instead of time-pressure exposure expressed in Langmuir units.

  3. 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.)

  4. 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.

  5. Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity

    Indian Academy of Sciences (India)

    Manoj Kumar Singh; Debkumar Bandyopadhyay

    2016-01-01

    Two nanoporous perylene bis-imide linked metalloporphyrin framework catalysts have been synthesized via condensation of 5,10,15,20-tetrakis-(4′-aminophenyl) iron(III) porphyrin chloride or 5,10, 15,20-tetrakis-(4′-aminophenyl) manganese(III) porphyrin chloride with perylene-3,4,9,10-tetracarboxylic dianhydride. Both the materials were crystalline in nature and were characterized by electron microscopy techniques, solid-state 1H-13C CP/MS NMR, powder X-ray diffraction (PXRD), and magnetic susceptibility measurements. The nitrogen gas physisorption study has indicated that both materials are porous in nature and have BET surface area with 653 m2/g and 974 m2/g with uniform pore size of 2.8 nm. These materials were found to act as very good heterogeneous catalysts for selective oxidation of alkanes and alkenes with tert-butyl hydroperoxide and were not degraded even after multiple uses up to 10 cycles.

  6. 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.

  7. Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

    Institute of Scientific and Technical Information of China (English)

    Tingzhen Li; Yong Yang; Chenghua Zhang; Zhichao Tao; Haijun Wan; Xia An; Hongwei Xiang; Yongwang Li

    2007-01-01

    A systematic study was undertaken to investigate the effects of the manganese incorporation manner on the textural properties,bulk and surface phase compositions,reduction/carburization behaviors,and surface basicity of an iron-based Fischer-Tropsch synthesis (FTS) catalyst.The catalyst samples were characterized by N2 Physisorption,X-ray photoelectron spectroscopy(XPS),H2(or CO) temperature-programmed reduction(TPR),CO2 temperature-programmed desorption(TPD),and Mossbauer spectroscopy.The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor(CSTR).The characterization results indicated that the manganese promoter incor-porated by using the coprecipitation method could improve the dispersion of iron oxide,and decrease the size of the iron oxide crystallite.The manganese incorporated with the impregnation method is enriched on the catalyst's surface.The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H2,CO,and syngas because of the excessive enrichment of manganese on the catalyst surface.The catalyst added manganese using the coprecipitation method has the highest CO conversion (51.9%) and the lowest selectivity for heavy hydrocarbons(C12+).

  8. 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.

  9. 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.

  10. Adsorbate Electric Fields on a Cryogenic Atom Chip

    CERN Document Server

    Chan, K S; Hufnagel, C; Dumke, R

    2013-01-01

    We investigate the behaviour of electric fields originating from adsorbates deposited on a cryogenic atom chip as it is cooled from room temperature to cryogenic temperature. Using Rydberg electromagnetically induced transparency we measure the field strength versus distance from a 1 mm square of YBCO patterned onto a YSZ chip substrate. We find a localized and stable dipole field at room temperature and attribute it to a saturated layer of chemically adsorbed rubidium atoms on the YBCO. As the chip is cooled towards 83 K we observe a change in sign of the electric field as well as a transition from a localized to a delocalized dipole density. We relate these changes to the onset of physisorption on the chip surface when the van der Waals attraction overcomes the thermal desorption mechanisms. Our findings suggest that, through careful selection of substrate materials, it may be possible to reduce the electric fields caused by atomic adsorption on chips, opening up experiments to controlled Rydberg-surface co...

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

    Directory of Open Access Journals (Sweden)

    Y. Gucbilmez

    2012-01-01

    Full Text Available 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 heteropoly acid incorporation into MCM-48 type materials.

  12. Synthesis and physicochemical characterization of titanium oxide and sulfated titanium oxide obtained by thermal hydrolysis of titanium tetrachloride

    Directory of Open Access Journals (Sweden)

    H. Esteban Benito

    2014-09-01

    Full Text Available This work reports the synthesis of titanium oxide (TiO2 and sulfated titanium oxide (TiO2-SO4(2- obtained by thermal hydrolysis of titanium tetrachloride. Titanium hydroxide synthesized by this method was impregnated with a 1 N H2SO4 solution, to give amounts of sulfate ions (SO4(2- of 3 and 7 wt%. The synthesized samples were dried at 120 °C during 24 h and then calcined for 3 h at 400 °C. Thermal analyses, X-ray diffraction, nitrogen physisorption, infrared spectroscopy, potentiometric titration with n-butylamine, U.V.-visible diffuse reflectance spectroscopy and scanning electron microscopy were used to characterize the materials. The results of physicochemical characterization revealed that a mixture of crystalline structures, anatase, brookite and rutile developed in the titanium oxide, stabilizing the anatase structure in the sulfated titanium oxides, and coexisting with a small amount of brookite structure. The synthesized mesoporous materials developed specific surface areas between 62 and 70 m² g-1, without detecting an important influence of sulfation on this parameter. The presence of sulfate ions improved the acidity of titanium oxide and modified the characteristics of light absorption in the 425-600 nm region, which suggests the possibility of using these materials in reactions assisted by visible light.

  13. Charge inversion, water splitting, and vortex suppression due to DNA sorption on ion-selective membranes and their ion-current signatures.

    Science.gov (United States)

    Slouka, Zdenek; Senapati, Satyajyoti; Yan, Yu; Chang, Hsueh-Chia

    2013-07-02

    The physisorption of negatively charged single-stranded DNA (ssDNA) of different lengths onto the surface of anion-exchange membranes is sensitively shown to alter the anion flux through the membrane. At low surface concentrations, the physisorbed DNAs act to suppress an electroconvection vortex instability that drives the anion flux into the membrane and hence reduce the overlimiting current through the membrane. Beyond a critical surface concentration, determined by the total number of phosphate charges on the DNA, the DNA layer becomes a cation-selective membrane, and the combined bipolar membrane has a lower net ion flux, at low voltages, than the original membrane as a result of ion depletion at the junction between the cation- (DNA) and anion-selective membranes. However, beyond a critical voltage that is dependent on the ssDNA coverage, water splitting occurs at the junction to produce a larger overlimiting current than that of the original membrane. These two large opposite effects of polyelectrolyte counterion sorption onto membrane surfaces may be used to eliminate limiting current constraints of ion-selective membranes for liquid fuel cells, dialysis, and desalination as well as to suggest a new low-cost membrane surface assay that can detect and quantify the number of large biomolecules captured by probes functionalized on the membrane surface.

  14. Activation of the metal-organic framework MIL-47 for selective adsorption of xylenes and other difunctionalized aromatics.

    Science.gov (United States)

    Alaerts, Luc; Maes, Michael; Jacobs, Pierre A; Denayer, Joeri F M; De Vos, Dirk E

    2008-05-28

    The capacity and selectivity of the metal-organic framework MIL-47 for liquid phase adsorption are shown to heavily depend on the pretreatment of the material, as illustrated in detail by the particular case of selective xylene adsorption. By totally removing the uncoordinated terephthalic acid from the pores and simultaneously avoiding oxidation to nonporous V(2)O(5), pore volume and uptake of xylenes can be maximized. The presence of uncoordinated terephthalic acid in the pores improves the selectivity between p- and m-xylene. Calcination bed thickness and oven geometry influence the optimal calcination procedure. The physicochemical modifications of MIL-47 during its activation are investigated in detail with XRD, SEM, nitrogen physisorption, TGA and diffuse reflectance UV-Vis spectroscopy. Using optimally pretreated MIL-47 as adsorbent for xylene, ethyltoluene, dichlorobenzene, toluidine or cresol isomers, the para-isomer is in each case preferred over the meta-isomer in pulse chromatographic and batch experiments. The role of stacking in the selective adsorption of these isomers is discussed. In the case of the dichlorobenzenes, the meta- and para-isomers can be separated in a breakthrough experiment with a selectivity of 5.0.

  15. Incorporation of Vanadium Oxide in Silica Nanofiber Mats via Electrospinning and Sol-Gel Synthesis

    Directory of Open Access Journals (Sweden)

    Jeanne E. Panels

    2006-01-01

    Full Text Available Submicron scale vanadia/silica hybrid nanofiber mats have been produced by electrospinning silica sol-gel precursor containing vanadium oxytriisopropoxide (VOTIP, followed by calcinations at high temperature. The properties of the resulting inorganic hybrid nanofiber mats are compared to those of electrospun pure silica nanofibers. SEM images show fibers are submicron in diameter and their morphology is maintained after calcination. Physisorption experiments reveal that silica nanofiber mats have a high specific surface area of 63 m2/g. FT-IR spectra exhibit Si—O vibrations and indicate the presence of V2O5 in the fibers. XPS studies reveal that the ratio of Si to O is close to 0.5 on the surface of fibers and the amount of vanadium on the surface of fibers increases with calcination. XRD diffraction patterns show that silica nanofibers are amorphous and orthorhombic V2O5 crystals have formed after calcination. EFTEM images demonstrate the growth of crystals on the surface of fibers containing vanadium after calcination. SEM images of fibers with high-vanadium content (50 mol% V: Si show that vanadia crystals are mostly aligned along the fiber axis. XPS shows an increase in vanadium contents at the surface, and XRD patterns exhibit an increase in the degree of crystallinity. A coaxial electrospinning scheme has successfully been employed to selectively place V2O5 in the skin layer.

  16. 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.

  17. Selective recognition and discrimination of water-soluble azo dyes by a seven-channel molecularly imprinted polymer sensor array.

    Science.gov (United States)

    Long, Zerong; Lu, Yi; Zhang, Mingliang; Qiu, Hongdeng

    2014-10-01

    A seven-channel molecularly imprinted polymer sensor array was prepared and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, UV-Vis spectroscopy, and nitrogen physisorption studies. The results revealed that the imprinted polymers have distinct-binding affinities from those of structurally similar azo dyes. Analysis of the UV-Vis spectral response patterns of the seven dye analytes against the imprinted polymer array suggested that the different selectivity patterns of the array were closely connected to the imprinting process. To evaluate the effectiveness of the array format, the binding of a series of analytes was individually measured for each of the seven polymers, made with different templates (including one control polymer synthesized without the use of a template). The response patterns of the array to the selected azo dyes were processed by canonical discriminant analysis. The results showed that the molecularly imprinted array was able to discriminate each analyte with 100% accuracy. Moreover, the azo dyes in two real samples, spiked chrysoidin in smoked bean curd extract and Fanta lime soda (containing tartrazine), were successfully classified by the array.

  18. Enhanced adsorptive removal of Safranine T from aqueous solutions by waste sea buckthorn branch powder modified with dopamine: Kinetics, equilibrium, and thermodynamics

    Science.gov (United States)

    Xu, Xiaohui; Bai, Bo; Wang, Honglun; Suo, Yourui

    2015-12-01

    Polydopamine coated sea buckthorn branch powder (PDA@SBP) was facilely synthesized via a one-pot bio-inspired dip-coating approach. The as-synthesized PDA@SBP was characterized using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The adsorption progresses of Safranine T on the surface of PDA@SBP adsorbent were systematically investigated. More specifically, the effects of solution pH, contact time, initial concentration and temperature were evaluated, respectively. The experimental results showed the adsorption capacity of PDA@SBP at 293.15 K could reach up to 54.0 mg/g; the adsorption increased by 201.7% compared to that of native SBP (17.9 mg/g). Besides, kinetics studies showed that pseudo-second-order kinetic model adequately described the adsorption behavior. The adsorption experimental data could be fitted well a Freundlich isotherm model. Thermodynamic analyses showed that the ST adsorption was a physisorption endothermic process. Regeneration of the spent PDA@SBP adsorbent was conducted with 0.1 M HCl without significant reduction in adsorption capacity. On the basis of these investigations, it is believed that the PDA@SBP adsorbent could have potential applications in sewage disposal areas because of their considerable adsorption capacities, brilliant regeneration capability, and cost-effective and eco-friendly preparation and use.

  19. 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.

  20. Assessment of Sericin Biosorbent for Selective Dye Removal

    Institute of Scientific and Technical Information of China (English)

    CHEN Xinqing; LAM Koon Fung; MAK Shuk Fong; CHING Wai Kwong; NG Tsz Nok; YEUNG King Lun

    2012-01-01

    The silk sericin is the main residue in silk production and it is found to be a low cost and efficient bio-sorbent. In this study, sericin was characterized with various techniques including SEM (scanning electron micro- scope), XRD, N2 physisorption, FTIR (Fourier transformed infrared spectroscopy) and XPS (X-ray photoelectron spectroscopy). The nitrogen content of sericin was ca. 8.5 mmol.g-1 according to elemental analysis. Dye adsorption by sericin biosorbent was investigated with the acid yellow (AY), methylene blue (MB) and copper (II) phthalocyanine-3,4'4"4'"-tetrasulfonic acid (CuPc) dyes from water. Sericin displayed large capacity for AY andCuPc adsorption with adsorption capacities of respectively 3.1 and 0.35 mmol.g-1, but it did not adsorbed methyl- ene blue dye. This selectivity is due to the basicity of amide groups in seriein biosorbents.

  1. 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.

  2. Thermodynamic study of seven micropollutants adsorption onto an activated carbon cloth: Van't Hoff method, calorimetry, and COSMO-RS simulations.

    Science.gov (United States)

    Masson, Sylvain; Vaulot, Cyril; Reinert, Laurence; Guittonneau, Sylvie; Gadiou, Roger; Duclaux, Laurent

    2017-04-01

    The thermodynamic of the adsorption of seven organic pollutants, namely benzotriazol, bisphenol A, caffeine, carbamazepine, diclofenac, ofloxacin, and pentachlorophenol, was studied on a microporous-activated carbon fabric. The isosteric adsorption quantities (Gibbs energy, enthalpy, and entropy variations) at high coverage ratio (around 1 mmol/g) have been determined from the adsorption isotherms at three temperatures (13, 25, and 40 °C). The adsorption heats at very low coverage (about 10(-5) mmol/g) have been measured by flow micro calorimetry. The experimental adsorption energies were correlated to the adsorbate-adsorbent and the adsorbate-solvent interaction energies calculated by simulations using the COSMO-RS model. The main role of the van der Waals forces in the adsorption of the studied molecules was established. The bulkier the adsorbate is, the lower the adsorption Gibbs energy variation at high coverage deduced from the isotherms. The heterogeneity of the adsorption sites was brought out by calorimetric measurements. At high coverage, a physisorption phenomenon was observed. At very low coverage, high values of the adsorption heats were found (ranging from -58 to -110 kJ/mol), except for pentachlorophenol characterized by an athermal adsorption controlled by Pi-anions interactions.

  3. Green corrosion inhibition of mild steel to aqueous sulfuric acid by the extract of Corchorus olitorius stems

    Science.gov (United States)

    Gobara, Mohamed; Zaghloul, Basem; Baraka, Ahmad; Elsayed, Mohamed; Zorainy, Mahmoud; Mokhtar Kotb, Mohamed; Elnabarawy, Hany

    2017-04-01

    Extract of Corchorus olitorius stems (ECS) was used as a green inhibitor for the inhibition of mild steel corrosion in 0.5 M H2SO4 solution. GC/MS was used for both qualitative and quantitative analysis of the extract. The corrosion performance of the extract was evaluated using electrochemical impedance spectroscopy, potentiodynamic polarization and weight loss. The results showed that ECS is a mixed-type inhibitor which reduces both anodic and cathodic reactions and the inhibition efficiency was reached up to 93%. Adsorption isotherm data was recorded at different temperatures and analyzed by selected adsorption isotherm models to reveal characteristics of inhibition. Thermodynamic calculations showed that the inhibition efficiency increases with increasing inhibitor concentration, and decreases with increasing temperature. Adsorption of ECS on the mild steel surface was found to be spontaneous and exothermic. Adsorption is suggested to be physisorption according to El-Awady isotherm model. Also, the scanning electron microscopy (SEM) was used to investigate the surface morphology to confirm the corrosion results.

  4. CO and Soot Oxidation over Ce-Zr-Pr Oxide Catalysts.

    Science.gov (United States)

    Andana, Tahrizi; Piumetti, Marco; Bensaid, Samir; Russo, Nunzio; Fino, Debora; Pirone, Raffaele

    2016-12-01

    A set of ceria, ceria-zirconia (Ce 80 at.%, Zr 20 at.%), ceria-praseodymia (Ce 80 at.%, Pr 20 at.%) and ceria-zirconia-praseodymia (Ce 80 at.%, Zr 10 at.% and Pr 10 at.%) catalysts has been prepared by the solution combustion synthesis (SCS). The effects of Zr and Pr as dopants on ceria have been studied in CO and soot oxidation reactions. All the prepared catalysts have been characterized by complementary techniques, including XRD, FESEM, N2 physisorption at -196 °C, H2-temperature-programmed reduction, and X-ray photoelectron spectroscopy to investigate the relationships between the structure and composition of materials and their catalytic performance. Better results for CO oxidation have been obtained with mixed oxides (performance scale, Ce80Zr10Pr10 > Ce80Zr20 > Ce80Pr20) rather than pure ceria, thus confirming the beneficial role of multicomponent catalysts for this prototypical reaction. Since CO oxidation occurs via a Mars-van Krevelen (MvK)-type mechanism over ceria-based catalysts, it appears that the presence of both Zr and Pr species into the ceria framework improves the oxidation activity, via collective properties, such as electrical conductivity and surface or bulk oxygen anion mobility. On the other hand, this positive effect becomes less prominent in soot oxidation, since the effect of catalyst morphology prevails.

  5. Carbon Dioxide Sorption Isotherm Study on Pristine and Acid-Treated Olivine and Its Application in the Vacuum Swing Adsorption Process

    Directory of Open Access Journals (Sweden)

    Jiajie Li

    2015-05-01

    Full Text Available This paper investigates the potential of pristine and acid-treated olivine as a substrate for CO2 capture using a vacuum swing adsorption (VSA process from the gas-solid phase. The experiments tested the isotherm of pure CO2 adsorption with partial pressure from 10−5 to 1 bar at ambient temperature. The CO2 adsorption capacity and actual expected working capacity (EWC curves of pristine and acid-treated olivine were determined. Isotherm studies predict that physisorption dominates chemisorptions at ambient temperatures. The adsorption capacity enhances with the increase of specific surface area, pore volume, and the appearance of Mg complexed on the mineral’s surface. Actual EWC studies showed that acid-treated olivine is an adsorbent choice for the VSA process, due to enhanced CO2 adsorption capacities compared to olivine and the potential for 100% recovery of CO2 during the regeneration process. Pristine olivine is not suitable for the VSA process because of bad regenerability, but it can be used in capturing and sequestering dilute CO2 in process streams. Our research reveals excellent viability for the application of VSA in the area of CO2 capture using pristine olivine and acid-treated olivine.

  6. Tuning the flexibility in MOFs by SBU functionalization.

    Science.gov (United States)

    Bon, Volodymyr; Kavoosi, Negar; Senkovska, Irena; Müller, Philipp; Schaber, Jana; Wallacher, Dirk; Többens, Daniel M; Mueller, Uwe; Kaskel, Stefan

    2016-03-14

    A new approach for the fine tuning of flexibility in MOFs, involving functionalization of the secondary building unit, is presented. The "gate pressure" MOF [Zn3(bpydc)2(HCOO)2] was used as a model material and SBU functionalization was performed by using monocarboxylic acids such as acetic, benzoic or cinnamic acids instead of formic acid in the synthesis. The resulting materials are isomorphous to [Zn3(bpydc)2(HCOO)2] in the "as made" form, but show different structural dynamics during the guest removal. The activated materials have entirely different properties in the nitrogen physisorption experiments clearly showing the tunability of the gate pressure, at which the structural transformation occurs, by using monocarboxylic acids with varying backbone structure in the synthesis. Thus, increasing the number of carbon atoms in the backbone leads to the decreasing gate pressure required to initiate the structural transition. Moreover, in situ adsorption/PXRD data suggest differences in the mechanism of the structural transformations: from "gate opening" in the case of formic acid to "breathing" if benzoic acid is used.

  7. 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.

  8. 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)

  9. 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)

  10. Nanomaterials driven energy, environmental and biomedical research

    Science.gov (United States)

    Sharma, Prakash C.; Srinivasan, Sesha S.; Wilson, Jeremiah F.

    2014-03-01

    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 RuO2 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 MgH2 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 ZnFe2O4 have been synthesized and optimized for biomedical applications such as targeted drug delivery and tumor diagnostic sensing (MRI).

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

    Energy Technology Data Exchange (ETDEWEB)

    Mohan, N., E-mail: mohan29@yahoo.com [Defence Bio-Engineering and Electro Medical Laboratory (DEBEL), Defence R and D Organisation (DRDO), C.V.Raman Nagar, Bangalore (India); Kannan, G.K.; Upendra, S. [Defence Bio-Engineering and Electro Medical Laboratory (DEBEL), Defence R and D Organisation (DRDO), C.V.Raman Nagar, Bangalore (India); Subha, R. [Siddaganga Institute of Technology (SIT), Dept of Chem. Engg, Tumkur, Karnataka (India); Kumar, N.S. [Defence Bio-Engineering and Electro Medical Laboratory (DEBEL), Defence R and D Organisation (DRDO), C.V.Raman Nagar, Bangalore (India)

    2009-09-15

    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{sup -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{sup -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.

  12. Role of vacancies in tuning the electronic properties of Au-MoS{sub 2} contact

    Energy Technology Data Exchange (ETDEWEB)

    Su, Jie, E-mail: sujie0105@mail.nwpu.edu.cn, E-mail: lpfeng@nwpu.edu.cn; Li, Ning; Zhang, Yingying; Feng, Liping, E-mail: sujie0105@mail.nwpu.edu.cn, E-mail: lpfeng@nwpu.edu.cn; Liu, Zhengtang [State Key Lab of Solidification Processing, College of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an, Shaanxi, 710072 (China)

    2015-07-15

    Understanding the electronic properties between molybdenum disulfide (MoS{sub 2}) and metal electrodes is vital for the designing and realization of nanoelectronic devices. In this work, influence of intrinsic vacancies in monolayer MoS{sub 2} on the electronic structure and electron properties of Au-MoS{sub 2} contacts is investigated using first-principles calculations. Upon formation of vacancies in monolayer MoS{sub 2}, both tunnel barriers and Schottky Barriers between metal Au and monolayer MoS{sub 2} are decreased. Perfect Au-MoS{sub 2} top contact exhibits physisorption interface with rectifying character, whereas Au-MoS{sub 2} contact with Mo-vacancy shows chemisorption interface with Ohmic character. Partial density of states and electron density of defective Au-MoS{sub 2} top contacts are much higher than those of perfect one, indicating the lower contact resistance and higher electron injection efficiency of defective Au-MoS{sub 2} top contacts. Notably, Mo-vacancy in monolayer MoS{sub 2} is beneficial to get high quality p-type Au-MoS{sub 2} top contact, whereas S-vacancy in monolayer MoS{sub 2} is favorable to achieve high quality n-type Au-MoS{sub 2} top contact. Our results provide guidelines for designing and fabrication of novel 2D nanoelectronic devices.

  13. Dynamics of Protonated Peptide Ion Collisions with Organic Surfaces: Consonance of Simulation and Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Pratihar, Subha; Barnes, George L.; Laskin, Julia; Hase, William L.

    2016-08-18

    In this Perspective mass spectrometry experiments and chemical dynamics simulations are described which have explored the atomistic dynamics of protonated peptide ions, peptide-H+, colliding with organic surfaces. These studies have investigated surface-induced dissociation (SID) for which peptide-H+ fragments upon collision with the surface, peptide-H+ physisorption on the surface, soft landing (SL), and peptide-H+ reaction with the surface, reactive landing (RL). The simulations include QM+MM and QM/MM direct dynamics. For collisions with self-assembled monolayer (SAM) surfaces there is quite good agreement between experiment and simulation in the efficiency of energy transfer to the peptide-H+ ion’s internal degrees of freedom. Both the experiments and simulations show two mechanisms for peptide-H+ fragmentation, i.e. shattering and statistical, RRKM dynamics. Mechanisms for SL are probed in simulations of collisions of protonated dialanine with a perfluorinated SAM surface. RL has been studied experimentally for a number of peptide-H+ + surface systems, and qualitative agreement between simulation and experiment is found for two similar systems.

  14. 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.

  15. 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%.

  16. Electrochemical and anticorrosion properties of 5-hydroxytryptophan on mild steel in a simulated well-acidizing fluid

    Directory of Open Access Journals (Sweden)

    Ekemini Ituen

    2017-09-01

    Full Text Available The anticorrosion effect of 5-hydroxytryptophan (5-HTP on mild steel (MS was investigated by gravimetric and electrochemical techniques. Two different concentrations (1 M and 15% of hydrochloric acid were used to simulate well-acidizing fluid. The results show that 10 × 10−5 M 5-HTP is 96.1% efficient in 1 M HCl and 78.1% efficient in 15% HCl at 30 °C. The efficiency decreases as the temperature increases, reaching 66.9% and 39.8% in 1 M and 15% HCl, respectively, at 90 °C. When 5-HTP is blended with potassium iodide and glutathione, the efficiency increases to above 88% and 78% in 1 M and 15% HCl, respectively, at 90 °C. Increasing the 5-HTP concentration decreases the double-layer capacitance and increases the charge-transfer resistance. 5-HTP behaves as a mixed‐type corrosion inhibitor with anodic predominance and is spontaneously adsorbed on the steel surface. Physisorption of 5-HTP is best described by the Langmuir adsorption model and is also exothermic with a resultant decrease in the entropy of the bulk solution. The results of SEM/EDAX, FTIR and UV–VIS studies support the hypothesis that a protective film of 5-HTP forms on MS facilitated by O, N and CC functionalities.

  17. 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...... not cause increased N2O formation or unselective oxidation of NH3. NH3-TPD showed that promotion by HPA instead of WO3 causes the catalysts to possess a higher number of acid sites, both in fresh and alkali poisoned form, which might explain their higher potassium tolerance. Ex-situ EPR spectroscopy......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...

  18. Origin of the contact angle hysteresis of water on chemisorbed and physisorbed self-assembled monolayers.

    Science.gov (United States)

    Belman, Nataly; Jin, Kejia; Golan, Yuval; Israelachvili, Jacob N; Pesika, Noshir S

    2012-10-16

    Self-assembled monolayers (SAMs) are known to form on a variety of substrates either via chemisorption (i.e., through chemical interactions such as a covalent bond) or physisorption (i.e., through physical interactions such as van der Waals forces or "ionic" bonds). We have studied the behavior and effects of water on the structures and surface energies of both chemisorbed octadecanethiol and physisorbed octadecylamine SAMs on GaAs using a number of complementary techniques including "dynamic" contact angle measurements (with important time and rate-dependent effects), AFM, and electron microscopy. We conclude that both molecular overturning and submolecular structural changes occur over different time scales when such SAMs are exposed to water. These results provide new insights into the time-dependent interactions between surfaces and colloids functionalized with SAMs when synthesized in or exposed to high humidity or bulk water or wetted by water. The study has implications for a wide array of phenomena and applications such as adhesion, friction/lubrication and wear (tribology), surfactant-solid surface interactions, the organization of surfactant-coated nanoparticles, etc.

  19. 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.

  20. Influence of Mg concentration on physico-chemical properties of Cd ferrites (CdMg{sub 1.5x}Fe{sub 2−x}O{sub 4}) synthesized by sol–gel combustion method

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Munish [Department of Chemistry, Centre for Advanced Studies-II, Guru Nanak Dev University, Amritsar, Punjab 143005 (India); Department of Chemistry, D A V College, Amritsar, Punjab 143001 (India); Gupta, Manik, E-mail: manuchemistry@gmail.com [Department of Chemistry, Guru Gobind Singh College, Chandigarh 160019 (India); Randhawa, B.S., E-mail: balwinderrandhawa@yahoo.co.in [Department of Chemistry, Centre for Advanced Studies-II, Guru Nanak Dev University, Amritsar, Punjab 143005 (India)

    2015-03-25

    Highlights: • Highly crystalline, single phase ferrites are obtained. • Saturation magnetization increases with increase in Mg{sup 2+} doping up to x = 0.7. • Nanosized particles tend to form inverted spinel structure. • Ferrites obtained have large surface area. - Abstract: The nanofabrication, characterization, microstructural and magnetic properties of pure and Mg{sup 2+} doped cadmium ferrite (CdFe{sub 2−x}Mg{sub 1.5x}O{sub 4}; x = 0.0–0.7) have been carried out. Morphology and the microstructure of the nanostructured oxide materials obtained through sol–gel process using hydrated metal-citrate precursor were studied by powder X-ray diffraction (XRD), electron microscopy (SEM, TEM) and N{sub 2}-physisorption (BET) showing an ordered cubic arrangement of 11–23 nm diameter pores with single-phase spinel grains averaging 13–38 nm in diameter. Room temperature magnetic measurements using magnetometer (VSM) demonstrate that the nature and concentration of dopant both control the site preference in the crystal lattices, suggesting the partial inverted spinel structure of soft Cd ferrites, which differs from bulk CdFe{sub 2}O{sub 4} showing practically no inversion in structure. An increase in Mg{sup 2+} substitution leads to a decrease in the lattice parameter, an increase in saturation magnetization as well as BET surface area of the as-synthesized ferrites.

  1. 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.

  2. 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.

  3. Accurate Evaluation of the Dispersion Energy in the Simulation of Gas Adsorption into Porous Zeolites.

    Science.gov (United States)

    Fraccarollo, Alberto; Canti, Lorenzo; Marchese, Leonardo; Cossi, Maurizio

    2017-03-07

    The force fields used to simulate the gas adsorption in porous materials are strongly dominated by the van der Waals (vdW) terms. Here we discuss the delicate problem to estimate these terms accurately, analyzing the effect of different models. To this end, we simulated the physisorption of CH4, CO2, and Ar into various Al-free microporous zeolites (ITQ-29, SSZ-13, and silicalite-1), comparing the theoretical results with accurate experimental isotherms. The vdW terms in the force fields were parametrized against the free gas densities and high-level quantum mechanical (QM) calculations, comparing different methods to evaluate the dispersion energies. In particular, MP2 and DFT with semiempirical corrections, with suitable basis sets, were chosen to approximate the best QM calculations; either Lennard-Jones or Morse expressions were used to include the vdW terms in the force fields. The comparison of the simulated and experimental isotherms revealed that a strong interplay exists between the definition of the dispersion energies and the functional form used in the force field; these results are fairly general and reproducible, at least for the systems considered here. On this basis, the reliability of different models can be discussed, and a recipe can be provided to obtain accurate simulated adsorption isotherms.

  4. Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose.

    Science.gov (United States)

    Zhou, Lipeng; Liu, Zhen; Shi, Meiting; Du, Shanshan; Su, Yunlai; Yang, Xiaomei; Xu, Jie

    2013-10-15

    Sulfonated hierarchical H-USY zeolite was prepared and characterized by X-ray diffraction, N2 physisorption, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, temperature-programmed desorption of ammonia, and acid-base titration. It was proved that sulfonic group was successfully anchored onto the hierarchical H-USY zeolite. The acidity of the hierarchical H-USY was remarkably improved. Sulfonated hierarchical H-USY zeolite was efficient for the hydrolysis of hemicellulose and cellulose. The yield of TRS for hydrolysis of hemicellulose reached 78.0% at 140 °C for 9h. For hydrolysis of α-cellulose, 60.8% conversion with 22.4% yield of glucose was obtained. Even for microcrystalline cellulose, 43.7% conversion with 15.1% yield of glucose can be obtained. These results are much higher than those obtained over hierarchical H-USY zeolite, indicating that both the acidity and the pore structure determine the activity of zeolite as catalyst in the hydrolysis of biomass. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Experimental tests on a high-temperature H{sub 2}S removal bench-scale system

    Energy Technology Data Exchange (ETDEWEB)

    Caterina Frau; Alessandra Madeddu; M. Giorgia Cutrufello; Carla Cannas; Giampaolo Mura; Paolo Deiana [Sotacarbo S.p.A., Carbonia (Italy)

    2009-07-01

    The behaviour of different commercial sorbents based on zinc oxides has been investigated as high temperature desulphurizing agents from a syngas from high sulphur content coal. A non-reducing gaseous streams containing 1.5 % H{sub 2}S diluted in N{sub 2} has been used as simulated syngas. Comparative tests have been performed isothermally in a bench-scale fixed-bed reactor. In order to check the modifications induced by desulphurization process and to correlate the physicochemical properties of different samples with their performance as H{sub 2}S sorbents, fresh and sulphurized samples were characterized by X-Ray Diffraction (XRD), N{sub 2} physisorption at -196{sup o}C, CHS Elemental Analysis (EA), Scanning Electron Microscopy (SEM), Temperature-Programmed Desorption/Reduction/Oxidation (TPD/R/O). Sorbents showed a good performance as desulphurizing agents and maintained the H{sub 2}S concentration in the outlet gas below 10 ppm. This paper shows the main results of the experimental tests on the bench-scale reactor. Moreover a simulation model has been developed and validated. Under the operating conditions considered, the rate of ZnO pellet sulphidation was limited by mass-transfer resistance, and kinetic parameters of overall reaction were obtained assuming a shrinking core model. A good agreement was obtained between theoretical and experimental results. 14 refs., 10 figs.

  6. A theoretical study on the interaction of amphetamine and single-walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Hafizi, Hamid [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Najafi Chermahini, Alireza, E-mail: anajafi@cc.iut.ac.ir [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Mohammadnezhad, Gholamhossein [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Teimouri, Abbas [Chemistry Department, Payame Noor University (PNU), Tehran 19395-4697 (Iran, Islamic Republic of)

    2015-02-28

    Graphical abstract: - Highlights: • Interaction energy between several armchair CNTs and amphetamine is investigated. • The adsorption of amphetamine molecule is observed to be exothermic and physical in nature. • HOMO–LUMO for pure CNTs, amphetamine and their corresponded complexes are studied. • Density of states (DOS) near the Fermi level is calculated and presented. - Abstract: The adsorption of 1-phenyl-2-aminopropane (amphetamine) on the (4,4), (5,5), (6,6), and (7,7) single-walled carbon nanotubes (SWCNTs) has been theoretically investigated. The molecule has been located in different modes including parallel, perpendicular, and oblique on the outer surface of carbon nanotubes. The physisorption of amphetamine onto SWCNT sidewall is thermodynamically favored; as a consequence, it modulates the electronic properties of pristine nanotube in the vicinity of Fermi region. The adsorption energies for the parallel and oblique modes found in the range of −1.13 to −1.88 and −1.27 to −2.01 kcal/mol, respectively. Projected density of states (PDOS) and frontier orbital analysis in the vicinity of Fermi level region suggest the electronic states to be contributed from SWCNT rather than amphetamine molecule.

  7. Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces.

    Science.gov (United States)

    Liu, Jing; Cheney, Marcos A; Wu, Fan; Li, Meng

    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(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(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(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.

  8. Isotherm, kinetic, and thermodynamic studies on Hg(II) adsorption from aqueous solution by silica- multiwall carbon nanotubes.

    Science.gov (United States)

    Saleh, Tawfik A

    2015-11-01

    Silica combined with 2% multiwall carbon nanotubes (SiO2-CNT) was synthesized and characterized. Its sorption efficacy was investigated for the Hg(II) removal from an aqueous solution. The effect of pH on the percentage removal by the prepared material was examined in the range from 3 to 7. The adsorption kinetics were well fitted by using a pseudo-second-order model at various initial Hg(II) concentrations with R (2) of >0.99. The experimental data were plotted using the interparticle diffusion model, which indicated that the interparticle diffusion is not the only rate-limiting step. The data is well described by the Freundlich isotherm equation. The activation energy (Ea) for adsorption was 12.7 kJ mol(-1), indicating the process is to be physisorption. Consistent with an endothermic process, an increase in the temperature resulted in increasing mercury removal with a ∆H(o) of 13.3 kJ/mol and a ∆S(o) 67.5 J/mol K. The experimental results demonstrate that the combining of silica and nanotubes is a promising alternative material, which can be used to remove the mercury from wastewaters.

  9. High removal efficacy of Hg(II) and MeHg(II) ions from aqueous solution by organoalkoxysilane-grafted lignocellulosic waste biomass.

    Science.gov (United States)

    Saman, Norasikin; Johari, Khairiraihanna; Song, Shiow-Tien; Kong, Helen; Cheu, Siew-Chin; Mat, Hanapi

    2017-03-01

    An effective organoalkoxysilanes-grafted lignocellulosic waste biomass (OS-LWB) adsorbent aiming for high removal towards inorganic and organic mercury (Hg(II) and MeHg(II)) ions was prepared. Organoalkoxysilanes (OS) namely mercaptoproyltriethoxylsilane (MPTES), aminopropyltriethoxylsilane (APTES), aminoethylaminopropyltriethoxylsilane (AEPTES), bis(triethoxysilylpropyl) tetrasulfide (BTESPT), methacrylopropyltrimethoxylsilane (MPS) and ureidopropyltriethoxylsilane (URS) were grafted onto the LWB using the same conditions. The MPTES grafted lignocellulosic waste biomass (MPTES-LWB) showed the highest adsorption capacity towards both mercury ions. The adsorption behavior of inorganic and organic mercury ions (Hg(II) and MeHg(II)) in batch adsorption studies shows that it was independent with pH of the solutions and dependent on initial concentration, temperature and contact time. The maximum adsorption capacity of Hg(II) was greater than MeHg(II) which respectively followed the Temkin and Langmuir models. The kinetic data analysis showed that the adsorptions of Hg(II) and MeHg(II) onto MPTES-LWB were respectively controlled by the physical process of film diffusion and the chemical process of physisorption interactions. The overall mechanism of Hg(II) and MeHg(II) adsorption was a combination of diffusion and chemical interaction mechanisms. Regeneration results were very encouraging especially for the Hg(II); this therefore further demonstrated the potential application of organosilane-grafted lignocellulosic waste biomass as low-cost adsorbents for mercury removal process.

  10. Mercury removal from coal combustion flue gas by modified fly ash

    Institute of Scientific and Technical Information of China (English)

    Wenqing Xu; Hairui Wang; Tingyu Zhu; Junyan Kuang; Pengfei Jing

    2013-01-01

    Fly ash is a potential alternative to activated carbon for mercury adsorption.The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated.X-ray fluorescence spectroscopy,X-ray photoelectron spectroscopy,and other methods were used to characterize the samples.Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption.High specific surface areas and small pore diameters are beneficial to efficient mercury removal.Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency,in particular.The C-M bond,which is formed by the reaction of C and Ti,Si and other elements,may improve mercury oxidation.The samples modified with CuBr2,CuCl2 and FeCl3 showed excellent performance for Hg removal,because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+).Cu2+ and Fe3+ can also promote Hg0 oxidation as catalysts.HCland O2 promote the adsorption of Hg by modified fly ash,whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites.Fly ash samples modified with CuBr2,CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.

  11. The adsorption of mercury-species on relaxed and rumpled CaO (0 0 1) surfaces investigated by density functional theory.

    Science.gov (United States)

    Blowers, Paul; Kim, Bo Gyeong

    2011-03-01

    This research examines the importance of several computational choices in modeling mercury species adsorption on calcium oxide surfaces and is the second in a series of papers. The importance of surface relaxation was tested and it was found that adsorption energies changed for HgCl(2), moving adsorption from being at the borderline of physisorption and chemisorption to being strongly chemisorbed. Results for Hg and HgCl were unaffected. A second computational choice, that of the cluster or periodic model size was tested in both the plane of the model (4 × 4 or 5 × 5 model sizes) and for the depth (two or three layers). It was found that the minimum cluster size for handling mercury adsorption was 5 × 5 and that only two layers of depth were needed. The energetic results show that rumpled CaO surfaces will only weakly physisorb elemental mercury, but could be used to capture HgCl(2) from coal combustion flue gases, which is in agreement with limited experimental data.

  12. Modification of smectite structure by sulfuric acid and characteristics of the modified smectite

    Directory of Open Access Journals (Sweden)

    Tomić Zorica P.

    2011-01-01

    Full Text Available Bentonite samples from Petrovac and Aleksinac were treated with sulfuric acid of different molarities. Differences in structure and texture of the initial and modified bentonite were determined by chemical analysis and Xraypowder diffraction (XRPD, infra-red spectroscopy (FTIR, scanning electron microscopy (SEM and physisorption nitrogen at −196°C. Sulfuric acid caused an exchange of Al3+, Fe3+ and Mg2+ with H+ ions which led to a modification of the smectite crystalline structure. The Mg and Fe substitution in the octahedral sheet promoted the dispersion of those layers and forming of amorphous silicon. The sequence according to which the cations left the octahedral sheets was as follows: Mg2+>Fe3+>Al3+. The sulfuric acid activated bentonites exhibiting a lower cation exchange capacity (CEC and а change of specific surface area (SBET from 6 to 387 for bentonite from Petrovac and from 44 to 1784 m2 g-1 for bentonite from Aleksinac, positioning them as an excellent absorber in wine technology and in the protection of soil and environment.

  13. Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism.

    Science.gov (United States)

    Li, Zhengkui; Wang, Yueming; Wu, Ningmei; Chen, Qichun; Wu, Kai

    2013-03-01

    This study aims to synthesize 2-hydroxyethyl acrylate (HEA) and 2-acrylamido-2-methylpropane sulfonic (AMPS) acid-based hydrogels by gamma radiation and to investigate their swelling behavior and heavy metal ion adsorption capabilities. The copolymer hydrogels prepared were characterized via scanning electron microscopy, Fourier transformed infrared spectra, thermal gravimetric analysis, and X-ray photoelectron spectroscopy. The research showed that the copolymer hydrogel was beneficial for permeation due to its porous structure. In addition, the experimental group A-2-d [70 % water volume ratio and (n (AMPS)/n (HEA)) =1:1] was an optimal adsorbent. The optimal pH was 6.0 and the optimal temperature was 15 °C. Pb(2+), Cd(2+), Cu(2+), and Fe(3)+ achieved adsorption equilibriums within 24 h, whereas Cr(3+) reached equilibrium in 5 h. Pb(2)+, Cd(2+), Cr(3+), and Fe(3+) maximum load capacity was 1,000 mg L(-1), whereas the Cu(2+) maximum capacity was 500 mg L(-1). The priority order in the multicomponent adsorption was Cr(3+)>Fe(3+)>Cu(2+)>Cd(2+)>Pb(2+). The adsorption process of the HEA/AMPS copolymer hydrogel for the heavy metal ions was mainly due to chemisorption, and was only partly due to physisorption, according to the pseudo-second-order equation and Langmuir adsorption isotherm analyses. The HEA/AMPS copolymer hydrogel was confirmed to be an effective adsorbent for heavy metal ion adsorption.

  14. 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)

  15. Study of the stabilization of uranium dioxide fuel with carbon dioxide gas; Estudio del pasivado de oxido de uranio utilizando dioxido de carbono

    Energy Technology Data Exchange (ETDEWEB)

    Perez de Perel, L.; Gonzalez Scardaoni, S.; Marajofsky, A. [Comision Nacional de Energia Atomica, Buenos Aires (Argentina)

    2002-07-01

    Stabilization of the UO{sub 2} is an important step in the manufacturing process of fuel powder. After the reduction the UO{sub 2} powder is made chemically passive by slight oxidation to quite a large extent fixed by specifications that allow to storage powder till the sintering process is performed. In this work the UO{sub 2} powder is oxidized with a versatile automated physisorption/chemisorption analyzer as to generate adsorption isotherms with different pressures and temperatures of gaseous CO{sub 2} sequentially added to the samples. The reduction process is carried out in the same device as to obtain the same fluorite structure UO{sub 2.00} to perform control oxidation experiences so to get 2.04 and 2.06 UO{sub 2} powder. To check the extend of oxidation of UO{sub 2} powder, samples are characterized for O/U ratio analyses. The advantage of using CO{sub 2} is the possibility of high temperature controlled oxidative step which definitely is very beneficial for fuel manufacturing from an economic point of view. (author)

  16. Experimental and DFT Studies on the Behavior of Caffeine as Effective Corrosion Inhibitor of Copper in 1M HNO3

    Directory of Open Access Journals (Sweden)

    Victorien Kouakou

    2016-04-01

    Full Text Available Caffeine was tested as copper corrosion inhibitor in 1M HNO3 using mass loss technique at 308-328K and theoretical studies based on quantum chemistry. The inhibition efficiency is concentration and temperature dependent: Caffeine showed an inhibition efficiency of 78% at 5mM for T =328K. The thermodynamic adsorption parameters ( were determined and analyzed. They revealed a spontaneous adsorption process and a strong interaction between Caffeine and the metal surface. Adsorption isotherms including Langmuir, Temkin and El-Awady were tested. It was found that Caffeine adsorbs on copper according to the modified Langmuir adsorption isotherm. The Dubinin Raduskevitch model was used to distinguish between chemisorption and physisorption. Activation parameters ( were also determined and discussed. Furthermore, the quantum chemical properties/descriptors most relevant to the potential action of the molecule as corrosion inhibitor such as highest occupied molecular energy (EHOMO, lowest unoccupied molecular orbital energy (ELUMO, energy gap(∆E, dipole moment ( and charges on heteroatoms were calculated using DFT at B3LYP level with 6-31+G (d and LanL2DZ basis sets. Fukui indices were also determined and discussed. The theoretical results are consistent with the experimental data reported. DOI: http://dx.doi.org/10.17807/orbital.v8i2.804 

  17. Steam induced structural changes of a poly(ethylenimine) impregnated γ-alumina sorbent for CO2 extraction from ambient air.

    Science.gov (United States)

    Sakwa-Novak, Miles A; Jones, Christopher W

    2014-06-25

    Poly(ethylenimine) (PEI) impregnated mesoporous γ-alumina sorbents are utilized for CO2 adsorption from dry and humid simulated ambient air, and the sorbents are regenerated under an environment of flowing steam for times ranging from 5 min to 24 h of continuous exposure. The sorbents are compared on the basis of equilibrium CO2 capacities from simulated air at 400 ppm of CO2, 50% relative humidity, and 30 °C as well as their physiochemical characterization by means of X-ray diffraction (XRD), (27)Al NMR spectroscopy, IR spectroscopy, Raman spectroscopy, N2 physisorption, and elemental analysis. The sorbents retain better than 90% of the initial equilibrium capacity of ∼1.7 mmol/g at steam exposure times up to 12 h; however, PEI leaching reduced the capacity of the sorbent to 0.66 mmol/g after 24 h of continuous treatment. It is demonstrated that the γ-alumina support partially hydrates to form a boehmite crystal phase at steam times of 90 min and longer but that this phase transition occurs predominately between 90 min and 12 h of steam treatment, slowing at longer times of 12 and 24 h of treatment. Evidence is presented to suggest that the presence of boehmite on the sorbent surface does not significantly alter the amine efficiency of impregnated PEI. The collected results suggest that γ-alumina/PEI composite materials are promising sorbents for CO2 capture from ambient air with regeneration in flowing steam.

  18. An investigation of the activity and stability of Pd and Pd-Zr modified Y-zeolite catalysts for the removal of PAH, CO, CH{sup 4} and NO{sup x} emissions

    Energy Technology Data Exchange (ETDEWEB)

    Klingstedt, F.; Kalantar Neyestanaki, A.; Lindfors, L.-E.; Salmi, T. [Process Chemistry Group, Laboratory of Industrial Chemistry, Abo Akademi University, Biskopsg. 8, FIN-20500 Turku (Finland); Heikkila, T.; Laine, E. [Laboratory of Industrial Physics, Department of Physics, University of Turku, Vesilinnant. 5, FIN-20014 Turku (Finland)

    2003-01-30

    Pd-Y- and Pd-Zr-Y-zeolite catalysts were prepared by the ion-exchange of parent NH{sub 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{sub 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{sub 2}O, 16h). The de-activation was attributed to the de-alumination as well as to the migration of Pd{sup 2+} cations. The catalysts were characterised by XRD, SEM-EDXA, N{sub 2}-physisorption, O{sub 2}/SO{sub 2}/NH{sub 3}/naphthalene-TPD, XRF and DCP.

  19. Hexane cracking over steamed phosphated zeolite H-ZSM-5: promotional effect on catalyst performance and stability.

    Science.gov (United States)

    van der Bij, Hendrik E; Meirer, Florian; Kalirai, Sam; Wang, Jian; Weckhuysen, Bert M

    2014-12-15

    The nature behind the promotional effect of phosphorus on the catalytic performance and hydrothermal stability of zeolite H-ZSM-5 has been studied using a combination of (27) Al and (31) P MAS NMR spectroscopy, soft X-ray absorption tomography and n-hexane catalytic cracking, complemented with NH3 temperature-programmed desorption and N2 physisorption. Phosphated H-ZSM-5 retains more acid sites and catalytic cracking activity after steam treatment than its non-phosphated counterpart, while the selectivity towards propylene is improved. It was established that the stabilization effect is twofold. First, the local framework silico-aluminophosphate (SAPO) interfaces, which form after phosphatation, are not affected by steam and hold aluminum atoms fixed in the zeolite lattice, preserving the pore structure of zeolite H-ZSM-5. Second, the four-coordinate framework aluminum can be forced into a reversible sixfold coordination by phosphate. These species remain stationary in the framework under hydrothermal conditions as well. Removal of physically coordinated phosphate after steam-treatment leads to an increase in the number of strong acid sites and increased catalytic activity. We propose that the improved selectivity towards propylene during catalytic cracking can be attributed to local SAPO interfaces located at channel intersections, where they act as impediments in the formation of bulky carbenium ions and therefore suppress the bimolecular cracking mechanism.

  20. Removal of anionic azo dyes from aqueous solution by functional ionic liquid cross-linked polymer

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Hejun [Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100 (China); Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, China West Normal University, Nanchong 637000 (China); Kan, Taotao [CNOOC Energy Technology and Services-oilfield Technology Services Co., Tanggu, Tianjin 300452 (China); Zhao, Siyuan; Qian, Yixia; Cheng, Xiyuan; Wu, Wenli [School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Wang, Xiaodong [Shandong Provincial Analysis and Test Center, Jinan 250100 (China); Zheng, Liqiang, E-mail: lqzheng@sdu.edu.cn [Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100 (China)

    2013-10-15

    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.

  1. 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.

  2. Removal of methylene blue dye from water by a spent bleaching earth biosorbent.

    Science.gov (United States)

    Belhaine, Ali; Ghezzar, Mouffok Redouane; Abdelmalek, Fatiha; Tayebi, Kamel; Ghomari, Abdelhamid; Addou, Ahmed

    2016-12-01

    This work is about the valorization of spent bleaching earth (SBE) at low cost from the AFIA oil refinery in Algeria's western region. The biowaste has been burned to eliminate the oil traces, then it has been valorized in two ways: (i) chemically, using phosphoric acid to obtain SBEC and (ii) thermally at 750 °C to create SBEH. The obtained materials were used for the first time as biosorbents in the wastewater treatment field. The three biomaterials show very interesting adsorption properties, with specific surfaces of 194.2, 784.6 and 888.5 m(2) g(-1) for SBE, SBEC and SBEH, respectively. The analysis has revealed that the obtained materials are alumino-silicates. The three biowastes have been used to remove methylene blue dye from water. The dye was totally eliminated by a physisorption mechanism in the presence of 1 g L(-1) of each biowaste after 8, 10, 20 min of contact time. The highest correlation coefficient (R(2) = 0.99) was related to the Langmuir isotherm, indicating a good fit with this model, and explaining the biosorption as a monolayer process. According to this model, the adsorption capacities were 123.3, 185.2 and 188.7 mg g(-1) for SBE, SBEH and SBEC, respectively. This study shows that SBE can be used as an alternative to commercial adsorbents for dye removal from water.

  3. Porous graphitic materials obtained from carbonization of organic xerogels doped with transition metal salts

    Indian Academy of Sciences (India)

    W Kiciński; M Bystrzejewski; M H Rümmeli; T Gemming

    2014-02-01

    Porous carbons with a well developed graphitic phase were obtained via the pyrolysis of FeCl3-, NiCl2-, and CoCl2-doped organic xerogels. Doping was realized through salt solubilization in a water/methanol solution of resorcinol and furfural. Carbon xerogels with tailored particles, porous morphology and various degrees of graphitization were obtained depending of the water/methanol ratio and the salt content and type in the starting solution of substrates. When obtained via pyrolysis, carbon xerogels retain the overall open-celled structure exhibiting depleted microporosity and a well-developed mesoporic region that expands into macropores. The removal of metal leads to carbon xerogels with specific surface areas between 170 and 585 m2/g and pore volume up to 0.76 cm3/g. The possibility of enhancing the porosity of xerogels via templating with colloidal silica was also investigated. It was assumed that from the three investigated salts, FeCl3 makes the best choice for graphitization catalyst precursor to obtain uniformly graphitized mesoporous carbon xerogels. The obtained carbon samples were characterized by means of SEM, TEM, X-ray diffraction, Raman spectroscopy, N2 physisorption and thermogravimetric analysis.

  4. Evaluation of the Thermodynamic Properties of H(2) Binding in Solid State Dihydrogen Complexes [M(η(2)-H(2))(CO)dppe(2)][BArF(24)] (M = Mn, Tc, Re): an Experimental and First Principles Study.

    Science.gov (United States)

    Abrecht, David G; Fultz, Brent

    2012-10-25

    The solid state complex [Mn(CO)dppe(2)][BArF(24)] was synthesized and the thermodynamic behavior and properties of the hydrogen absorption reaction to form the dihydrogen complex [Mn(η(2)-H(2))dppe(2)][BArF(24)] were measured over the temperature range 313K-373K and pressure range 0-600 torr using the Sieverts method. The absorption behavior was accurately described by Langmuir isotherms, and enthalpy and entropy values of ΔH(∘)=-52.2 kJ/mol and ΔS(∘)=-99.6 J/mol-K for the absorption reaction were obtained from the Langmuir equilibrium constant. The observed binding strength was similar to metal hydrides and other organometallic complexes, despite rapid kinetics suggesting a site-binding mechanism similar to physisorption materials. Electronic structure calculations using the LANL2DZ-ECP basis set were performed for hydrogen absorption over the organometallic fragments [M(CO)dppe(2)](+) (M= Mn, Tc, Re). Langmuir isotherms derived from calculation for absorption onto the manganese fragment successfully simulated both the pressure-composition behavior and thermodynamic properties obtained from experiment. Results from calculations for the substitution of the metal center reproduced qualitative binding strength trends of 5d > 3d > 4d previously reported for the group 6 metals.

  5. Liquid-phase oxidation of alkylaromatics to aromatic ketones with molecular oxygen over a Mn-based metal-organic framework.

    Science.gov (United States)

    Kuwahara, Yasutaka; Yoshimura, Yukihiro; Yamashita, Hiromi

    2017-07-04

    Liquid-phase oxidation of alkylaromatics with molecular O2 was examined using a microporous Mn-based metal-organic framework (Mn-MOF-74). Mn-MOF-74 consisting of trimeric Mn clusters and 2,5-dihydroxyterephthalate (dhtp) linkers exhibits superior catalytic activity with good ketone selectivity compared to conventional oxide-supported Mn catalysts without showing any lengthy induction period. Combined analyses by means of XRD, FE-SEM, N2 physisorption and Mn K-edge XAFS reveal that the superior catalytic performance is attributed to the inherently-formed Mn(iii)2(dhtp) moieties embedded in the Mn-MOF-74 framework rather than structural factors associated with the MOF. The catalyst is reusable over multiple catalytic runs along with retaining its original catalytic activity due to the ability of the dhtp ligand to stabilize active Mn(iii) atoms. Owing to high activity, reusability and nontoxicity, Mn-MOF-74 can offer a simple, inexpensive and efficient protocol for the oxidation of some important alkylaromatics, such as ethylbenzene and diphenylmethane to produce the corresponding aromatic ketones.

  6. N2 and CO2 Adsorption by Soils with High Kaolinite Content from San Juan Amecac, Puebla, México

    Directory of Open Access Journals (Sweden)

    Karla Quiroz-Estrada

    2016-07-01

    Full Text Available Carbon dioxide (CO2 is considered one of the most important greenhouse gases in the study of climate change. CO2 adsorption was studied using the gas chromatography technique, while the Freundlich and Langmuir adsorption models were employed for processing isotherm data in the temperature range of 473–573 K. The isosteric heat of adsorption was calculated from the Clausius–Clapeyron equation. Moreover, the thermodynamic properties ΔG, ΔU, and ΔS were evaluated from the adsorption isotherms of Langmuir using the Van’t Hoff Equation. The four soil samples were recollected from San Juan Amecac, Puebla, Mexico, and their morphologies were investigated through X-ray diffraction (XRD and N2 adsorption at 77 K. The SJA4 soil has a crystalline Kaolinite phase, which is one of its non-metallic raw materials, and N2 isotherms allowed for the determination of pore size distributions and specific surface areas of soil samples. The Barrett–Joyner–Halenda (BJH distribution of pore diameters was bimodal with peaks at 1.04 and 3.7 nm, respectively. CO2 adsorption showed that the SJA1 soil afforded a higher amount of adsorbed CO2 in the temperature range from 453 to 573 K followed by SJA4 and finally SJA2, classifying this process as exothermic physisorption.

  7. Effective hydrogen storage: a strategic chemistry challenge.

    Science.gov (United States)

    David, William I F

    2011-01-01

    This paper gives an overview of the current status and future potential of hydrogen storage from a chemistry perspective and is based on the concluding presentation of the Faraday Discussion 151--Hydrogen Storage Materials. The safe, effective and economical storage of hydrogen is one of the main scientific and technological challenges in the move towards a low-carbon economy. One key sector is transportation where future vehicles will most likely be developed around a balance of battery-electric and hydrogen fuel-cell electric technologies. Although there has been a very significant research effort in solid-state hydrogen storage, high-pressure gas storage combined with conventional metal hydrides is still seen as the current intermediate-term candidate for car manufacturers. Significant issues have arisen in the search for improved solid-state hydrogen storage materials; for example, facile reversibility has been a major challenge for many recently studied complex hydrides while physisorption in porous structures is still restricted to cryogenic temperatures. However, many systems fulfil the majority of necessary criteria for improved hydrogen storage--indeed, the discovery of reversibility in multicomponent hydride systems along with recent chemistry breakthroughs in off-board and solvent-assisted regeneration suggest that the goal of both improved on-board reversible and off-board regenerated hydrogen storage systems can be achieved.

  8. β-Cyclodextrin capped graphene-magnetite nanocomposite for selective adsorption of Bisphenol-A.

    Science.gov (United States)

    Ragavan, K V; Rastogi, Navin K

    2017-07-15

    Beta-cyclodextrin capped Graphene-magnetite (G-Fe3O4-BCD) nanocomposite was synthesized by ethylenediamine conjugation and used as an adsorbent for selective removal of Bisphenol-A (BPA) in water. Characterization of nanocomposite revealed BCD conjugated to Fe3O4 nanoparticles (30-40nm) embedded on graphene. Adsorption process followed Langmuir model and pseudo second order kinetics with an adsorption capacity of 59.6mg/g. It was found to be highly favourable physisorption and endothermic process as indicated by ΔG° (-3.36kJ/mol) and ΔH° (2.08kJ/mol) values at ambient temperatures. The nanocomposite was highly specific towards BPA compared to its analogs, largely driven by host-guest interaction between BCD and BPA. Nanocomposite had a high magnetization of 97emu/g with superparamagnetic property at room temperature which helps in faster separation using an external magnetic field. Nanocomposite can be regenerated with methanol and can be reused without much loss in adsorption efficiency (adsorption of target molecules. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Design of β-cyclodextrin modified TiO(2) nanotubes for the adsorption of Cu(II): Isotherms and kinetics study.

    Science.gov (United States)

    Triki, Mohamed; Tanazefti, Haythem; Kochkar, Hafedh

    2017-05-01

    This paper builds on previous literature showing the interesting adsorptive properties of TiO2 nanotubes. It further explores the positive effect of β-cyclodextrin on these properties. Hence, β-cyclodextrin modified TiO2 nanotubes were successfully prepared and characterized by XRD, N2 physisorption at 77K, Raman, FTIR-ATR, (1)H NMR, TEM and EPR. The adsorptive interaction of Cu(II) with materials was investigated in aqueous solution at pH 9.25 (NH4(+)/NH3). The main conclusion is that copper(II)-ammonia complexation equilibria play an important role in the adsorption process. The β-cyclodextrin was found to improve the Cu(NH3)4(2+) adsorption mainly by retarding its precipitation to high concentrations values (>400mgL(-1)). Adsorption experimental data showed good fit with the pseudo-second-order model and the Langmuir isotherm model. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Fe3O4–wheat straw: preparation, characterization and its application for methylene blue adsorption

    Directory of Open Access Journals (Sweden)

    A. Ebrahimian Pirbazari

    2014-09-01

    Full Text Available The removal of methylene blue (MB from aqueous solution by NaOH-treated wheat straw from agriculture biomass impregnated with Fe3O4 magnetic nanoparticles (MNP-NWS was investigated. Magnetic nanoparticles (Fe3O4 were prepared by chemical precipitation of a mixture of Fe2+ and Fe3+ salts from solution aqueous by ammonia. These magnetic nanoparticles of the adsorbent Fe3O4 were characterized by Field Emission Scanning Electron Microscopy (FESEM, X-ray Diffraction (XRD, nitrogen physisorption and Fourier Transform Infrared Spectroscopy (FTIR. FTIR results showed complexation and ion exchange appears to be the principal mechanism for MB adsorption. The adsorption isotherm data were fitted to Langmuir, Sips, Redlich–Peterson and Freundlich equations. Langmuir adsorption capacity, Qmax, was found to be 1374.6 mgg−1. The Freundlich equation yielded the best fit to the experimental data in comparison to the other isotherm models. The removal of MB by MNP-NWS followed pseudo-first-order reaction kinetics based on Lagergren equations.

  11. 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)

  12. Feasibility of using demolition waste as an alternative heavy metal immobilising agent.

    Science.gov (United States)

    Damrongsiri, Seelawut

    2017-05-01

    Demolition waste consisting of cement paste, lightweight concrete and bricks is a worthless material generated by a growing city. However, research suggests that it may be applied as an alternative heavy metal immobilising agent. The diverse characteristics of demolition waste were examined. Cadmium was selected as there presentative heavy metal to investigate demolition waste adsorption capacity. The solid-liquid distribution coefficients (Kd) were observed. The adsorption isotherms were applied to investigate adsorption characteristics. Carbon content in the demolition waste materials was low and mainly in inorganic form. Cement paste and lightweight concrete had an alkaline pH with very high acid neutralising capacity (ANC). The surface area and cation exchange capacity (CEC) of these materials were low. Cement paste possessed the highest pH, ANC, CEC and surface area, with the highest Kd; however, its specific surface area and CEC were low compared to activated carbon and organic material. The adsorption isotherms indicated surface heterogeneity with favourable conditions for adsorption and the mean free energy suggested physisorption with multilayer formation. The Kd values of the tested materials were comparable to soil which was not effective in immobilising heavy metal via adsorption mechanisms. However, the high pH and ANC of cement paste and lightweight concrete can improve the heavy metal adsorption capacity of soil and soil ANC that help prevents and controls leaching by heavy metals.

  13. Adsorption ability of rare earth elements on clay minerals and its practical performance

    Institute of Scientific and Technical Information of China (English)

    肖燕飞; 龙志奇; 黄莉; 冯宗玉; 王良士

    2016-01-01

    The adsorption behaviors of rare earth elements on clay minerals would have great influence on the mineralization process and the leaching process of the ion-adsorption type rare earths ore. In this work, the adsorption thermodynamics of REEs on kaolin were investigated thoroughly and systematically. The experimental results showed that the adsorption characteristics of La, Nd, Y on kaolin did fit well with the Langmuir isotherm model and their saturated adsorption capacities were 1.731, 1.587 and 0.971 mg/g, re-spectively. The free energy change (ΔG) values were –16.91 kJ/mol (La), –16.05 kJ/mol (Nd) and –15.58 kJ/mol (Y), respectively. The negative values ofΔG demonstrated that the adsorption of rare earth on kaolin was a spontaneously physisorption process. The deposit characteristic of the volcanic ion-adsorption type rare earths ore and the behavior of the rare earth in the column leaching process were also developed here. With the increase of the ore body depth, the distribution of the LREEs decreased and the HREEs increased. And the slight differences in the adsorption ability of REEs on clay minerals led to the fractionation effect in the column leaching process. These developed more evidences and better understanding of metallogenic regularity, and provided a theoretical ba-sis and scientific approach to separation of the HREEs and LREEs in the leaching process.

  14. Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH2 framework and their impact on hydrogen sorption properties

    Science.gov (United States)

    Žunkovič, E.; Mazaj, M.; Mali, G.; Rangus, M.; Devic, T.; Serre, C.; Logar, N. Zabukovec

    2015-05-01

    Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH2) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac)2 or 2 molecules of Mg(acac)2 were incorporated into one unit cell of UiO-66-NH2. 1H-13C CPMAS and 1H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH2 framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH2. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue.

  15. Modification of the Mg/DOBDC MOF with Amines to Enhance CO2 Adsorption from Ultradilute Gases.

    Science.gov (United States)

    Choi, Sunho; Watanabe, Taku; Bae, Tae-Hyun; Sholl, David S; Jones, Christopher W

    2012-05-03

    The MOF Mg/DOBDC has one of the highest known CO2 adsorption capacities at the low to moderate CO2 partial pressures relevant for CO2 capture from flue gas but is difficult to regenerate for use in cyclic operation. In this work, Mg/DOBDC is modified by functionalization of its open metal coordination sites with ethylene diamine (ED) to introduce pendent amines into the MOF micropores. DFT calculations and experimental nitrogen physisorption and thermogravimetric analysis suggest that 1 ED molecule is added to each unit cell, on average. This modification both increases the material's CO2 adsorption capacity at ultradilute CO2 partial pressures and increases the regenerability of the material, allowing for cyclic adsorption-desorption cycles with identical adsorption capacities. This is one of the first MOF materials demonstrated to yield significant adsorption capacities from simulated ambient air (400 ppm CO2), and its capacity is competitive with the best-known adsorbents based on amine-oxide composites.

  16. 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

  17. Hydrogen sulfide adsorption on MOFs and MOF/graphite oxide composites.

    Science.gov (United States)

    Petit, Camille; Mendoza, Barbara; Bandosz, Teresa J

    2010-12-03

    Composites of a copper-based metal-organic framework (MOF) and graphite oxide (GO) were tested for hydrogen sulfide removal at ambient conditions. In order to understand the mechanisms of adsorption, the initial and exhausted samples were analyzed by various techniques including X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analyses, and sorption of nitrogen. Compared to the parent materials, an enhancement in hydrogen sulfide adsorption was found. It was the result of physical adsorption of water and H(2)S in the pore space formed at the interface between the MOF units and the graphene layers where the dispersive forces are the strongest. Besides physisorption, reactive adsorption was found as the main mechanism of retention. H(2)S molecules bind to the copper centers of the MOF. They progressively react with the MOF units resulting in the formation of copper sulfide. This leads to the collapse of the MOF structure. Water enhances adsorption in the composites as it allows the dissolution of hydrogen sulfide.

  18. A Stimuli-Responsive Zirconium Metal-Organic Framework Based on Supermolecular Design.

    Science.gov (United States)

    Krause, Simon; Bon, Volodymyr; Stoeck, Ulrich; Senkovska, Irena; Többens, Daniel M; Wallacher, Dirk; Kaskel, Stefan

    2017-08-28

    A flexible, yet very stable metal-organic framework (DUT-98, Zr6 O4 (OH)4 (CPCDC)4 (H2 O)4 , CPCDC=9-(4-carboxyphenyl)-9H-carbazole-3,6-dicarboxylate) was synthesized using a rational supermolecular building block approach based on molecular modelling of metal-organic chains and subsequent virtual interlinking into a 3D MOF. Structural characterization via synchrotron single-crystal X-ray diffraction (SCXRD) revealed the one-dimensional pore architecture of DUT-98, envisioned in silico. After supercritical solvent extraction, distinctive responses towards various gases stimulated reversible structural transformations, as detected using coupled synchrotron diffraction and physisorption techniques. DUT-98 shows a surprisingly low water uptake but a high selectivity for pore opening towards specific gases and vapors (N2 , CO2 , n-butane, alcohols) at characteristic pressure resulting in multiple steps in the adsorption isotherm and hysteretic behavior upon desorption. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Catalytic characterization of bi-functional catalysts derived from Pd–Mg–Al layered double hydroxides

    Indian Academy of Sciences (India)

    N N Das; S C Srivastava

    2002-08-01

    Hydrotalcite like precursors containing PdII–MgII–AlIII with varying molar ratios, (Pd + Mg)/Al ≈ 3 and Mg/Pd ≈ 750 to 35, were prepared by coprecipitation of metal nitrates at constant pH. Characterization of samples as synthesized and their calcined products by elemental analyses, powder XRD, TG–DTA, FT–IR spectroscopy, TPR and N2 physisorption indicated a well crystalline hydrotalcite like structure with incorporation of Pd2+ in the brucite layers. Thermal decomposition of hydrotalcite precursors at intermediate temperatures led to amorphous mixed oxides, Pd/MgAl(O), which on reduction yielded bi-functional catalyst, Pd°/MgAl(O). The resultant catalysts with acid, base and hydrogenating sites, were highly active and selective for one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen. The results showed an optimal balance between acid-base and metallic sites were required to increase the selectivity of MIBK and stability of the catalysts.

  20. 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.

  1. 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.

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

    Science.gov (United States)

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

    2012-11-30

    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.

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

    Institute of Scientific and Technical Information of China (English)

    白素丽; 黄承都; 吕静; 李振花

    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 N2-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/Si02 catalyst showed an enhanced activity, C5+ selectivity and catalytic stability as compared to the conventional thermal calcined Co/SiO2 catalyst.

  4. Plasma-based surface modification of polystyrene microtiter plates for covalent immobilization of biomolecules.

    Science.gov (United States)

    North, Stella H; Lock, Evgeniya H; Cooper, Candace J; Franek, James B; Taitt, Chris R; Walton, Scott G

    2010-10-01

    In recent years, polymer surfaces have become increasingly popular for biomolecule attachment because of their relatively low cost and desirable bulk physicochemical characteristics. However, the chemical inertness of some polymer surfaces poses an obstacle to more expansive implementation of polymer materials in bioanalytical applications. We describe use of argon plasma to generate reactive hydroxyl moieties at the surface of polystyrene microtiter plates. The plates are then selectively functionalized with silanes and cross-linkers suitable for the covalent immobilization of biomolecules. This plasma-based method for microtiter plate functionalization was evaluated after each step by X-ray photoelectron spectroscopy, water contact angle analysis, atomic force microscopy, and bioimmobilization efficacy. We further demonstrate that the plasma treatment followed by silane derivatization supports direct, covalent immobilization of biomolecules on microtiter plates and thus overcomes challenging issues typically associated with simple physisorption. Importantly, biomolecules covalently immobilized onto microtiter plates using this plasma-based method retained functionality and demonstrated attachment efficiency comparable to commercial preactivated microtiter plates.

  5. Surface defect passivation of MoS2 by sulfur, selenium, and tellurium

    Science.gov (United States)

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

    2016-04-01

    Few-layer MoS2 field-effect transistors often show an n-type conduction behavior due to the presence of high-density sulfur vacancies. Here, we investigated the possibility of surface defect passivation of MoS2 by sulfur treatment in (NH4)2S solution or coating with an ultrathin layer of selenium or tellurium. It was found that all three elements investigated are able to induce a p-doping effect through suppressing the residual electron concentration by an amount exceeding 0.5 × 1012 cm-2 in few-layer MoS2. Among them, the sulfur-treatment exhibits the most superior thermal stability that survives thermal annealing at temperatures ≥120 °C for at least 10 h. Tellurium exhibits the strongest p-doping effect due to electron trapping by physisorption-induced gap states near the valence band edge. On the other hand, selenium is highly volatile on MoS2; it evaporates and desorbs easily due to Joule heating during electrical measurements in vacuum. The results of first-principles calculations support the experimental observations.

  6. 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.

  7. 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.

  8. Adsorption of CO2 by alginate immobilized zeolite beads

    Science.gov (United States)

    Suratman, A.; Kunarti, E. S.; Aprilita, N. H.; Pamurtya, I. C.

    2017-03-01

    Immobilized zeolit in alginate beads for adsorption of CO2 was developed. Alginate immobilized zeolit beads was generated by dropping the mixture of Na-alginate and zeolite solution into Ca2+ solution. The adsorption efficacy such as the influence of contact time, mass of zeolite, flowrate of CO2, and mass of adsorbent was evaluated. The adsorption of CO2 onto alginate immobilized zeolit beads was investigated by performing both equilibrium and kinetic batch test. Bead was characterized by FTIR and SEM. Alginate immobilized zeolit beads demonstrated significantly higher sorption efficacy compared to plain alginate beads and zeolite with 0.25 mmol CO2 adsorbed /g adsorbent. Optimum condition was achieved with mass composition of alginate:zeolite (3:1), flowrate 50 mL/min for 20 minutes. The alginate immobilized zeolit beads showed that adsorption of CO2 followed Freundlich isotherm and pseudo second order kinetic model. Adsorption of CO2 onto alginate immobilized zeolite beads is a physisorption with adsorption energy of 6.37 kJ/mol. This results indicates that the alginate immobilized zeolit beads can be used as promising adsorbents for CO2.

  9. 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)

  10. 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.)

  11. Removal of Pb(II) ions from aqueous solution by adsorption using bael leaves (Aegle marmelos).

    Science.gov (United States)

    Chakravarty, S; Mohanty, Ashok; Sudha, T Nag; Upadhyay, A K; Konar, J; Sircar, J K; Madhukar, A; Gupta, K K

    2010-01-15

    Biosorption of Pb(II) on bael leaves (Aegle marmelos) was investigated for the removal of Pb(II) from aqueous solution using different doses of adsorbent, initial pH, and contact time. The maximum Pb loading capacity of the bael leaves was 104 mg g(-1) at 50 mg L(-1) initial Pb(II) concentration at pH 5.1. SEM and FT-IR studies indicated that the adsorption of Pb(II) occurs inside the wall of the hollow tubes present in the bael leaves and carboxylic acid, thioester and sulphonamide groups are involved in the process. The sorption process was best described by pseudo second order kinetics. Among Freundlich and Langmuir isotherms, the latter had a better fit with the experimental data. The activation energy E(a) confirmed that the nature of adsorption was physisorption. Bael leaves can selectively remove Pb(II) in the presence of other metal ions. This was demonstrated by removing Pb from the effluent of exhausted batteries.

  12. 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.

  13. Adsorptive potential of cationic Basic Yellow 2 (BY2) dye onto natural untreated clay (NUC) from aqueous phase: Mass transfer analysis, kinetic and equilibrium profile

    Science.gov (United States)

    Öztürk, A.; Malkoc, E.

    2014-04-01

    In this work, natural untreated clay (NUC) was studied for the removal of Basic Yellow 2 (BY2) from aqueous solution in batch system. The effects of initial BY2 concentration, contact time, solution temperature and solution pH on BY2 adsorption were investigated. Nitrogen sorption measurements were employed to investigate the variation in surface and pore properties after dye adsorption. The adsorbent was characterized by means of FTIR, PSD, TEM, XRD and BET analysis. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin and Scatchard isotherm models. The maximum monolayer adsorption capacity was found to be 833.33 mg/g at 25 °C (at room temperature). The pseudo-second-order kinetic model provided the best fit to the experimental datas compared with pseudo-first-order kinetic adsorption models. To explain mass transfer mechanism of BY2 adsorption, obtained experimental datas were applied Weber and Morris model, Body and Frusawa and Smith models. The results show that the adsorption process is controlled by film diffusion. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were determined. Adsorption of BY2 on NUC is exothermic and spontaneous in nature. The calculated activation energy of adsorption was found to be 5.24 kJ/mol for BY2. This value indicates that the adsorption process is a physisorption.

  14. Robust nanogap electrodes by self-terminating electroless gold plating.

    Science.gov (United States)

    Serdio V, Victor M; Azuma, Yasuo; Takeshita, Shuhei; Muraki, Taro; Teranishi, Toshiharu; Majima, Yutaka

    2012-11-21

    Robust nanogap electrodes for nanodevices with a separation of 3.0 ± 1.7 nm were simultaneously mass-produced at a yield of 90% by a combination of electron beam lithography (EBL) and electroless gold plating (EGP). Nanogap electrodes demonstrated their robustness as they maintained their structure unchanged up to temperatures of 170 °C, during the isotropic oxygen plasma ashing removal of the amorphous carbon overlayer resulting from scanning electron microscopy observations, therefore maintaining their surface reactivity for EGP and formation of a self-assembled monolayer. A gold layer grows over the electrode surface during EGP, narrowing the separation between the electrodes; growth stops around 3 nm due to a self-termination phenomenon. This is the main factor in the high yield and reproducibility of the EGP process because it prevents contact between the electrodes. A 90% yield is achieved by also controlling the etching and physisorption of gold clusters, which is accomplished by reduction of triiodide ions and heat treatment of the EGP solution, respectively. A mixed self-assembled monolayer of octanethiol and decanedithiol can be formed at the surface of the nanogap electrodes after the oxygen plasma treatment, and decanethiol-protected Au nanoparticles were chemisorbed between the self-terminated nanogap electrodes via decanedithiol. Chemically assembled single-electron transistors based on the nanogap electrodes exhibit ideal, stable, and reproducible Coulomb diamonds.

  15. 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.

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

    Science.gov (United States)

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

    2010-04-01

    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.

  17. 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.

  18. The modulator driven polymorphism of Zr(IV) based metal-organic frameworks

    Science.gov (United States)

    Drache, Franziska; Bon, Volodymyr; Senkovska, Irena; Getzschmann, Jürgen; Kaskel, Stefan

    2017-01-01

    The reaction of ZrCl4 and 2,5-thiophenedicarboxylic acid (H2tdc) in the presence of trifluoroacetic acid (Htfa) as modulator results in the formation of the new metal-organic framework (MOF) named DUT-126 (DUT = Dresden University of Technology). The nature and concentration of modulators are found to be decisive synthetic parameters affecting the topology of the formed product. DUT-126 (hbr) extends the series of polymorphs differing in topology, namely DUT-67 (reo), DUT-68 (bon) and DUT-69 (bct) to four, where DUT-67 and DUT-68 show the same eight-connected secondary building units as in DUT-126. In DUT-126, linker molecules have a peculiar orientation, resulting in hbr topology, which is described for the first time in this work for MOFs. DUT-126 contains three pore types, including two micropores surrounding mesoporous channels. DUT-126 is stable against hydrolysis and features permanent porosity with a specific surface area of 1297 m2 g-1 and a total pore volume of 0.48 cm3 g-1, calculated from the nitrogen physisorption isotherm measured at 77 K. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  19. Discriminating between Metallic and Semiconducting Single-Walled Carbon Nanotubes Using Physisorbed Adsorbates: Role of Wavelike Charge-Density Fluctuations

    Science.gov (United States)

    Gao, Wang; Chen, Yun; Jiang, Qing

    2016-12-01

    Discriminating between metallic (M ) and semiconducting (S ) single-walled carbon nanotubes (SWNTs) remains a fundamental challenge in the field of nanotechnology. We address this issue by studying the adsorption of the isotropic atoms Xe, Kr, and a highly anisotropic molecule n heptane on M - and S -SWNTs with density functional theory that includes many-body dispersion forces. We find that the distinct polarizabilities of M - and S -SWNTs exhibit significantly different physisorption properties, which are also strongly controlled by the SWNT's diameter, adsorption site, adsorbate coverage, and the adsorbate's anisotropy. These findings stem from the wavelike nature of charge-density fluctuations in SWNTs. Particularly, these results allow us to rationalize the unusual √{3 }×√{3 }R 3 00 phase of Kr atoms on small gap M -SWNTs and the double desorption peak temperatures of n heptane on M -SWNTs in experiments, and also propose the n heptane as an effective sensor for experimentally discriminating M - and S -SWNTs.

  20. Enhancement of CO2 sorption uptake on hydrotalcite by impregnation with K2CO3.

    Science.gov (United States)

    Lee, Jung Moo; Min, Yoon Jae; Lee, Ki Bong; Jeon, Sang Goo; Na, Jeong Geol; Ryu, Ho Jung

    2010-12-21

    The awareness of symptoms of global warming and its seriousness urges the development of technologies to reduce greenhouse gas emissions. Carbon dioxide (CO(2)) is a representative greenhouse gas, and numerous methods to capture and storage CO(2) have been considered. Recently, the technology to remove high-temperature CO(2) by sorption has received lots of attention. In this study, hydrotalcite, which has been known to have CO(2) sorption capability at high temperature, was impregnated with K(2)CO(3) to enhance CO(2) sorption uptake, and the mechanism of CO(2) sorption enhancement on K(2)CO(3)-promoted hydrotalcite was investigated. Thermogravimetric analysis was used to measure equilibrium CO(2) sorption uptake and to estimate CO(2) sorption kinetics. The analyses based on N(2) gas physisorption, X-ray diffractometry, Fourier transform infrared spectrometry, Raman spectrometry, transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy were carried out to elucidate the characteristics of sorbents and the mechanism of enhanced CO(2) sorption. The equilibrium CO(2) sorption uptake on hydrotalcite could be increased up to 10 times by impregnation with K(2)CO(3), and there was an optimal amount of K(2)CO(3) for a maximum equilibrium CO(2) sorption uptake. In the K(2)CO(3)-promoted hydrotalcite, K(2)CO(3) was incorporated without changing the structure of hydrotalcite and it was thermally stabilized, resulting in the enhanced equilibrium CO(2) sorption uptake and fast CO(2) sorption kinetics.

  1. Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers.

    Science.gov (United States)

    Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B; Ebenso, Eno E

    2016-08-12

    Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results.

  2. Removal of Toluene over NaX Zeolite Exchanged with Cu2+

    Directory of Open Access Journals (Sweden)

    Douglas Romero

    2015-09-01

    Full Text Available Toluene is a major air pollutant emitted from painting and metal coating processes and might have some health effects. Adsorption and catalytic complete oxidation are promising ways to retain or convert toluene into harmless products. The present work aims to develop a bifunctional material which can be used as an adsorbent and catalyst for low-temperature toluene removal. Copper zeolites were obtained by exchanging the sodium in the parent NaX zeolite with copper from aqueous solutions of Cu(NO32∙2.5H2O. Several characterization techniques, H2-TPR, XPS, XRD and N2 physisorption, were used in order to evaluate the redox, surface, structural and textural properties of the materials, respectively. The various materials were tested in adsorption and catalytic processes. The sample with low copper content (1 wt. % exhibited promising features in terms of toluene adsorption capacity and total oxidation. The results can be correlated to the presence of micropores and well-dispersed CuO species.

  3. Preparation of diethylene glycol monomethyl ether monolaurate catalyzed by active carbon supported KF/CaO.

    Science.gov (United States)

    Lou, Shengfeng; Jia, Lihua; Guo, Xiangfeng; Wu, Ping; Gao, Lianbing; Wang, Jianjun

    2015-01-01

    Diethylene glycol monomethyl ether monolaurate (DGMEML) was synthesized via the reaction of diethylene glycol monomethyl ether (DGME) with methyl laurate (ML) by a new solid base catalyst of KF/CaO/AC, which was prepared by impregnation method using active carbon as carrier. The catalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), nitrogen physisorption-desorption and Hammett indicator methods; the effect of the mole ratio of KF to CaO, DGME to ML molar ratio, amount of catalyst, reaction time and temperature on the yield of DGMEML were studied; and the relationship between the structure of the catalyst and the yield of DGMEML was investigated. The formed KCaF3 and K2O were acting as the main active components in the catalytic transesterification; the highest yield of 96.3 % was obtained as KF-to-CaO molar ratio of 2.0, DGME to ML molar ratio of 4.0, catalyst amount of 5 wt%, and reaction time of 30 min at 75 °C; and the catalyst displayed good stability in the transesterification.

  4. 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.

  5. A facile one-pot synthesis of starch functionalized graphene as nano-carrier for pH sensitive and starch-mediated drug delivery.

    Science.gov (United States)

    Liu, Kunping; Wang, Yimin; Li, Huiming; Duan, Yixiang

    2015-04-01

    A fast, green and facile method was developed to prepare starch functionalized graphene nanosheets (starch-GNS) via the reduction of exfoliated graphene oxides by soluble starch, which acted both as a reductant and as a functionalization reagent for capping graphene nanosheets to prevent aggregation. The as-prepared starch-GNS exhibited good biocompatibility, which was deemed crucial for the biomedical application of graphene. Cellular toxicity tests suggested that the starch-GNS was nontoxic to SW-620 cells even at the relatively concentration of 200 μg mL(-1). After the loading of the commonly used anticancer drug hydroxycamptothecin (HCPT) via physisorption on starch-GNS, the HCPT@starch-GNS composite exhibited a high drug loading capacity and was therefore used for cellular imaging and drug delivery studies. Through the nonspecific endocytosis effect, the HCPT@starch-GNS composite was encapsulated into cytoplasm by SW-620 cancer cells. With the double action of an acid microenvironment and the diastase in SW-620 cells, the HCPT@starch-GNS composite showed high toxicity to the SW-620 cells and experienced a pH sensitive as well as a starch-mediated in vitro sustained release process, which had the potential advantage of improving therapeutic efficacy. Therefore, the starch-GNS composite could be used as an ideal nano-carrier for drug delivery and offered a new avenue for broadening the application of graphene in biomedicine. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Ferromagnetism of Na0.5Bi0.5TiO3 (1 0 0) surface with O2 adsorption

    Science.gov (United States)

    Ju, Lin; Xu, Tongshuai; Zhang, Yongjia; Shi, Changmin; Sun, Li

    2017-08-01

    Na0.5Bi0.5TiO3 (NBT) nanocrystalline powders prepared by sol-gel method with annealing at 900 °C in air 1 h present room-temperature ferromagnetism (FM). The subsequent annealing in vacuum at 900 °C for 30 min weakens the room-temperature FM, while subsequent treatments in oxygen atmosphere at room-temperature enhances the room-temperature FM, indicating that the room-temperature FM may be induced by the adsorbed oxygen on the NBT nanoparticle surface. The adsorption of O2 molecule on the NBT (1 0 0) surface is studied by using density functional theory within local density approximation plus on-site effect method. The physisorption of configuration R5 is the most stable, whereas the chemisorption of O2 is unfavorable at all adsorption sites. The physisorbed O2 molecule on the NBT (1 0 0) surface with a magnetic moment (MM) closes to that for an isolated O2 molecule. The magnetism of configuration R5 is mainly from the O p orbitals. The stable ferromagnetic coupling mechanism is the direct exchange interaction between the nearest-neighbor O2 molecules adsorbed on the surface. The adsorption of O2 molecule on ferroelectric materials may be a promising approach to achieve multiferroic materials.

  7. 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.

  8. A New and Simple Approach to Determine the Abundance of Hydrogen Molecules on Interstellar Ice Mantles

    CERN Document Server

    Hincelin, Ugo; Herbst, Eric

    2014-01-01

    Water is usually the main component of ice mantles, which cover the cores of dust grains in cold portions of dense interstellar clouds. When molecular hydrogen is adsorbed onto an icy mantle through physisorption, a common assumption in gas-grain rate equation models is to use an adsorption energy for molecular hydrogen on a pure water substrate. However, at high density and low temperature, when H2 is efficiently adsorbed onto the mantle, its surface abundance can be strongly overestimated if this assumption is still used. Unfortunately, the more detailed microscopic Monte Carlo treatment cannot be used to study the abundance of H2 in ice mantles if a full gas-grain network is utilized. We present a numerical method adapted for rate-equation models that takes into account the possibility that an H2 molecule can, while diffusing on the surface, find itself bound to another hydrogen molecule, with a far weaker bond than the H2-water bond, which can lead to more efficient desorption. We label the ensuing desorp...

  9. Corrosion Inhibition of Aluminum in 0.5 M HCl by Garlic aqueous extract

    Directory of Open Access Journals (Sweden)

    Saedah R. Al-Mhyawi

    2014-06-01

    Full Text Available The inhibition efficiency of extract of Garlic on aluminium in hydrochloric acid solutions has been evaluated by weight loss techniques. Values of inhibition efficiency obtained are dependent upon the concentration of inhibitor and temperature. Generally, inhibition was found to increase with inhibitor concentration, half-life, activation energy but decrease with temperature and first-order rate constant at the temperatures studied. Physical adsorption mechanism has been proposed for the inhibition and Langmuir , Temkin adsorption isotherm was obeyed. Garlic is an inhibitor of aluminium corrosion in 0.5 M hydrochloric acid solution.The values of standard free energy of adsorption suggest that the adsorption of inhibitor on aluminium surface occurred by physisorption mechanism. the negative sign of the Free Energy of adsorption indicates that the adsorption of the inhibitors on the aluminum surface was a spontaneous process.the negative values of enthalpy of adsorption (ΔH suggest that the chemical reaction involved in the adsorption of the inhibitors on the metal surface is an exothermic process, hence increase in the reaction temperature of the medium will decrease the inhibition efficiency.

  10. Effect of Activated Carbon as a Support on Metal Dispersion and Activity of Ruthenium Catalyst for Ammonia Synthesis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Ten kinds of activated carbon from different raw materials were used as supports to prepare ruthenium catalysts. N2 physisorption and CO chemisorption were carried out to investigate the pore size distribution and the ruthenium dispersion of the catalysts. It was found that the Ru dispersion of the catalyst was closely related to not only the texture of carbon support but also the purity of activated carbon. The activities of a series of the carbon-supported barium-promoted Ru catalysts for ammonia synthesis were measured at 425 ℃, 10.0 MPa and 10 000 h-1. The result shows that the same raw material activated carbon, with a high purity, high surface area, large pore volume and reasonable pore size distribution might disperse ruthenium and promoter sufficiently, which activated carbon as support, could be used to manufacture ruthenium catalyst with a high activity for ammonia synthesis. The different raw material activated carbon as the support would greatly influence the catalytic properties of the ruthenium catalyst for ammonia synthesis. For example, with coconut shell carbon(AC1) as the support, the ammonia concentration in the effluent was 13.17% over 4%Ru-BaO/AC1 catalyst, while with the desulfurized coal carbon(AC10) as the support, that in the effluent was only 1.37% over 4%Ru-BaO/AC10 catalyst.

  11. Highly Efficient Adsorption of Copp er 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 pH 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.

  12. 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.

  13. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    CERN Document Server

    Al-Hamdani, Yasmine S; von Lilienfeld, O Anatole; Michaelides, Angelos

    2016-01-01

    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. ...

  14. The hybrid nanobiointerface between nitrogen-doped graphene oxide and lipid membranes: a theoretical and experimental study

    Directory of Open Access Journals (Sweden)

    P. Di Pietro

    2016-12-01

    Full Text Available In this study, we present a comparison between graphene oxide (GO and nitrogen-doped GO (N-GO in terms of spectroscopic properties and biomolecule-binding potentiality features. Specifically, GO nanosheets, both in aqueous dispersion and in solid state, were successfully modified with different amino-containing moieties, in order to obtain graphene-based nanostructures able to respond to chemical stimuli (e.g., pH and with tunable surface properties. The physisorption of dye-labelled lipid vesicles loaded with curcumin, was scrutinised both theoretically and experimentally. The energetics of the hybrid lipid membrane-curcumin-GO interface at different pH values, representative respectively of physiological (7.4 and pathological (5.5 environment, were estimated by molecular dynamics (MD simulations. The GO and GO-N samples characterization by Raman, fluorescence, and UV-vis spectroscopies, as well as confocal microscopy demonstrated promising features of the (N-GO/lipid platforms for fluorescence imaging and drug delivery applications.

  15. Facile hydrothermal preparation of recyclable S-doped graphene sponge for Cu2+ adsorption.

    Science.gov (United States)

    Zhao, Lianqin; Yu, Baowei; Xue, Fumin; Xie, Jingru; Zhang, Xiaoliang; Wu, Ruihan; Wang, Ruijue; Hu, Zhiyan; Yang, Sheng-Tao; Luo, Jianbin

    2015-04-09

    Graphene sponge (GS) has been widely employed for water purification, but adsorption capacity loss frequently occurs during the formation of spongy structure. In this study, we reported the hydrothermal preparation of S-doped GS for the removal of Cu(2+) with a huge adsorption capacity of 228 mg/g, 40 times higher than that of active carbon. The adsorption isotherm could be well fitted into the Freundlich model with a KF value of 36.309(L/mg)(1/n). The equilibrium adsorption could be fully achieved in the first 5 min. In the thermodynamics study, the negative ΔG indicated that the adsorption was spontaneous and physisorption in nature. The positive ΔH implied that the adsorption was endothermic. The changes of both pH and ionic strength had no apparent influence on the adsorption. S-doped GS could be easily regenerated by washing with acidic thiourea. Moreover, S-doped GS could be used for the adsorption of other heavy metal ions, too. The implication to the applications of S-doped GS in water treatment is discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. 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.

  17. Improvement of Energy Capacity with Vitamin C Treated Dual-Layered Graphene-Sulfur Cathodes in Lithium-Sulfur Batteries.

    Science.gov (United States)

    Kim, Jin Won; Ocon, Joey D; Kim, Ho-Sung; Lee, Jaeyoung

    2015-09-07

    A graphene-based cathode design for lithium-sulfur batteries (LSB) that shows excellent electrochemical performance is proposed. The dual-layered cathode is composed of a sulfur active layer and a polysulfide absorption layer, and both layers are based on vitamin C treated graphene oxide at various degrees of reduction. By controlling the degree of reduction of graphene, the dual-layered cathode can increase sulfur utilization dramatically owing to the uniform formation of nanosized sulfur particles, the chemical bonding of dissolved polysulfides on the oxygen-rich sulfur active layer, and the physisorption of free polysulfides on the absorption layer. This approach enables a LSB with a high specific capacity of over 600 mAh gsulfur (-1) after 100 cycles even under a high current rate of 1C (1675 mA gsulfur (-1) ). An intriguing aspect of our work is the synthesis of a high-performance dual-layered cathode by a green chemistry method, which could be a promising approach to LSBs with high energy and power densities.

  18. Alkaloids extract of Retama monosperma (L.) Boiss. seeds used as novel eco-friendly inhibitor for carbon steel corrosion in 1 M HCl solution: Electrochemical and surface studies

    Science.gov (United States)

    El Hamdani, Naoual; Fdil, Rabiaa; Tourabi, Mustapha; Jama, Charafeddine; Bentiss, Fouad

    2015-12-01

    Current research efforts now focus on the development of non-toxic, inexpensive and environmentally friendly corrosion inhibitors as alternatives to different organic and non-organic compounds. In this field, alkaloids extract of Retama monosperma (L.) Boiss. seeds (AERS) was tested for the first time as corrosion inhibitor for carbon steel in 1 M HCl medium using electrochemical and surface characterization techniques. The obtained results showed that this plant extract's acts as an efficient corrosion inhibitor for carbon steel in 1 M HCl and an inhibition efficiency of 94.4% was reached with 400 mg/L of AERS at 30 °C. Ac impedance experimental data revealed a frequency distribution of the capacitance, simulated as constant phase element. Impedance results demonstrated that the addition of the AERS in the corrosive solution decreases the charge capacitance and simultaneously increases the function of the charge/discharge of the interface, facilitating the formation of an adsorbed layer over the steel surface. Polarization curves indicated that AERS is a mixed inhibitor. Adsorption of such alkaloid extract on the steel surface obeyed to the Langmuir adsorption isotherm. X-ray photoelectron spectroscopy (XPS) showed that the inhibition of steel corrosion in normal hydrochloric solution by AERS is mainly controlled by a physisorption process and the inhibitive layer is composed of an iron oxide/hydroxide mixture where AERS molecules are incorporated.

  19. Removal of nickel on Bofe bentonite calcined clay in porous bed.

    Science.gov (United States)

    Vieira, M G A; Almeida Neto, A F; Gimenes, M L; da Silva, M G C

    2010-04-15

    Bentonite clays have been showing good adsorbing characteristics and are used as an alternative material in the removal of heavy metals. The purpose of this study is to evaluate the removal of nickel on Bofe bentonite calcined clay in porous bed. Firstly, a study was conducted to define the operation outflow, based on the minimum mass transfer zone (MTZ) obtained, useful (q(U)) and total adsorbed (q(T)) removal amounts and total nickel removal percentage (Rem (%)). Assays of nickel adsorption on clay were conducted according to a 2(2) factorial design with three central points to evaluate the effect of the particle diameter and initial adsorbate concentration on variables q(U), q(T) and Rem (%). Tests to obtain the adsorbent physical and chemical characteristics were performed on samples of Bofe clay in natura, calcined, and calcined submitted to nickel adsorption. This clay was characterized according to the following techniques: Energy Dispersive Spectroscopy (EDS), Thermogravimetry (TG), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), Fourier Transformed Infrared Spectroscopy (FTIR), Physisorption of N(2) (BET), Helium Picnometry and Scanning Electron Microscope (SEM) with metal mapping. 2009 Elsevier B.V. All rights reserved.

  20. Kinetic and thermodynamics of the removal of Zn2+ and Cu2+ from aqueous solution by sulphate and phosphate-modified Bentonite clay.

    Science.gov (United States)

    Olu-Owolabi, Bamidele I; Unuabonah, Emmanuel I

    2010-12-15

    The modification of pristine Bentonite clay with sulphate and phosphate anions was found to increase its cation-exchange capacity (CEC), adsorption capacity and overall pseudo-second order kinetic rate constant for the adsorption of Cu(2+) and Zn(2+). Modification with sulphate and phosphate anion decreased the specific surface area of pristine Bentonite clay. Phosphate-modified Bentonite clay was found to give the highest adsorption capacity for both metal ions. The adsorption process was observed to be endothermic and spontaneous in nature for both metal ions with Zn(2+) being more adsorbed. Modification with phosphate anion increased the spontaneity of the adsorption process. The effective modification of pristine Bentonite clay with sulphate anion was confirmed from hypochromic shifts in the range of 13-18 cm(-1) which is typical of physisorption while modification with phosphate anion was confirmed by its hyperchromic shifts typical of chemisorption in the infrared red region using Fourier transformed infrared spectroscopy (FTIR). Using the model efficiency indicator, kinetic data were found to show very strong fit to the pseudo-second order kinetic model implying that the adsorption of Cu(2+) and Zn(2+) were basically by chemisorption. Copyright © 2010 Elsevier B.V. All rights reserved.

  1. 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.

  2. Stereospecific growth of densely populated rutile mesoporous TiO{sub 2} nanoplate films: a facile low temperature chemical synthesis approach

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Go-Woon; Cho, Young-Jin; Mane, Rajaram S; Shashikala, V; Yadav, Jyotiprakash; Gaikwad, Rajendra S; Jung, Kwang-Deog; Joo, Oh-Shim [Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 130-650 (Korea, Republic of); Ambade, Swapnil B; Lee, Soo-Hyoung [School of Semiconductor and Chemical Engineering, Nanomaterials Processing Research Center, Chonbuk National University, Jeonju (Korea, Republic of); Han, Sung-Hwan, E-mail: shlee66@jbnu.ac.kr, E-mail: joocat@kist.re.kr [Inorganic Nanomaterials Laboratory, Chemistry Department, Hanyang University, Seoul (Korea, Republic of)

    2010-03-12

    We report for the first time, using a simple and environmentally benign chemical method, the low temperature synthesis of densely populated upright-standing rutile TiO{sub 2} nanoplate films onto a glass substrate from a mixture of titanium trichloride, hydrogen peroxide and thiourea in triply distilled water. The rutile TiO{sub 2} nanoplate films (the phase is confirmed from x-ray diffraction analysis, selected area electron diffraction, energy-dispersive x-ray analysis, and Raman shift) are 20-35 nm wide and 100-120 nm long. The chemical reaction kinetics for the growth of these upright-standing TiO{sub 2} nanoplate films is also interpreted. Films of TiO{sub 2} nanoplates are optically transparent in the visible region with a sharp absorption edge close to 350 nm, confirming an indirect band gap energy of 3.12 eV. The Brunauer-Emmet-Teller surface area, Barret-Joyner-Halenda pore volume and pore diameter, obtained from N{sub 2} physisorption studies, are 82 m{sup 2} g{sup -1}, 0.0964 cm{sup 3} g{sup -1} and 3.5 nm, respectively, confirming the mesoporosity of scratched rutile TiO{sub 2} nanoplate powder that would be ideal for the direct fabrication of nanoscaled devices including upcoming dye-sensitized solar cells and gas sensors.

  3. 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.

    Science.gov (United States)

    Sánchez-De la Torre, Fernando; De la Rosa, Javier Rivera; Kharisov, Boris I; Lucio-Ortiz, Carlos J

    2013-09-30

    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.

  4. Binary Oxides with Defined Hierarchy of Pores in the Esterification of Glycerol

    Directory of Open Access Journals (Sweden)

    Nuryana Ferreira Alves

    2016-09-01

    Full Text Available Various porous binary oxides with elevated textural properties were obtained in this work. The as-synthesized solids were calcined or modified by reflux and extraction processes. Characterizations through SEM, nitrogen physisorption and TEM techniques demonstrated the formation of porous metal oxide networks over all solids. XRD, thermal analyses and FTIR measurements showed the existence of nanosized rutile TiO2, tetragonal ZrO2, SiO2 and γ-Al2O3 phases on the solids. The structure and texture of the as-synthesized SiAl sol-gel derived solid resulted in the formation of well-dispersed nanoparticles on the support. The removal of the organic compounds by ethanol extraction or reflux from SiAl resulted in the presence of structures with defined hierarchy of pores. Among the solids studied, the catalytic results in the esterification of glycerol with acetic acid indicated that best performances were obtained over SiAl sample when submitted to extraction and reflux treatments. This was due to the creation of accessible pores, which facilitated the reaction occurrence at glycerol to acetic acid molar ratio = 1:3 and T = 80 °C for 20 h using 75 mg of catalyst. The solids can be reused three times without complete loss of their catalytic performance.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vilchis-Granados, J. [Instituto Nacional de Investigaciones Nucleares, Departamento de Química, A.P. 18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, DF (Mexico); Universidad Autónoma del Estado de México, Facultad de Química, Av. Paseo Colón esquina con Paseo Tollocan s/n Toluca, México (Mexico); Granados-Correa, F., E-mail: francisco.granados@inin.gob.mx [Instituto Nacional de Investigaciones Nucleares, Departamento de Química, A.P. 18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, DF (Mexico); Barrera-Díaz, C.E. [Universidad Autónoma del Estado de México, Facultad de Química, Av. Paseo Colón esquina con Paseo Tollocan s/n Toluca, México (Mexico)

    2013-08-15

    This work examines the surface fractal dimensions (D{sub 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{sub 2}-physisorption measurements. Surface fractal dimensions were determined using single N{sub 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{sub 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.

  6. 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)

  7. Influence of temperature inhomogeneity on product profile of reactions occurring within zeolites

    Indian Academy of Sciences (India)

    A V Anil Kumar; S Yashonath; G Ananthakrishna

    2003-10-01

    In zeolites, diffusion is often accompanied by a reaction or sorption which in turn can induce temperature inhomogeneities. Monte Carlo simulations of Lennard-Jones atoms in zeolite NaCaA are reported for the presence of a hot zone presumed to be created by a reaction or chemi- or physi-sorption site. These simulations show that the presence of localized hot regions can alter both kinetic and transport properties such as diffusion. Further, we show that enhancement of diffusion constant is greater for systems with larger barrier height, a surprising result that may be of considerable significance in many chemical and biological processes. We find an unanticipated coupling between reaction and diffusion due to the presence of a hot zone in addition to that which normally exists via concentration. Implications of this coupling for the product profile of a reaction are discussed. We also propose a mechanism by which mobility of ions or diffusion of molecular species within biomembranes may take place.

  8. Molecular origin of drug release by water boiling inside carbon nanotubes from reactive molecular dynamics simulation and DFT perspectives.

    Science.gov (United States)

    Ganji, M Darvish; Mirzaei, Sh; Dalirandeh, Z

    2017-07-05

    Owing to their nanosized hollow cylindrical structure, CNTs hold the promise to be utilized as desired materials for encapsulating molecules which demonstrate wide inferences in drug delivery. Here we evaluate the possibility of drug release from the CNTs with various types and edge chemistry by reactive MD simulation to explain the scientifically reliable relations for proposed process. It was shown that heating of CNTs (up to 750 K) cannot be used for release of incorporated drug (phenylalanine) into water and even carbonated water solvent with very low boiling temperature. This is due to the strong physisorption (π-stacking interaction) between the aromatic of encapsulated drug and CNT sidewall which causes the drug to bind the nanotube sidewall. We have further investigated the interaction nature and release mechanism of water and drug confined/released within/from the CNTs by DFT calculations and the results confirmed our MD simulation findings. The accuracy of DFT method was also validated against the experimental and theoretical values at MP2/CCSD level. Therefore, we find that boiling of water/carbonated water confined within the CNTs could not be a suitable technique for efficient drug release. Our atomistic simulations provide a well-grounded understanding for the release of drug molecules confined within CNTs.

  9. 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.

  10. A study on the adsorption of methylene blue onto gum ghatti/TiO2 nanoparticles-based hydrogel nanocomposite.

    Science.gov (United States)

    Mittal, Hemant; Ray, Suprakas Sinha

    2016-07-01

    The objective of this work was to study the isotherm and kinetic models for the adsorption of methylene blue (MB) onto a TiO2 nanoparticle (TiO2NP)-containing hydrogel nanocomposite (HNC) of polyacrylamide-grafted gum ghatti (PAAm-g-Gg). The grafting of PAAm onto Gg was conducted using N,N'-methylene-bis-acrylamide (MBA) as a crosslinker, and different weight percentages of TiO2NPs were incorporated into the hydrogel matrix during the grafting reaction. The graft co-polymerization and the formation of the HNC were confirmed using FTIR, XRD, BET, SEM, TEM and EDS analyses. The adsorption of MB was studied in batch mode and it was found to be highly dependent on solution pH, ionic strength temperature and adsorbent loading. The MB-adsorption process followed the pseudo-second-order rate model and Langmuir adsorption isotherm with a maximum adsorption capacity of 1305.5mgg(-1). Thermodynamic studies revealed that the adsorption of MB onto the HNC surface was spontaneous, endothermic and through a process of physisorption. The results also showed that the HNC was much more effective for the adsorption of cationic dyes than anionic dyes, and it retained its original adsorption capacity for five successive cycles of adsorption-desorption. In conclusion, the hydrogel nanocomposite showed huge potential for remediating industrial wastewater polluted by toxic cationic dyes.

  11. Thermodynamics of adsorption of light alkanes and alkenes in single-walled carbon nanotube bundles

    CERN Document Server

    Cruz, Fernando J A L

    2016-01-01

    The thermodynamics of adsorption of light alkanes and alkenes (CH4, C2H6, C2H4, C3H8, and C3H6) in single-walled carbon nanotube bundles is studied by configurational-bias grand canonical Monte Carlo simulation. The bundles consist of uniform nanotubes with diameters in the range 11.0 < D (A) < 18.1, arranged in the usual close-packed hexagonal lattice. The phase space is systematically analyzed with calculations for adsorption at room temperature and reduced pressure range of 8.7 x 10-9 < (p/p0) < 0.9. The simulation results are interpreted in terms of the molecular nature of the adsorbate and the corresponding solid-fluid interactions. It is shown that confinement in the internal volume of the bundle (interstitial and intratubular) is energetically more favorable than physisorption on the external surface (grooves and exposed surfaces of peripheral tubes), as indicated by the curves of isosteric heat as a function of reduced pressure. However, the zero-loading properties suggest a crossover poin...

  12. Benzene on Cu(111): II. Molecular assembly due to Lateral van der Waals and Surface-State-Mediated Indirect Interactions

    Science.gov (United States)

    Hyldgaard, Per; Berland, Kristian; Einstein, T. L.

    2010-03-01

    Experiments show that benzene condenses into two different structural phases: a compact and a sparse phase, both of approximately hexagonal symmetry. The vdW-DF calculations demonstrate that the denser benzene-overlayer phase, with lattice constant 6.74 ,s due to direct benzene-benzene vdW attraction. The structure of the second, sparser phase, with lattice spacing 10.24 ,s attributed to the indirect electronic interactions mediated by the well-known metallic surface state on Cu(111). To support this claim, we use a formal Harris-functional approach to evaluate nonperturbatively the asymptotic form of this indirect interaction. Our extended vdW-DF scheme---which combines calculations of molecular physisorption, of direct intermolecular vdW coupling, and of indirect electronic interactions between the molecular adsorbates---accounts well for the structural phases of benzene on Cu(111). Our preliminary vdW-DF study of acene and quinone interactions provides building blocks for modeling of anthraquinone assembly on Cu(111).footnotetextG. Pawin, , L. Bartels, Science 313 (2006) 961

  13. 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.

  14. 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.)

  15. 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.

  16. Role of vacancies in tuning the electronic properties of Au-MoS2 contact

    Directory of Open Access Journals (Sweden)

    Jie Su

    2015-07-01

    Full Text Available Understanding the electronic properties between molybdenum disulfide (MoS2 and metal electrodes is vital for the designing and realization of nanoelectronic devices. In this work, influence of intrinsic vacancies in monolayer MoS2 on the electronic structure and electron properties of Au-MoS2 contacts is investigated using first-principles calculations. Upon formation of vacancies in monolayer MoS2, both tunnel barriers and Schottky Barriers between metal Au and monolayer MoS2 are decreased. Perfect Au-MoS2 top contact exhibits physisorption interface with rectifying character, whereas Au-MoS2 contact with Mo-vacancy shows chemisorption interface with Ohmic character. Partial density of states and electron density of defective Au-MoS2 top contacts are much higher than those of perfect one, indicating the lower contact resistance and higher electron injection efficiency of defective Au-MoS2 top contacts. Notably, Mo-vacancy in monolayer MoS2 is beneficial to get high quality p-type Au-MoS2 top contact, whereas S-vacancy in monolayer MoS2 is favorable to achieve high quality n-type Au-MoS2 top contact. Our results provide guidelines for designing and fabrication of novel 2D nanoelectronic devices.

  17. Efficient Removal of Cobalt from Aqueous Solution by Zinc Oxide Nanoparticles: Kinetic and Thermodynamic Studies

    Science.gov (United States)

    Khezami, L.; Taha, Kamal K.; Modwi, A.

    2017-05-01

    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.

  18. 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.

  19. Insight into highly efficient co-removal of p-nitrophenol and lead by nitrogen-functionalized magnetic ordered mesoporous carbon: Performance and modelling.

    Science.gov (United States)

    Zhou, Yaoyu; Liu, Xiaocheng; Tang, Lin; Zhang, Fengfeng; Zeng, Guangming; Peng, Xiangqi; Luo, Lin; Deng, Yaochen; Pang, Ya; Zhang, Jiachao

    2017-07-05

    Highly efficient simultaneous removal of Pb(II) and p-nitrophenol (PNP) contamination from water was accomplished by nitrogen-functionalized magnetic ordered mesoporous carbon (N-Fe/OMC). The mutual effects and inner mechanisms of their adsorption onto N-Fe/OMC were systematically investigated by sole and binary systems, and thermodynamic, sorption isotherm and adsorption kinetics models. The liquid-film diffusion step might be the rate-limiting step for PNP and Pb(II). The fitting of experimental data with Temkin model indicates that the adsorption process of PNP and Pb(II) involve physisorption and chemisorption. There exist site competition and enhancement of PNP and Pb(II) on the sorption to N-Fe/OMC. Moreover, N-Fe/OMC could be regenerated effectively and recycled by using dilute NaOH and acetone. These demonstrated superior properties of N-Fe/OMC indicate that it could be applied to treatment of wastewaters containing both lead and PNP. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Structural Effect on Electrochemical Performance of Ordered Porous Carbon Electrodes for Na-Ion Batteries.

    Science.gov (United States)

    Jo, Changshin; Park, Yuwon; Jeong, Jooyoung; Lee, Kyu Tae; Lee, Jinwoo

    2015-06-10

    Ordered meso- or macro-porous carbons (OMCs) were applied as anodes in Na ion battery (NIB) systems. Three different block copolymers (BCPs) enabled us to control the pore sizes (6, 33, and 60 nm) while maintaining the same 2-D hexagonal structure. To exclude other effects, the factors including precursors, particle sizes, and degrees of graphitization were controlled. The structures of OMCs were characterized by nitrogen physisorption, Raman spectroscopy, X-ray analyses (XRD and SAXS), and microscopies (TEM and SEM). With a galvanostatic charge/discharge, we confirmed that OMC electrode with medium pore size (OMC-33) exhibited a higher reversible capacity of 134 mA h g(-1) (at 20th cycle) and faster rate capability (61% retention, current densities from 50 to 5000 mA g(-1)) than those of OMC-6, and OMC-60 electrodes. The high performance of OMC-33 is attributed to the combined effects of pore size and wall thickness which was supported by charge/discharge and electrochemical impedance spectroscopy (EIS) analyses.

  1. Removal of Cd (II) from synthetic wastewater by alginate-Ayous wood sawdust (Triplochiton scleroxylon) composite material.

    Science.gov (United States)

    Njimou, Jacques Romain; Măicăneanu, Andrada; Indolean, Cerasella; Nanseu-Njiki, Charles Péguy; Ngameni, Emmanuel

    2016-01-01

    The biosorption characteristics of Cd (II) ions from synthetic wastewater using raw Ayous wood sawdust (Triplochiton scleroxylon), r-AS, immobilized by sodium alginate were investigated with respect to pH, biomass quantity, contact time, initial concentration of heavy metal, temperature and stirring rate. The experimental data fitted well with the Langmuir isotherm, suggesting that monolayer adsorption of the cadmium ions onto alginate-Ayous sawdust composite (a-ASC). The obtained monolayer adsorption capacity of a-ASC for Cd (II) was 6.21 mg/g. From the Dubinin-Radushkevich isotherm model, a 5.39 kJ/mol value for the mean free energy was calculated, indicating that Cd (II) biosorption could include an important physisorption stage. Thermodynamic calculations showed that the Cd (II) biosorption process was feasible, endothermic and spontaneous in nature under examined conditions. The results indicated that a-ASC could be an alternative material replacing more costly adsorbents used for the removal of heavy metals.

  2. Applications of Quantum Chemistry to the Study of Carbon Nanotubes

    Science.gov (United States)

    Jaffe, Richard L.

    2005-01-01

    For several years, scientists at NASA Ames have been studying the properties of carbon nanotubes using various experimental and computational methods. In this talk, I will compare different strategies for using quantum chemistry calculations to describe the electronic structure, deformation and chemical functionalization of single wall carbon nanotubes (SWNT) and the physisorption of small molecules on nanotube surfaces. The SWNT can be treated as an infinite (periodic) or finite length carbon cylinder or as a polycyclic aromatic hydrocarbon (PAH) molecule with an imposed curvature maintained by external constraints (as if it were cut out of the SWNT surface). Calculations are carried out using DFT and MP2 methods and a variety of atomic orbital basis sets from minimal (STO-3G) to valence triple zeta. The optimal approach is based on the particular SWNT property of interest. Examples to be discussed include: nanotube fluorination and other functionalization reactions; coating of nanotubes by water vapor and low-molecular weight organic molecules; and the nature of the interface between SWNT and liquids such as water and amines. In many cases, the quantum chemistry calculations are used to parameterize or validate force fields for molecular dynamics simulations. The results of these calculations have helped explain experimental data and contributed to the design of novel materials and sensors based on carbon nanotubes. Some of this research is described in the following papers:

  3. Removal of hazardous azopyrazole dye from an aqueous solution using rice straw as a waste adsorbent: Kinetic, equilibrium and thermodynamic studies.

    Science.gov (United States)

    El-Bindary, Ashraf A; El-Sonbati, Adel Z; Al-Sarawy, Ahmad A; Mohamed, Khaled S; Farid, Mansour A

    2015-02-05

    In this research, activated carbonmade from rice straw (ACRS) was synthesized simply by a low cost and nontoxic procedure and used for the adsorption of hazardous azopyrazole dye. The effect of different variables in the batch method as a function of solution pH, contact time, concentration of adsorbate, adsorbent dosage and temperature were investigated and optimal experimental conditions were ascertaine. Surface modification of ACRS using scanning electron microscopy (SEM) was obtained. More than 75% removal efficiency was obtained within 75min at adsorbent dose of 0.5g for initial dye concentration of 30-100mgL(-1) at pH 3. The experimental equilibrium data were tested by the isotherm models namely, Langmuir and Freundlich adsorption and the isotherm constants were determined. The kinetic data obtained with different initial concentration and temperature were analyzed using a pseudo-first-order and pseudo-second-order equations. The activation energy of adsorption was also evaluated and found to be +13.25kJmol(-1) indicating that the adsorption is physisorption. The thermodynamics of the adsorption indicated spontaneous and exothermic nature of the process. The results indicate that ACRS could be employed as low-cost material for the removal of acid dyes from aqueous solution.

  4. Shape-Controllable Synthesis of Peroxidase-Like Fe3O4 Nanoparticles for Catalytic Removal of Organic Pollutants

    Science.gov (United States)

    Wan, Dong; Li, Wenbing; Wang, Guanghua; Wei, Xiaobi

    2016-10-01

    The shape of Fe3O4 nanoparticles is controlled using a simple oxidation-precipitation method without any surfactant. The morphology and structure of the obtained Fe3O4 nanoparticles were characterized by using x-ray diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, N2 physisorption and vibrating sample magnetometer. As-prepared Fe3O4 samples showed octahedron, cube, hexagonal plate and sphere morphologies. Peroxidase-like activity of the four nanostructures was evaluated for catalytic removal of organic pollutants in the presence of H2O2, using rhodamine B as a model compound. The results showed that the H2O2-activating ability of the Fe3O4 nanocrystals was structure dependent and followed the order sphere > cube > octahedron > hexagonal plate, which was closely related to their surface FeII/FeIII ratios or crystal planes. The reusability of Fe3O4 spheres was also investigated after five successive runs, which demonstrated the promising application of the catalyst in the degradation of organic pollutants. This investigation is of great significance for the heterogeneous catalysts with enhanced activity and practical application.

  5. Titania-alumina aerogel materials for degradation of rhodamine B dye: Impact of particle size of titania

    Science.gov (United States)

    Shrestha, Sunav

    Disposal of pollutants, mainly organic dyes from textile industries are the primary sources of water pollution in developing countries, and often leading to scarcity of clean water. These dyes can undergo further oxidation and form several toxic compounds, which possess threat to the water ecosystem. It is therefore necessary to remove these organics from effluents for a clean environment. Among the various methods, Advanced Oxidation Processes (AOPs) called heterogeneous photocatalysis is considered as an effective method for the removal of organics from water sources. In this regard, a set of titania-alumina (TiO2-Al2O3) mixed oxide materials were prepared by supercritical drying method and investigated towards the degradation of a model pollutant, rhodamine B (RhB). The physico-chemical properties of the synthesized materials were studied in detail using several techniques that include powder X-ray diffraction, nitrogen physisorption, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy (XPS). The Electrospray ionization-Mass spectroscopic (ESI-MS) studies were also carried out to confirm the degradation of the RhB by identifying its intermediate products. The results indicate that the particle size of the photoactive species, titania, was the key factor for effective photocatalytic degradation of the RhB dye over the titania-alumina mixed oxide materials.

  6. 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.

  7. Performance of Terminalia catappa on mild steel corrosion in HCl medium

    Science.gov (United States)

    Omotosho, Olugbenga Adeshola; Okeniyi, Joshua Olusegun; Loto, Cleophas Akintoye; Popoola, Abimbola Patricia Idowu; Obi, Chukwunonso Ezekiel; Sonoiki, Oluwatobi Oluwasegun Oluwagbenga; Oni, Adeoluwa Barnabas; Alabi, Ayomide Samuel; Olarewaju, Abisola Ebunoluwa

    2016-07-01

    This work investigates Terminalia catappa leaf-extract performance on mild steel corrosion in 0.5 M hydrochloric acid (HCl). Electrochemical linear-sweep-voltametry (LSV) and gravimetric techniques were employed for assessing the mild steel corrosion in the HCl test-environment of immersion having different concentrations of the leaf-extract. Results showed that all the concentrations of the Terminalia catappa leaf-extract employed inhibited mild steel corrosion from the electrochemical (potentiodynamic) and the gravimetric considerations. Also, corrosion rate from LSV exhibited excellent correlation (R = 95.77%, Nash-Sutcliffe Efficiency (NSE) = 91.72% and p-value = 0.02383) with linear function of the corrosion rate from gravimetric method, for the leaf-extract concentrations employed. From the experimental model, 6 g/L Terminalia catappa exhibited optimal inhibition efficiency, η = 78.07%, while 8 g/L Terminalia catappa was predicted as optimally effective, η = 75.41%, by the correlation fitting model, at inhibiting mild steel corrosion in the medium. However, adsorption isotherm modelling showed that the experimental gravimetric, experimental potentiodynamic and predicted potentiodynamic data exhibited agreements in following the Langmuir adsorption isotherm. All the three data models indicated favourable adsorption and identified physisorption as the prevalent adsorption mechanism of Terminalia catappa leaf-extract on mild steel immersed in the 0.5 M HCl medium.

  8. The adsorption and inhibition effect of calcium lignosulfonate on Q235 carbon steel in simulated concrete pore solution

    Science.gov (United States)

    Wang, Yishan; Zuo, Yu; Zhao, Xuhui; Zha, Shanshan

    2016-08-01

    The corrosion inhibition of calcium lignosulfonate (CLS) for Q235 carbon steel in saturated Ca(OH)2 + 0.1 mol/L NaCl solution was studied by means of weight loss, polarization, fluorescence microscopy (FM), scanning electron microscopy/energy dispersive spectrometry (SEM/EDS), microscopic infrared spectral imaging (M-IR) and X-ray photoelectron spectroscopy (XPS). For the steel in simulated concrete pore solution (pH 12.6), an increase of Eb value and a decrease of icorr value occurred with different concentrations of CLS. The optimal content of CLS was 0.001 mol/L at which the inhibition rate was 98.86% and the Eb value increased to 719 mV after 10 h of immersion. In mortar solution and in reinforced concrete environment, CLS also showed good inhibition for steel. The preferential adsorption of CLS around pits was detected by M-IR. The result illustrates that at the early stage the adsorption of CLS was heterogeneous and CLS may have a competitive adsorption with chloride ions at the active sites, which would be beneficial for decreasing the susceptibility of pitting corrosion. After the pre-filming time, an intact adsorption CLS film formed on carbon steel surface. The adsorption between CLS and calcium presented as Casbnd Osbnd S bonds. The adsorption of CLS on carbon steel surface occurred probably by both physisorption and chemisorption.

  9. Inhibition of cold rolled steel corrosion by Tween-20 in sulfuric acid: weight loss, electrochemical and AFM approaches.

    Science.gov (United States)

    Mu, Guannan; Li, Xianghong

    2005-09-01

    The inhibiting action of a nonionic surfactant of Tween-20 on the corrosion of cold rolled steel (CRS) in 0.5-7.0 M sulfuric acid (H(2)SO(4)) was studied by weight loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the surface conditions. The results show that inhibition efficiency increases with the inhibitor concentration, while it decreases with the sulfuric acid concentration. The adsorption of inhibitor on the cold rolled steel surface obeys the Langmuir adsorption isotherm equation. Effect of immersion time was studied and discussed. The effect of temperature on the corrosion behavior of cold rolled steel was also studied at four temperatures ranging from 30 to 60 degrees C, the thermodynamic parameters such as adsorption heat, adsorption free energy, and adsorption entropy were calculated. The results revealed that the adsorption was physisorption mechanism. A kinetic study of cold rolled steel in uninhibited and inhibited acid was also discussed. The kinetic parameters such as apparent activation energy, pre-exponential factor, rate constant, and reaction constant were calculated for the reactions of corrosion. The inhibition effect is satisfactorily explained by both thermodynamic and kinetic models. Polarization curves show that Tween-20 is a cathodic-type inhibitor in sulfuric acid. The results obtained from weight loss and potentiodynamic polarization are in good agreement, and the Tween-20 inhibition action could also be evidenced by surface AFM images.

  10. Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film.

    Science.gov (United States)

    Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

    2016-12-28

    Fabrication of thin films made of metal-organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs. Here, we report that chemisorption-induced two-way structural transformation in a nanometer-sized MOF thin film. We prepared a two-dimensional layered-type MOF Fe[Pt(CN)4] thin film using a step-by-step approach. Although the as-synthesized film showed poor crystallinity, the dehydrated form of this thin film had a highly oriented crystalline nature (Film-D) as confirmed by synchrotron X-ray diffraction (XRD). Surprisingly, under water and pyridine vapors, Film-D showed chemisorption-induced dynamic structural transformations to Fe(L)2[Pt(CN)4] thin films [L = H2O (Film-H), pyridine (Film-P)], where water and pyridine coordinated to the open Fe(2+) site. Dynamic structural transformations were also confirmed by in situ XRD, sorption measurement, and infrared reflection absorption spectroscopy. This is the first report of chemisorption-induced dynamic structural response in a MOF thin film, and it provides useful insights, which would lead to future practical applications of MOFs utilizing chemisorption-induced structural responses.

  11. 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.

  12. Studies of biosorption of Pb2+, Cd2+ and Cu2+ from aqueous solutions using Adansonia digitata root powders.

    Science.gov (United States)

    Ekere, N R; Agwogie, A B; Ihedioha, J N

    2016-01-01

    The potentials of Adansonia digitata root powders (ADRP) for adsorption of Pb(2+), Cd(2+) and Cu(2+) from aqueous solutions was investigated. Physico-chemical analysis of the adsorbent (ADRP) shows that hydroxyl, carbonyl and amino groups were predominant on the surface of the adsorbent. Scanning Electron Microscope (SEM) image revealed its high porosity and irregular pores in the adsorbent while the Energy Dispersive X-ray Spectrum showed the major element with 53.0% Nitrogen, 23.8% carbon, 9.1% calcium, 7.5% potassium and 6.6% magnesium present. The found optimal conditions were: initial concentration of the metal ions = 0.5 mg/L, pH = 5, contact time = 90 min, adsorbent dose = 0.4 g and particle size = 32 µm. Freundlich isotherm showed good fit for the adsorption of Pb(2+), Cd(2+) and Cu(2+). Dubinin-Radushkevich isotherm revealed that the adsorption processes were physisorption Cd(II) and Cu(II) but chemisorption with respect to Pb(II) ions. The kinetics and thermodynamic studies showed that Pseudo-second order and chemisorptions provided the best fit to the experimental data of Pb (II) ions only. Batch desorption result show that desorption in the acidic media for the metal ions were more rapid and over 90% of the metal ions were recovered from the biomass.

  13. Bioaccumulation and biosorption of Cd(2+) and Zn(2+) by bacteria isolated from a zinc mine in Thailand.

    Science.gov (United States)

    Limcharoensuk, Tossapol; Sooksawat, Najjapak; Sumarnrote, Anchana; Awutpet, Thiranun; Kruatrachue, Maleeya; Pokethitiyook, Prayad; Auesukaree, Choowong

    2015-12-01

    The three bacteria, Tsukamurella paurometabola A155, Pseudomonas aeruginosa B237, and Cupriavidus taiwanensis E324, were isolated from soils collected from a zinc mine in Tak Province, Thailand. Among these bacteria, P. aeruginosa B237 and C. taiwanensis E324 were tolerant of both cadmium and zinc, while T. paurometabola A155 was highly tolerant of zinc only. Bioaccumulation experiment revealed that Cd(2+) and Zn(2+) were mainly adsorbed on the cell walls of these bacteria rather than accumulated inside the cells. During Cd(2+) and Zn(2+) biosorption, P. aeruginosa B237 and T. paurometabola A155 showed the highest removal efficiencies for Cd(2+) and Zn(2+), respectively. The maximum biosorption capacities of P. aeruginosa B237 and T. paurometabola A155 biomasses for Cd(2+) and Zn(2+) biosorptions were 16.89 and 16.75 mg g(-1), respectively, under optimal conditions. The experimental data of Cd(2+) and Zn(2+) biosorptions fitted well with Langmuir isotherm model, suggesting that Cd(2+) and Zn(2+) adsorptions occurred in a monolayer pattern on a homogeneous surface. Furthermore, the pseudo-second order and pseudo-first order kinetic models best described the biosorption kinetics of Cd(2+) and Zn(2+) adsorptions, respectively, suggesting that the Cd(2+) and Zn(2+) adsorptions took place mainly by chemisorption (Cd(2+)) and physisorption (Zn(2+)). Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Isothermal Kinetics Modelling of the Fischer-Tropsch Synthesis over the Spray-Dried Fe-Cu-K Catalyst

    Institute of Scientific and Technical Information of China (English)

    Xiaohui Guo; Ying Liu; Jie Chang; Liang Bai; Yuanyuan Xu; Hongwei Xiang; Yongwang Li

    2006-01-01

    The isothermal kinetics of the Fischer-Tropsch synthesis (FTS) over Fe-Cu-K spray-dried catalyst was studied in a spinning basket reactor. The experiments were carried out at a constant temperature of 523 K, n(H2)/n(CO) feed ratios of 0.8-2.0, reactor pressures of 1.1-2.5 MPa, and space velocity of 0.556× 10-3 Nm3/kgcat.s. Kinetic model for hydrocarbon formation was derived on the basis of simplified carbide mechanism to reduce the number of parameters. Two individual rate constants for methane and ethene were considered. Furthermore, the model was modified empirically by non-intrinsic effect, such as physisorption and fictitious olefin pressures that were taken into account, and the influences of secondary reaction of α-olefins on product distribution. The simulation results showed that the experimental phenomena of FTS and the deviations from ASF distribution, such as the relatively high yield of methane and low yield of ethene observed experimentally could be depicted basically.

  15. Gold stabilized aqueous sols immobilized on mesoporous CeO2-Al2O3 as catalysts for the preferential oxidation of carbon monoxide.

    Science.gov (United States)

    Storaro, Loretta; Lenarda, Maurizio; Moretti, Elisa; Talon, Aldo; Porta, Francesca; Moltrasio, Bernardo; Canton, Patrizia

    2010-10-15

    Nanostructured Au/Al(2)O(3)-CeO(2) catalysts with a low content of precious metal (0.9% wt.) were prepared immobilizing two different stabilized Au sols on a high surface area Al(2)O(3)-CeO(2) mixed oxide with a uniform pore size distribution, synthesized by a one-pot methodology. The samples were characterized by elemental analysis, N(2) physisorption, XRPD, TEM and (27)Al-MAS NMR techniques. The catalytic activity of the two samples in the preferential oxidation of CO in excess of H(2) (CO-PROX) was comparatively evaluated in the 35-110 degrees C temperature range. The Au-THPS/AlCe20 sample, prepared immobilizing a sol obtained reducing an aqueous solution of gold tetrachloroaurate salt with bis[tetrakis(hydroxymethyl)phosphonium sulfate], resulted very active and selective at low temperatures and its catalytic activity was correlated with the structural characteristics of the metal particles and of the ordered mesoporous support. Copyright 2010 Elsevier Inc. All rights reserved.

  16. High-resolution electron tomography study of an industrial Ni-Mo/gamma-Al2O3 hydrotreating catalyst.

    Science.gov (United States)

    de Jong, Krijn P; van den Oetelaar, Leon C A; Vogt, Eelco T C; Eijsbouts, Sonja; Koster, Abraham J; Friedrich, Heiner; de Jongh, Petra E

    2006-06-01

    The growing demand for high-quality transportation fuels requires their cost-effective production by hydrodesulfurization of crude oils using heterogeneous catalysts. To study the three-dimensional (3D) structure of such a commercial, sulfided Ni-Mo/gamma-Al2O3 catalyst, electron tomography was applied. The MoS2 particles form an interconnected complex structure within the mesopores of the alumina support. Spatial organization, morphology, and orientation of the MoS2 particles in the pores were resolved with sufficient accuracy to display the 6-A-spaced MoS2 crystal planes. The proximity of the MoS2 edge planes and more loosely interacting MoS2 basal planes to the alumina support showed the presence of pores smaller than 3 nm, which was confirmed by physisorption experiments. The actual shape of the MoS2 particles cannot be described by simple models as derived from studies on model catalysts. Electron tomography is a unique tool to study the actual 3D structure of complex industrial catalysts with sub-nanometer resolution.

  17. 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.

  18. Interaction between F2 gas with the pristine and 3C-doped(4, 4 armchair boron phosphide nanotubes: a DFT study

    Directory of Open Access Journals (Sweden)

    M Rezaei-Sameti

    2015-12-01

    Full Text Available In this research, the structure, quantum and NQR (Nuclear quadrupole resonanceparameters of F2 gas adsorption on the pristine and 3C-doped (4,4 armchair models of boron phosphide nanotubes (BPNTs have been investigated in the framework of density functional theory. For this purpose, at the first step, four models for F2 adsorption on the inner and outer surfaces of pristine and 3C-doped BPNTS are considered and then all structures are optimized by using Gaussian 03 program package. The optimized structures are used to calculate the quantum and NQR parameters. The calculated results reveal that the adsorption energy of pristine and 3C-doped models of BPNTs are exothermic and adsorption process is a physisorption process due to the weak Van der Waals interaction. The substitution of three carbons with three B atoms of nanotube decreases significantly the adsorption energies. The F2 adsorption and 3C-doping decrease the band gap, global hardness, and ionization potential of the pristine BPNTs. The calculated NQR parameters of all the models show that CQ and &etaQ values of the first layer are larger than those of the other layers.

  19. 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.

  20. 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.

  1. Effect of aluminum modification on catalytic properties of PtSn-based catalysts supported on SBA-15 for propane dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    Yongzheng Duan; Yuming Zhou; Yiwei Zhang; Xiaoli Sheng; Shijian Zhou; Zewu Zhang

    2012-01-01

    The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15,such as Al-incorporated SBA-15 (AlSBA-15) and alumina-modified SBA-15 (Al2O3/SBA-15),for propane dehydrogenation were investigated.Al2O3/SBA-15 was prepared either by an impregnation method using aluminum nitrate aqueous solution,or by the treatment of SBA-15 with a Al(OC3H7)3 solution in anhydrous toluene.N2-physisorption,FT-IR spectroscopy,solid-state 27Al MAS NMR spectroscopy,hydrogen chemisorption,XRF,NH3 temperature-programmed desorption,X-ray photoelectron spectroscopy and TPO were used to characterize these samples.Among these catalysts,the PtSn-based catalyst supported on Al2O3/SBA-15,which was grafted with Al(OC3H7)3,exhibited the best catalytic performance in terms of activity and stability The possible reason was due to the high Pt metal dispersion and/or the strong interactions among Pt,Sn,and the support.

  2. Cobalt- and iron-based nanoparticles hosted in SBA-15 mesoporous silica and activated carbon from biomass: Effect of modification procedure

    Science.gov (United States)

    Tsoncheva, Tanya; Genova, Izabela; Paneva, Daniela; Dimitrov, Momtchil; Tsyntsarski, Boyko; Velinov, Nicolay; Ivanova, Radostina; Issa, Gloria; Kovacheva, Daniela; Budinova, Temenujka; Mitov, Ivan; Petrov, Narzislav

    2015-10-01

    Ordered mesoporous silica of SBA-15 type and activated carbon, prepared from waste biomass (peach stones), are used as host matrix of nanosized iron and cobalt particles. The effect of preparation procedure on the state of loaded nanoparticles is in the focus of investigation. The obtained materials are characterized by Boehm method, low temperature physisorption of nitrogen, XRD, UV-Vis, FTIR, Mossbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic behaviour of the samples is tested in methanol decomposition. The dispersion, oxidative state and catalytic behaviour of loaded cobalt and iron nanoparticles are successfully tuned both by the nature of porous support and the metal precursor used during the samples preparation. Facile effect of active phase deposition from aqueous solution of nitrate precursors is assumed for activated carbon support. For the silica based materials the catalytic activity could be significantly improved when cobalt acetylacetonate is used during the modification. The complex effect of pore topology and surface functionality of different supports on the active phase formation is discussed.

  3. Bismuth-embedded SBA-15 mesoporous silica for radioactive iodine capture and stable storage

    Science.gov (United States)

    Yang, Jae Hwan; Cho, Yong-Jun; Shin, Jin Myeong; Yim, Man-Sung

    2015-10-01

    Efficient capture and stable storage of the long-lived iodine-129 (129I), released as off-gas from nuclear fuel reprocessing, have been of significant concern in the waste management field. In this study, bismuth-embedded SBA-15 mesoporous silica was firstly applied for iodine capture and storage. SBA-15 was functionalized with thiol (-SH) groups, followed by bismuth adsorption with Bi-S bonding, which was thermally treated to form Bi2S3 within SBA-15. The bismuth-embedded SBA-15s demonstrated high iodine loading capacities (up to 540 mg-I/g-sorbent), which benefitted from high surface area and porosity of SBA-15 as well as the formation of thermodynamically stable BiI3 compound. Iodine physisorption was effectively suppressed due to the large pores present in SBA-15, resulting in chemisorption as a main mechanism for iodine confinement. Furthermore, a chemically durable iodine-bearing material was made with a facile post-sorption process, during which the iodine-incorporated phase was changed from BiI3 to chemically durable Bi5O7I. Thus, our results showed that both efficient capture and stabilization of 129I would be possible with the bismuth-embedded SBA-15, in contrast to other sorbents mainly focused on iodine capture.

  4. Microfluidic enzymatic biosensing systems: A review.

    Science.gov (United States)

    Mross, Stefan; Pierrat, Sebastien; Zimmermann, Tom; Kraft, Michael

    2015-08-15

    Microfluidic biosensing systems with enzyme-based detection have been extensively studied in the last years owing to features such as high specificity, a broad range of analytes and a high degree of automation. This review gives an overview of the most important factors associated with these systems. In the first part, frequently used immobilization protocols such as physisorption and covalent bonding and detection techniques such as amperometry and fluorescence measurements are discussed with respect to effort, lifetime and measurement range. The Michaelis-Menten model describing the kinetics of enzymatic reactions, the role of redox mediators and the limitations of the linear measurement range of enzymatic sensors are introduced. Several possibilities of extending the linear measurement range in microfluidic systems such as diffusion-limiting membranes and the flow injection setup are presented. Regarding the integration of enzymes into microfluidic systems during the fabrication process, the constraints imposed by the biomolecules due to the limited usage of high temperatures and solvents are addressed. In the second part, the most common forms of enzyme integration into microfluidic systems, i.e. in channels and on electrodes, on microparticles, on paper and thread and as injected enzyme solutions, are reviewed, focusing on fabrication, applications and performance.

  5. Phenyl-functionalized magnetic palm-based powdered activated carbon for the effective removal of selected pharmaceutical and endocrine-disruptive compounds.

    Science.gov (United States)

    Wong, Kien Tiek; Yoon, Yeomin; Snyder, Shane A; Jang, Min

    2016-06-01

    Triethoxyphenylsilane (TEPS)-functionalized magnetic palm-based powdered activated carbon (MPPAC-TEPS) was prepared and characterized using various spectroscopic methods, and then tested for the removal of bisphenol A, carbamazepine, ibuprofen and clofibric acid. Magnetite film on MPPAC-TEPS was homogeneously coated on the outer surface of palm-based powdered activated carbon (PPAC) through a hydrothermal co-precipitation technique. Followed by silanization of phenyl-functionalized organosilane on MPPAC's magnetic film. As results, micro/mesopore surface area and volume increased without significant pore clogging and iron (Fe) dissolution under the acidic conditions was greatly decreased. The unique structural and chemical features of MPPAC-TEPS were found to be the main reasons for the enhanced adsorption rates and removal capacities of POPs. The presence of electrolytes and different pH values greatly affected the sorption efficiencies. The dominant sorption mechanism of POPs by MPPAC-TEPS was determined to be π-π interaction (physisorption), based on thermodynamic (ΔG°) and differential scanning calorimetry (DSC). Thermal regeneration at a low temperature (350 °C) was an effective method to desorb the retained POPs and enabled to reactivate MPPAC-TEPS with sustained sorption rates and capacities, whereas PPAC was largely exhausted. As a new type of sorbent for POPs, MPPAC-TEPS has operational advantages, such as magnetic separation and stable regeneration.

  6. 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.

  7. Response of Si- and Al-doped graphenes toward HCN: A computational study

    Energy Technology Data Exchange (ETDEWEB)

    Rastegar, Somayeh F.; Peyghan, Ali Ahmadi [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Hadipour, Nasser L., E-mail: hadipour_n@yahoo.com [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer Sensitivity of Si- and Al-doped graphene (SiG and AlG) toward HCN is investigated. Black-Right-Pointing-Pointer The electronic properties of AlG are significantly changed in the presence of HCN. Black-Right-Pointing-Pointer 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.

  8. Inexpensive sol-gel synthesis of multiwalled carbon nanotube-TiO2 hybrids for high performance antibacterial materials.

    Science.gov (United States)

    Abbas, Nadir; Shao, Godlisten N; Haider, M Salman; Imran, Syed Muhammad; Park, Sung Soo; Jeon, Sun-Jeong; Kim, Hee Taik

    2016-11-01

    This study reports an inexpensive sol-gel method to synthesize TiO2-CNT hybrid materials. Synthesized TiO2-CNT materials show strong antibacterial activity in the absence of light. Cheap TiO2 source TiOCl2 is used during synthesis in the absence of high temperatures, high pressures and organic solvents. TiO2-CNT materials with 0, 2, 5, 10, 15 and 20wt% 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 TiO2-CNT samples with a CNT loading of 10wt% or more nearly removed all of the E.coli bacteria. HaCaT cell proliferation studies of synthesized hybrid materials illustrated that prepared TiO2-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. Copyright © 2016. Published by Elsevier B.V.

  9. 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, N2-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.

  10. Titania-supported silver-based bimetallic nanoparticles as photocatalysts.

    Science.gov (United States)

    Barakat, M A; Al-Hutailah, R I; Hashim, M H; Qayyum, E; Kuhn, J N

    2013-06-01

    Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag-Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO(2)-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO(2)). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.

  11. Tuning the Graphene on Ir(111) adsorption regime by Fe/Ir surface-alloying

    Science.gov (United States)

    Brede, Jens; Sławińska, Jagoda; Abadia, Mikel; Rogero, Celia; Ortega, J. Enrique; Piquero-Zulaica, Ignacio; Lobo-Checa, Jorge; Arnau, Andres; Iribas Cerdá, Jorge

    2017-03-01

    A combined scanning tunneling microscopy, x-ray photoelectron spectroscopy, angle-resolved photoemission spectroscopy, and density functional theory study of graphene on a Fe-Ir(111) alloy with variable Ir concentration is presented. Starting from an intercalated Fe layer between the graphene and Ir(111) surface we find that graphene-substrate interaction can be fine-tuned by Fe-Ir alloying at the interface. When a critical Ir-concentration close to 0.25 is reached in the Fe layer, the Dirac cone of graphene is largely restored and can thereafter be tuned across the Fermi level by further increasing the Ir content. Indeed, our study reveals an abrupt transition between a chemisorbed phase at small Ir concentrations and a physisorbed phase above the critical concentration. The latter phase is highly reminiscent of the graphene on the clean Ir(111) surface. Furthermore, the transition is accompanied by an inversion of the graphene’s induced magnetization due to the coupling with the Fe atoms from antiferromagnetic when chemisorbed to weakly ferromagnetic in the physisorption regime, with spin polarizations whose magnitude may be tuned with the amount of Fe content.

  12. Uptake and retention of amitriptyline by kaolinite.

    Science.gov (United States)

    Lv, Guocheng; Stockwell, Christie; Niles, Jacqueline; Minegar, Skylar; Li, Zhaohui; Jiang, Wei-Teh

    2013-12-01

    As the most commonly prescribed tricyclic antidepressant, amitriptyline (AT) is frequently detected in wastewater, surface runoff, and effluents from sewage treatment plants, and could potentially reach agriculture land through the application of municipal biosolids or reclaimed water. Kaolinite is one of the most important soil components under warm and humid climate conditions. In this study, the uptake and retention of AT by kaolinite from aqueous solution were investigated by batch tests, XRD, and FTIR analyses. The uptake of AT on kaolinite was instantaneous, attributed to surface adsorption as confirmed by XRD analyses. Quantitative correlation between desorption of exchangeable cations and AT adsorption confirmed experimentally that cation exchange was the dominant mechanism of AT uptake on kaolinite. The values for free energy of adsorption also suggested physi-sorption such as cation exchange. Solution pH had minimal influence at pH 5-11 even though the pKa value of AT was 9.4 and the surface charge of kaolinite was pH-dependent. Copyright © 2013 Elsevier Inc. All rights reserved.

  13. Binding energy and work function of organic electrode materials phenanthraquinone, pyromellitic dianhydride and their derivatives adsorbed on graphene.

    Science.gov (United States)

    Yu, Yang-Xin

    2014-09-24

    Electroactive organic compounds are a novel group of green cathode materials for rechargeable metal-ion batteries. However, the organic battery life is short because the organic compounds can be dissolved by nonaqueous electrolytes. Here a comparative investigation of phenanthraquinone (PQ), pyromellitic dianhydride (PMDA) and their derivatives, i.e., benzo[1,2-b:4,3-b']difuran-4,5-dione (BDFD), benzo[1,2-b:4,3-b']dithiophene-4,5-quinone (BDTQ), 3,8-phenanthroline-5,6-dione (PAD), pyromellitic dithioanhydride (PMDT), pyromellitic diimide (PMDI) and 1,4,5,8-anthracenetetrone (ATO), adsorbed on graphene is performed using a density functional theory (DFT) with a van der Waals (vdW) dispersion-correction. The computed results show a strong physisorption with the binding energies between 1.10 and 1.56 eV. A sequence of the calculated binding energies from weak to strong is found to be BDFD work functions for the nanocomposites are found to be strongly affected by the work function of each organic compound. To understand the DFT results, a novel simple expression is proposed to predict the work function of the nanocomposites from the interfacial dipole and the work functions of the isolated graphene nanosheet and organic molecules. The predicted work functions for the nanocomposites from the new equation agree quite well with the values calculated from the vdW dispersion-corrected DFT.

  14. Stereospecific growth of densely populated rutile mesoporous TiO2 nanoplate films: a facile low temperature chemical synthesis approach

    Science.gov (United States)

    Lee, Go-Woon; Ambade, Swapnil B.; Cho, Young-Jin; Mane, Rajaram S.; Shashikala, V.; Yadav, Jyotiprakash; Gaikwad, Rajendra S.; Lee, Soo-Hyoung; Jung, Kwang-Deog; Han, Sung-Hwan; Joo, Oh-Shim

    2010-03-01

    We report for the first time, using a simple and environmentally benign chemical method, the low temperature synthesis of densely populated upright-standing rutile TiO2 nanoplate films onto a glass substrate from a mixture of titanium trichloride, hydrogen peroxide and thiourea in triply distilled water. The rutile TiO2 nanoplate films (the phase is confirmed from x-ray diffraction analysis, selected area electron diffraction, energy-dispersive x-ray analysis, and Raman shift) are 20-35 nm wide and 100-120 nm long. The chemical reaction kinetics for the growth of these upright-standing TiO2 nanoplate films is also interpreted. Films of TiO2 nanoplates are optically transparent in the visible region with a sharp absorption edge close to 350 nm, confirming an indirect band gap energy of 3.12 eV. The Brunauer-Emmet-Teller surface area, Barret-Joyner-Halenda pore volume and pore diameter, obtained from N2 physisorption studies, are 82 m2 g - 1, 0.0964 cm3 g - 1 and 3.5 nm, respectively, confirming the mesoporosity of scratched rutile TiO2 nanoplate powder that would be ideal for the direct fabrication of nanoscaled devices including upcoming dye-sensitized solar cells and gas sensors.

  15. Nirmali Seed as a Natural Biosorbent; Evaluation of its Potential for Iron (II Removal from Steel Plant Effluents and Sewage Disinfecting Capacity

    Directory of Open Access Journals (Sweden)

    Y. Avasn Maruthi

    2013-10-01

    Full Text Available The idea of water clarification by natural coagulants is many centuries old. Naturalcoagulants like Moring oelifera, Mangifera indica and Prunusarmeniaca,Strychnospotatorum are used for the treatment of waste waters. Nirmali Seed is a naturalcoagulant material with polyelectrolytes. These polyelectrolytes are responsible forcoagulation property of Nirmali seeds. In general, the studies rampant in the literaturereported application of Nirmali seed powder as water extract or as powder with doseselection using jar test. The treatment in most of the cases is based upon coagulation andremoval. But in this study it has been modified that the methodology to suit our objectivesas wanted to test the potential of Nirmali seed as a solid bio-sorbent surface in solidsolution equilibrium adsorption studies. The dose selection has been done keeping in mindthe amount of polyelectrolyte released when the seed powder is left in solution. Theproperty of physi-sorption aided with chemi-sorption with minimum dose has been givenimportance in the present study.The chief goal of this study is to find out the feasibility of applications of Nirmali Seedsfor both Iron (II reduction as well as disinfecting agent for sewage samples.

  16. DFT study of hydrogen fluoride and sulfur trioxide interactions on the surface of Pt-decorated graphene

    Science.gov (United States)

    Rad, Ali Shokuhi

    2016-08-01

    In this study, we investigate the adsorption properties of hydrogen florid (HF) and sulfur trioxide (SO3) on the surface of platinum decorated graphene (PtG) using density functional theory. We found one optimized configuration for HF and two ones for SO3 upon adsorption on the surface of PtG. Our result show significant adsorption on PtG with calculated energy adsorption of -73.6 (-54.2 BSSE) kJ/mol for HF at its only position and -172.4 (-144.8 BSSE) and -62.7 (-53.7 BSSE) kJ/mol for SO3 at its two positions; P1 and P2, respectively), whereas there is weak physisorption of these analytes on pristine graphene (PG). Results of charge analyses reveled interesting net charge transfer; while the direction of charge is from HF to PtG, reverse direction is found for SO3 for its two configurations. To deep understand the concept of adsorption properties, we used orbital analyses including density of states for interaction of mentioned analytes on the surface of PtG.

  17. Adsorption of sodium diclofenac on graphene: a combined experimental and theoretical study.

    Science.gov (United States)

    Jauris, I M; Matos, C F; Saucier, C; Lima, E C; Zarbin, A J G; Fagan, S B; Machado, F M; Zanella, I

    2016-01-21

    The interactions of sodium diclofenac drug (s-DCF) with different graphene species were investigated using both first principles calculations based on Density Functional Theory (DFT) and adsorption experiments. Through batch adsorption experiments, it was found that rGO was a good adsorbent for removing the s-DCF drug from aqueous solutions. The general-order kinetic model shows the best fit to the experimental data compared with pseudo-first order and pseudo-second order kinetic adsorption models. The equilibrium data (at 25 °C) were fitted to the Liu isotherm model. The maximum sorption capacity for adsorption of the s-DCF drug was 59.67 mg g(-1) for rGO. The s-DCF adsorption onto pristine graphene, graphene with a vacancy, reduced oxide graphene (rGO) and functionalized graphene nanoribbons were simulated providing a good understanding of the adsorption process of this molecule on graphene-family surfaces. The results predict a physisorption regime in all cases. Based on these results, the ab initio calculations and the adsorption experiments point out that the graphene-family are promising materials for extracting s-DCF from wastewater effluents.

  18. Static adsorptive fouling of extracellular polymeric substances with different membrane materials.

    Science.gov (United States)

    Su, Xinying; Tian, Yu; Zuo, Wei; Zhang, Jun; Li, Hui; Pan, Xiaoyue

    2014-03-01

    Adsorptive fouling of microbial extracellular polymeric substances (EPS) greatly influences the fouling behavior and membrane characteristics in a membrane bioreactor (MBR). In this study, adsorptive fouling of the EPS on different membrane materials was compared and adsorptive mechanism between membranes and EPS was investigated by thermodynamic analysis. The results suggested that both the absolute and relative changes of hydraulic resistances should be considered to evaluate fouling of membranes with different materials, and Sips isotherm was the most suitable model to describe the EPS carbohydrate and protein adsorptions on membranes. Thermodynamic analysis showed that both EPS carbohydrate and protein adsorptions were spontaneous (ΔrG(θ)  0), and entropy driven (ΔrS(θ) > 0). Decreasing ΔrG(θ) values with temperature suggested that EPS adsorptive fouling can be limited by reducing temperature. In addition, physisorption processes and hydrogen bonding interactions between EPS and membranes might play a relatively major role in the adsorption mechanism of EPS on the membrane surface. Atomic force microscopy (AFM) and contact angle analysis confirmed that the adsorptive fouling modified the membrane surface, making the membrane surface more heterogeneous and more hydrophobic.

  19. Processing and characterization of diatom nanoparticles and microparticles as potential source of silicon for bone tissue engineering.

    Science.gov (United States)

    Le, Thi Duy Hanh; Bonani, Walter; Speranza, Giorgio; Sglavo, Vincenzo; Ceccato, Riccardo; Maniglio, Devid; Motta, Antonella; Migliaresi, Claudio

    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.

  20. 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.