Modelling of a chemisorption refrigeration and power cogeneration system

International Nuclear Information System (INIS)

Bao, Huashan; Wang, Yaodong; Roskilly, Anthony Paul

2014-01-01

Highlights: • An adsorption cogeneration was proposed and simulated for cooling and electricity. • A dynamic model was built and studied to demonstrate the variability of the system. • A dynamic model included the complex coupling of thermodynamic and chemical kinetic. • Mutual constrains between main components and optimisation methods were discussed. • The highest theoretical COP and exergy efficiency of cogeneration is 0.57 and 0.62. - Abstract: The present work for the first time explores the possibility of a small-scale cogeneration unit by combining solid–gas chemisorption refrigeration cycle and a scroll expander. The innovation in this work is the capability of producing refrigeration and electricity continuously and simultaneously without aggravating the energy scarcity and environmental impact. Individual modelling for each component, which has been validated by experimental data, was firstly investigated in order to identify the proper operation condition for the cogeneration mode achieving 1000 W power output. Subsequently, with the integrated modelling of two components the cogeneration performance was studied to demonstrate the viability of this concept. However, because of the mutual constraint between the chemisorption and the expansion when they link in series, the power output of the cogeneration mode was only around one third of the original expectation under the same condition identified in the individual modelling. Methods of improving the global performance including the selection of reactive mediums were also discussed and would be of referable value for the future practical investigation

First principles analysis of hydrogen chemisorption on Pd-Re alloyed overlayers and alloyed surfaces

DEFF Research Database (Denmark)

Pallassana, Venkataraman; Neurock, Matthew; Hansen, Lars Bruno

2000-01-01

Gradient corrected periodic density functional theory (DFT-GGA) slab calculations were used to examine the chemisorption of atomic hydrogen on various Pd-Re alloyed overlayers and uniformly alloyed surfaces. Adsorption was examined at 33% surface coverage, where atomic hydrogen preferred the thre...

Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

Energy Technology Data Exchange (ETDEWEB)

Luo, Xuan; Jiang, Bin, E-mail: bjiangch@ustc.edu.cn [Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Juaristi, J. Iñaki [Centro de Física de Materiales CFM/MPC(CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080 San Sebastián (Spain); Alducin, Maite [Centro de Física de Materiales CFM/MPC(CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Guo, Hua [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

2016-07-28

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH{sub 4}/CH{sub 3}D/CHD{sub 3} on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH{sub 4}/CH{sub 3}D/CHD{sub 3} have been carried out on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.

Mode Specific Electronic Friction in Dissociative Chemisorption on Metal Surfaces: H2 on Ag(111)

Science.gov (United States)

Maurer, Reinhard J.; Jiang, Bin; Guo, Hua; Tully, John C.

2017-06-01

Electronic friction and the ensuing nonadiabatic energy loss play an important role in chemical reaction dynamics at metal surfaces. Using molecular dynamics with electronic friction evaluated on the fly from density functional theory, we find strong mode dependence and a dominance of nonadiabatic energy loss along the bond stretch coordinate for scattering and dissociative chemisorption of H2 on the Ag(111) surface. Exemplary trajectories with varying initial conditions indicate that this mode specificity translates into modulated energy loss during a dissociative chemisorption event. Despite minor nonadiabatic energy loss of about 5%, the directionality of friction forces induces dynamical steering that affects individual reaction outcomes, specifically for low-incidence energies and vibrationally excited molecules. Mode-specific friction induces enhanced loss of rovibrational rather than translational energy and will be most visible in its effect on final energy distributions in molecular scattering experiments.

A theoretical investigation of Brønsted acids chemisorption on ZnO(0001)

Science.gov (United States)

Casarin, Maurizio; Maccato, Chiara; Tondello, Eugenio; Vittadini, Andrea

1995-12-01

Density functional theory coupled to the molecular cluster approach has been used to investigate the chemisorption of simple Brønsted acids (H 2O, H 2S and HCN) on the ZnO(0001) polar surface. Geometrical parameters and vibrational frequencies for species molecularly and dissociatively chemisorbed have been computed. The agreement with experimental measurements, when available, has been found to be very good. The nature of the bonding between the conjugate base of each examined Brønsted acid and the Lewis acid site on the investigated surface has been thoroughly discussed. In particular, it has been elucidated the role played by the interaction between completely occupied levels in determining the actual chemisorption geometry. Enthalpy variations associated to titration displacement reactions have been evaluated, confirming the leading role played by the bonding between the Brønsted conjugate base anions and the Lewis acid site available on the surface in determining the actual relative acidity scale. The strength of this interaction follows the order OH - ≈ CN ->SH -.

Chemisorption on the (111) and (100) faces of platinum-tin bimetallic surfaces

Science.gov (United States)

Panja, Chameli

2000-10-01

Chemisorption and reaction of CH3OH (methanol), C2H 5OH (ethanol), and H2O (water) on Pt(111) and Sn/Pt(111) alloys, and CO (carbon monoxide), NO (nitric oxide), and C2D 2 (acetylene) on Pt(100) and Sn/Pt(100) have been studied under ultrahigh vacuum conditions using temperature programmed desorption (TPD), Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and high resolution electron energy loss spectroscopy (HREELS). Small organic molecules like CH3OH and C2H5OH are potential fuels for low-temperature hydrocarbon fuel cells and it is important to understand the role of tin as a promoter in electrooxidation of these molecules. Also, the catalytic reactions of CO, NO and C2H2 are of considerable interest for improving of automotive exhaust-gas catalytic converters and other heterogeneous catalysts. Ordered Pt-Sn alloys can be prepared by vapor deposition of Sn on Pt surfaces. A (2 x 2) structure (theta Sn = 0.25) and a (√3x√/3)R30° structure are formed on Pt(111), and a c(2 x 2) and (3√2x√2)R45° structures with theta Sn = 0.5 and 0.67, respectively, are formed on Pt(100). CH3OH, C2H5OH and H2O are all weakly bound and reversibly adsorbed on Pt(111) and both of the Sn/Pt(111) alloys under UHV conditions. Alloying Sn into the Pt(111) surface weakens the adsorption of these molecules from that on Pt(111) and leads to a lower reactivity as the surface concentration of Sn increases. TPD measurements reveal a reduction in the saturation coverage and chemisorption bond energy for CO, NO and C2HL chemisorption, on the two Sn/Pt(100)alloys compared to that on Pt(100). CO chemisorption is completely reversible on these two Sn/Pt(100) alloys. However, NO is partially reduced to form N2O on these alloys, so that N2O along with NO and O2 desorption was observed. We propose that dinitrosyl species, i.e., two NO molecules bound to one Pt atom, are intermediates in N2O formation from adsorbed NO on these Sn

Spectroscopic characterization of TeF and oxygen chemisorption onto silicon (111)

International Nuclear Information System (INIS)

Newlin, D.E.

1979-01-01

Chemiluminescence from the reactions of H 2 Te and D 2 Te with fluorine was observed at 3900 to 8600 A. Two separate band systems are attributed to the B 2 Σ-X 2 π and A 2 π-X 2 π transitions of the TeF radical. Moessbauer spectra were obtained of H 2 Te and D 2 Te in an argon matrix, and of TeF produced in the reaction of hydrogen telluride with fluorine. These are discussed with respect to the isotope effect and electron density calculations for the tellurium nucleus. Kinetics of chemisorption of oxygen on a silicon (111) surface were studied at 298 to 473 0 K using ESCA. Results are interpreted assuming immobile adsorption requiring two nearest neighbor surface sites. The initial sticking coefficient (theta << 1) is found to be S approx. = 0.1, and the activation energy of adsorption is determined as E/sub a/ = 1.6 +- 0.3 kcal/mole at theta = 0.4. Higher values of the sticking coefficient are obtained when the surface is contaminated with carbon produced at heated filaments in the vacuum system, so any consideration of oxygen adsorption onto an atomically clean silicon surface should use the lower values of the sticking coefficient reported in the literature. Results of this study are consistent with a model for oxygen chemisorption involving two surface sites per oxygen molecule

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.

Unique coexistence of dispersion stability and nanoparticle chemisorption in alkylamine/alkylacid encapsulated silver nanocolloids.

Science.gov (United States)

Aoshima, Keisuke; Hirakawa, Yuya; Togashi, Takanari; Kurihara, Masato; Arai, Shunto; Hasegawa, Tatsuo

2018-04-17

Surface encapsulation of metal nanoparticles (NPs) is fundamental to achieve sufficient dispersion stability of metal nanocolloids, or metal nanoink. However, the feature is incompatible with surface reactive nature of the metal NPs, although these features are both essential to realizing the functional applications into printed electronics technologies. Here we show that two different kinds of encapsulation for silver NPs (AgNPs) by alkylamine and alkylacid together are the key to achieve unique compatibility between the high dispersion stability as dense nanoclolloids and the AgNP chemisorption printing on activated patterned polymer surfaces. Advanced confocal dynamic light scattering study reveals that an additive trace amount of oleic acid is the critical parameter for controlling the dispersion and coagulative (or surface-reactive) characteristics of the silver nanocolloids. The composition of the disperse media is also important for obtaining highly concentrated but low-viscosity silver nanocolloids that show very stable dispersion. The results demonstrate that the high-resolution AgNP chemisorption printing is possible only by using unique silver nanocolloids composed of an exceptional balance of ligand formulation and dispersant composition.

Electron Spectroscopy Studies of Iron, Iron Sulfides and Supported Iron Surfaces: Chemisorption of Simple Gases.

Science.gov (United States)

Lee, Yiu Chung

EELS was used to investigate the chemisorption of oxygen and carbon on iron. The EELS spectra of oxidized iron show characteristic features with strong enhancement of the interband transitions involving the Fe 3d band (4.6 and 7.5 eV) and moderate enhancement of the M(,2,3) transition doublet (54.4 and 58.2 eV). The changes in the electron energy loss structures with an overlayer of graphitic or carbidic carbon were investigated. The adsorption and growth of iron on Ni(100) has been studied using the combined techniques of LEED and EELS. Initially iron grows by a layer-by-layer mechanism for the first few layers. High iron coverages result in the observation of complex LEED patterns with satellites around the main (1 x 1) diffraction sports. This is due to the formation of b.c.c. Fe(110) crystallites arranged in domains with different orientations. EELS studies show the presence of three stages in the growth of iron on Ni(100): low-coverage, film-like and bulk-like. Auger and EELS were used to study the iron sulfide (FeS(,2), Fe(,7)S(,8) and FeS) surfaces. A characteristic M(,2,3) VV Auger doublet with a separation of 5.0 eV was observed on the sulfides. An assignment of the electron energy loss peaks was made based on the energy dependence of the loss peaks and previous photoemission results. The effect of argon ion bombardment was studied. Peaks with strong iron and sulfur character were observed. Heating the damaged sulfides results in reconstruction of the sulfide surfaces. The reactions of the sulfides with simple gases, such as H(,2), CO, CH(,4), C(,2)H(,4), NH(,3) and O(,2) were also studied. Using XPS, the chemisorption of SO(,2) on CaO(100) has been studied. The chemical state of sulfur has been identified as that of sulfate. The kinetics of SO(,2) chemisorption on CaO are discussed. The binding states of Fe and Na on CaO were determined to be Fe('2+) and Na('+) respectively. At low Fe or Na coverages (< 0.5 ML), there is a large increase in the rate of

Chemisorption of iodine-125 to gold nanoparticles allows for real-time quantitation and potential use in nanomedicine

Energy Technology Data Exchange (ETDEWEB)

Walsh, Adrian A, E-mail: a.walsh@nanobiosols.com [Liverpool Science Park, Nano Biosols Ltd (United Kingdom)

2017-04-15

Gold nanoparticles have been available for many years as a research tool in the life sciences due to their electron density and optical properties. New applications are continually being developed, particularly in nanomedicine. One drawback is the need for an easy, real-time quantitation method for gold nanoparticles so that the effects observed in in vitro cell toxicity assays and cell uptake studies can be interpreted quantitatively in terms of nanoparticle loading. One potential method of quantifying gold nanoparticles in real time is by chemisorption of iodine-125, a gamma emitter, to the nanoparticles. This paper revisits the labelling of gold nanoparticles with iodine-125, first described 30 years ago and never fully exploited since. We explore the chemical properties and usefulness in quantifying bio-functionalised gold nanoparticle binding in a quick and simple manner. The gold particles were labelled specifically and quantitatively simply by mixing the two items. The nature of the labelling is chemisorption and is robust, remaining bound over several weeks in a variety of cell culture media. Chemisorption was confirmed as potassium iodide can remove the label whereas sodium chloride and many other buffers had no effect. Particles precoated in polymers or proteins can be labelled just as efficiently allowing for post-labelling experiments in situ rather than using radioactive gold atoms in the production process. We also demonstrate that interparticle exchange of I-125 between different size particles does not appear to take place confirming the affinity of the binding.

Chemisorption of iodine-125 to gold nanoparticles allows for real-time quantitation and potential use in nanomedicine

Science.gov (United States)

Walsh, Adrian A.

2017-04-01

Gold nanoparticles have been available for many years as a research tool in the life sciences due to their electron density and optical properties. New applications are continually being developed, particularly in nanomedicine. One drawback is the need for an easy, real-time quantitation method for gold nanoparticles so that the effects observed in in vitro cell toxicity assays and cell uptake studies can be interpreted quantitatively in terms of nanoparticle loading. One potential method of quantifying gold nanoparticles in real time is by chemisorption of iodine-125, a gamma emitter, to the nanoparticles. This paper revisits the labelling of gold nanoparticles with iodine-125, first described 30 years ago and never fully exploited since. We explore the chemical properties and usefulness in quantifying bio-functionalised gold nanoparticle binding in a quick and simple manner. The gold particles were labelled specifically and quantitatively simply by mixing the two items. The nature of the labelling is chemisorption and is robust, remaining bound over several weeks in a variety of cell culture media. Chemisorption was confirmed as potassium iodide can remove the label whereas sodium chloride and many other buffers had no effect. Particles precoated in polymers or proteins can be labelled just as efficiently allowing for post-labelling experiments in situ rather than using radioactive gold atoms in the production process. We also demonstrate that interparticle exchange of I-125 between different size particles does not appear to take place confirming the affinity of the binding.

Chemisorption of iodine-125 to gold nanoparticles allows for real-time quantitation and potential use in nanomedicine

International Nuclear Information System (INIS)

Walsh, Adrian A

2017-01-01

Gold nanoparticles have been available for many years as a research tool in the life sciences due to their electron density and optical properties. New applications are continually being developed, particularly in nanomedicine. One drawback is the need for an easy, real-time quantitation method for gold nanoparticles so that the effects observed in in vitro cell toxicity assays and cell uptake studies can be interpreted quantitatively in terms of nanoparticle loading. One potential method of quantifying gold nanoparticles in real time is by chemisorption of iodine-125, a gamma emitter, to the nanoparticles. This paper revisits the labelling of gold nanoparticles with iodine-125, first described 30 years ago and never fully exploited since. We explore the chemical properties and usefulness in quantifying bio-functionalised gold nanoparticle binding in a quick and simple manner. The gold particles were labelled specifically and quantitatively simply by mixing the two items. The nature of the labelling is chemisorption and is robust, remaining bound over several weeks in a variety of cell culture media. Chemisorption was confirmed as potassium iodide can remove the label whereas sodium chloride and many other buffers had no effect. Particles precoated in polymers or proteins can be labelled just as efficiently allowing for post-labelling experiments in situ rather than using radioactive gold atoms in the production process. We also demonstrate that interparticle exchange of I-125 between different size particles does not appear to take place confirming the affinity of the binding.

Measurement of Total Free Iron in Soils by H2S Chemisorption and Comparison with the Citrate Bicarbonate Dithionite Method

Directory of Open Access Journals (Sweden)

Shui-Sheng Fan

2016-01-01

Full Text Available Free iron is one of the major analytical items for soil basic properties. It is also an important indicator for understanding the genesis of soil, soil classification, and soil distribution behavior. In this study, an alternative analytical method (chemisorption based on thermodynamic knowledge was proposed for measurement of total free iron oxides in soils. Several representative soil samples belonging to alfisols, ultisols, inceptisols, and entisols were collected from Taiwan and tested by the chemisorption, and the estimated total free iron oxides were compared with those measured from the traditional citrate bicarbonate dithionite (CBD method. Experimental results showed that the optimal operating temperature was found to be at 773 K and the carbon monoxide (CO is the best gaseous reagent to promote the formation of FeS. The estimated total free iron oxides for soil samples determined from the chemisorption in the presence of CO were very close to those from the CBD technique. The result of regression indicates that the estimated total free iron is strongly correlated with the CBD-Fe content (R2=0.999 in the presence of CO.

Oxygen chemisorption on a stepped Ru (approx.001) crystal

International Nuclear Information System (INIS)

Parrott, S.L.; Praline, G.; Koel, B.E.; White, J.M.; Taylor, T.N.

1979-01-01

The 300 K chemisorption of oxygen on a stepped Ru (approx.001) single crystal [17(001) x (100)] gives 2 x 2 complete half-order, 1 x 2 complete or incomplete half-order, and 1 x 1 integral-order LEED patterns depending on oxygen exposure and sample annealing. The corresponding relative AES oxygen signals are 0.25, 0.50, and 1.0, respectively. Under certain surface conditions, the presence of the steps is seen to break the threefold degenerate growth habit of 1 x 2 domains. The 1 x 1 pattern forms at 300 K only after lengthy exposure at relatively high pressure (10 -5 Torr) and is stable to 600 K. Prolonged exposure gives rise to relative AES oxygen signals greater than unity suggesting penetration into the subsurface region

Electronic structure, bonding and chemisorption in metallic hydrides

International Nuclear Information System (INIS)

Ward, J.W.

1980-01-01

Problems that can arise during the cycling steps for a hydride storage system usually involve events at surfaces. Chemisorption and reaction processes can be affected by small amounts of contaminants that may act as catalytic poisons. The nature of the poisoning process can vary greatly for the different metals and alloys that form hydrides. A unifying concept is offered, which satisfactorily correlates many of the properties of transition-metal, rare-earth and actinide hydrides. The metallic hydrides can be differentiated on the basis of electronegativity, metallic radius (valence) and electronic structure. For those systems where there are d (transition metals) or f (early actinides) electrons near the Fermi level a broad range of chemical and catalytic behaviors are found, depending on bandwidth and energy. The more electropositive metals (rare-earths, actinides, transition metals with d > 5) dissolve hydrogen and form hydrides by an electronically somewhat different process, and as a class tend to adsorb electrophobic molecules. The net charge-transfer in either situation is subtle; however, the small differences are responsible for many of the observed structural, chemical, and catalytic properties in these hydride systems

Chemisorption of SO2 at the surface of In2O3 modified by zink

International Nuclear Information System (INIS)

Vinokurova, M.V.; Derlyukova, L.E.; Vinokurov, A.A.

2005-01-01

Chemisorption of SO 2 and O 2 at the surface of In 2 O 3 involving zink addition (0.4-2.7 at.%) are investigated in the temperature range 22-200 Deg C. No less than three forms of sorbed SO 2 are available at the surface of modified In 2 O 3 . Temperature effects on the ratio of forms of SO 2 sorption and, consequently, on varying the electric conductivity. Previous sorption of O 2 is favorable to the formation of donor form of chemisorbed SO 2 [ru

The gamma-ray induced chemisorption of oxygen on perovskite type catalysts: determination by reduction with hydrazine sulphate/hydroxylamine hydrochloride

International Nuclear Information System (INIS)

Srinivas, B.; Rao, V.R.S.; Kuriacose, J.C.

1986-01-01

Chemisorbed oxygen can be determined quantitatively by the measurement of gaseous N 2 /N 2 O liberated by treatment with hydrazine sulfate/hydroxylamine hydrochloride. The amount of chemisorbed oxygen depends on the degree of dispersion during irradiation and also on the γ-dose. The chemisorption is enhanced in the presence of moisture. The partial reduction of the transition metal ion favours the formation of chemisorbed oxygen. (author)

First-principles electronic functionalization of silicene and germanene by adatom chemisorption

Energy Technology Data Exchange (ETDEWEB)

Broek, B. van den; Houssa, M.; Scalise, E. [Semiconductor Physics Laboratory, Department of Physics and Astronomy, University of Leuven, Celestijnenlaan 200 D, B-3001 Leuven (Belgium); Pourtois, G. [IMEC, 75 Kapeldreef, B-3001 Leuven (Belgium); Department of Chemistry, Plasmant Research Group, University of Antwerp, B-2610 Wilrijk-Antwerp (Belgium); Afanas‘ev, V.V.; Stesmans, A. [Semiconductor Physics Laboratory, Department of Physics and Astronomy, University of Leuven, Celestijnenlaan 200 D, B-3001 Leuven (Belgium)

2014-02-01

This study presents first-principles results on the electronic functionalization of silicene and germanene monolayers by means of chemisorption of adatom species H, Li, F, Sc, Ti, V. Three general adatom-monolayer configurations are considered, each having its distinct effect on the electronic structure, yielding metallic or semiconducting dispersions depending on the adatom species and configuration. The induced bandgap is a (in)direct Γ gap ranging from 0.2 to 2.3 eV for both silicene and germanene. In general the alternating configuration was found to be the most energetically stable. The boatlike and chairlike conformers are degenerate with the former having anisotropic effective carrier masses. The top configuration leads to the planar monolayer and predominately to a gapped dispersion. The hollow configuration with V adatoms retains the Dirac cone, but with strong orbital planar hybridization at the Fermi level. We also observe a planar surface state the Fermi level for the latter systems.

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

Science.gov (United States)

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

2016-05-19

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

Quantum dynamics of water dissociative chemisorption on rigid Ni(111): An approximate nine-dimensional treatment

International Nuclear Information System (INIS)

Jiang, Bin; Song, Hongwei; Yang, Minghui; Guo, Hua

2016-01-01

The quantum dynamics of water dissociative chemisorption on the rigid Ni(111) surface is investigated using a recently developed nine-dimensional potential energy surface. The quantum dynamical model includes explicitly seven degrees of freedom of D 2 O at fixed surface sites, and the final results were obtained with a site-averaging model. The mode specificity in the site-specific results is reported and analyzed. Finally, the approximate sticking probabilities for various vibrationally excited states of D 2 O are obtained considering surface lattice effects and formally all nine degrees of freedom. The comparison with experiment reveals the inaccuracy of the density functional theory and suggests the need to improve the potential energy surface.

A LCAO-LDF study of Brønsted acids chemisorption on ZnO(0001)

Science.gov (United States)

Casarin, Maurizio; Maccato, Chiara; Tabacchi, Gloria; Vittadini, Andrea

1996-05-01

The local density functional theory coupled to the molecular cluster approach has been used to study the chemisorption of Br∅nsted acids (H 2O, H 2S, HCN, CH 3OH and CH 3SH) on the ZnO(0001) polar surface. Geometrical parameters and vibrational frequencies for selected species molecularly and dissociatively chemisorbed have been computed. The agreement with literature experimental data, when available, has been found to be good. The nature of the interaction between the conjugate base of the examined Br∅nsted acids and the Lewis acid site available on the surface has been elucidated, confirming its leading role in determining the actual relative acidity scale obtained by titration displacement reactions. The strength of this interaction follows the order OH - ≈ CN - > CH 3O - > SH - > CH 3S -.

Chemisorption studies of Pt/SnO2 catalysts

Science.gov (United States)

Brown, Kenneth G.; Ohorodnik, Susan K.; Vannorman, John D.; Schryer, Jacqueline; Upchurch, Billy T.; Schryer, David R.

1990-01-01

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Study by Auger spectrometry and mass spectrometry of the chemisorption of carbon monoxide on polycrystalline molybdenum

International Nuclear Information System (INIS)

Gillet, E.; Chiarena, J.C.; Gillet, M.

1976-01-01

A combination of Auger spectrometry and mass spectrometry was employed to study CO chemisorption on polycrystalline Mo surfaces at room temperature. Five adsorption states were observed and the binding parameters (E,n 0 ,tau 0 ) were calculated for the three important states. The results obtained by the two methods are in accord but the occurence of electronic desorption in Auger experiments was pointed out. Contamination effects by C atoms in such studies were investigated by repeated cycles of adsorption-desorption and a characteristic evolution of flash desorption was observed. The results are discussed in this point of view enhancing the importance of a control of the adsorption surface cleanness by a method of great sensibility like Auger spectrometry. (Auth.)

Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

Energy Technology Data Exchange (ETDEWEB)

Asiaee, Alireza; Benjamin, Kenneth M., E-mail: kenneth.benjamin@sdsmt.edu [Department of Chemical and Biological Engineering, South Dakota School of Mines and Technology, 501 E. Saint Joseph St., Rapid City, South Dakota 57701 (United States)

2016-08-28

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0–1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

DFT Study of PH3 Physisorption and Chemisorptions on Boron Nitride Nanotubes

Science.gov (United States)

Rakhshi, Mahdi; Mohsennia, Mohsen; Rasa, Hossein

2018-03-01

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

Relaxation of the chemical bond skin chemisorption size matter ZTP mechanics H2O myths

CERN Document Server

Sun, Chang Q

2014-01-01

The aim of this book is to explore the detectable properties of a material to the parameters of bond and non-bond involved and to clarify the interdependence of various properties. This book is composed of four parts; Part I deals with the formation and relaxation dynamics of bond and non-bond during chemisorptions with uncovering of the correlation among the chemical bond, energy band, and surface potential barrier (3B) during reactions; Part II is focused on the relaxation of bonds between atoms with fewer neighbors than the ideal in bulk with unraveling of the bond order-length-strength (BOLS) correlation mechanism, which clarifies the nature difference between nanostructures and bulk of the same substance; Part III deals with the relaxation dynamics of bond under heating and compressing with revealing of rules on the temperature-resolved elastic and plastic properties of low-dimensional materials; Part IV is focused on the asymmetric relaxation dynamics of the hydrogen bond (O:H-O) and the anomalous behav...

Theoretical analysis of hydrogen chemisorption on Pd(111), Re(0001) and PdML/Re(0001), ReML/Pd(111) pseudomorphic overlayers

DEFF Research Database (Denmark)

Pallassana, Venkataraman; Neurock, Matthew; Hansen, Lars Bruno

1999-01-01

not appear to provide an independent parameter for assessing surface reactivity. The weak chemisorption of hydrogen on the Pd-ML/Re(0001) surface relates to substantial lowering of the d-band center of Pd, when it is pseudomorphically deposited as a monolayer on a Re substrate. [S0163-1829(99)00331-2].......Gradient-corrected density-functional theory (DFT-GGA) periodic slab calculations have been used to analyze the binding of atomic hydrogen on monometallic Pd(111), Re(0001), and bimetallic Pd-mL/Re(0001) [pseudomorphic monolayer of Pd(111) on Re(0001)] and Re-ML/Pd(111) surfaces. The computed...

Wastewater centrate ammonia removal by chemisorption processes

International Nuclear Information System (INIS)

Barbachem, M.J.

2002-01-01

'Full text:' This presentation will describe the nature, scope, and findings of a third-party evaluation of a patent-protected wastewater treatment technology identified as the ThermoEnergy Ammonia Recovery Process TM (ARP). The ARP is a reversible chemisorption process using a zinc-impregnated ion exchange resin, and it is unique in that it removes/reduces the ammonia-nitrogen load in the solids processing liquor of municipal sewage treatment plants and recycles the recovered product into a pelletized ammonium salt that can be used as an agricultural fertilizer. The primary objective of the ARP evaluation was to perform well-defined field and laboratory tests to provide data on process performance. The evaluation process was overseen and coordinated by the Environmental Technology Evaluation Center (EvTEC), a program of the Civil Engineering Research Foundation (CERF), the research and technology transfer arm of the American Society of Civil Engineers (ASCE). EvTEC is a pilot program evaluating innovative environmental technologies under the US Environmental Protection Agency's (USEPA) Environmental Technology Verification (ETV) Program. A pilot scale ARP treatment facility was constructed and tested at the Oakwood Beach Water Pollution Control Plant (WPCP) in Staten Island, New York, from September through December of 1998. While operating during the 3 month period using the anaerobically digested centrate normally produced at the WPCP, the pilot study demonstrated that the ARP process was capable of removing/recovering ammonia with efficiencies ranging from 75-99+ % at influent concentrations exceeding 400 mg/L. During the pilot plant operations, forty-eight (48) complete validated runs of centrate processing were performed. The plant processed the centrate under normal day-to-day conditions at the WPCP, and no special operational considerations were given to the centrifuge operation to accommodate the ARP pilot plant. The Oakwood WPCP operated exactly the way

Molecular dynamics simulation investigations of H2/D2 dissocitive chemisorption dynamics on Cun(n=13-14) Rigid/nonrigid clusters

International Nuclear Information System (INIS)

Elzein, N.

2004-01-01

In this work with a use of molecular dynamic simulations we have reported the results of a quasiclassical simulation study of the interaction of H2/(D2) with Cu N (N=13-14) atoms in both rigid /(non rigid) clusters.The geometry of the cluster is obtained by an embedded-atom (EA) mode potential, and the interaction between the molecule and cIuster is described by a LEPS -London-Eyring -Polanyi-Sato) potential energy function.Both channels the reactive dissociative adsorption of the molecule on the cIuster) and non reactive (scattering of the molecule from the cluster) are considered. The dissociative chemisorption probability, cross section and rate constant are studied as functions of the initial quantal rovibrational state of the molecule, collision energy, impact parameter and the temperature (OK,296K,834K ,1014K,1554K) of the clusters

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

Science.gov (United States)

Huang, C. J.; Yeager, E.; Ogrady, W. E.

1975-01-01

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

Energy Technology Data Exchange (ETDEWEB)

Guo, Han; Jackson, Bret, E-mail: jackson@chem.umass.edu [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States)

2016-05-14

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.

Facilitated Oxygen Chemisorption in Heteroatom-Doped Carbon for Improved Oxygen Reaction Activity in All-Solid-State Zinc-Air Batteries.

Science.gov (United States)

Liu, Sisi; Wang, Mengfan; Sun, Xinyi; Xu, Na; Liu, Jie; Wang, Yuzhou; Qian, Tao; Yan, Chenglin

2018-01-01

Driven by the intensified demand for energy storage systems with high-power density and safety, all-solid-state zinc-air batteries have drawn extensive attention. However, the electrocatalyst active sites and the underlying mechanisms occurring in zinc-air batteries remain confusing due to the lack of in situ analytical techniques. In this work, the in situ observations, including X-ray diffraction and Raman spectroscopy, of a heteroatom-doped carbon air cathode are reported, in which the chemisorption of oxygen molecules and oxygen-containing intermediates on the carbon material can be facilitated by the electron deficiency caused by heteroatom doping, thus improving the oxygen reaction activity for zinc-air batteries. As expected, solid-state zinc-air batteries equipped with such air cathodes exhibit superior reversibility and durability. This work thus provides a profound understanding of the reaction principles of heteroatom-doped carbon materials in zinc-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of preadsorbed oxygen on the sign and magnitude of the chemisorption-induced resistance change for H2 adsorption onto Fe films

Science.gov (United States)

Shanabarger, M. R.

1986-01-01

Measurements have been made of the chemisorption-induced resistance change for H2 adsorbed onto Fe film substrates predosed with fixed coverages of chemisorbed oxygen. The measurements were made at temperatures from 295 to 340 K and for estimated oxygen coverages of less than 0.1 monolayers. Two distinct resistance change components were observed in both the adsorption kinetics and the equilibrium isotherms: a positive component which is associated with the adsorption of H2 onto a clean Fe surface, and a negative component which was correlated with the presence of the chemisorbed oxygen. The resistance change isotherms can be fit with a model which assumes that each of the resistance change components result from dissociative chemisorbed hydrogen. Possible mechanisms for the chemisorbed-oxygen-induced negative resistance change are discussed.

Calculations of chemisorption of hydrogen and nitrogen on titanium using Xα-SW and SCF-CI methods

International Nuclear Information System (INIS)

Hung, S.C.

1983-01-01

Two theoretical studies are used as examples of chemisorption on transition metal surfaces. The first calculation employs the SCF-Sα-SW method to determine the electronic structures of several close-packed Ti-Ti and Ti-H systems. The relative importance of Ti s, p, and electron bonding to its Ti neighbors and to H are reported. The roles of the d electrons in the Ti-Ti and Ti-H bond are discussed. The effect of the presence of an H atom on the first few layers of the metal is also studied. The second set of calculations employs the Hartree-Fock-Roothaan SCF formulation supplemented by configuration-interaction (CI) to determine the energetics of adsorption of an N 2 molecule at a Ti surface. These calculations are made tractable by using a Ti core potential and by a unitary localization transformation to define a local surface region of localized lattice plus adsorbate orbitals. The results show that an underlayer of N atoms forms at the octahedral sites. The calculated adsorption energy of 115 kcal/mole compares favorably with experiment. Binding energy contributions in the several successive steps of the calculations are discussed. Eigenvalue spectra for the selected lattice-adsorbate geometries are compared to the UPS experimental data

Chemisorption of Na on the Ti Nanoparticle surface and its effects on the Na-H{sub 2}O reaction reactivity

Energy Technology Data Exchange (ETDEWEB)

Kim, Soo Jae; Park, Gunyeop; Baek, Jehyun; Park, Hyun Sun [POSTECH, Pohang (Korea, Republic of); Kim, Moo Hwan [Korea institute of Nuclear Safety, Daejeon (Korea, Republic of)

2015-10-15

This accident showed that elimination of SWR risk should be one of the most significant design criteria for the development of safe SFRs. Design solutions to ensure isolation of the Na from the water have been proposed; these include double-walled structures in the steam generator and at coolant boundaries and guard vessels or guard piping lines filled with inert gas. However, those methods cannot be ultimate solutions because the system still has a possibility of failure. An alternative approach to reduce the severity of the SWR is to reduce the reactivity of Na. Recently, this goal has been achieved by suspending a small amount of Ti nanoparticles (NPs) in liquid Na. Adding 2 at% of 10-nm Ti NPs in liquid Na reduced the heat of the reaction up to 80% and H{sub 2} production rate by 10%. The number of adsorbed Na atoms onto Ti NPs with respect to the various temperature and pressure was calculated by using ab-initio and thermodynamics. Furthermore, the model which relates the Na chemisorption and SWR reactivity was proposed. The repression of SWR by Ti NPs was expected to be caused by strong chemical interaction between Ti NP surface and Na atoms; ab initio calculation using density functional theory and atomistic thermodynamic approach were conducted to test this hypothesis. Adsorption of 0.25ML Na at hcp hollow sites was the most favorable adsorption surface state and strong chemical adsorption was confirmed by the adsorption energy of -1.65 eV. A covalent-like metallic bond was confirmed between adsorbed Na and Ti atoms on the Ti(0001) surface; this bond affects the hydration energy of Na atoms and the activation barrier of the SWR. Using adsorption energy from the ab-initio calculation and atomistic thermodynamics, the thermodynamically most stable adsorption state at (T,P) was determined Na chemisorption effect on the SWR reactivity regression rate is modeled. The model predict χ variation with respect to time well especially dramatic reduction of χ; the �

A soft x-ray photoemission study of the chemisorption and reaction of diethylsilane on Si(100)

International Nuclear Information System (INIS)

Lapiano-Smith, D.A.; Himpsel, F.J.

1993-06-01

Soft x-ray synchrotron radiation was utilized as the excitation source in a high-resolution photoemission experiment on chemisorption and subsequent reaction of diethylsilane on the Si(100) surface. We have found that diethylsilane chemisorbs dissociatively to form Si-CH 2 CH 3 surface species on Si(100) following a room temperature exposure. These species are identified by two very sharp peaks observed in the valence band spectra positioned at 17.9 and 14.3 eV binding energy. In addition, C 1s core level spectra, measured following exposures of Si(100) substrates as a function of surface temperature, show that carbon, in some form, exists on the Si surface following exposures at every temperature from room temperature to about 600C. While only -CH 2 CH 3 , ethyl groups are observed on the surface at room temperature, these species appear to partially dehydrogenate at 300C, producing a mixture of -CH 2 CH 3 groups and other intermediate carbonaceous species. At a growth temperature of about 400C the intermixing of elemental carbon with Si begins. At higher temperatures, we observe the continued degradation of diethylsilane to produce a Si + C alloy on the surface at 600C. Results indicate that diethylsilane has potential as a molecular precursor for SiC formation by chemical vapor deposition techniques

SFG experiment and ab initio study of the chemisorption of CN - on low-index platinum surfaces

Science.gov (United States)

Tadjeddine, M.; Flament, J.-P.; Le Rille, A.; Tadjeddine, A.

2006-05-01

A dual analysis is proposed in order to have a better understanding of the adsorption of the cyanide ions on a platinum electrode. The SFG (Sum Frequency Generation) spectroscopy allows the in situ vibrational study and the SFG spectra of the CN - species adsorbed on single crystal Pt electrode allow a systematic study of the low-index platinum surfaces. This experimental work is supported by ab initio calculations using density functional theory and cluster models. For each surface orientation and each geometry, a cluster model of 20-30 Pt atoms has been built in order to interpret the chemisorption of the CN - ions through four kinds of adsorption geometry: on-top or bridge site, bonding via C or N atoms. Geometries have been optimized and adsorption energies, electronic properties and vibrational frequencies have been computed. From the electronic properties, we can propose an analysis of the bonding mechanism for each studied kind of adsorption. The SFG spectra of the CN -/Pt(1 1 1) system present an unique resonance owing to the top C adsorption. It is mainly the same for the CN -/Pt(1 0 0) system. It is also the case for the SFG spectra of the CN -/Pt(1 1 0) system recorded at negative electrochemical voltage; at more positive voltage, a second resonance appears at a lower frequency, owing to the top N adsorption. Experimental and theoretical values of the C-N stretching frequencies are in excellent agreement.

Heat treatment effects on the surface chemisorption behavior of strained uranium: The H2O/U reaction

International Nuclear Information System (INIS)

Tiferet, E.; Mintz, M.H.; Zalkind, S.; Jacob, I.; Shamir, N.

2007-01-01

The initial interaction of H 2 O vapor with polycrystalline uranium surfaces was studied with samples initially strained, then strain relieved by heat treatments, performed in the temperature range up to ∼650 K. The chemisorption characteristics of these surfaces were studied by a combination of direct recoils spectrometry and X-ray photoelectron spectroscopy. X-ray diffraction measurements were used to determine the level of strain relief induced by each of the heat treatments. For all the samples, full water dissociation on the metal surface is observed. The reactivity of the samples towards water is clearly strain dependent, with the sticking coefficient decreasing as strain is relieved. It also seems that for strained samples the initial growth of the oxide is mostly inwards, while for the more relaxed samples lateral growth is dominant. Two interesting phenomena were observed for specific samples. For the 420 K relieved sample, partial dissociation process is observed on top of the forming oxide, in contrast to the full dissociation observed for the other samples. For the ∼650 K relieved sample, clustering of the adsorbed hydrogen atoms (resulted by water dissociation) on the metal surface is observed, in contrast to the homogeneous dispersion of H, occurring on the surface of all other samples. These two phenomena will further be studied in conjunction with microscopic metallurgical observations

A first-principles study of the SCN− chemisorption on the surface of AlN, AlP, and BP nanotubes

International Nuclear Information System (INIS)

Soltani, Alireza; Taghartapeh, Mohammad Ramezani; Mighani, Hossein; Pahlevani, Amin Allah; Mashkoor, Reza

2012-01-01

Graphical abstract: Adsorption properties of SCN − on AlN, AlP, and BP nanotubes based on density functional theory. ▶ We demonstrate the most stable configurations (N-side) of SCN − on AlN, AlP, and BP nanotubes models. Highlights: ► The SCN − Adsorption on surface of AlN, AlP, and BP nanotubes were studied via density functional theory (DFT). ► The interaction of SCN − on the electronic properties and the NBO charge distribution of mentioned configurations are investigated. ► The studies suggest that the adsorption energies of SCN − on AlPNT is most notable in comparison with AlNNT and BPNT. - Abstract: We have performed first-principles calculations to explore the adsorption behavior of the SCN − on electronic properties of AlN, AlP, and BP nanotubes. The adsorption value of SCN − for the most stable formation on the AlPNT is about −318.16 kJ mol −1 , which is reason via the chemisorptions of SCN anion. The computed density of states (DOS) indicates that a notable orbital hybridization take place between SCN − and AlP nanotube in adsorption process. Finally, the AlP nanotube can be used to design as useful sensor for nanodevice applications.

Strong Capillarity, Chemisorption, and Electrocatalytic Capability of Crisscrossed Nanostraws Enabled Flexible, High-Rate, and Long-Cycling Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Zhang, Wenjun; Wang, Lei; Hu, Yi; Zhu, Guoyin; Wang, Yanrong; Chen, Renpeng; Chen, Tao; Tie, Zuoxiu; Liu, Jie; Jin, Zhong

2018-05-22

The development of flexible lithium-sulfur (Li-S) batteries with high energy density and long cycling life are very appealing for the emerging flexible, portable, and wearable electronics. However, the progress on flexible Li-S batteries was limited by the poor flexibility and serious performance decay of existing sulfur composite cathodes. Herein, we report a freestanding and highly flexible sulfur host that can simultaneously meet the flexibility, stability, and capacity requirements of flexible Li-S batteries. The host consists of a crisscrossed network of carbon nanotubes reinforced CoS nanostraws (CNTs/CoS-NSs). The CNTs/CoS-NSs with large inner space and high conductivity enable high loading and efficient utilization of sulfur. The strong capillarity effect and chemisorption of CNTs/CoS-NSs to sulfur species were verified, which can efficiently suppress the shuttle effect and promote the redox kinetics of polysulfides. The sulfur-encapsulated CNTs/CoS-NSs (S@CNTs/CoS-NSs) cathode in Li-S batteries exhibits superior performance, including high discharge capacity, rate capability (1045 mAh g -1 at 0.5 C and 573 mAh g -1 at 5.0 C), and cycling stability. Intriguingly, the soft-packed Li-S batteries based on S@CNTs/CoS-NSs cathode show good flexibility and stability upon bending.

Oxidation of Propylene on catalytic Pt-Cu/y alumina. (Part I) Characterization of catalysts of Pt-Cu/y alumina for chemisorption of H2

International Nuclear Information System (INIS)

Carballo, Luis M; Zea, Hugo R

1999-01-01

In this work the effect of the composition of catalysts of Pt-Cu/y-alumina is analyzed on the superficial area it reactivates corresponding to the total oxidation of propylene. The experimental essays were also made in a differential reactor that was used so much for the characterization of the catalyst in situ by means of the measurement of the selective chemisorption of H 2 , the effects and the bimetallic interactions are discussed that frequently happen in the supported catalysts. Starting from the studies of chemical adsorption of H 2 on the supported catalysts of Pt-Cu was, by means of the application of the theory of the regular solution to the surface of the glasses and keeping in mind that the H 2 it adsorbs chemically only on the superficial atoms of Pt (it was observed that the hydrogen not it chemi-absorb on the Cu) that the Cu atoms are segregated to the surface of the bimetallic crystals

Alloy formation and chemisorption at Zn/Pt(111) bimetallic surfaces using alkali ISS, XPD, and TPD.

Science.gov (United States)

Ho, Chih-Sung; Martono, Eddie; Banerjee, Santanu; Roszell, John; Vohs, John; Koel, Bruce E

2013-11-21

Alloy formation and chemisorption at bimetallic surfaces formed by vapor-depositing Zn on a Pt(111) single crystal were investigated primarily by using X-ray photoelectron diffraction (XPD), X-ray photoelectron spectroscopy (XPS), low-energy alkali ion scattering spectroscopy (ALISS), low electron energy diffraction (LEED), and temperature programmed desorption (TPD). A wide range of conditions were investigated to explore whether deposition and annealing of Zn films could produce well-defined, ordered alloy surfaces, similar to those encountered for Sn/Pt(111) surface alloys. These attempts were unsuccessful, although weak, diffuse (2 × 2) spots were observed under special conditions. The particular PtZn bimetallic alloy created by annealing one monolayer of Zn on Pt(111) at 600 K, which has a Zn composition in the surface layer of about 5 at. %, was investigated in detail by using XPD and ALISS. Only a diffuse (1 × 1) pattern was observed from this surface by LEED, suggesting that no long-range, ordered alloy structure was formed. Zn atoms were substitutionally incorporated into the Pt(111) crystal to form a near-surface alloy in which Zn atoms were found to reside primarily in the topmost and second layers. The alloyed Zn atoms in the topmost layer are coplanar with the Pt atoms in the surface layer, without any "buckling" of Zn, that is, displacement in the vertical direction. This result is expected because of the similar size of Pt and Zn, based on previous studies of bimetallic Pt alloys. Zn atoms desorb upon heating rather than diffusing deep into the bulk of the Pt crystal. Temperature programmed desorption (TPD) measurements show that both CO and NO have lower desorption energies on the PtZn alloy surface compared to that on the clean Pt(111) surface.

Coupled cluster and density functional theory calculations of atomic hydrogen chemisorption on pyrene and coronene as model systems for graphene hydrogenation.

Science.gov (United States)

Wang, Ying; Qian, Hu-Jun; Morokuma, Keiji; Irle, Stephan

2012-07-05

Ab initio coupled cluster and density functional theory studies of atomic hydrogen addition to the central region of pyrene and coronene as molecular models for graphene hydrogenation were performed. Fully relaxed potential energy curves (PECs) were computed at the spin-unrestricted B3LYP/cc-pVDZ level of theory for the atomic hydrogen attack of a center carbon atom (site A), the midpoint of a neighboring carbon bond (site B), and the center of a central hexagon (site C). Using the B3LYP/cc-pVDZ PEC geometries, we evaluated energies at the PBE density functional, as well as ab initio restricted open-shell ROMP2, ROCCSD, and ROCCSD(T) levels of theory, employing cc-pVDZ and cc-pVTZ basis sets, and performed a G2MS extrapolation to the ROCCSD(T)/cc-pVTZ level of theory. In agreement with earlier studies, we find that only site A attack leads to chemisorption. The G2MS entrance channel barrier heights, binding energies, and PEC profiles are found to agree well with a recent ab initio multireference wave function theory study (Bonfanti et al. J. Chem. Phys.2011, 135, 164701), indicating that single-reference open-shell methods including B3LYP are sufficient for the theoretical treatment of the interaction of graphene with a single hydrogen atom.

Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

Energy Technology Data Exchange (ETDEWEB)

Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen; Morris, Allen R.; Holles, Joseph H.

2016-10-20

Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, further providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.

Disilane chemisorption on Si(x)Ge(1-x)(100)-(2 x 1): molecular mechanisms and implications for film growth rates.

Science.gov (United States)

Ng, Rachel Qiao-Ming; Tok, E S; Kang, H Chuan

2009-07-28

At low temperatures, hydrogen desorption is known to be the rate-limiting process in silicon germanium film growth via chemical vapor deposition. Since surface germanium lowers the hydrogen desorption barrier, Si(x)Ge((1-x)) film growth rate increases with the surface germanium fraction. At high temperatures, however, the molecular mechanisms determining the epitaxial growth rate are not well established despite much experimental work. We investigate these mechanisms in the context of disilane adsorption because disilane is an important precursor used in film growth. In particular, we want to understand the molecular steps that lead, in the high temperature regime, to a decrease in growth rate as the surface germanium increases. In addition, there is a need to consider the issue of whether disilane adsorbs via silicon-silicon bond dissociation or via silicon-hydrogen bond dissociation. It is usually assumed that disilane adsorption occurs via silicon-silicon bond dissociation, but in recent work we provided theoretical evidence that silicon-hydrogen bond dissociation is more important. In order to address these issues, we calculate the chemisorption barriers for disilane on silicon germanium using first-principles density functional theory methods. We use the calculated barriers to estimate film growth rates that are then critically compared to the experimental data. This enables us to establish a connection between the dependence of the film growth rate on the surface germanium content and the kinetics of the initial adsorption step. We show that the generally accepted mechanism where disilane chemisorbs via silicon-silicon bond dissociation is not consistent with the data for film growth kinetics. Silicon-hydrogen bond dissociation paths have to be included in order to give good agreement with the experimental data for high temperature film growth rate.

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

Science.gov (United States)

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

2016-03-09

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

Magnetism and chemisorption

International Nuclear Information System (INIS)

Johnson, P.D.

1989-01-01

Spin polarized photoemission studies of different adsorbates on an Fe (001) substrate show the interaction between the adsorbate and the substrate d bands. Studies of the adsorption of oxygen reveal exchange split adsorbate bands indicative of both a magnetic moment on the adsorbate atom and also a strong adsorbate p z substrate d z 2 bond. The oxygen p z bands show a large variation in exchange splitting across the surface zone, an observation that is not predicted in first principles calculations of this system. Spin Polarized Auger Electron Spectroscopy studies of sulfur adsorbed on the same surface provide some indication of the magnetic moment on the adsorbate. It is found to be of the order of 0.1 μB. Studies of carbon monoxide adsorption in two different configurations, vertical and tilted, reveal little or no exchange splitting in the molecular 5σ orbital suggesting that the interaction of this orbital with the substrate d bands is much weaker. 38 refs., 11 figs

Adsorption-induced restructuring of gold nanochains

DEFF Research Database (Denmark)

Bahn, Sune Rastad; Lopez, Nuria; Nørskov, Jens Kehlet

2002-01-01

The chemical properties of single-atomic chains of gold atoms are investigated using density functional calculations. The nanochains are shown to be unusually chemically active with strong chemisorption of oxygen atoms and carbon monoxide. The chemisorption energies vary significantly with the st......The chemical properties of single-atomic chains of gold atoms are investigated using density functional calculations. The nanochains are shown to be unusually chemically active with strong chemisorption of oxygen atoms and carbon monoxide. The chemisorption energies vary significantly...... with the strain/stress conditions for the chain. Oxygen atoms are found to energetically prefer to get incorporated into a chain forming a new type of gold-oxygen nanochain with a conductance of one quantum unit. We suggest that the long bond lengths observed in electron microscopy investigations of gold chains...

Reactivity of niobium cluster anions with nitrogen and carbon monoxide

Science.gov (United States)

Mwakapumba, Joseph; Ervin, Kent M.

1997-02-01

Reactions of small niobium cluster anions, Nbn-(n = 2-7), with CO and N2 are investigated using a flow tube reactor (flowing afterglow) apparatus. Carbon monoxide chemisorption on niobium cluster anions occurs with faster reaction rates than nitrogen chemisorption on corresponding cluster sizes. N2 addition to niobium cluster anions is much more size-selective than is CO addition. These general trends follow those reported in the literature for reactions of neutral and cationic niobium clusters with CO and N2. Extensive fragmentation of the clusters is observed upon chemisorption. A small fraction of the larger clusters survive and sequentially add multiple CO or N2 units without fragmentation. However, chemisorption saturation is not reached at the experimentally accessible pressure and reagent concentration ranges. The thermochemistry of the adsorption processes and the nature of the adsorbed species, molecular or dissociated, are discussed.

Prediction of coal reactivity during combustion and gasification by using petrographic data

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; Palmer, A.D.; Kalkreuth, W.D.; Cameron, A.R.; Kovacik, G.

1990-06-01

Petrographic data were correlated with calorific value, oxygen content, fuel ratio, ignition temperature, oxygen chemisorption and selected gasification reactivity data of twenty one Canadian coals (17 from Western and 4 from Eastern Canada). Both parameters are suitable for predicting other coal properties in the absence of mineral matter effects. Using ignition temperature and oxygen chemisorption the series of coals can be divided into three groups. The first group, characterized by low ignition temperatures and low oxygen chemisorption, had mean vitrinite reflectance and/or petrofactor less than 0.6 and/or 7.0 The second group, characterized by the largest oxygen chemisorption and intermediate ignition temperatures had mean vitrinite reflectance and/or petrofactor in the range of 0.6 to 1.0 and/or 7.0 to 11.0. The third group, characterized by the highest ignition temperatures and the lowest oxygen chemisorption had mean vitrinite reflectance and/or petrofactor greater than about 1.0 and/or 11.0. Calorific value and ignition temperature are good correlating parameters for low rank coals, whereas fuel ratio is suitable for higher rank coals. The petrofactor as a correlating parameter offered little advantage compared with the mean vitrinite reflectance. 20 refs., 15 figs., 4 tabs.

Performance Analysis of Thiocarbonohydrazide as a Novel Selective Depressant for Chalcopyrite in Molybdenite-Chalcopyrite Separation

Directory of Open Access Journals (Sweden)

Changping Guan

2018-04-01

Full Text Available A novel surfactant, thiocarbonohydrazide (TCH, was synthesized and tested for the first time as a selective chalcopyrite depressant in Cu-Mo separation. Its adsorption mechanisms on chalcopyrite were studied by flotation tests, zeta potential, FTIR, XPS and ToF-SIMS measurements. FTIR and zeta potential analyses suggested that there was a strong chemisorption reaction between TCH and chalcopyrite, resulting in the formation of TCH–copper complexes. XPS and ToF-SIMS measurements further confirmed the chemisorption of TCH onto the chalcopyrite surface and showed that this chemisorption reaction is due to its S and N atoms, which form five-membered chelating rings by releasing H ions.

Progress in surface and membrane science

CERN Document Server

Cadenhead, D A; Rosenberg, M D

1975-01-01

Progress in Surface and Membrane Science, Volume 9 covers the developments in surface and membrane science. The book discusses the physical adsorption of gases and vapors in micropores; the chemisorption theory; and the role of radioisotopes in the studies of chemisorption and catalysis. The text also describes the interaction of ions with monolayers; and the isolation and characterization of mycoplasma membranes. Chemists, physical chemists, and microbiologists will find the book useful.

Electrical double layer structure at the gallium metals in a methanol solution of a surface-inactive electrolyte

International Nuclear Information System (INIS)

Emets, V.V.

1997-01-01

The structure of double electric layer on Ga-, In-Ga- and Tl-Ga-electrodes in methanol solutions of surface-inactive electrolyte has been studied. It is shown that in the absence of chemisorption interaction between metal and solvent, the distance of the nearest approach of methanol dipoles to the surface of Ga-, In-Ga- and Tl-Ga-electrodes is practically the same. Accordingly, the specificity of the metals contact with solvent is reduced solely to their chemisorption interaction. In the zero charge area and for negative charges the chemisorption interaction with methanol molecules increases in the sequence Tl-Ga< In-Ga< Ga. The growth correlates both with the metals acceptor ability towards electron, which is characterized by the work of metal electron escape to vacuum, and donor ability of the solvent characterized by its donor number

Some unusual properties of activated and reduced AgNaA zeolites

Energy Technology Data Exchange (ETDEWEB)

Jacobs, P.A. (Katholieke Univ. Leuven); Uytterhoeven, J.B.; Beyer, H.K.

1979-01-01

In a study of chemisorption on dehydrated silver-exchanged A zeolite by volumetric sorption and temperature-programed desorption techniques, an autoreductive process which created intense color centers, occurred on degassing the zeolite because of the formation of silver covalent bonds. The chemisorption of hydrogen was proportional to the amount of autoreduction, indicating that the process occurred on the color centers. Both oxygen and hydrogen chemisorbed dissociatively, as shown by tracing with labeled oxygen and by the ability of one water molecule to replace two hydrogen atoms. Carbon monoxide, however, was chemisorbed on the available silver ions in the zeolite supercages, whether or not they were a part of the cluster formation. Linear silver ion/silver/silver ion clusters are apparently formed in the zeolite cubo-octahedra upon activation; the ends form chemisorption sites for hydrogen and oxygen.

Chlorine-induced modifications in the electronic structure of Ag surfaces: a metastable deexcitation spectroscopy and photoemission comparative study

CERN Document Server

Pasquali, L; Canepa, M; Staicu-Casagrande, E M; Esaulov, V A

2003-01-01

Surface-sensitive spectroscopic techniques, namely metastable deexcitation spectroscopy (MDS) and ultraviolet photoemission (UPS), have been applied to investigate the effects of chlorine chemisorption on the electronic properties (surface density of states and charge density) of Ag(100), Ag(110) and Ag(111) surfaces. Initial stages of chemisorption, up to the formation of a saturated Cl overlayer, have been examined. In particular, MDS permitted us to observe at low Cl gas exposure a progressive depletion of the Ag (5s) charge due to transfer and bonding with Cl atoms. From both MDS and UPS it was possible to observe the development of Cl (3p) bonding and anti-bonding states, the amount of their splitting increasing with coverage. Differences between chemisorption at the three surfaces have been noticed and they have been justified in terms of the different adatom packing and possible formation of small AgCl clusters (especially for the Ag(111) surface).

Uranium uptake by the filamentous fungal biomass, Aspergillus fumigatus and mechanism of biosorption

International Nuclear Information System (INIS)

Bhainsa, Kuber C.; D'Souza, S.F.

2010-01-01

Uptake of uranium by Aspergillus fumigatus was investigated in a batch study. Previously, we had reported good uranium uptake capacity, i.e., 423 mg U/g by this fungal biomass. The objective of the present study was to investigate the uranium uptake and mechanism of biosorption by Aspergillus fumigatus. The metal uptake was rapid and 80% of metal ion could be removed within 4 minutes of contact time. Kinetic modeling indicated that the uptake of uranium followed Lagergren's pseudo-second order reaction indicating the process to be mediated through chemisorption mechanism. Further studies on isotherm modeling were carried out using D-R isotherm to confirm the same. The energy of biosorption obtained from D-R isotherm was found to be 14.4 kJ/mol. This energy corresponds to the energy of chemisorption (ion-exchange) which varies between 8-16 kJ/mol. All these results suggest that uranium uptake by Aspergillus fumigatus is mediated through chemisorptions mechanism. (author)

Chlorine-induced modifications in the electronic structure of Ag surfaces: a metastable deexcitation spectroscopy and photoemission comparative study

International Nuclear Information System (INIS)

Pasquali, L; Nannarone, S; Canepa, M; Staicu-Casagrande, E M; Esaulov, V A

2003-01-01

Surface-sensitive spectroscopic techniques, namely metastable deexcitation spectroscopy (MDS) and ultraviolet photoemission (UPS), have been applied to investigate the effects of chlorine chemisorption on the electronic properties (surface density of states and charge density) of Ag(100), Ag(110) and Ag(111) surfaces. Initial stages of chemisorption, up to the formation of a saturated Cl overlayer, have been examined. In particular, MDS permitted us to observe at low Cl gas exposure a progressive depletion of the Ag (5s) charge due to transfer and bonding with Cl atoms. From both MDS and UPS it was possible to observe the development of Cl (3p) bonding and anti-bonding states, the amount of their splitting increasing with coverage. Differences between chemisorption at the three surfaces have been noticed and they have been justified in terms of the different adatom packing and possible formation of small AgCl clusters (especially for the Ag(111) surface)

CHEMISORPtION OF SULFUR (IV OXIDeBY PoLYETHYLENEPOLYAMINE IMPREGNATED FIBROUS MATERIALS. 1. HYDROPHILIC POLYETHYLENEPOLYAMINE IMPREGNATED FIBROUS MATERIALS

Directory of Open Access Journals (Sweden)

A. A. Ennan

2015-03-01

Full Text Available The hydrophilicity of artificial and synthetic fibers and polyethylenepolyamine (PEPA impregnated fibrous materials based on them was investigated under static conditions using a vacuum sorption installation. Water vapor sorption isotherms were analyzed and monolayer capacitance values  and a water molecules adsorption in the first layer heats were determined in the framework of polymolecular adsorption Brunauer – Emmett – Teller. It has been found that the hydrophilicity of the fibers studied to change in the following sequence: viscose > VION AN-3 > VION KN-1 > nylon-polyester > nitrone > polyester > polypropylene; PEPA modified hydrophilic fibrous material does not depend essentially on the chemical nature of the carrier.

Adsorption and collective paramagnetism

CERN Document Server

Selwood, Pierce W

1962-01-01

Adsorption and Collective Paramagnetism describes a novel method for studying chemisorption. The method is based on the change in the number of unpaired electrons in the adsorbent as chemisorption occurs. The method is applicable to almost all adsorbates, but it is restricted to ferromagnetic adsorbents such as nickel, which may be obtained in the form of very small particles, that is to say, to ferromagnetic adsorbents with a high specific surface. While almost all the data used illustratively have been published elsewhere this is the first complete review of the subject. The book is addresse

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Adsorption on metal oxides Studies with the metastable impact electron spectroscopy

CERN Document Server

Krischok, S; Kempter, V

2002-01-01

An overview is given on the application of metastable impact electron spectroscopy, in combination with UPS, to the study of clean magnesia and titania surfaces and their interaction with metal atoms and small molecules. The mechanisms for metal adsorption on reducible (titania) and non-reducible (magnesia) substrates are different: while on titania the metal atom often bonds by electron transfer to Ti3d states, it is hybridization of the adsorbate and anion wavefunctions which accounts for the bonding on MgO. In the case of H sub 2 O, molecular adsorption takes place both on MgO and TiO sub 2; on the other hand, water-alkali coadsorption leads to hydroxide formation. In the case of CO sub 2 , chemisorption takes place in form of carbonate (CO sub 3) species. These originate from the CO sub 2 interaction with O sup 2 sup - surface anions. While for CaO chemisorption takes place at regular oxygen sites, for MgO this occurs at low-coordinated oxygen ions only; for TiO sub 2 chemisorption requires alkali coadsor...

Reduction of dioxins-furans formed in combustion and Denovo synthesis

International Nuclear Information System (INIS)

Teller, A.J.

1991-01-01

This paper reports that the acceptance that Denovo synthesis of dioxins and furans occurs on the surface of flyash particles in the temperature range of 200 degrees C-400 degrees C, establishes that post combustion formation of dioxins must be addressed. Dioxin-guran emission reduction can be achieved by addition of synthesis inhibitors, adsorbers, catalytic destruction, or utilization of the inherent capability of silica-alumina for chemisorption of the dioxins and furans within appropriate temperature ranges. The chemisorption procedure, as applied to commercial incinerator operation adds no additional equipment or capital and operating costs to the system. The equilibria rather kinetics controls the absorption. Thus, wide variation in inlets are accepted by the system with no externally induced system response required. Experience at the Commerce, California waste to energy system established reductions of total dioxin and furan cogeners to 1.9 ng/Nm 3 from inlet concentrations ranging from 28 to 735 ng/Mm 3 , within the existing acid gas-particulate-heavy metal removal system, using only temperature control to affect the removal by chemisorption

Adsorption on metal oxides: Studies with the metastable impact electron spectroscopy

International Nuclear Information System (INIS)

Krischok, S.; Hoefft, O.; Kempter, V.

2002-01-01

An overview is given on the application of metastable impact electron spectroscopy, in combination with UPS, to the study of clean magnesia and titania surfaces and their interaction with metal atoms and small molecules. The mechanisms for metal adsorption on reducible (titania) and non-reducible (magnesia) substrates are different: while on titania the metal atom often bonds by electron transfer to Ti3d states, it is hybridization of the adsorbate and anion wavefunctions which accounts for the bonding on MgO. In the case of H 2 O, molecular adsorption takes place both on MgO and TiO 2 ; on the other hand, water-alkali coadsorption leads to hydroxide formation. In the case of CO 2 , chemisorption takes place in form of carbonate (CO 3 ) species. These originate from the CO 2 interaction with O 2- surface anions. While for CaO chemisorption takes place at regular oxygen sites, for MgO this occurs at low-coordinated oxygen ions only; for TiO 2 chemisorption requires alkali coadsorption

Carbon monoxide adsorption studies on Ru:Mn bimetallic catalysts supported on alumina, silica and titania supported for the determination of metal surface area overview

International Nuclear Information System (INIS)

Hussain, S.T.

1992-01-01

Supported Ru: Mn bimetallic samples were studied using CO-chemisorption on alumina, silica and titania supports for the determination of active metal site/metal surface area. The data indicates the presence of Mn on the surface of Ru. With the increase of Mn loadings a decrease in the CO adsorption occurred indicating that presence of Mn masks the active sites responsible for Co-adsorption. On the titania supported system reduced at high and low temperature the CO-chemisorption data suggest the unusual behaviour. This behaviour is possibly caused due to creation of new active surface sites. (author)

BEP-relations for N2 dissociation over stepped transition metal and alloy surfaces

DEFF Research Database (Denmark)

Fronczek-Munter, Ture Rønved; Bligaard, Thomas; Christensen, Claus H.

2008-01-01

, a perfectly linear Bronsted-Evans-Polanyi (BEP) relation between the transition-state potential energy and the dissociative chemisorption energy is obtained. The perfect BEP relation, which extends over 12 eV in chemisorption energy, suggests that the manifestation of BEP relations for surface reactions...... is a general electronic structure effect, and that geometric effects are responsible for the scatter which is normally observed around the BEP line. The BEP relation is also shown to be valid for both surface and bulk alloys. The scatter is, however, larger than for the pure elements. This can be understood...

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.

Surface effects of electrode-dependent switching behavior of resistive random-access memory

KAUST Repository

Ke, Jr Jian

2016-09-26

The surface effects of ZnO-based resistive random-access memory (ReRAM) were investigated using various electrodes. Pt electrodes were found to have better performance in terms of the device\\'s switching functionality. A thermodynamic model of the oxygen chemisorption process was proposed to explain this electrode-dependent switching behavior. The temperature-dependent switching voltage demonstrates that the ReRAM devices fabricated with Pt electrodes have a lower activation energy for the chemisorption process, resulting in a better resistive switching performance. These findings provide an in-depth understanding of electrode-dependent switching behaviors and can serve as design guidelines for future ReRAM devices.

Tailoring silver nanoparticle construction using dendrimer templated silica networks

International Nuclear Information System (INIS)

Liu Xiaojun; Kakkar, Ashok

2008-01-01

We have examined the role of the internal environment of dendrimer templated silica networks in tailoring the construction of silver nanoparticle assemblies. Silica networks from which 3,5-dihydroxybenzyl alcohol based dendrimer templates have been completely removed, slowly wet with an aqueous solution of silver acetate. The latter then reacts with internal silica silanol groups, leading to chemisorption of silver ions, followed by the growth of silver oxide nanoparticles. Silica network constructed using generation 4 dendrimer contains residual dendrimer template, and mixes with aqueous silver acetate solution easily. Upon chemisorption, silver ions get photolytically reduced to silver metal under a stabilizing dendrimer environment, leading to the formation of silver metal nanoparticles

Importance of the oxygen bond strength for catalytic activity in soot oxidation

DEFF Research Database (Denmark)

Christensen, Jakob M.; Grunwaldt, Jan-Dierk; Jensen, Anker D.

2016-01-01

(loose contact) the rate constants for a number of catalytic materials outline a volcano curve when plotted against their heats of oxygen chemisorption. However, the optima of the volcanoes correspond to different heats of chemisorption for the two contact situations. In both cases the activation...... oxidation. The optimum of the volcano curve in loose contact is estimated to occur between the bond strengths of α-Fe2O3 and α-Cr2O3. Guided by an interpolation principle FeaCrbOx binary oxides were tested, and the activity of these oxides was observed to pass through an optimum for an FeCr2Ox binary oxide...

In situ XAFS studies of the oxygen reduction reaction on carbon supported platinum and platinum nickel nano-scale alloys as cathode catalysts in fuel cells

Science.gov (United States)

Jia, Qingying

Platinum based bimetallic alloys have been investigated by conducting Pt L3 and Ni K edge in situ XAFS measurements on carbon supported Pt and PtNi(1:1) nanoscale catalysts under a wide range of operating potentials. We observed that (1) the Pt-Pt bond distance in PtNi alloys is shorter than that of Pt, and the bond distance between Pt and oxygen adsorbate is longer for PtNi. (2) Pt has a tendency to stay on the surface while Ni is mostly underneath the surface. (3) While a change in oxidation of pure Pt was clearly observed at different potentials, the Pt in the PtNi alloy remained nearly oxygen-free at all potentials, but an accompanying oxidation change of Ni was observed instead. (4) PtNi has higher open circuit voltage than Pt/C. These results indicate that the chemisorption energy between Pt and oxygen adsorbate is reduced in PtNi alloys, which prevents the poison of oxygen adsorbate and hence improves the reactivity. In addition, the strain and ligand effects in PtNi nanoparticle alloys were studied by FEW calculations using experimental data as a guide to understand the factors causing the reduction of chemisorptions energy of Pt. Our calculation indicates that Pt d-band is broader and lower in energy when the bond distance between Pt is shorter, resulting in weaker chemisorption energy between Pt and absorbed oxygen atom on top, and vice verse. Meanwhile, the investigation of ligand effect shows two trends in modifying Pt's properties within alloyed transition metals. The strain effect dominates in PtNi bimetallic system, corresponding to weaker chemisorptions energy and lower white intensity of Pt L3 edge, which is in consistent with our experimental results. The implications of these results afford a good guideline in understanding the reactivity enhancement mechanism and in the context of alloy catalysts design.

Nature of adsorption on TiC(111) investigated with density-functional calculations

Science.gov (United States)

Ruberto, Carlo; Lundqvist, Bengt I.

2007-06-01

Extensive density-functional calculations are performed for chemisorption of atoms in the three first periods (H, B, C, N, O, F, Al, Si, P, S, and Cl) on the polar TiC(111) surface. Calculations are also performed for O on TiC(001), for full O(1×1) monolayer on TiC(111), as well as for bulk TiC and for the clean TiC(111) and (001) surfaces. Detailed results concerning atomic structures, energetics, and electronic structures are presented. For the bulk and the clean surfaces, previous results are confirmed. In addition, detailed results are given on the presence of C-C bonds in the bulk and at the surface, as well as on the presence of a Ti-based surface resonance (TiSR) at the Fermi level and of C-based surface resonances (CSR’s) in the lower part of the surface upper valence band. For the adsorption, adsorption energies Eads and relaxed geometries are presented, showing great variations characterized by pyramid-shaped Eads trends within each period. An extraordinarily strong chemisorption is found for the O atom, 8.8eV /adatom. On the basis of the calculated electronic structures, a concerted-coupling model for the chemisorption is proposed, in which two different types of adatom-substrate interactions work together to provide the obtained strong chemisorption: (i) adatom-TiSR and (ii) adatom-CSR’s. This model is used to successfully describe the essential features of the calculated Eads trends. The fundamental nature of this model, based on the Newns-Anderson model, should make it apt for general application to transition-metal carbides and nitrides and for predictive purposes in technological applications, such as cutting-tool multilayer coatings and MAX phases.

Finite Size Effects in Submonolayer Catalysts Investigated by CO Electrosorption on PtsML/Pd(100).

Science.gov (United States)

Yuan, Qiuyi; Doan, Hieu A; Grabow, Lars C; Brankovic, Stanko R

2017-10-04

A combination of scanning tunneling microscopy, subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), and density functional theory (DFT) is used to quantify the local strain in 2D Pt clusters on the 100 facet of Pd and its effect on CO chemisorption. Good agreement between SNIFTIRS experiments and DFT simulations provide strong evidence that, in the absence of coherent strain between Pt and Pd, finite size effects introduce local compressive strain, which alters the chemisorption properties of the surface. Though this effect has been widely neglected in prior studies, our results suggest that accurate control over cluster sizes in submonolayer catalyst systems can be an effective approach to fine-tune their catalytic properties.

Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface

DEFF Research Database (Denmark)

Demers-Carpentier, Vincent; Goubert,, Guillaume; Masini, Federico

2011-01-01

The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that conti......The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex...... functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different...

Alkali promotion effect in Fischer-Tropsch cobalt-alumina catalyst

Energy Technology Data Exchange (ETDEWEB)

Eliseev, O.L.; Tsapkina, M.V.; Davydov, P.E.; Kazantsev, R.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry; Belousova, O.S.; Lapidus, A.L. [Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation)

2011-07-01

Promoting Co-alumina Fischer-Tropsch synthesis catalysts with alkali and alkaline-earth metals was studied. XRD, oxygen titration and CO chemisorption were used for the characterization of the catalysts. The best results in terms of catalyst selectivity and long-chain alkanes content in synthesized products were obtained with K-promoted catalyst. Catalytic performance strongly depends on K:Co atomic ratio as well as preparation procedure. Effect of K loading on selectivities is non-linear with extreme point at K:Co=0.01. Significant increase in C{sub 5+} selectivity of K-promoted catalyst may be explained as a result of strong CO adsorption on the catalyst surface, as was confirmed in CO chemisorption experiments. (orig.)

Mercury chemisorption by sulfur adsorbed in porous materials

NARCIS (Netherlands)

Steijns, M.; Peppelenbos, A.; Mars, P.

1976-01-01

The sorption of mercury vapor by adsorbed sulfur in the zeolites CaA (= 5A) and NaX (=13X) and two types of active carbon has been measured at a temperature of 50°C. With increasing degree of micropore filling by sulfur the fraction of sulfur accessible to mercury atoms decreased for CaA and NaX.

Electronic shell structure and chemisorption on gold nanoparticles

DEFF Research Database (Denmark)

Larsen, Ask Hjorth; Kleis, Jesper; Thygesen, Kristian Sommer

2011-01-01

to distort considerably, creating large band gaps at the Fermi level. For up to 200 atoms we consider structures generated with a simple EMT potential and clusters based on cuboctahedra and icosahedra. All types of cluster geometry exhibit jelliumlike electronic shell structure. We calculate adsorption...... energies of several atoms on the cuboctahedral clusters. Adsorption energies are found to vary abruptly at magic numbers. Using a Newns-Anderson model we find that the effect of magic numbers on adsorption energy can be understood from the location of adsorbate-induced states with respect to the cluster...

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

International Nuclear Information System (INIS)

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

2017-01-01

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

Density functional theory study on the interactions of l-cysteine with graphene: adsorption stability and magnetism

International Nuclear Information System (INIS)

Luo, Huijuan; Li, Hejun; Fu, Qiangang; Chu, Yanhui; Cao, Xiaoyu; Sun, Can; Yuan, Xiaoyan; Liu, Lei

2013-01-01

Understanding the interactions between graphene and biomolecules is of fundamental relevance to the area of nanobiotechnology. Herein, we take l-cysteine as the probe biomolecule and investigate its adsorption on pristine graphene and B-, N-, Al-, Ni-, Ga-, Pd-doped graphene using density functional theory calculations. Three kinds of upright adsorption configurations, via unprotonated functional groups (–SH, –NH 2 , –COOH), are considered. The calculations reveal pristine graphene physically adsorbs l-cysteine. N-doped graphene shows physisorption towards the S-end and N-end l-cysteine, and chemisorption towards the O-end radical. Strong chemisorption, with site-specific preference, occurs on Al-, Ni-, Ga- and Pd-doped graphene, accompanied by severe structural changes. Spin polarization with an unusual mirror symmetry on Ni- and Pd-doped graphene is induced by chemisorption of unprotonated l-cysteine, except for O-end adsorption on Pd-doped graphene. The magnetization arises mainly from spin polarization of the C 2p z orbital, with a minor magnetism located on Ni or Pd. The influence of van der Waals forces is also evaluated. A thorough analysis of the adsorption stability and magnetism of these systems would be beneficial to facilitate applications in graphene-based biosensing, biomolecule immobilization, magnetic bio-separation and other fields in bionanotechnology. (paper)

Tensile properties of ADI material in water and gaseous environments

Energy Technology Data Exchange (ETDEWEB)

Rajnovic, Dragan, E-mail: draganr@uns.ac.rs [Faculty of Technical Sciences, University of Novi Sad, Trg D. Obradovića 6, 21000 Novi Sad (Serbia); Balos, Sebastian; Sidjanin, Leposava [Faculty of Technical Sciences, University of Novi Sad, Trg D. Obradovića 6, 21000 Novi Sad (Serbia); Eric Cekic, Olivera [Innovation Centre, Faculty of Mechanical Engineering, University of Belgrade, Kraljice Marije 16, 11120 Belgrade (Serbia); Grbovic Novakovic, Jasmina [Vinca Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11000 Belgrade (Serbia)

2015-03-15

Austempered ductile iron (ADI) is an advanced type of heat treated ductile iron, having comparable mechanical properties as forged steels. However, it was found that in contact with water the mechanical properties of austempered ductile irons decrease, especially their ductility. Despite considerable scientific attention, the cause of this phenomenon remains unclear. Some authors suggested that hydrogen or small atom chemisorption causes the weakening of the surface atomic bonds. To get additional reliable data of that phenomenon, in this paper, two different types of austempered ductile irons were tensile tested in various environments, such as: argon, helium, hydrogen gas and water. It was found that only the hydrogen gas and water gave a statistically significant decrease in mechanical properties, i.e. cause embrittlement. Furthermore, the fracture surface analysis revealed that the morphology of the embrittled zone near the specimen surface shares similarities to the fatigue micro-containing striation-like lines, which indicates that the morphology of the brittle zone may be caused by cyclic local-chemisorption, micro-embrittlement and local-fracture. - Highlights: • In contact with water and other liquids the ADI suddenly exhibits embrittlement. • The embrittlement is more pronounced in water than in the gaseous hydrogen. • The hydrogen chemisorption into ADI surface causes the formation of a brittle zone. • The ADI austempered at lower temperatures (300 °C) is more resistant to embrittlement.

Technical and economical feasibility of the hybrid adsorption compression heat pump concept for industrial applications

International Nuclear Information System (INIS)

Pal, Michel van der; Wemmers, Anton; Smeding, Simon; Boer, Robert de

2013-01-01

Heat pump technologies offer a significant potential for primary energy savings in industrial processes. Thermally driven heat pumps can use waste heat as driving energy source to provide either heating or cooling. A chemi-sorption heat transformer can upgrade a waste heat source to temperatures of 150–200 °C. The specific heat transformer process however requires waste heat temperatures in the range of 120 °C, whereas waste heat sources of lower temperatures are more abundant. Using this lower temperature waste heat, and still reach the desired higher output temperatures can be achieved by the integration of a chemisorption and mechanical compression step in a single hybrid heat pump concept. This concept can offer an increased flexibility in temperatures, both for the waste heat source as for the heat delivery. The technical and economical feasibility of the proposed hybrid heat pump concept is evaluated. The range of operating temperatures of different chemi-sorption working pairs for as heat driven and as hybrid systems are defined, as well as their energy efficiencies. Investment costs for the hybrid systems are derived and payback times are calculated. The range of payback times is from 2 to 9 years and are strongly influenced by the number of operating hours, the electrical COP of the compression stage, and the energy prices

Surface effects of electrode-dependent switching behavior of resistive random-access memory

KAUST Repository

Ke, Jr Jian; Wei, Tzu Chiao; Tsai, Dung Sheng; Lin, Chun-Ho; He, Jr-Hau

2016-01-01

of the oxygen chemisorption process was proposed to explain this electrode-dependent switching behavior. The temperature-dependent switching voltage demonstrates that the ReRAM devices fabricated with Pt electrodes have a lower activation energy

Desulfurization of Hydrocarbon Fuels at Ambient Conditions Using Supported Silver Oxide-Titania Sorbents

Science.gov (United States)

2010-12-13

Potentiometric titration ------------------------------------------------------------------ 27 II.10 Equilibrium isotherms...chemisorption ------------------------------------------------ 104 VI.1.5 Potentiometric titration ...Figure VI.7. The relationship between bronsted surface acidity measured by potentiometric titration and sulfur adsorption capacity using JP5 fuel (1172

Effects of Cu over Pd based catalysts supported on silica or niobia

Directory of Open Access Journals (Sweden)

Roma M.N.S.C.

2000-01-01

Full Text Available Palladium and palladium-copper catalysts supported on silica and niobia were characterized by H2 chemisorption and H2-O2 titration. Systems over silica were also analyzed by transmission electron microscopy and EXAFS. The metallic dispersion decreased from 20% to 7% when the content of Pd was increased from 0.5wt.-% to 3wt.-% in monometallic catalysts. The addition of 3 wt.-% Cu to obtain Pd-Cu catalysts caused a remarkable capacity loss of hydrogen chemisorption. TPR analysis suggested an interaction between the two metals and EXAFS characterization of the catalyst supported on silica confirmed the formation of Pd-Cu alloy. Pd/Nb2O5 catalysts showed turnover numbers higher than those obtained with the Pd/SiO2 systems in the cyclohexane dehydrogenation. However, the bimetallic catalysts showed very low turnover numbers.

Selective depression behavior of guar gum on talc-type scheelite flotation

Science.gov (United States)

Zhang, Yong-zhong; Gu, Guo-hua; Wu, Xiang-bin; Zhao, Kai-le

2017-08-01

The depression behavior and mechanism of guar gum on talc-type scheelite flotation were systematically investigated by flotation experiments, adsorption tests, zeta-potential measurements, and infrared spectroscopic analyses. The flotation results for monominerals, mixed minerals, and actual mineral samples indicated that guar gum exhibited much higher selective depression for talc than for scheelite. Bench-scale closed-circuit tests showed that a tungsten concentrate with a WO3 grade of 51.43% and a WO3 recovery of 76.18% was obtained. Adsorption tests, zeta-potential measurements, and infrared spectral analyses confirmed that guar gum absorbed more strongly onto the talc surface than onto the scheelite surface because of chemisorption between guar gum and talc. This chemisorption is responsible for the guar gum's highly selective depression for talc and small depression for scheelite. The flotation results provide technical support for talc-type scheelite flotation.

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

Science.gov (United States)

Gupta, Varun; Kumar, Ankit; Ray, Nirat

2018-05-01

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

Density-functional study of the compressed (2√3 × 2√3)R30°-CO overlayer on the ferromagnetic Co(0001) surface

Czech Academy of Sciences Publication Activity Database

Pick, Štěpán

2012-01-01

Roč. 606, 7-8 (2012), s. 692-696 ISSN 0039-6028 Institutional research plan: CEZ:AV0Z40400503 Keywords : density functional calculations * chemisorption * magnetic films Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.838, year: 2012

Density-functional study of the CO adsorption on ferromagnetic Co(0001) and Co(111) surfaces

Czech Academy of Sciences Publication Activity Database

Pick, Štěpán

2007-01-01

Roč. 601, č. 23 (2007), s. 5571-5575 ISSN 0039-6028 Institutional research plan: CEZ:AV0Z40400503 Keywords : density functional calculation * chemisorption * magnetic films Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.855, year: 2007

Biosorption of fluoride ion from water using the seeds of the ...

African Journals Online (AJOL)

Biosorption of fluoride ion from water using the seeds of the cabbage tree ( Moringa ... The maximum fluoride sorption capacity was found to be 1.32 mg.g-1 of dry weight ... Key words: Biosorption, chemisorption, desorption, fluoride, isotherm, ...

Density-functional study of the CO adsorption on the ferromagnetic fcc Co(001) film surface

Czech Academy of Sciences Publication Activity Database

Pick, Štěpán

2010-01-01

Roč. 604, 3-4 (2010), s. 265-268 ISSN 0039-6028 Institutional research plan: CEZ:AV0Z40400503 Keywords : Density functional calculations * chemisorption * magnetic films Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.010, year: 2010

Performance of Mn2+-modified Bentonite Clay for the Removal

African Journals Online (AJOL)

NICOLAAS

Clay minerals are promising materials for defluoridation of ... edge of the bentonite sheet. ... surface area analyzer (Autosorb-iQ & Quadrasorb SI, USA). .... used to describe chemisorption, as well as cation exchange reac- tions.14 t q. 1. K q. 1.

The role of Ni in sulfided carbon-supported Ni-Mo hydrodesulfurization catalysts

NARCIS (Netherlands)

Bouwens, S.M.A.M.; Barthe-Zahir, N.; Beer, de V.H.J.; Prins, R.

1991-01-01

The thiophene hydrodesulfurization activities of Ni and Ni---Mo sulfide catalysts supported on activated carbon were measured at atmospheric pressure and the catalyst structures were studied by means of X-ray photoelectron spectroscopy, dynamic oxygen chemisorption, and chemical sulfur analysis. The

Comparison of chlorine and oxygen adsorption on the ferromagnetic Fe(0 0 1) surface: Density-functional theory study

Czech Academy of Sciences Publication Activity Database

Pick, Štěpán

2008-01-01

Roč. 602, č. 24 (2008), s. 3733-3736 ISSN 0039-6028 Institutional research plan: CEZ:AV0Z40400503 Keywords : density functional calculation * spin-dependent phenomena * chemisorption Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.731, year: 2008

Surface effects in metallic iron nanoparticles

DEFF Research Database (Denmark)

Bødker, Franz; Mørup, Steen; Linderoth, Søren

1994-01-01

Nanoparticles of metallic iron on carbon supports have been studied in situ by use of Mossbauer spectroscopy. The magnetic anisotropy energy constant increases with decreasing particle size, presumably because of the influence of surface anisotropy. Chemisorption of oxygen results in formation...

Supersonic bare metal cluster beams

International Nuclear Information System (INIS)

Smalley, R.E.

1991-01-01

Progress continued this past year on two principal fronts in the study of bare metal clusters: photoelectron spectroscopy of mass selected negative ions, and surface chemisorption of cluster ions levitated in a superconducting magnet as monitored by fourier transform ion cyclotron resonance

A specific 2,4-disubstituted-adamantane interaction with plasma-grown aluminum oxide. Inelastic-electron-tunneling spectroscopy study

NARCIS (Netherlands)

Meijer, E.W.; Raas, M.C.; Velzen, van P.N.T.

1987-01-01

The interaction of several mono- and disubstituted adamantanes with plasma-grown aluminum oxide has been studied using inelastic-electron-tunneling (IET) spectroscopy. The IET spectra evidence the chemisorption of 2,4-adamantanedione onto the aluminum oxide surface as the carboxylate anion of

Functionalisation of cross-linked polyethylenimine for the removal of ...

African Journals Online (AJOL)

... and describe the experimental data. The thermodynamic study of the adsorption process indicated high activation energies (55.91 kJ mol-1) which confirms chemisorption as a mechanism of interaction between As and PCPEI. Keywords: Adsorption; arsenic; phosphonated cross-linked polyethylenimine, functionalisation ...

Gas absorption technique by half-dry method

Energy Technology Data Exchange (ETDEWEB)

Nakago, K; Haseba, S

1974-11-19

The removal or recovery of nitrogen oxides and sulfur oxides by chemisorption using sodium chlorite or sodium hypochlorite solutions is described. The sorption tower consists of a packed layer of porous carrier such as alumina, silica gel or zeolite, gas inlet and outlet valves, inlet and outlet valves connected to the reaction solution tank, an inlet valve from the regeneration solution tank, and an outlet valve to a separatory device where reaction products, unreacted reaction solution, and regeneration solution are separated and returned to corresponding tanks. The carrier is immersed in a reaction solution, and excessive reaction solution is drained back to the tank. Then the gas valves are opened for chemisorption removal of NOx and SOx. Finally, the reaction product on the carrier is removed with the regeneration solution. More than two towers are placed in a series for more complete removal of the designated gases.

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.

On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

Energy Technology Data Exchange (ETDEWEB)

Vojvodic, Aleksandra

2011-08-22

Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

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

Science.gov (United States)

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

2018-03-01

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

Silver-Loaded Aluminosilicate Aerogels As Iodine Sorbents

Energy Technology Data Exchange (ETDEWEB)

Riley, Brian J. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Kroll, Jared O. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Peterson, Jacob A. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Matyáš, Josef [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Olszta, Matthew J. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Li, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Vienna, John D. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States

2017-09-14

This paper discusses the development of aluminosilicates aerogels as scaffolds for Ag0 nanoparticles used for chemisorption of I2(g). The starting materials for these scaffolds included both Na-Al-Si-O and Al-Si-O aerogels, both synthesized from metal alkoxides. The Ag0 particles are added by soaking the aerogels in AgNO3 followed by drying and flowing under H2/Ar to reduce Ag+ → Ag0. In some cases, samples were soaked in 3-(mercaptopropyl)trimethoxysilane under supercritical CO2 to add –SH tethers to the aerogel surfaces for more effective binding of Ag+. During the Ag+-impregnation steps, for the Na-Al-Si-O aerogels, Na was replaced with Ag, and for the Al-Si-O aerogel, Si was replaced with Ag. The Ag-loading of thiolated versus non-thiolated Na-Al-Si-O aerogels was comparable at ~35 at% whereas the Ag-loading in unthiolated Al-Si-O aerogels was significantly lower at ~ 7 at% after identical treatment. Iodine loadings in both thiolated and unthiolated Ag0-functionalized Na-Al-Si-O aerogels were > 0.5 g g-1 showing almost complete utilization of the Ag through chemisorption to form AgI. Iodine loading in the thiolated Al-Si-O aerogel was 0.31 g g-1. The control of Ag uptake over solution residence time and [AgNO3] demonstrates the ability to customize the Ag-loading in the base sorbent to regulate the capacity of iodine chemisorption. Consolidation experimental results are also presented.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

SBA-15, KIT-6, SiO₂ supported catalysts with 10% Cu loading have been prepared by impregnation techniques. The prepared catalysts have been characterized by BET technique, X-ray diffraction, Temperature programmed reduction (TPR), XPS and N₂O pulse chemisorption techniques. Dehydrogenation of ...

Hydrogen dissociation on metal surfaces

NARCIS (Netherlands)

Wijzenbroek, M.

2016-01-01

Dissociative chemisorption is an important reaction step in many catalytic reactions. An example of such a reaction is the Haber-Bosch process, which is used commercially to produce ammonia, an important starting material in the production of fertilisers. In theoretical descriptions of such chemical

When Langmuir is too simple: H-2 dissociation on Pd(111) at high coverage

DEFF Research Database (Denmark)

Lopez, Nuria; Lodziana, Zbigniew; Illas, F.

2004-01-01

Recent experiments of H-2 adsorption on Pd(111) [T. Mitsui et al., Nature (London) 422, 705 (2003)] have questioned the classical Langmuir picture of second order adsorption kinetics at high surface coverage requiring pairs of empty sites for the dissociative chemisorption. Experiments find that ...

Adsorption of phosphate from municipal effluents using cryptocrystalline magnesite: complementing laboratory results with geochemical modelling

CSIR Research Space (South Africa)

Masindi, Vhahangwele

2015-11-01

Full Text Available chemisorption. Adsorption isotherms fitted well to Langmuir adsorption isotherm than Freundlich adsorption isotherms, demonstrating monolayer adsorption. PHREEQC geochemical model showed Mg(sub3)(PO(sub4))(sub2) and MgHPO(sub4):3H(sub2)O as the phosphatebearing...

The 'Invisible' Metal Particles in Catalysis

NARCIS (Netherlands)

Koningsberger, D.C.; Diaz-Moreno, S.; Muñoz-Paez, A.

1997-01-01

An easy, reliable and straightforward method to determine the sizes of small metal particles in supported metal catalyst which are invisible for most techniques (chemisorption, XRD, HRTEM) is presented. The technique we consider more appropriate is EXAFS, because it detects metal metal bonds even

Adsorption of 5-halouracils on Au(111)

Czech Academy of Sciences Publication Activity Database

Plekan, O.; Feyer, V.; Tsud, N.; Vondráček, Martin; Cháb, Vladimír; Matolín, V.; Prince, K. C.

2012-01-01

Roč. 606, 3-4 (2012), s. 435-443 ISSN 0039-6028 R&D Projects: GA MŠk(CZ) LC06058 Institutional support: RVO:68378271 Keywords : 5-halouracils * gold * chemisorption * XPS * NEXAFS Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.838, year: 2012

Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3

NARCIS (Netherlands)

Navarro, R.M.; Melián-Cabrera, I.; Boutonnet, M.; Birgersson, H.; Agrell, J.; Fierro, J.L.G.

2003-01-01

Production of H2 from methanol by steam reforming, partial oxidation, or a combination thereof was studied over Cu/ZnO-based catalysts. The catalysts were characterized by a variety of techniques, including N2O chemisorption, X-ray photoelectron spectroscopy, X-ray diffraction, and

New insight in the microscopic mechanism of the catalytic synthesis of ammonia

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

1995-01-01

Theoretical quantum calculations and molecular beam experiments of the dissociative chemisorption of N-2 molecules on catalytic active metal surfaces have given new insight in the fundamental process of the ammonia synthesis. This new approach to the study of catalytic process supplements the con...

On the Gas Adsorption Effect upon Electronic Structure of Ferromagnetic Co(0001)

Czech Academy of Sciences Publication Activity Database

Pick, Štěpán; Dreyssé, H.

2003-01-01

Roč. 540, - (2003), s. 389-394 ISSN 0039-6028 Grant - others:Eur. Res. Training Network(XE) HPRN-CT-2000-00143 Institutional research plan: CEZ:AV0Z4040901 Keywords : density functional calculations * chemisorption * cobalt Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.063, year: 2003

The Electronic Structure Effect in Heterogeneous Catalysis

DEFF Research Database (Denmark)

Nilsson, A.; Pettersson, L. G. M.; Hammer, Bjørk

2005-01-01

Using a combination of density functional theory calculations and X-ray emission and absorption spectroscopy for nitrogen on Cu and Ni surfaces, a detailed picture is given of the chemisorption bond. It is suggested that the adsorption bond strength and hence the activity of transition metal surf...

Solid spectroscopy: semiconductors

International Nuclear Information System (INIS)

Silva, C.E.T.G. da

1983-01-01

Photoemission as technique of study of the semiconductor electronic structure is shortly discussed. Homogeneous and heterogeneous semiconductors, where volume and surface electronic structure, core levels and O and H chemisorption in GaAs, Schottky barrier are treated, respectively. Amorphous semiconductors are also discussed. (L.C.) [pt

Impact of bulk reduction on TiO.sub.2./sub.(100)/K

Czech Academy of Sciences Publication Activity Database

Lindsay, R.; Michelangeli, E.; Daniels, B. G.; Polčík, Martin; Verdini, A.; Floreano, L.; Morgante, A.; Thornton, G.

566-568, - (2004), s. 921-925 ISSN 0039-6028 Institutional research plan: CEZ:AV0Z1010914 Keywords : photoelectron spectroscopy * electron-solid diffraction * titanium oxide * alkali metals * low index single crystal * surface chemisorption Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.168, year: 2004

Investigating the adsorption of H2O on ZnO nanoclusters by first principle calculations

KAUST Repository

Al-Sunaidi, Abdullah A.; Goumri-Said, Souraya

2011-01-01

and their physical properties like the binding energy and the band gap energy depend strongly on the shape and size of the cluster. Depending on the stability of the cluster, H2O show both chemisorption and dissociation on the surfaces of the clusters. We analyzed

Kinetic models for irreversible processes on a lattice

Energy Technology Data Exchange (ETDEWEB)

Wolf, N.O.

1979-04-01

The development and application of kinetic lattice models are considered. For the most part, the discussions are restricted to lattices in one-dimension. In Chapter 1, a brief overview of kinetic lattice model formalisms and an extensive literature survey are presented. A review of the kinetic models for non-cooperative lattice events is presented in Chapter 2. The development of cooperative lattice models and solution of the resulting kinetic equations for an infinite and a semi-infinite lattice are thoroughly discussed in Chapters 3 and 4. The cooperative models are then applied to the problem of theoretically dtermining the sticking coefficient for molecular chemisorption in Chapter 5. In Chapter 6, other possible applications of these models and several model generalizations are considered. Finally, in Chapter 7, an experimental study directed toward elucidating the mechanistic factors influencing the chemisorption of methane on single crystal tungsten is reported. In this it differs from the rest of the thesis which deals with the statistical distributions resulting from a given mechanism.

Selective removal of mercury from aqueous solutions using thiolated cross-linked polyethylenimine

Science.gov (United States)

Saad, Dalia M.; Cukrowska, Ewa M.; Tutu, Hlanganani

2013-06-01

A successful approach to develop an insoluble form of polyethylenimine with a thiol-based functional group for selective removal of Hg(II) from aqueous solutions is reported. The selectivity of the modified polymer for Hg(II) as well as its ability to be regenerated for re-use has been studied. The synthesised polymer exhibited high selectivity for Hg(II) with high removal efficiency of up to 97 %, even in the presence of competing ions. The Freundlich isotherm was found to best fit and describe the experimental data. The pseudo-second-order equation explains the adsorption kinetics most effectively implying chemisorption. The thermodynamic study of the adsorption process revealed high activation energies >41 kJ mol-1, further confirming chemisorption as the mechanism of interaction between mercury ions and the polymer surface. The polymer exhibited good potential for re-use after many cycles of regeneration, giving good removal efficiency up to the fifth cycle.

ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

Energy Technology Data Exchange (ETDEWEB)

Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

1977-12-11

The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

Kinetic models for irreversible processes on a lattice

International Nuclear Information System (INIS)

Wolf, N.O.

1979-04-01

The development and application of kinetic lattice models are considered. For the most part, the discussions are restricted to lattices in one-dimension. In Chapter 1, a brief overview of kinetic lattice model formalisms and an extensive literature survey are presented. A review of the kinetic models for non-cooperative lattice events is presented in Chapter 2. The development of cooperative lattice models and solution of the resulting kinetic equations for an infinite and a semi-infinite lattice are thoroughly discussed in Chapters 3 and 4. The cooperative models are then applied to the problem of theoretically dtermining the sticking coefficient for molecular chemisorption in Chapter 5. In Chapter 6, other possible applications of these models and several model generalizations are considered. Finally, in Chapter 7, an experimental study directed toward elucidating the mechanistic factors influencing the chemisorption of methane on single crystal tungsten is reported. In this it differs from the rest of the thesis which deals with the statistical distributions resulting from a given mechanism

Initial oxidation processes of Si(001) surfaces by supersonic O2 molecular beams. Different oxidation mechanisms for clean and partially-oxidized surfaces

International Nuclear Information System (INIS)

Teraoka, Yuden; Yoshigoe, Akitaka

2002-01-01

Potential energy barriers for dissociative chemisorption of O 2 molecules on Si(001) clean surfaces were investigated using supersonic O 2 molecular beams and photoemission spectroscopy. Relative initial sticking probabilities of O 2 molecules and the saturated oxygen amount on the Si(001) surface were measured as a function of incident energy of O 2 molecules. Although the probability was independent on the incident energy in the region larger than 1 eV, the saturated oxygen amount was dependent on the incident energy without energy thresholds. An Si-2p photoemission spectrum of the Si(001) surface oxidized by thermal O 2 gas revealed the oxygen insertion into dimer backbond sites. These facts indicate that a reaction path of the oxygen insertion into dimer backbonds through bridge sites is open for the clean surface oxidation, and the direct chemisorption probability at the backbonds is negligibly small comparing with that at the bridge sites. (author)

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

Science.gov (United States)

Lu, Haichang; Guo, Yuzheng; Robertson, John

2016-08-01

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

Equilibrium, kinetic and thermodynamic studies of adsorption of Th(IV) from aqueous solution onto kaolin

International Nuclear Information System (INIS)

Hongxia Zhang; Zhiwei Niu; Zhi Liu; Zhaodong Wen; Weiping Li; Xiaoyun Wang; Wangsuo Wu

2015-01-01

The kinetics and thermodynamics of the adsorption of Th(IV) on the kaolin were studied by using batch method. In addition, the experimental data were studied by dynamic and thermodynamic models. The results showed that the adsorption capacity of the adsorbent increased with increasing temperature and solid liquid ratio, but decreased with increasing initial Th(IV) ion concentration, and the best fit was obtained for the pseudo-second-order kinetics model. The calculated activation energy for adsorption was about 45 kJ/mol, which indicated the adsorption process to be chemisorption. The adsorption isotherm data could be well described by the Langmuir as well as Dubinin-Radushkevich model. The mean free energy (E) of adsorption was calculated to be about 15 kJ/mol. The thermodynamic data calculated showed that the adsorption was spontaneous and enhanced at higher temperature. Considering kinetics and equilibrium studies, the adsorption on the sites was the rate-limiting step and that adsorption was mainly a chemisorption process through cation exchange. (author)

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

CERN Document Server

Souda, R

2002-01-01

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

Interaction of hydrogen with palladium clusters deposited on graphene

Energy Technology Data Exchange (ETDEWEB)

Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J. [Departamento de Física Teórica, Atómica y Optica, Universidad de Valladolid, 47011 Valladolid (Spain)

2015-12-31

Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H{sub 2} on Pd{sub 6} anchored on a graphene vacancy has been studied in detail.

Interaction of hydrogen with palladium clusters deposited on graphene

Science.gov (United States)

Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J.

2015-12-01

Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H2 on Pd6 anchored on a graphene vacancy has been studied in detail.

Active chemisorption sites in functionalized ionic liquids for carbon capture.

Science.gov (United States)

Cui, Guokai; Wang, Jianji; Zhang, Suojiang

2016-07-25

Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined.

Transfer matrix treatment of atomic chemisorption on transition metal surface

International Nuclear Information System (INIS)

Mariz, A.M.; Koiller, B.

1980-05-01

The atomic adsorption of hydrogen on paramagnetic nickel 100 surface is studied, using the Green's function formalism and the transfer matrix technique, which allows the treatment of the geometry of the system in a simple manner. Electronic correlation at the adatom orbital in a self consistent Hartree-Fock approach is incorporated. The adsorption energy, local density of states and charge transfer between the solid and the adatom are calculated for different crystal structures (sc and fcc) and adatom positions at the surface. The results are discussed in comparison with other theories and with available experimental data, with satisfactory agreement. (Author) [pt

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

Science.gov (United States)

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Copper nitrate redispersion to arrive at highly active silica-supported copper catalysts

NARCIS (Netherlands)

Munnik, P.|info:eu-repo/dai/nl/328228524; Wolters, M.|info:eu-repo/dai/nl/304829560; Gabrielsson, A.; Pollington, S.D.; Headdock, G.; Bitter, J.H.|info:eu-repo/dai/nl/160581435; de Jongh, P.E.|info:eu-repo/dai/nl/186125372; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

2011-01-01

In order to obtain copper catalysts with high dispersions at high copper loadings, the gas flow rate and gas composition was varied during calcination of silica gel impregnated with copper nitrate to a loading of 18 wt % of copper. Analysis by X-ray diffraction (XRD), N2O chemisorption, and

Bulletin of Materials Science | Indian Academy of Sciences

Indian Academy of Sciences (India)

Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was used to prepare twodimensional self-assembled monolayer (SAM) on silicon substrate. The terminal –SH group was in situ oxidized to –SO3H group to endow the film with good chemisorption ability. Then TiO2 thin films were deposited on the ...

Pt-Rh/g Al2O3 Influence of Catalyst Preparation Methods on Metallic Particle Dispersion and Size Distribution

Directory of Open Access Journals (Sweden)

N.M. da Fonseca

1998-06-01

Full Text Available - Pt-Rh/Al2O3 catalysts were prepared by successive incipient impregnations or coimpregnation. Characterization was achieved by H2 chemisorption and transmission electron microscopy. It was verified that method of preparation, ratio of metal weights and sequence of deposition are factors that result in very distinct catalysts.

Tantalum induced butterfly-like clusters on Si (111)-7 x 7 surface: STM/STS study at low coverage

Czech Academy of Sciences Publication Activity Database

Shukrynau, Pavel; Mutombo, Pingo; Švec, Martin; Hietschold, M.; Cháb, Vladimír

2012-01-01

Roč. 606, 3-4 (2012), s. 356-361 ISSN 0039-6028 R&D Projects: GA AV ČR IAA1010413 Institutional research plan: CEZ:AV0Z10100521 Keywords : tantalum * silicon * chemisorption * scanning tunneling microscopy * scanning tunneling spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.838, year: 2012

Atomic and molecular adsorption on Rh(111)

DEFF Research Database (Denmark)

Mavrikakis, Manos; Rempel, J.; Greeley, Jeffrey Philip

2002-01-01

A systematic study of the chemisorption of both atomic (H, O, N, S, C), molecular (N-2, CO, NO), and radical (CH3, OH) species on Rh(111) has been performed. Self-consistent, periodic, density functional theory (DFT-GGA) calculations, using both PW91 and RPBE functionals, have been employed to de...

Materials Down Select Decisions Made Within the Department of Energy Hydrogen Sorption Center of Excellence

Energy Technology Data Exchange (ETDEWEB)

Simpson, Lin [National Renewable Energy Lab. (NREL), Golden, CO (United States)

2009-11-30

Technical report describing DOE's Hydrogen Sorption Center of Excellence investigation into various adsorbent and chemisorption materials and progress towards meeting DOE's hydrogen storage targets. The report presents a review of the material status as related to DOE hydrogen storage targets and explains the basis for the down select decisions.

A first-principles study of structure, orbital interactions and atomic oxygen and OH adsorption on Mo-, Sc- and Y-doped nickel bimetallic clusters

International Nuclear Information System (INIS)

Das, Nishith Kumar; Shoji, Tetsuo

2013-01-01

Highlights: •Mo-doped nickel clusters are energetically more stable than the Sc and Y-doped clusters (n ⩾ 10). •Mo atom exhibits center at the cluster rather than edge, while Sc and Y atom sit at the edge. •The metallic s, d orbitals are mainly dominated on the stability of nanoclusters. •The oxygen and OH adsorption energy of Mo-doped cluster are higher than those of other nanoclusters. •2p Orbitals are strongly bonds with Mo 4d, and a weakly interacts with Ni 3d, 4s and Mo 5s orbitals. -- Abstract: Density functional theory (DFT) has been used to study the stability, orbitals interactions and oxygen and hydroxyl chemisorption properties of Ni n M (1 ⩽ n ⩽ 12) clusters. A single atom doped-nickel clusters increase the stability, and icosahedral Ni 12 Mo cluster is the most stable structure. Molybdenum atom prefers to exhibit center at the cluster (n ⩾ 10) rather than edge, while Sc and Y atom remain at the edge. The Ni–Mo bond lengths are smaller than the Ni–Sc and Ni–Y. The pDOS results show that the d–d orbitals interactions are mainly dominating on the stability of clusters, while p orbitals have a small effect on the stability. The Mo-doped nanoclusters have the highest oxygen and OH chemisorption energy, and the most favorable adsorption site is on the top Mo site. The larger cluster distortion is found for the Sc- and Y-doped structures compared to other clusters. The oxygen 2p orbitals are strongly hybridizing with the Mo 4d orbitals (n < 9) and a little interaction between oxygen 2p and Ni 3d, 4s and Mo 5s orbitals. The Mo-doped clusters are significantly increased the chemisorption energies that might improve the passive film adherence of nanoalloys

Coordination to transition metal surfaces : a theoretical study

NARCIS (Netherlands)

Santen, van R.A.

1985-01-01

A theoretical framework is developed that describes the chemisorption of CO to transition metal surfaces analogous to the HOMO-LUMO concept of MO theory. An explanation is given for the exptl. observation that CO adsorbs on top at the (111), face of Pt, but bridge at the (111) face of Ni. One is due

Efficient protection of mercury peaks; Effizienter Schutz vor Quecksilberspitzen

Energy Technology Data Exchange (ETDEWEB)

Esser-Schmittmann, Wolfgang; Schmitz, Simone [Carbon Service und Consulting GmbH und Co. KG, Vettweiss (Germany)

2010-07-15

Exhaust gases from the combustion of wastes and substitute fuels temporarily exhibit again and again emission peaks of mercury which in individual cases cannot be caught by the exhaust after-treatment system designed for the stationary plant operation. The problem can be solved inexpensively by dosage of small quantities of chemisorptive powder activated charcoal.

Annual Technical Report, Materials Research Laboratory July 1, 1979 - June 30, 1980.

Science.gov (United States)

1980-06-30

TeO2 in the glasses contributes to the formation of four-coordinated boron atoms. There is an apparent change in the coordination of tellurium atoms... Glasses , W. M. Risen, Jr., and Chemisorption and Related Surface Interactions, P. J. Estrup. Since many of the research areas are interrelated, cross...8 IInorganic Glasses .................................................................. 24 Introduction

Mercury removal from coal combustion flue gas by fly ash

Energy Technology Data Exchange (ETDEWEB)

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

2013-07-01

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

Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

2013-05-15

We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

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.

Another way of looking at bonding on bimetallic surfaces: the role of spin polarization of surface metal d states

International Nuclear Information System (INIS)

Escano, M C; Nguyen, T Q; Nakanishi, H; Kasai, H

2009-01-01

The nature of electronic and chemical properties of an unstrained Pt monolayer on a 3d transition metal substrate, M (M = Cr, Mn, Fe), is studied using spin-polarized density functional theory calculations. High spin polarization of Pt d states is noted, verifying the magnetization induced on Pt, which is observed to be responsible for redirecting the analysis of bond formation on a metal surface towards a different perspective. While the shift in the Pt d band center (the average energy of the Pt d band, commonly used to predict the reactivity of surfaces) does give the expected trend in adsorbate (oxygen) chemisorption energy across the bimetallic surfaces in this work, our results show that for spin-polarized Pt d states, the variation in strength of adsorption with respect to the Fermi level density of states is more predictive of Pt chemisorption properties. Hence, this study introduces a scheme for analyzing trends in reactivity of bimetallic surfaces where adsorption energies are used as reactivity parameters and where spin polarization effects cannot be neglected. (fast track communication)

Gasification under CO2–Steam Mixture: Kinetic Model Study Based on Shared Active Sites

Directory of Open Access Journals (Sweden)

Xia Liu

2017-11-01

Full Text Available In this work, char gasification of two coals (i.e., Shenfu bituminous coal and Zunyi anthracite and a petroleum coke under a steam and CO2 mixture (steam/CO2 partial pressures, 0.025–0.075 MPa; total pressures, 0.100 MPa and CO2/steam chemisorption of char samples were conducted in a Thermogravimetric Analyzer (TGA. Two conventional kinetic models exhibited difficulties in exactly fitting the experimental data of char–steam–CO2 gasification. Hence, a modified model based on Langmuir–Hinshelwood model and assuming that char–CO2 and char–steam reactions partially shared active sites was proposed and had indicated high accuracy for estimating the interactions in char–steam–CO2 reaction. Moreover, it was found that two new model parameters (respectively characterized as the amount ratio of shared active sites to total active sites in char–CO2 and char–steam reactions in the modified model hardly varied with gasification conditions, and the results of chemisorption indicate that these two new model parameters mainly depended on the carbon active sites in char samples.

Long-Range Interfacial Electrochemical Electron Transfer of Pseudomonas aeruginosa Azurin-Gold Nanoparticle Hybrid Systems

DEFF Research Database (Denmark)

Jensen, Palle Skovhus; Chi, Qijin; Zhang, Jingdong

2009-01-01

We have prepared a "hybrid" of the blue copper protein azurin (Pseudomonas aeruginosa) and a 3 nm gold nanoparticle (AuNP). The AuNP/azurin hybrid was assembled on a Au(111)-electrode surface in a two-step process. The AuNP was first attached to the Au(111) electrode via Au-S chemisorption of a 4...

Interaction of ethylene with palladium clusters supported on oxidized tungsten foil

Czech Academy of Sciences Publication Activity Database

Jirka, Ivan; Plšek, Jan; Vondráček, Martin; Šutara, F.; Matolin, V.; Cháb, Vladimír; Prince, K. C.

2007-01-01

Roč. 601, č. 14 (2007), s. 3114-3124 ISSN 0039-6028 R&D Projects: GA ČR(CZ) GA202/05/0244 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z10100521 Keywords : synchrotron radiation photoelectron spectroscopy * thermal desorption spectroscopy * chemisorption * palladium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.855, year: 2007

Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

Science.gov (United States)

Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

2018-03-01

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

Chemisorption of pentacene on Pt(111) with a little molecular distortion

DEFF Research Database (Denmark)

Brivio, Gian Paolo; Ugolotti, Aldo; Harivyasi, Shashank S.

2017-01-01

We investigated the adsorption of pentacene on the (111) surface of platinum, which is an archetypal system for a junction with a low charge-injection barrier. We probed the structural and electronic configurations of pentacene by scanning tunnelling microscopy (STM), X-ray photoemission...

Ultra violet photoemission studies of CO2 and NO adsorbed on W(100) surface

International Nuclear Information System (INIS)

Bhattacharya, A.K.; Broughton, J.Q.; Perry, D.L.

1978-01-01

In the last few years ultra violet photoelectron spectroscopy (UPS) has been successfully empolyed to determine the nature and bonding of the species formed when gases absorb on metal surfaces. This information is necessary to understand the mechanism of hetergeneous catalysis. The present report deals with UPS investigation of the chemisorption of CO 2 and NO on a W(100) surface. (Auth.)

Deposition on disordered substrates with precursor layer diffusion

Science.gov (United States)

Filipe, J. A. N.; Rodgers, G. J.; Tavassoli, Z.

1998-09-01

Recently we introduced a one-dimensional accelerated random sequential adsorption process as a model for chemisorption with precursor layer diffusion. In this paper we consider this deposition process on disordered or impure substrates. The problem is solved exactly on both the lattice and continuum and for various impurity distributions. The results are compared with those from the standard random sequential adsorption model.

Modified energetics and growth kinetics on H-terminated GaAs (110)

International Nuclear Information System (INIS)

Galiana, B.; Benedicto, M.; Díez-Merino, L.; Tejedor, P.; Lorbek, S.; Hlawacek, G.; Teichert, C.

2013-01-01

Atomic hydrogen modification of the surface energy of GaAs (110) epilayers, grown at high temperatures from molecular beams of Ga and As 4 , has been investigated by friction force microscopy (FFM). The reduction of the friction force observed with longer exposures to the H beam has been correlated with the lowering of the surface energy originated by the progressive de-relaxation of the GaAs (110) surface occurring upon H chemisorption. Our results indicate that the H-terminated GaAs (110) epilayers are more stable than the As-stabilized ones, with the minimum surface energy value of 31 meV/Å 2 measured for the fully hydrogenated surface. A significant reduction of the Ga diffusion length on the H-terminated surface irrespective of H coverage has been calculated from the FFM data, consistent with the layer-by-layer growth mode and the greater As incorporation coefficient determined from real-time reflection high-energy electron diffraction studies. Arsenic incorporation through direct dissociative chemisorption of single As 4 molecules mediated by H on the GaAs (110) surface has been proposed as the most likely explanation for the changes in surface kinetics observed

Modified energetics and growth kinetics on H-terminated GaAs (110)

Energy Technology Data Exchange (ETDEWEB)

Galiana, B. [Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Inés de la Cruz 3, 28049 Madrid (Spain); Departamento de Física, Universidad Carlos III de Madrid, Avenida de la Universidad 30, 28911 Madrid (Spain); Benedicto, M.; Díez-Merino, L.; Tejedor, P. [Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Inés de la Cruz 3, 28049 Madrid (Spain); Lorbek, S.; Hlawacek, G.; Teichert, C. [Institut für Physik, Montanuniversität Leoben, Franz Josef St., 18A-8700 Leoben (Austria)

2013-10-28

Atomic hydrogen modification of the surface energy of GaAs (110) epilayers, grown at high temperatures from molecular beams of Ga and As{sub 4}, has been investigated by friction force microscopy (FFM). The reduction of the friction force observed with longer exposures to the H beam has been correlated with the lowering of the surface energy originated by the progressive de-relaxation of the GaAs (110) surface occurring upon H chemisorption. Our results indicate that the H-terminated GaAs (110) epilayers are more stable than the As-stabilized ones, with the minimum surface energy value of 31 meV/Å{sup 2} measured for the fully hydrogenated surface. A significant reduction of the Ga diffusion length on the H-terminated surface irrespective of H coverage has been calculated from the FFM data, consistent with the layer-by-layer growth mode and the greater As incorporation coefficient determined from real-time reflection high-energy electron diffraction studies. Arsenic incorporation through direct dissociative chemisorption of single As{sub 4} molecules mediated by H on the GaAs (110) surface has been proposed as the most likely explanation for the changes in surface kinetics observed.

Phosphorous removal from aqueous solution can be enhanced through the calcination of lime sludge.

Science.gov (United States)

Bal Krishna, K C; Niaz, Mohamed R; Sarker, Dipok C; Jansen, Troy

2017-09-15

Water treatment plants generate an enormous amount of the sludge which is normally treated as waste. In the recent past, many investigations have been focused on developing an economical adsorbent using water treatment sludge to remove phosphorous (P) from aqueous solutions. However, the great extents of the studies have been limited in the use of alum- and iron-based sludges. This study, therefore, investigated the P removal performance of the calcined lime sludge. Calcined lime sludge at 700 °C significantly enhanced the P removal efficiency whereas marginal improvement was noted when the sludge calcined at 400 °C was tested. With increase P removal efficiency, final pH values of the solution also significantly increased. P removal efficiency of the calcined sludge decreased with increasing the initial P concentrations. However, the removal efficiency could be improved by increasing the weight of the sludge. Further analysis demonstrated that P removal trend followed both pseudo-second order and diffusion-chemisorption kinetics signifying the P removal is potentially due to a multi-mechanistic reaction in which, the process is controlled by intra-particle diffusion followed by chemisorptions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalytic Activity Control via Crossover between Two Different Microstructures

KAUST Repository

Zhou, Yuheng

2017-09-08

Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply-twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g. water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in non-polar solvent (e.g. toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in-situ TEM and leads to a drastic modulation of catalytic activity towards the gas-phase selective oxidation of alcohols. There is a quasi-linear relationship between TOFs and MTP concentrations. Based on the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

Volatilization from borosilicate glass melts of simulated Savannah River Plant waste

International Nuclear Information System (INIS)

Wilds, G.W.

1979-01-01

Laboratory scale studies determined the rates at which the semivolatile components sodium, boron, lithium, cesium, and ruthenium volatilized from borosilicate glass melts that contained simulated Savannah River Plant waste sludge. Sodium and boric oxides volatilize as the thermally stable compound sodium metaborate, and accounted for approx. 90% of the semivolatiles that evolved. The amounts of semivolatiles that evolved increased linearly with the logarithm of the sodium content of the glass-forming mixture. Cesium volatility was slightly suppressed when titanium dioxide was added to the melt, but was unaffected when cesium was added to the melt as a cesium-loaded zeolite rather than as a cesium carbonate solution. Volatility of ruthenium was not suppressed when the glass melt was blanketed with a nonoxidizing atmosphere. Trace quantities of mercury were removed from vapor streams by adsorption onto a silver-exchanged zeolite. A bed containing silver in the ionic state removed more than 99.9% of the mercury and had a high chemisorption capacity. Beds of lead-, copper-, and copper sulfide-exchanged zeolite-X and also an unexchanged zeolite-X were tested. None of these latter beds had high removal efficiency and high chemisorption capacity

Volatilization from borosilicate glass melts of simulated Savannah River Plant waste

International Nuclear Information System (INIS)

Wilds, G.W.

1978-01-01

Laboratory scale studies determined the rates at which the semivolatile components sodium, boron, lithium, cesium, and ruthenium volatilized from borosilicate glass melts that contained simulated Savannah River Plant waste sludge. Sodium and boric oxides volatilize as the thermally stable compound sodium metaborate, and accounted for approx. 90% of the semivolatiles that evolved. The amounts of semivolatiles that evolved increased linearly with the logarithm of the sodium content of the glass-forming mixture. Cesium volatility was slightly suppressed when titanium dioxide was added to the melt, but was unaffected when cesium was added to the melt as a cesium-loaded zeolite rather than as a cesium carbonate solution. Volatility of ruthenium was not suppressed when the glass melt was blanketed with a nonoxidizing atmosphere. Trace quantities of mercury were removed from vapor streams by adsorption onto a silver-exchanged zeolite. A bed containing silver in the ionic state removed more than 99.9% of the mercury and had a high chemisorption capacity. Beds of lead-, copper-, and copper sulfide-exchanged zeolite-X and also an unexchanged zeolite-X were tested. None of these latter beds had high removal efficiency and high chemisorption capacity

A bonding study of c-C5H8 adsorption on Pt(111)

International Nuclear Information System (INIS)

Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

2006-01-01

The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

Surface thermodynamics

International Nuclear Information System (INIS)

Garcia-Moliner, F.

1975-01-01

Basic thermodynamics of a system consisting of two bulk phases with an interface. Solid surfaces: general. Discussion of experimental data on surface tension and related concepts. Adsorption thermodynamics in the Gibbsian scheme. Adsorption on inert solid adsorbents. Systems with electrical charges: chemistry and thermodynamics of imperfect crystals. Thermodynamics of charged surfaces. Simple models of charge transfer chemisorption. Adsorption heat and related concepts. Surface phase transitions

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

Czech Academy of Sciences Publication Activity Database

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

2008-01-01

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

Segregation gettering by implantation-formed cavities and B-Si precipitates in silicon

International Nuclear Information System (INIS)

Myers, S.M.; Petersen, G.A.; Follstaedt, D.M.

1998-01-01

The authors show that Fe, Co, Cu, and Au in Si undergo strong segregation gettering to cavities and B-Si precipitates formed by He or B ion implantation and annealing. The respective mechanisms are argued to be chemisorption on the cavity walls and occupation of solution sites within the disordered, B-rich, B-Si phase. The strengths of the reactions are evaluated, enabling prediction of gettering performance

Multidimensional effects in dissociative chemisorption: H2 on Cu and Ni surfaces

DEFF Research Database (Denmark)

Engdahl, C.; Lundqvist, Bengt; Nielsen, U.

1992-01-01

It is shown that, in order to describe and understand the trends found experimentally for the variation of the H2 sticking probability with crystal face on Cu and Ni surfaces, the dynamics of all six molecular degrees of freedom must be included. The effective-medium theory is used to estimate...

Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

KAUST Repository

Allian, Ayman Daoud

2011-03-30

Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O2 pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O2 activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C16O-18O2-16O 2 reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O2 activation steps involve direct O2* (or O2) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO 2 and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O2. These CO-assisted O2 dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O2 dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O2 reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with 12CO- 13CO mixtures showed that the binding, dynamics, and thermodynamics of CO chemisorbed at saturation coverages do not depend on Pt cluster size in a range that strongly affects the coordination of Pt atoms exposed at cluster surfaces. These data and their theoretical and mechanistic interpretations indicate that the remarkable structure insensitivity observed for CO oxidation reactions reflects average CO binding properties that are essentially independent of cluster size. Theoretical estimates of rate and equilibrium constants for surface reactions and CO adsorption show that both parameters increase as the coordination of exposed Pt atoms decreases in Pt201 cluster surfaces; such compensation dampens but does not eliminate coordination and cluster size effects on measured rate constants. The structural features and intrinsic non-uniformity of cluster surfaces weaken when CO forms saturated monolayers on such surfaces, apparently because surfaces and adsorbates restructure to balance CO surface binding and CO-CO interaction energies. © 2011 American Chemical Society.

Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

KAUST Repository

Allian, Ayman Daoud; Takanabe, Kazuhiro; Fujdala, Kyle L.; Hao, Xianghong; Truex., Timothy J.; Cai, Juan; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-01-01

Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis

Dissociative chemisorption of N2 on Rhenium: Dynamics at high impact energies

DEFF Research Database (Denmark)

Henriksen, Niels Engholm; Billing, Gert D.; Hansen, Flemming Yssing

1990-01-01

forcing model. It is found that the energy transfer from the molecule to the phonons of the crystal is very significant. The smaller than unity dissociative sticking probability found experimentally even at the highest impact energies well above the barrier energy can be accounted for by the Landau...

Chemisorption of organic iodine compounds forming from fission isotopes of radioactive iodine

International Nuclear Information System (INIS)

Tot, G.; Galina, F.; Zel'd, E.

1977-01-01

Studied is ethyl iodine adsorption, labelled by iodine 131, on palladium black and on aluminium oxide activized by palladium. The desorption of adsorbed iodine in the temperature range of 20-600 deg C by the mass spectroscopy and thermal gravimetric methods was investigated. At the ethyl iodine and palladium interaction the bond between carbon and iodine in the ethyl iodine molecule breaks down and extracting iodine reacts with palladium, forming a stable compound at high temperatures. Desorption of adsorbed iodine is insignificant up to the temperatures of 250-300 deg C. Thus, sorbents, containing palladium, may be successfully applied for iodine absorption from the organic iodine compounds. These compounds spontaneously appear from the iodine fragment ratio isotopes during their interaction with some environmental organic impurities

Effects of ELF-EMF on brain proteins in mice

Czech Academy of Sciences Publication Activity Database

Strašák, Luděk; Bártová, Eva; Krejčí, Jana; Fojt, Lukáš; Vetterl, Vladimír

2009-01-01

Roč. 28, č. 1 (2009), s. 96-104 ISSN 1536-8378 R&D Projects: GA ČR(CZ) GA204/06/0978 Grant - others:GA ČR(CZ) GP310/07/P480; GA MŠk(CZ) 1MO528 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : chemisorption * IR spectroscopy * electrochemistry Subject RIV: BO - Biophysics Impact factor: 0.729, year: 2009

Thermal effects in highly dispersed iron catalysts

International Nuclear Information System (INIS)

Alvarez, A.M.; Cagnoli, M.V.; Gallegos, N.G.; Marchetti, S.G.; Yeramian, A.A.; Mercader, R.C.

1994-01-01

The Moessbauer spectra of three Fe/SiO 2 catalysts with 5 wt% iron content show the presence of several Fe species and display different magnetic behaviours when the precursors are subjected to various thermal treatments. Based on the Moessbauer parameters and CO chemisorption measurements, the average crystal sizes of the catalysts are estimated and discussed in connection with the thermal pretreatment severity and magnetic properties of the samples. (orig.)

Changing of the electron structure of dispersed iron oxide during interaction with amines and borofluoride

International Nuclear Information System (INIS)

Hobert, H.; Arnold, D.

1975-01-01

The mechanism of chemisorption on the surface of iron oxide was studied by Moessbauer spectroscopy performed on samples of iron oxide finely dispersed in SiO 2 . It was found from Moessbauer spectra that the interaction of the oxide with amines resulted in a reversible electron transition from the amine to the adsorbent. The interaction with BF 3 brought about an irreversible electron transition from iron to boron. (A.K.)

Self-suspended permanent magnetic FePt ferrofluids

KAUST Repository

Dallas, Panagiotis

2013-10-01

We present the synthesis and characterization of a new class of self-suspended ferrofluids that exhibit remanent magnetization at room temperature. Our system relies on the chemisorption of a thiol-terminated ionic liquid with very low melting point on the surface of L10 FePt nanoparticles. In contrast, all types of ferrofluids previously reported employ either volatile solvents as the suspending media or superparamagnetic iron oxide nanoparticles (that lacks permanent magnetization) as the inorganic component. The ferrofluids do not show any sign of flocculation or phase separation, despite the strong interactions between the magnetic nanoparticles due to the strong chemisorption of the ionic liquid as evidenced by Raman spectroscopy and thermal analysis. Composites with high FePt loading (40 and 70. wt%) exhibit a pseudo solid-like rheological behavior and high remanent magnetization values (10.1 and 12.8. emu/g respectively). At lower FePt loading (12. wt%) a liquid like behavior is observed and the remanent and saturation magnetization values are 3.5 and 6.2. emu/g, respectively. The magnetic and flow properties of the materials can be easily fine tuned by controlling the type and amount of FePt nanoparticles used. © 2013 Elsevier Inc.

Carbon formation on nickel and nickel-copper alloy catalysts

Energy Technology Data Exchange (ETDEWEB)

Alstrup, I.; Soerensen, O.; Rostrup-Nielsen, J.R. [Haldor Topsoe Research Labs., Lyngby (Denmark); Tavares, M.T.; Bernardo, C.A.

1998-05-01

Equilibrium, kinetic and morphological studies of carbon formation in CH{sub 4} + H{sub 2}, CO, and CO + H{sub 2} gases on silica supported nickel and nickel-copper catalysts are reviewed. The equilibrium deviates in all cases from graphite equilibrium and more so in CO + CO{sub 2} than in CH{sub 4} + H{sub 2}. A kinetic model based on information from surface science results with chemisorption of CH{sub 4} and possibly also the first dehydrogenation step as rate controlling describes carbon formation on nickel catalyst in CH{sub 4} + H{sub 2} well. The kinetics of carbon formation in CO and CO + H{sub 2} gases are in agreement with CO disproportionation as rate determining step. The presence of hydrogen influences strongly the chemisorption of CO. Carbon filaments are formed when hydrogen is present in the gas while encapsulating carbon dominates in pure CO. Small amounts of Cu alloying promotes while larger amounts (Cu : Ni {>=} 0.1) inhibits carbon formation and changes the morphology of the filaments (``octopus`` carbon formation). Adsorption induced nickel segregation changes the kinetics of the alloy catalysts at high carbon activities. Modifications suggested in some very recent papers on the basis of new results are also briefly discussed. (orig.) 31 refs.

Defects and oxidation of group-III monochalcogenide monolayers

Science.gov (United States)

Guo, Yu; Zhou, Si; Bai, Yizhen; Zhao, Jijun

2017-09-01

Among various two-dimensional (2D) materials, monolayer group-III monochalcogenides (GaS, GaSe, InS, and InSe) stand out owing to their potential applications in microelectronics and optoelectronics. Devices made of these novel 2D materials are sensitive to environmental gases, especially O2 molecules. To address this critical issue, here we systematically investigate the oxidization behaviors of perfect and defective group-III monochalcogenide monolayers by first-principles calculations. The perfect monolayers show superior oxidation resistance with large barriers of 3.02-3.20 eV for the dissociation and chemisorption of O2 molecules. In contrast, the defective monolayers with single chalcogen vacancy are vulnerable to O2, showing small barriers of only 0.26-0.36 eV for the chemisorption of an O2 molecule. Interestingly, filling an O2 molecule to the chalcogen vacancy of group-III monochalcogenide monolayers could preserve the electronic band structure of the perfect system—the bandgaps are almost intact and the carrier effective masses are only moderately disturbed. On the other hand, the defective monolayers with single vacancies of group-III atoms carry local magnetic moments of 1-2 μB. These results help experimental design and synthesis of group-III monochalcogenides based 2D devices with high performance and stability.

Coated kapok fiber for removal of spilled oil

International Nuclear Information System (INIS)

Wang, Jintao; Zheng, Yian; Wang, Aiqin

2013-01-01

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

Characterization techniques for graphene-based materials in catalysis

Directory of Open Access Journals (Sweden)

Maocong Hu

2017-06-01

Full Text Available Graphene-based materials have been studied in a wide range of applications including catalysis due to the outstanding electronic, thermal, and mechanical properties. The unprecedented features of graphene-based catalysts, which are believed to be responsible for their superior performance, have been characterized by many techniques. In this article, we comprehensively summarized the characterization methods covering bulk and surface structure analysis, chemisorption ability determination, and reaction mechanism investigation. We reviewed the advantages/disadvantages of different techniques including Raman spectroscopy, X-ray photoelectron spectroscopy (XPS, Fourier transform infrared spectroscopy (FTIR and Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS, X-Ray diffraction (XRD, X-ray absorption near edge structure (XANES and X-ray absorption fine structure (XAFS, atomic force microscopy (AFM, scanning electron microscopy (SEM, transmission electron microscopy (TEM, high-resolution transmission electron microscopy (HRTEM, ultraviolet-visible spectroscopy (UV-vis, X-ray fluorescence (XRF, inductively coupled plasma mass spectrometry (ICP, thermogravimetric analysis (TGA, Brunauer–Emmett–Teller (BET, and scanning tunneling microscopy (STM. The application of temperature-programmed reduction (TPR, CO chemisorption, and NH3/CO2-temperature-programmed desorption (TPD was also briefly introduced. Finally, we discussed the challenges and provided possible suggestions on choosing characterization techniques. This review provides key information to catalysis community to adopt suitable characterization techniques for their research.

Gearing.

Science.gov (United States)

1985-12-01

trichloroethyl phosphite and a phosphate ester containing a pentachlorphenyl radical. Most of the Asperity heights phosphorous compounds in gear oils...108) found that phosphorous compounds chemisorption. These boundary films can be thinner than ( 1 0 u ts n 0.025 pm (I in ) or several microinches thick...Pinion 1 .. dibutylxanthic acid disulfide. Ŗ %- Lead soaps have been used in lubricants for many 02 years. They resist the wiping and sliding action in

MORE ACTIVE AND SULFUR RESISTANT BIMETALLIC Pd-Ni CATALYSTS

OpenAIRE

Betti, Carolina; Carrara, Nicolás; Badano, Juan; Lederhos, Cecilia; Vera, Carlos; Quiroga, Mónica

2018-01-01

The influence of the kind of metal precursor and the sequence of impregnation on the properties of Pd-Ni catalysts was evaluated during the test reaction of selective hydrogenation of styrene to ethylbenzene by means of physicochemical characterization. The focus was put on the final hydrogenating activity and the resistance to deactivation by sulfided compounds (thiophene). The used techniques of characterization were ICP, XPS, XDR, TPR, CO chemisorption and TEM. XPS results indicated the pr...

Reaction and Transport Effects in the Heterogeneous Systems for Lean Gas Purification.

Czech Academy of Sciences Publication Activity Database

Hartman, Miloslav; Svoboda, Karel; Pohořelý, Michael; Šyc, Michal; Skoblia, S.; Chyou, Y.-P.

2017-01-01

Roč. 71, č. 3 (2017), s. 563-577 ISSN 0366-6352 R&D Projects: GA ČR(CZ) GC14-09692J Grant - others:NSC(TW) 102WBS0300011; NSC(TW) 103-2923-E-042A-001-MY3 Institutional support: RVO:67985858 Keywords : differential reactor * gas chemisorption * alkaline solids Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Environmental sciences (social aspects to be 5.7) Impact factor: 1.258, year: 2016

Panus tigrinus as a potential biomass source for Reactive Blue decolorization: Isotherm and kinetic study

Directory of Open Access Journals (Sweden)

Monawar Munjid Mustafa

2017-03-01

Conclusion: The biosorption process provided vital information on the process parameters required to obtain the optimum level of dye removal. The isotherm study indicated the homogeneous distribution of active sites on the biomass surface, and the kinetic study suggested that chemisorption is the rate-limiting step that controlled the biosorption process. According to the obtained results, P. tigrinus biomass can be used effectively to decolorize textile dyes and tackle the pollution problems in the environment.

(Electronic structure and reactivities of transition metal clusters)

Energy Technology Data Exchange (ETDEWEB)

1992-01-01

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Hydrogen dissociation on metal surfaces

OpenAIRE

Wijzenbroek, M.

2016-01-01

Dissociative chemisorption is an important reaction step in many catalytic reactions. An example of such a reaction is the Haber-Bosch process, which is used commercially to produce ammonia, an important starting material in the production of fertilisers. In theoretical descriptions of such chemical processes often approximations need to be made in order to keep the computational cost feasible, such as fixing the surface atoms in place, rather than allowing them to vibrate. In this work, seve...

Hydrogen storage in porous carbons: modelling and performance improvements

International Nuclear Information System (INIS)

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

2006-01-01

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

Phase Transitions on Surfaces. An International Conference. Abstracts and Program, 3-7 August 1981, Orono, Maine.

Science.gov (United States)

1982-04-16

P. J. Estrup Chemisorption-Induced Phase Transitions and Adatom Interactions on GaAs(110) P. Skeath, C. Y. Su, P. W. Chye , I. Lindau and W. E. Spicer...Transitions and Adatom Interactions on GaAs(ll0)* Perry Skeath, C. Y. Su, P. W. Chye , I Lindau, and W. E. Spicer Stanford Electronics Labs Stanford...ORDER PHASE TRANSITIONS* P. KLEBAN and CHIN -KUN HU, Department of Physics and Astronomy and Laboratory for Surface Science and Technology University of

Influence of the precursors on the properties of alumina supported rhodium particles

International Nuclear Information System (INIS)

Coq, B.; Figueras, F.; Tazi, T.

1989-01-01

The effect of chlorine on the properties of Rh particles supported on alumina was studied using the hydroconversion of alkanes as a molecular probe. Chloride ions on the alumina have little influence on the Rh particles. Chlorine adsorbed on the Rh particles decreases the chemisorption capacity and increases the metal-support interaction, which results in modifications of their catalytic properties. Depending on the alkane processed, specific activity can be depressed up to four orders of magnitude. (orig.)

Desulphurization of flue gases

International Nuclear Information System (INIS)

Kovacs, B.; Fueloep, T.

1998-01-01

Sulphur dioxide pollution of the ambient air from fossil fuel plants is one of the most serious environmental problems in Hungary. Results of sulphur dioxide absorption in water and lime suspensions in Jet Bubbling Reactor are presented Efficiency of absorption was examined as the function of immersion depth of the sparger pipes and Ca 2+ concentration of the lime suspensions. It is shown that chemisorption is twice as effective in sulphur dioxide removal than absorption in water. (author)

Effect of chemisorption structure on the interfacial bonding characteristics of graphene-polymer composites

International Nuclear Information System (INIS)

Lv Cheng; Xue Qingzhong; Xia Dan; Ma Ming

2012-01-01

The influence of the chemical functionalization of graphene on the interfacial bonding characteristics between graphene and polymer was investigated using molecular mechanics and molecular dynamics simulations. In this study, three chemical functionalization, (a) phenyl groups, (b) -C 6 H 13 and(c) -C 2 H 4 (C 2 H 5 ) 2 , which have the same number of carbon atoms, were chosen to investigate the influence of the structure of functionalized groups on the bonding energy and shear stress in the graphene-polyethylene (PE) composites. Our simulations indicated that, the interfacial bonding energy between the graphene modified by -C 6 H 13 groups and PE matrix has the strongest enhancement, but the shear force between the graphene modified by -C 2 H 4 (C 2 H 5 ) 2 groups and PE matrix is the strongest in the graphene-polymer composites. Therefore, the suitable structure of chemical groups to the graphene surface may be an effective way to significantly improve the load transfer between the graphene and polymer when graphene is used to produce nanocomposites.

Nickel group cluster anion reactions with carbon monoxide: Rate coefficients and chemisorption efficiency

Science.gov (United States)

Hintz, Paul A.; Ervin, Kent M.

1994-04-01

Reactions of Ni-n(n=3-10), Pd-n(n=3-8), and Pt-n(n=3-7) with CO are studied in a flow tube reactor. Bimolecular rate coefficients are measured for the association reaction of CO adsorbing on the cluster surface. The rate coefficients range from about 10% of the collision rate for the trimer anions to near the collision rate for clusters larger than four atoms. The maximum number of CO molecules that bind to each cluster is determined. Whereas the saturation limits for nickel are typical for an 18 electron transition metal, the limits for platinum are lower, reflecting the electron deficient structures observed in condensed phase chemistry. The CO saturated palladium clusters represent the first examples of saturated binary palladium carbonyl compounds. Comparisons are made to similar studies on metal cation and neutral clusters and also to surface scattering studies of nickel group metals.

Temperature-dependent chemisorption of C60 on Mo(110) : precursors to cage destruction

NARCIS (Netherlands)

Hunt, Michael R.C.; Rajogopal, Aparna; Caudano, Roland; Rudolf, Petra

2000-01-01

The catalytically promoted decomposition of C60 has recently been observed on a variety of surfaces upon which the molecule can chemisorb strongly. It is now becoming clear that destruction occurs via conversion of a relatively weakly bound state arising from room-temperature adsorption into a

Results and progress of fundamental research on fission product chemistry. Progress report in 2015

International Nuclear Information System (INIS)

Osaka, Masahiko; Miwa, Shuhei; Nakajima, Kunihisa; Di Lemma, Fidelma Giulia; Suzuki, Chikashi; Miyahara, Naoya; Kobata, Masaaki; Okane, Tetsuo; Suzuki, Eriko

2016-12-01

A fundamental research program on fission product (FP) chemistry has been conducted since 2012 in order to establish a FP chemistry database in LWR under severe accidents and to improve FP chemical models based on the database. Research outputs are reflected as fundamental knowledge to both the R and D of decommissioning of Fukushima Daiichi Nuclear Power Station (1F) and enhancement of LWR safety. Four research items have thus been established considering the specific issues of 1F and the priority in the source term research area, as follows: effects of boron (B) release kinetics and thermal-hydraulic conditions on FP behavior, cesium (Cs) chemisorption and reactions with structural materials, enlargement of a thermodynamic and thermophysical properties database for FP compounds and development of experimental and analytical techniques for the reproduction of FP behavior and for direct measurement methods of chemical form of FP compounds. In this report, the research results and progress for the year 2015 are described. The main accomplishment was the installation of a reproductive test facility for FP release and transport behavior. Moreover, basic knowledge about the Cs chemisorption behavior was also obtained. In addition to the four research items, a further research item is being considered for deeper interpretation of FP behavior by the analysis of samples outside of the 1F units. (author)

Carbon 1s photoemission line analysis of C-based adsorbate on (111)In{sub 2}O{sub 3} surface: The influence of reducing and oxidizing conditions

Energy Technology Data Exchange (ETDEWEB)

Brinzari, V., E-mail: vbrinzari@mail.ru [State University of Moldova, Chisinau, str. Mateevich 60A, MD-2009, Republic of Moldova (Moldova, Republic of); Cho, B.K. [Gwangju Institute of Science and Technology, Gwangju (Korea, Republic of); Korotcenkov, G., E-mail: ghkoro@yahoo.com [Gwangju Institute of Science and Technology, Gwangju (Korea, Republic of)

2016-12-30

Highlights: • C 1s PE line of (111)In{sub 2}O{sub 3} layer after cleaning and gas probing in HV was studied. • C 1s line fine structure is formed by various residual C-based adsorbates. • Some C 1s line features were interpreted as CO adsorption and dissociation. • Redox properties of surface determine either adsorption or dissociation of CO. • Dissociation of CO on oxidized surface is responsible for acceptor-like effect. - Abstract: Synchrotron radiation photoemission study of C 1s line of (111) In{sub 2}O{sub 3} surface was carried out under HV (high vacuum) doses of oxygen, carbon monoxide and water. Gas interaction with the surface was activated by heating of In{sub 2}O{sub 3} monocrystalline film at temperatures of 160 or 250 °C. The study of complex structure of C 1 s line and evolution of its fine components allowed to establish their nature and to propose possible surface adsorbed species and reactions, including a direct chemisorption and dissociation of CO molecules. Reduction or oxidation of the surface determines whether the first (chemisorption) or the second (dissociation) process takes place. The latter is responsible for additional formation of ionosorbed oxygen. Both processes have not been previously reported for In{sub 2}O{sub 3} and for conductive metal oxides.

The adsorption of oleate on powellite and fluorapatite: A joint experimental and theoretical simulation study

Science.gov (United States)

Zhen, Wang

2017-07-01

Flotation and adsorption performance of sodium oleate(NaOl)on powellite and fluorapatite were investigated in this work through micro-flotation tests, work of adhesion calculations, molecular dynamics simulation, micro-topography studies and FTIR measurements. The micro-flotation results show a similar flotation behaviors of powellite and fluorapatite under alkaline conditions, but a considerable difference in mineral recoveries in the pH range 2-7, which demonstrates the possibilities for separating powillite from fluorapatite under acidic conditions. The great difference in mineral recovery displays a good accordance with the obvious difference in the work of adhesion of powellite and fluorapatite at NaOl dosage range of 40-80 mg/L, obtained from flotation and contact angle measurements, respectively. The more negative interaction energy (ΔE) between NaOl and powellite/water interface from molecular dynamics simulation reveals a more easily adsorption of NaOl onto powellite than onto fluorapatite, which excellently matches with the results of flotation and work of adhesion. The results of micro-topography study shows that the adsorption of NaOl on powellite is mainly ascribed to the chemisorption of oleate ions with Ca2+ on powellite lattice or the precipitation of calcium dioleate agglomerates on powellite surface when it was in the solution without or with Ca2+, respectively. The FTIR measurements further confirm the chemisorption of oleate ions with Ca2+ active sites on powellite surface.

Oxygen exchange between C18O2 and ''acidic'' oxide and zeolite catalysts

International Nuclear Information System (INIS)

Peri, J.B.

1975-01-01

The exchange of oxygen between C 18 O 2 and several high-area oxides, including silica, γ-alumina, silica--alumina, and zeolite catalysts, was studied. Infrared spectra of adsorbed CO 2 and of surface ''carbonates'' were used to follow the rate of oxygen exchange and investigate the nature of unusually exchangeable surface oxide ions, present at low concentrations. Interaction of CO 2 with the surface typically produced initial exchange of one oxygen atom, as expected from interaction with a single oxide ion (CO 2 + O 2- reversible CO 3 2- ), and the number of exchangeable ions increased with increasing temperature. The rate of oxygen exchange did not correlate with chemisorption to form stable surface carbonates or with the extent of strong physical adsorption of CO 2 . With dry silica, exchange was insignificant below 600 0 ; with catalytically active zeolites and dry γ-alumina, it was detectable at 200 0 and fairly rapid at 300--400 0 . Silica--alumina required 100--150 0 higher temperature for exchange than did an active zeolite. Activity for cracking and other hydrocarbon reactions may be related to the ease of exchange of some surface oxide ions with CO 2 . Active zeolites have reactive oxide sites resembling those on dry γ-alumina, but such sites on zeolites are probably less-readily eliminated by chemisorption of H 2 O or other compounds. (U.S.)

Synthesis of PEG-Iodine-Capped Gold Nanoparticles and Their Contrast Enhancement in In Vitro and In Vivo for X-Ray/CT

International Nuclear Information System (INIS)

Sun-Hee, K.; Eun-Mi, K.; Chang-Moon, L.; Dong, W.K.; Seok, T.L.; Myung-Hee, S.; Hwan-Jeong, J.

2012-01-01

We designed gold nanoparticles (AuNPs) capped with iodine and polyethylene glycol (PEG) to provide effective enhancement for X-ray CT imaging. The methoxy PEG-iodine-capped AuNPs were prepared through the chemisorption of iodine and substitution of methoxy PEG-SH onto the surface of gold nanoparticles, and severe aggregation in TEM was not observed. The binding energies of Au 4f 7/2 and I 3d 5/2 of the methoxy PEG-iodine-capped AuNPs were obtained as 84.1 eV and 619.3 eV, respectively. The binding energy shift of methoxy PEG-iodine-capped AuNPs would be resulted from the chemisorption between gold nanoparticles and iodine atoms. The methoxy PEG-iodine-capped AuNPs have higher enhancement compared to PEG-capped gold nanoparticles in the same amount of gold in vitro. After postinjection of methoxy PEG-iodine-capped AuNPs into the mice, dramatic contrast enhancement at the heart, aorta, liver, and kidney was observed, this was maintained up to 5 days, and there was no evidence of apparent toxicity. In conclusion, methoxy PEG-iodine-capped AuNPs might be a good candidate as a CT contrast agent for blood pool imaging, and this will also contribute to the prolongation of a blood circulation time for X-ray CT imaging.

DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

Science.gov (United States)

Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

2017-09-24

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-08-15

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Core Level Spectra of Organic Molecules Adsorbed on Graphene

Directory of Open Access Journals (Sweden)

Abhilash Ravikumar

2018-03-01

Full Text Available We perform first principle calculations based on density functional theory to investigate the effect of the adsorption of core-excited organic molecules on graphene. We simulate Near Edge X-ray absorption Fine Structure (NEXAFS and X-ray Photoemission Spectroscopy (XPS at the N and C edges for two moieties: pyridine and the pyridine radical on graphene, which exemplify two different adsorption characters. The modifications of molecular and graphene energy levels due to their interplay with the core-level excitation are discussed. We find that upon physisorption of pyridine, the binding energies of graphene close to the adsorption site reduce mildly, and the NEXAFS spectra of the molecule and graphene resemble those of gas phase pyridine and pristine graphene, respectively. However, the chemisorption of the pyridine radical is found to significantly alter these core excited spectra. The C 1s binding energy of the C atom of graphene participating in chemisorption increases by ∼1 eV, and the C atoms of graphene alternate to the adsorption site show a reduction in the binding energy. Analogously, these C atoms also show strong modifications in the NEXAFS spectra. The NEXAFS spectrum of the chemisorbed molecule is also modified as a result of hybridization with and screening by graphene. We eventually explore the electronic properties and magnetism of the system as a core-level excitation is adiabatically switched on.

Coalescence of 3-phenyl-propynenitrile on Cu(111) into interlocking pinwheel chains

Science.gov (United States)

Luo, Miaomiao; Lu, Wenhao; Kim, Daeho; Chu, Eric; Wyrick, Jon; Holzke, Connor; Salib, Daniel; Cohen, Kamelia D.; Cheng, Zhihai; Sun, Dezheng; Zhu, Yeming; Einstein, T. L.; Bartels, Ludwig

2011-10-01

3-phenyl-propynenitrile (PPN) adsorbs on Cu(111) in a hexagonal network of molecular trimers formed through intermolecular interaction of the cyano group of one molecule with the aromatic ring of its neighbor. Heptamers of trimers coalesce into interlocking pinwheel-shaped structures that, by percolating across islands of the original trimer coverage, create the appearance of gear chains. Density functional theory aids in identifying substrate stress associated with the chemisorption of PPN's acetylene group as the cause of this transition.

Some approaches to the quantum-chemical theory of heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Zhidomirov, G M

1977-09-01

A discussion of mathematical methods, models, and parameters used in various quantum-chemical descriptions of chemisorption and reaction at silica and aluminosilicate surfaces covers the continuous-surface model, the cluster model of the surface, the variation of pseudo-atom parameters to reduce the magnitude of boundary effects in the cluster model, the calculation of individual bond strengths in chemisorbed molecules, dissociative adsorption, applications to adsorption on silica and aluminosilicates, the mechanisms of hydrogen-deuterium exchange, etc. Diagrams, graphs, and 42 references.

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

OpenAIRE

Vahabi, Vahid; Soleymanabadi, Hamed

2016-01-01

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

Application of Elovich equation on uptake kinetics of 137Cs by living freshwater macrophytes - a short duration laboratory study

International Nuclear Information System (INIS)

Jaison, T.J.; Patra, A.K.; Ravi, P.M.; Tripathi, R.M.

2014-01-01

Application of Elovich equation on uptake kinetics of 137 Cs by two living macrophytes during controlled experiments on short duration exposure is studied. Compliance to 2 nd order kinetics indicates the mechanism could be chemi-sorption, involving polar functional groups present on the extracelluar surface of the macrophytes. Data analysis suggests that Myriophyllum s. exhibits faster adsorption rate than Hydrilla v. As Myriophyllum s. exhibits better kinetics than Hydrilla v., former could be a better natural adsorbing media for 137 Cs. (author)

Feasibility of N2 Binding and Reduction to Ammonia on Fe-Deposited MoS2 2D Sheets: A DFT Study

KAUST Repository

Azofra Mesa, Luis

2017-05-19

Based on the structure of the nitrogenase FeMo cofactor (FeMoco), it is reported that Fe deposited on MoS2 2D sheets exhibits high selectivity towards the spontaneous fixation of N2 against chemisorption of CO2 and H2 O. DFT predictions also indicate the ability of this material to convert N2 into NH3 with a maximum energy input of 1.02 eV as an activation barrier for the first proton-electron pair transfer.

The adsorption of oleate and its effect on the flotation of monazite

International Nuclear Information System (INIS)

Tran, Tam; Cheng, Tawui; Patridge, A.C.; Wong, P.L.M.

1993-01-01

The absorption of sodium oleate during the flotation of monazite has been investigated. Thermodynamic modelling was employed to study the surface chemistry of monazite. The experimental results show that the ionic distribution of the first hydroxyl rare earth species, RE(OH) 2+ , correlates well with the adsorption and flotation results. It is suggested that hydroxylation of rare earth cations at mineral surfaces could provide active sites for the chemisorption of oleate ions (sodium oleate) which enhances flotation. 13 refs., 11 figs

Ab initio calculations on hydrogen storage in porous carbons

International Nuclear Information System (INIS)

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

2005-01-01

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

Non stoichiometry in U3O(8±x), its temperature and oxygen pressure dependence

International Nuclear Information System (INIS)

Rodriguez De Sastre, M.S.; Philippot, J.; Moreau, C.

1967-01-01

The deviation from stoichiometry in uranium oxide U 3 O 8 obtained by oxidation of UO 2 , has been studied with respect to its dependence on temperature and oxygen pressure. It is shown that the ratio r = O/U increases with oxygen pressure up to 200 mm Hg at any temperature. At higher pressures, this ratio tends toward a limit which decreases with increasing temperatures. The curve r = f(P) suggest a chemisorption phenomenon as the reaction limiting mechanism. (authors) [fr

Electrochemical transformations of oxygen and the defect structure of solid solutions on the basis of alkaline earth metal ortho-vanadates

International Nuclear Information System (INIS)

Khodos, M.Ya.; Belysheva, G.M.; Brajnina, Kh.Z.

1986-01-01

Effect of iso- and heterovalent substitution in the structure of alkaline earth metal ortho-vanadates and synthesis conditions, simulating the definite type of their crystal lattice disordering, on the character of potentiodynamic anodic-cathodic curves has been investigated by the method of cyclic voltammetry. Correlation between signals observed and the defect structure of oxide compounds is refined. Oxygen chemisorption is shown to be determined by concentration of nonequilibrium oxygen vacancies, which formation is accompanied by appearance of quasi-free electrons

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Feasibility of N2 Binding and Reduction to Ammonia on Fe-Deposited MoS2 2D Sheets: A DFT Study

KAUST Repository

Azofra Mesa, Luis; Sun, Chenghua; Cavallo, Luigi; MacFarlane, Douglas R.

2017-01-01

Based on the structure of the nitrogenase FeMo cofactor (FeMoco), it is reported that Fe deposited on MoS2 2D sheets exhibits high selectivity towards the spontaneous fixation of N2 against chemisorption of CO2 and H2 O. DFT predictions also indicate the ability of this material to convert N2 into NH3 with a maximum energy input of 1.02 eV as an activation barrier for the first proton-electron pair transfer.

Photoassisted Kelvin probe force microscopy at GaN surfaces: The role of polarity

Science.gov (United States)

Wei, J. D.; Li, S. F.; Atamuratov, A.; Wehmann, H.-H.; Waag, A.

2010-10-01

The behavior of GaN surfaces during photoassisted Kelvin probe force microscopy is demonstrated to be strongly dependant on surface polarity. The surface photovoltage of GaN surfaces illuminated with above-band gap light is analyzed as a function of time and light intensity. Distinct differences between Ga-polar and N-polar surfaces could be identified, attributed to photoinduced chemisorption of oxygen during illumination. These differences can be used for a contactless, nondestructive, and easy-performable analysis of the polarity of GaN surfaces.

Tendências em modificação de eletrodos amperométricos para aplicações eletroanalíticas Trends in amperometric electrodes modification for electroanalytical applications

Directory of Open Access Journals (Sweden)

Arnaldo César Pereira

2002-11-01

Full Text Available The most relevant advances on the analytical applications of chemically modified electrodes (CME are presented. CME have received great attention due to the possibility of electrode surface modification including chemisorption, composite generation and polymer coating. In recent years, the interest in CME has increased overall to improve the sensitivity and selectivity of the electroanalytical probes, considering the electron mediator incorporation and the new conducting polymers development. The general procedures employed for the electrode modification and the operational characteristics of some electrochemical sensors are discussed.

D2 dissociative adsorption on and associative desorption from Si(100): Dynamic consequences of an ab initio potential energy surface

DEFF Research Database (Denmark)

Luntz, A. C.; Kratzer, Peter

1996-01-01

favors the symmetric one. Under the conditions of many experiments, either could dominate. The calculations show quite weak dynamic coupling to the Si lattice for both paths, i.e., weak surface temperature dependences to dissociation and small energy loss to the lattice upon desorption......Dynamical calculations are reported for D-2 dissociative chemisorption on and associative desorption from a Si(100) surface. These calculations use the dynamically relevant effective potential which is based on an ab initio potential energy surface for the ''pre-paired'' species. Three coordinates...

Heat pretreatment-induced activation of gadolinium surfaces towards the initial precipitation of hydrides

International Nuclear Information System (INIS)

Benamar, G.; Schweke, D.; Shamir, N.; Zalkind, S.; Livneh, T.; Danon, A.; Kimmel, G.; Mintz, M.H.

2010-01-01

A vacuum heat pretreatment is applied, in order to enhance the reactivity of hydride-forming metals towards hydrogen reaction. For gadolinium, as for other rare-earth metals and some actinides, pretreatment temperatures of about 470 K are sufficient to induce such activation. The different factors that may be involved in that activation mechanism are identified and analyzed for gadolinium and their role is evaluated. It is concluded that the most prominent effect is desorption of surface hydroxyl groups, which impede the dissociative chemisorptions of hydrogen.

Ab initio calculation of electron excitation energies in solids

International Nuclear Information System (INIS)

Louie, S.G.

1996-02-01

Progress in the first-principles calculation of electron excitation energies in solids is discussed. Quasiparticle energies are computed by expanding the electron self energy to first order in the screened Coulomb interaction in the so-called GW approximation. The method was applied to explain and predict spectroscopic properties of a variety of systems. Several illustrative applications to semiconductors, materials under pressure, chemisorption, and point defects in solids are presented. A recent reformulation of the method employing mixed- space functions and imaginary time techniques is also discussed

Quantum chemistry and scientific calculus

International Nuclear Information System (INIS)

Gervais, H.P.

1988-01-01

The 1988 progress report of the Polytechnic School research team, concerning the quantum chemistry and the scientific calculus. The research program involves the following topics: the transition metals - carbon monoxide systems, which are a suitable model for the chemisorption phenomena; the introduction of the vibronic perturbations in the magnetic screen constants; the gauge invariance method (used in the calculation of the magnetic perturbations), extended to the case of the static or dynamic electrical polarizabilities. The published papers, the congress communications and the thesis are listed [fr

The adsorption of mercury on tungsten (100) studied by ultra-violet photoelectron spectroscopy

International Nuclear Information System (INIS)

Egelhoff, W.F. Jr.; Perry, D.L.; Linnett, J.W.

1976-01-01

In recent years, photoelectron spectroscopy has been applied to the study of adsorption on several metal surfaces. A popular choice of substrate has been the 100 face of single crystal tungsten, since adsorption on this surface has been well-characterised by a wide variety of experimental techniques. In this letter a study of the adsorption of mercury on W(100) by ultra-violet photoelectron spectroscopy (UPS) is reported. These results, seen in the context of previous UPS studies of chemisorption, show a number of interesting features. (Auth.)

Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

International Nuclear Information System (INIS)

Tichomirowa, Marion; Junghans, Manuela

2009-01-01

Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

Study of the chemisorption and hydrogenation of propylene on platinum by temperature-programed desorption

Energy Technology Data Exchange (ETDEWEB)

Tsuchiya, S.; Nakamura, M.; Yoshioka, N.

1978-01-01

Temperature-programed desorption (TPD) chromotograms of propylene adsorbed on platinum black in the absence or presence of hydrogen preadsorbed, admitted simultaneously, or admitted later, all showed four peaks at about 260/sup 0/ (A), 380/sup 0/ (B), 570/sup 0/ (C), and higher than 720/sup 0/K (D). Peaks A and B were identified as mixtures of propylene and propane, and peaks C and D were methane formed by thermal decomposition of the chemisorbed propylene during desorption. When nitrogen rather than helium was used as the carrier gas for the TPD, only delta-hydrogen was observed; this suggested that propylene was more strongly adsorbed on the platinum than hydrogen. Studies of the reactivities with propylene of the various types of chemisorbed hydrogen previously detected by TPD showed that propylene reacted with ..gamma..-hydrogen present on the surface in the form of hydrogen atoms chemisorbed on top of platinum atoms and with ..beta..-hydrogen, molecular hydrogen chemisorbed in a bridged form, but did not react with delta-hydrogen. Tables and graph.

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

Science.gov (United States)

2013-09-01

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

Molecular orbital study of the chemisorption of carbon monoxide on a tungsten (100) surface

International Nuclear Information System (INIS)

Lee, T.H.; Rabalais, J.W.

1978-01-01

The adsorption energies of carbon monoxide chemisorbed at various sites on a tungsten (100) surface have been calculated by extended Hueckel molecular orbital theory (EHMO). The concept of a 'surface molecule' in which CO is bonded to an array of tungsten atoms Wsub(n) has been employed. Dissociative adsorption in which C occupies a four-fold, five-coordination site and O occupies either a four- or two-fold site has been found to be the most stable form for CO on a W surface. Stable one-fold and two-fold sites of molecularly adsorbed CO have also been found in which the CO group is normal to the surface plane and the C atom is nearest the surface. Adsorption energies and molecular orbitals for the stable molecularly and dissociatively adsorbed CO sites are compared with the experimental data on various types of adsorbed CO, i.e. virgin-, α-, and β-CO. Models are suggested for each of these adsorption types. The strongest bonding interactions occur between the CO 5sigma orbital and the totally symmetric 5d and 6s orbitals of the Wsub(n) cluster. Possible mechanisms for conversion of molecularly adsorbed CO to dissociatively adsorbed CO are proposed and the corresponding activation energies are estimated. (Auth.)

Metal compounds in zeolites as active components of chemisorption and catalysis. Quantum chemical approach

International Nuclear Information System (INIS)

Zhidomirov, G.M.

1996-01-01

A short review of possible catalitic active sites associated with various types of metal species in zoolite is presented. The structural and electronic peculiarity of aluminum ions in zeolite lattice and their distribution in the lattice are discussed on the basis of quantum chemical calculations in connection with the formation of Broensted activity of zeolites. Various molecular models of Lewis Acid Sites associated the extra-lattice oxide-hydroxide aluminum species have been investigated by means of density functional model cluster calculations using CO molecule as a probe. Probable ways of formation of the selective oxidation center in FeZSM-5 by decomposition of dinitrogen monoxide have been studied by ab-initio quantum chemical calculations. The immediate oxidizing site is reasonably represented by the binuclear iron-hydroxide cluster with peroxo-like fragment located between iron atoms. Various probable intermediates of the selective oxidation center formation resulted from interaction of a hydroperoxide molecule with a lattice titanium ion in titanium silicalite have been investigated by quantum chemical calculations. It was concluded that this reaction requires essential structural reconstruction in the vicinity of the titanium ion. Probability of this structural reconstruction is discussed. Possible reasons of an electron-deficient and electron-enriched state of metal particles entrapped in zoolite cavities are discussed. Also, various probable molecular models of such modified metal particles in zeolite are considered

Understanding the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets in activated carbon using a quantum mechanics/molecular mechanics computational approach.

Science.gov (United States)

Ha, Nguyen Ngoc; Cam, Le Minh; Ha, Nguyen Thi Thu; Goh, Bee-Min; Saunders, Martin; Jiang, Zhong-Tao; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z; El-Harbawi, Mohanad; Yin, Chun-Yang

2017-06-07

The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO 4 2- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO 4 2- . Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.

Adsorption of a novel reagent scheme on scheelite and calcite causing an effective flotation separation.

Science.gov (United States)

Gao, Yuesheng; Gao, Zhiyong; Sun, Wei; Yin, Zhigang; Wang, Jianjun; Hu, Yuehua

2018-02-15

The efficient separation of scheelite from calcium-bearing minerals, especially calcite, remains a challenge in practice. In this work, a novel reagent scheme incorporating a depressant of sodium hexametaphosphate (SHMP) and a collector mixture of octyl hydroxamic acid (HXMA-8) and sodium oleate (NaOl) was employed in both single and mixed binary mineral flotation, and it proved to be highly effective for the separation. Furthermore, the role of the pH value in the separation was evaluated. Additionally, the mechanism of the selective separation was investigated systemically via zeta potential measurements, fourier transform infrared (FTIR) spectroscopy analysis, X-ray photoelectron (XPS) spectroscopy analysis and crystal chemistry calculations. It turns out that the selective chemisorption of SHMP on calcite (in the form of complexation between H 2 PO 4 - /HPO 4 2- and Ca 2+ ) over scheelite is ascribed to the stronger reactivity and higher density of Ca ions on the commonly exposed surfaces of calcite minerals. The intense adsorption of HXMA-8 on scheelite over calcite due to the match of the OO distances in WO 4 2- of scheelite and CONHOH of HXMA-8 holds the key to the successful separation. We were also interested in warranting the previous claim that NaOl is readily adsorbed on both minerals via chemisorption. Our results provided valuable insights into the application of mixed collectors and an effective depressant for flotation separation. Copyright © 2017 Elsevier Inc. All rights reserved.

ThermoEnergy Ammonia Recovery Process for Municipal and Agricultural Wastes

Directory of Open Access Journals (Sweden)

Alex G. Fassbender

2001-01-01

Full Text Available The Ammonia Recovery Process (ARP is an award-winning, low-cost, environmentally responsible method of recovering nitrogen, in the form of ammonia, from various dilute waste streams and converting it into concentrated ammonium sulfate. The ThermoEnergy Biogas System utilizes the new chemisorption-based ARP to recover ammonia from anaerobically digested wastes. The process provides for optimal biogas production and significantly reduced nitrogen levels in the treated water discharge. Process flows for the ammonia recovery and ThermoEnergy biogas processes are presented and discussed. A comparison with other techniques such as biological nitrogen removal is made. The ARP technology uses reversible chemisorption and double salt crystal precipitation to recover and concentrate the ammonia. The ARP technology was successfully proven in a recent large-scale field demonstration at New York City’s Oakwood Beach Wastewater Treatment Plant, located on Staten Island. This project was a joint effort with Foster Wheeler Environmental Corporation, the Civil Engineering Research Foundation, and New York City Department of Environmental Protection. Independent validated plant data show that ARP consistently recovers up to 99.9% of the ammonia from the city’s centrate waste stream (derived from dewatering of sewage sludge, as ammonium sulfate. ARP technology can reduce the nitrogen (ammonia discharged daily into local bodies of water by municipalities, concentrated animal farming operations, and industry. Recent advances to ARP enhance its performance and economic competitiveness in comparison to stripping or ammonia destruction technologies.

Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures

International Nuclear Information System (INIS)

Samaane, Mikhail

1966-01-01

Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al 2 O 3 , NiAl 2 O 4 and NiO + NiAl 2 O 4 ) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al 2 O 3 catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O 2 and CO 2 on the 2NiO+Al 2 O 3 solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl 2 O 4 and NiO+NiAl 2 O 4 ) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O 2 and CO 2 on NiAl 2 O 4 , and the kinetic of the oxidation reaction are herein studied

Photoemission and electron-stimulated desorption studies of H on W(110): Single- versus two-binding-site models

International Nuclear Information System (INIS)

Weng, S.

1982-01-01

The chemisorption of H on W(110) at room temperature is studied with the use of angle-integrated photoemission and electron-stimulated desorption (ESD). The ESD cross sections of H + are found to be sol low that no significant H + signals with meaningful ion energy distributions are observed. The photoemission results show, however, two types of H adatoms, referred to as β 2 and β 1 states, for this chemisorptive system. Both states are found to appear simultaneously rather than sequentially as suggested by previous studies, and exhibit a simple 1-theta adsorption kinetics with different initial sticking coefficients. The β 2 state induces two binding energy levels at -2.0 and -6.0 eV, respectively, whereas the β 1 state induces a level at -3.8 eV. The work-function change (with a maximum value of -0.45 eV) is found to follow exactly with the intensity of the β 2 state. These results are found to be compatible with the two-binding-site model, inherently suggested by the reflection high-enery electron-diffraction data. However, the results can also be consistent with a single-binding-site model suggested by a recent angle-resolved photoemission and inelastic electron scattering study. A model based on the present results is proposed and critically compared with previous studies. Unresolved problems associated with both single- and two-binding-site models are also discussed

Catalysis studies

International Nuclear Information System (INIS)

Taylor, T.N.; Ellis, W.P.

1977-11-01

The New Research Initiatives Program (NRIP) project on catalysis in Los Alamos Scientific Laboratory (LASL) Group CMB-8 has made significant progress towards performing the first basic in situ experimental studies of heterogeneous catalysis on solid compound surfaces in a LEED-Auger system. To further understand the surface crystallography of a possible catalyst compound, LEED-Auger measurements were made on UO 2 (approximately 100) vicinal surfaces. These (approximately 100) vicinal surfaces were shown to decompose irreversibly into lower index facets, including prominent (100) facets, at temperatures below those needed for creation of lowest index faceting on (approximately 111) vicinal surfaces. LEED examination of fully faceted surfaces from both types of UO 2 vicinal cuts did not show evidence of cyclopropane or propene chemisorption. The existing LEED-Auger system was modified to allow catalytic reactions at approximately less than 10 -3 torr. A sample holder, specifically designed for catalysis measurements in the modified system, was tested while examining single crystals of CoO and Cr 2 O 3 . Extensive LEED-Auger measurements were made on CoO in vacuo and in the presence of light hydrocarbons and alcohols plus H 2 O, NO, and NH 3 . No chemisorptive behavior was observed except with H 2 O in the presence of the electron beam. Although only examined briefly, the Cr 2 O 3 was remarkable for the sharp LEED features obtained prior to any surface treatment in the vacuum system

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

Science.gov (United States)

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

2011-04-12

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

Materials for carbon dioxide separation

International Nuclear Information System (INIS)

Xu, Qingqing

2014-01-01

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

Near field chemical speciation: the reaction of uranium and thorium with Hanford basalt and elevated pH

International Nuclear Information System (INIS)

Perry, D.L.

1984-01-01

The hydrolysis of radionuclides such as thorium and uranium and their subsequent chemisorption on Hanford basalt have been studied using a variety of techniques, including x-ray photoelectron and infrared spectroscopy. Data obtained to date indicate mixed complexes of uranium and thorium to be on the basalt surface, the complexes being radionuclide oxides, hydrated oxides (hydroxides), and carbonates. These findings are discussed with respect to their importance for input for models describing speciation and dissolution processes involving nuclear waste repository materials such as Hanford basalt. 5 figures, 2 tables

Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals

DEFF Research Database (Denmark)

Hammer, Bjørk; Hansen, Lars Bruno; Nørskov, Jens Kehlet

1999-01-01

A simple formulation of a generalized gradient approximation for the exchange and correlation energy of electrons has been proposed by Perdew, Burke, and Ernzerhof (PBE) [Phys. Rev. Lett. 77, 3865 (1996)]. Subsequently Zhang and Yang [Phys. Rev. Lett. 80, 890 (1998)] have shown that a slight...... revision of the PBE functional systematically improves the atomization energies for a large database of small molecules. In the present work, we show that the Zhang and Yang functional (revPBE) also improves the chemisorption energetics of atoms and molecules on transition-metal surfaces. Our test systems...

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....

Molecular beam study of dissociative sticking of methane on Ni(100)

DEFF Research Database (Denmark)

Holmblad, Peter Mikal; Wambach, Jørg; Chorkendorff, Ib

1995-01-01

of the methane leads to a dramatic enhancement of the sticking, emphasizing that the initial vibrational state is of crucial importance. These results are consistent with a mechanism of direct activated dissociative chemisorption where the dynamics is dominated by a barrier in the potential energy surface mainly...... located in the vibrational coordinates. Normal-energy scaling is only approximately observed. The effect of surface temperature is also investigated but is found to be smaller than activation by translational or vibrational energy. A simplified analysis in terms of state resolved sticking curves, Snu...... American Institute of Physics....

Surface extended x-ray absorption fine structure of low-Z absorbates using fluorescence detection

International Nuclear Information System (INIS)

Stoehr, J.; Kollin, E.B.; Fischer, D.A.; Hastings, J.B.; Zaera, F.; Sette, F.

1985-05-01

Comparison of x-ray fluorescence yield (FY) and electron yield surface extended x-ray absorption fine structure spectra above the S K-edge for c(2 x 2) S on Ni(100) reveals an order of magnitude higher sensitivity of the FY technique. Using FY detection, thiophene (C 4 H 4 S) chemisorption on Ni(100) is studied with S coverages down to 0.08 monolayer. The molecule dissociates at temperatures as low as 100K by interaction with fourfold hollow Ni sites. Blocking of these sites by oxygen leaves the molecule intact

Reactivity of NO with small transition metal clusters II. Possible reaction mechanisms

International Nuclear Information System (INIS)

Martinez, A.; Vela, A.; Robles, J.

1994-01-01

Through extended Huckel (EHMO) calculations, we followed six possible reaction paths for the formation of Co 2 NO'+ and co 4 NO'+, whose stable structures were discussed in the previous paper of this series. The adduct formation enthalpy (DELTA h f ) and the global hardness (n) have been calculated in order to establish the more probable structures and the more probable routes of reaction for the chemisorption of NO on Co'+ x (x=2-4). It is shown that the maximum hardness principle, at the EHMO level, produces more realistic geometries. (Author) 11 refs

Tin oxide surfaces--8. An infrared study of the mechanism of formation of a surface isocyanate species on SnO/sub 2//0. 55 CuO during catalysis of the oxidation of carbon monoxide by nitric oxide

Energy Technology Data Exchange (ETDEWEB)

Harrison, P.G.; Thornton, E.W.

1978-01-01

In studies carried out at 470/sup 0/K, the measurements of the isotopic shifts of the 2189/cm pseudo-antisymmetric stretching vibration for carbon-13, nitrogen-15, and oxygen-18 substitution indicated that the oxygen atom of the surface isocyanate, formed as an intermediate in the reaction of CO with NO, originated from NO, not from CO as previously believed. The mechanism proposed involves the dissociative chemisorption of CO, the formation of a fulminate by the reaction of NO with the surface carbon atom, and rapid isomerization to the isocyanate.

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

Science.gov (United States)

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

2014-04-18

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

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.

Influence of alumina binder content on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone.

Directory of Open Access Journals (Sweden)

Xiangjin Kong

Full Text Available The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst.

Influence of alumina binder content on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone.

Science.gov (United States)

Kong, Xiangjin; Liu, Junhai

2014-01-01

The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst.

Plutonium separation and the measurement of its concentration in natural waters (1963); Separation du plutonium et mesure de sa concentration dans les eaux naturelles

Energy Technology Data Exchange (ETDEWEB)

Scheidhauer, J; Messainguiral, L; Meiraneisio, A M [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

1963-07-01

After concentration by chemisorption on a calcium fluoride suspension, the plutonium is purified and isolated by xylene extraction of the complex formed with T.T.A. The radioelement is measured by counting with a ZnS (Ag) scintillator after evaporation or electrolysis. (authors) [French] Apres concentration par chimisorption sur une suspension de fluorure de calcium, le plutonium est purifie et isole par extraction au xylene du complexe forme avec la T.T.A. La mesure du radioelement est effectuee par comptage au scintillateur S Zn (Ag) apres evaporation ou electrolyse. (auteurs)

Theoretical modelling of semiconductor surfaces microscopic studies of electrons and photons

CERN Document Server

Srivastava, G P

1999-01-01

The state-of-the-art theoretical studies of ground state properties, electronic states and atomic vibrations for bulk semiconductors and their surfaces by the application of the pseudopotential method are discussed. Studies of bulk and surface phonon modes have been extended by the application of the phenomenological bond charge model. The coverage of the material, especially of the rapidly growing and technologically important topics of surface reconstruction and chemisorption, is up-to-date and beyond what is currently available in book form. Although theoretical in nature, the book provides

Effect of NO2 and water on the catalytic oxidation of soot

DEFF Research Database (Denmark)

Christensen, Jakob Munkholt; Grunwaldt, Jan-Dierk; Jensen, Anker Degn

2017-01-01

The influence of adding NO2 to 10 vol% O2/N2 on non-catalytic soot oxidation and soot oxidation in intimate or loose contact with a catalyst has been investigated. In non-catalytic soot oxidation the oxidation rate is increased significantly at lower temperatures by NO2. For soot oxidation in tig...... exhibited a volcano-curve dependence on the heat of oxygen chemisorption, and among the tested pure metals and oxides Cr2O3 was the most active catalyst. Further improvements were achieved with a FeaCrbOx binary oxide catalyst....

Trends in the exchange current for hydrogen evolution

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Bligaard, Thomas; Logadottir, Ashildur

2005-01-01

A density functional theory database of hydrogen chemisorption energies on close packed surfaces of a number of transition and noble metals is presented. The bond energies are used to understand the trends in the exchange current for hydrogen evolution. A volcano curve is obtained when measured...... exchange currents are plotted as a function of the calculated hydrogen adsorption energies and a simple kinetic model is developed to understand the origin of the volcano. The volcano curve is also consistent with Pt being the most efficient electrocatalyst for hydrogen evolution. (c) 2005...

Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures; Contribution a l'etude de la reaction d'oxydation de l'oxyde de carbone au contact des catalyseurs issus de la decomposition a diverses temperatures des hydroaluminates de nickel

Energy Technology Data Exchange (ETDEWEB)

Samaane, Mikhail

1966-09-26

Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al{sub 2}O{sub 3}, NiAl{sub 2}O{sub 4} and NiO + NiAl{sub 2}O{sub 4}) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al{sub 2}O{sub 3} catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O{sub 2} and CO{sub 2} on the 2NiO+Al{sub 2}O{sub 3} solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl{sub 2}O{sub 4} and NiO+NiAl{sub 2}O{sub 4}) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O{sub 2} and CO{sub 2} on NiAl{sub 2}O{sub 4}, and the kinetic of the oxidation reaction are herein studied.

Corrosion inhibition performance of 2,5-bis(4-dimethylaminophenyl)-1,3,4-oxadiazole for carbon steel in HCl solution: Gravimetric, electrochemical and XPS studies

Energy Technology Data Exchange (ETDEWEB)

Bouanis, M.; Tourabi, M.; Nyassi, A. [Laboratoire de Catalyse et de Corrosion des Matériaux (LCCM), Faculté des Sciences, Université Chouaib Doukkali, B.P. 20, M-24000 El Jadida (Morocco); Zarrouk, A. [LCAE-URAC 18, Faculty of Science, First Mohammed University, PO Box 717, M-60 000 Oujda (Morocco); Jama, C. [UMET-ISP, CNRS UMR 8207, ENSCL, Université Lille Nord de France, CS 90108, F-59652 Villeneuve d' Ascq Cedex (France); Bentiss, F., E-mail: fbentiss@gmail.com [Laboratoire de Catalyse et de Corrosion des Matériaux (LCCM), Faculté des Sciences, Université Chouaib Doukkali, B.P. 20, M-24000 El Jadida (Morocco); UMET-ISP, CNRS UMR 8207, ENSCL, Université Lille Nord de France, CS 90108, F-59652 Villeneuve d' Ascq Cedex (France)

2016-12-15

Highlights: • 2,5-Bis(4-dimethylaminophenyl)-1,3,4-oxadiazole is good corrosion inhibitor for carbon steel in 1 M HCl. • XPS analysis has provided the composition of adsorbed protective layer on the steel surface. • The adsorption of the investigated 1,3,4-oxadiazole is mainly due to chemisorption. - Abstract: Corrosion inhibition of carbon steel in normal hydrochloric acid solution at 30 °C by 2,5-bis(4-dimethylaminophenyl)-1,3,4-oxadiazole (DAPO) has been studied by weight loss measurements and electrochemical techniques (polarization and AC impedance). The experimental results showed that DAPO acted as an efficient inhibitor against the carbon steel corrosion in 1 M HCl, and its inhibition efficiency increased with the inhibitor concentration reaching a value up to 93% at 1 mM. Polarization studies showed that the DAPO was a mixed-type inhibitor. The adsorption of this 1,3,4-oxadiazole derivative on the carbon steel surface in 1 M HCl solution followed the Langmuir adsorption isotherm and the corresponding value of the standard Gibbs free energy of adsorption (ΔG°{sub ads}) is associated to a chemisorption mechanism. Scanning Electron Microscopy (SEM) and X-Ray Photoelectron Spectroscopy (XPS) analyses were carried out to characterize the chemical composition of the inhibitive film formed on the steel surface. The surfaces studies showed that the inhibitive layer is composed of an iron oxide/hydroxide mixture where DAPO molecules are incorporated. The cytotoxicity of DAPO was also determined using cell culture system.

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

Directory of Open Access Journals (Sweden)

Subbarao Duvvuri

2011-11-01

Full Text Available Abstract This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR, temperature-programmed oxidation (TPO, CO-chemisorption, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM-EDX and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low, 650°C (medium and 731°C (high. The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1% while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%.

Immobilization of immunoglobulin G in a highly oriented manner on a protein-A terminated multilayer system

Energy Technology Data Exchange (ETDEWEB)

Zengin, Adem [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.tr [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

2011-01-01

In this study, we have fabricated a multilayer system consisting of 3-glycidoxypropyldimethylmethoxysilane (GPDS), poly(dimethylsiloxane) bis 3-aminopropyl terminated (PDMS) and protein-A on a silicon wafer surface for oriented immobilization of immunoglobilin G (IgG). The multilayer system with a different component in each layer was characterized by ellipsometry, contact-angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) and fluorescence microscopy. The epoxy-terminated monolayer was formed by the chemisorption of GPDS molecules on the hydroxylated silicon surface. The PDMS film about 4.5 nm thick was produced on the GPDS-monolayer by the chemical reaction between the amine groups at the end of PDMS chain and the epoxy groups of GPDS molecules. By introducing the PDMS chains, the hydrophilic character of GPDS-monolayer decreased. Study of the time dependence of polymer grafting showed that the chemisorption of GPDS is fast, whereas at least 16 h is needed to generate the homogeneous PDMS layer. For immobilization of IgG molecules in a highly oriented manner, protein-A molecules were first chemically bound to an ultrathin ({approx}4.5 nm) PDMS reactive polymer layer and later used to capture IgG. It was shown that the existence of protein-A in the multilayer system has a strong influence on the binding properties of IgG not only in the efficiency of binding, but also in its specificity. In conclusion, the multilayer system with protein-A has the potential to be further developed into an efficient immunoassay protein chip.

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

Science.gov (United States)

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

Science.gov (United States)

Manzoor, Dar; Pal, Sourav

2015-06-18

Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Kinetics and equilibrium study for the adsorption of textile dyes on coconut shell activated carbon

Directory of Open Access Journals (Sweden)

Aseel M. Aljeboree

2017-05-01

Full Text Available The preparation of activated carbon from coconut husk with H2SO4 activation (CSAC and its ability to remove textile dyes (maxilon blue GRL, and direct yellow DY 12, from aqueous solutions were reported in this study. The adsorbent was characterized with Fourier transform infrared spectrophotometer (FT-IR, and scanning electron microscope (SEM. Various physiochemical parameters such as, contact time, initial dye concentration, adsorbent dosage, particle size, pH of dye solution and temperature were investigated in a batch-adsorption technique. Result showed that the adsorption of both GRL and DY 12 dyes was favorable at acidic pH. The adsorption uptake was found to increase with increase in initial dye concentration, and contact time but decreases with the amount of adsorbent, particle size, and temperature of the system. The chemisorption, intra-particle diffuse, pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second order exhibited the best fit for the kinetic studies, which indicates that adsorption of (GRL, and DY 12 is limited by chemisorption process. The equilibrium data were evaluated using Langmuir, Freundlich, Temkin and Fritz–Schlunder isotherms. The Fritz–Schlunder model best describes the uptake of (GRL and DY 12 dye, which implies that the adsorption of textiles dyes in this study onto coconut husk activated carbon is heterogeneous with multi-layers. Thermodynamic parameters such as Gibbs free energy, enthalpy and entropy were determined. It was found that (GRL and DY 12 dye adsorption was spontaneous and endothermic.

Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

Energy Technology Data Exchange (ETDEWEB)

Harnisch, Jennifer Anne [Iowa State Univ., Ames, IA (United States)

2001-01-01

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performance both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.

An improved Zircaloy-steam reaction model for use with the March 2 (Meltdown Accident Response Characteristics) code

International Nuclear Information System (INIS)

Manahan, M.P.

1983-01-01

An improved Zircaloy-steam oxidation reaction model has been incorporated into the MARCH 2 code which includes: (1) improved physical modeling for solid-state process oxidation, (2) improved geometric modeling for gaseous diffusion oxidation, (3) chemisorption/dissociation retardation due to high hydrogen partial pressures, and (4) laminar and turbulent flow conditions. Several accident sequences have been analyzed using the model, and for the sequences considered, the results indicate that the integrated and averaged variables are not significantly altered for the current level of fuel modeling, however, the localized variables such as nodal temperature and oxide thickness are affected

Gas adsorption during storage of plutonium dioxide powders

International Nuclear Information System (INIS)

Cuillerdier, C.; Cossonnet, C.; Germain, M.

1984-10-01

Adsorption phenomena occuring in plutonium dioxide containers are studied for the determination of safe conditions for storage and transportation of plutonium dioxide powders. Adsorption on dried PuO 2 of air individual gases, influence of powder isotopic composition, chemisorption, effect of moisture are determined. Adsorption of dry air obeys an Elovich's law for its kinetics it is greatly exchange by α radiolysis. Pressure in the container can be reduced by storage under dry inert gas (Ar), decreasing the PuO 2 load and using powder containing preadsorbed water or wet air then radiolysis may occur (H 2 formation)

CO{sub 2} reforming of CH{sub 4} over stabilized mesoporous Ni-CaO-ZrO{sub 2} composites

Energy Technology Data Exchange (ETDEWEB)

Shuigang Liu; Lianxiu Guan; Junping Li; Ning Zhao; Wei Wei; Yuhan Sun [Chinese Academy of Sciences, Taiyuan (China). State Key Laboratory of Coal Conversion

2008-09-15

Mesoporous Ni-CaO-ZrO{sub 2} nanocomposites with high thermal stability were designed and employed in the CO{sub 2}/CH{sub 4} reforming. The nanocomposites with appropriate Ni/Ca/Zr molar ratios exhibited excellent activity and prominent coking resistivity. The Ni crystallites were effectively controlled under the critical size for coke formation in such nanocomposites. It was found that low Ni content resulted in high metal dispersion and good catalytic performance. Moreover, the basicity of the matrices improved the chemisorption of CO{sub 2} and promoted the gasification of deposited coke on the catalyst. 33 refs., 5 figs., 1 tab.

NOM removal technologies – Norwegian experiences

Directory of Open Access Journals (Sweden)

H. Ødegaard

2010-01-01

Full Text Available The paper gives an overview of the methods for removal of natural organic matter (NOM in water, particularly humic substances (HS, with focus on the Norwegian experiences. It is demonstrated that humic substances may be removed by a variety of methods, such as; molecular sieving through nanofiltration membranes, coagulation with subsequent floc separation (including granular media or membrane filtration, oxidation followed by biofiltration and sorption processes including chemisorption (ion exchange and physical adsorption (activated carbon. All these processes are in use in Norway and the paper gives an overview of the operational experiences.

Measurement of penetration depths of plutonium and americium in sediment from the ocean floor

International Nuclear Information System (INIS)

Fried, S.; Friedman, A.; Hines, J.; Sjoblom, R.; Schmitz, G.; Schreiner, F.

1979-01-01

The clay-like sediment covering the ocean floor constitutes the last barrier that shields the biosphere from contamination by radionuclides stemming from the nuclear wastes of a subseabed repository. In the event of a failure of the engineered barriers the mobility of the released radionuclides in the sediment determines the rate and the extent of entry into the water of the ocean. The initial results of measurements designed to determine the mobility of transuranium elements in sediment from the ocean floor are presented. Data indicate very low migration rates and imply strong chemisorptive interaction with the sediment

mBEEF-vdW: Robust fitting of error estimation density functionals

DEFF Research Database (Denmark)

Lundgård, Keld Troen; Wellendorff, Jess; Voss, Johannes

2016-01-01

. The functional is fitted within the Bayesian error estimation functional (BEEF) framework [J. Wellendorff et al., Phys. Rev. B 85, 235149 (2012); J. Wellendorff et al., J. Chem. Phys. 140, 144107 (2014)]. We improve the previously used fitting procedures by introducing a robust MM-estimator based loss function...... catalysis, including datasets that were not used for its training. Overall, we find that mBEEF-vdW has a higher general accuracy than competing popular functionals, and it is one of the best performing functionals on chemisorption systems, surface energies, lattice constants, and dispersion. We also show...

Preliminary concentration and determination of Sr-90 in natural and waste water of Kursk region

International Nuclear Information System (INIS)

Basargin, N.N.; Rozovskij, Yu.G.; Grebennikova, R.V.; Salikhov, V.D.

2001-01-01

Synthesis and study of cheating sorbents containing functional analytical ortho-oxy-aza-ortho'-sulfonyl group are presented. Physicochemical properties of sorbents and chemisorption of Sr and Sr 90 are studied. A rapid method of preliminary concentration with subsequent atomic absorption and radiometric determination of Sr in natural and waste water is proposed. Samples of aqua-objects of Kursk region were analyzed using developed method. The results of radiometric investigations into control of strontium-90 content in cooling systems of Kursk NPP, waste waters, waters of Sejm river testifies higher values of concentration in the april - september period [ru

Radioelement studies in the oceans. Progress report, April 15, 1981-April 14, 1982

International Nuclear Information System (INIS)

Bowen, V.T.; Livingston, H.D.; Cochran, J.K.; Sholkovitz, E.R.; Hess, M.R.

1981-11-01

Progress for the report period is reported under the following section headings: bibliographic summary - 1981; cruise reports and sampling activities; abstracts of reports published, submitted, or presented at meetings; and, brief summaries of work in progress. Research in progress includes the following studies: post-depositional chemistry of radionuclides: interstitial water composition and laboratory remobilizaton studies; thorium isotope studies in seawater; radionuclide measurements on samples from ocean weather ship MIKE, in the Norwegian Sea; counting technique optimization for Cs isotopes collected by chemisorption; Pu oxidation states in the Aleutian Trench water column; intercalibrations and standard materials; and radionuclides in deep water bathypelagic biota

Study of calcium forms and their effect in carbon stabilization in fertile soils by FTIR and XPS

International Nuclear Information System (INIS)

Araujo, J.R.; Assis, K.L.S.; Calil, V.L.; Souza, K.R.; Beltrao, M.S.S.; Sena, L.A.; Archanjo, B.S.; Achete, C.A.

2013-01-01

Organic matter or black carbon atoms of Terra Preta de Indio (Amazonian Dark Earth) soils are composed of oxidized carbon groups as phenols, epoxide, carbonyl and carboxyl groups in their surface. At the pH of soil, carboxylate groups are deprotonated generating carboxylate anions leaving the surface of these soils with negative charges. Calcium cations can interact with oxidized carbon groups by chemisorption interactions lowering the total system energy. In this work, Terra Preta de Indio was examined by X-ray photoelectron spectroscopy and Infrared spectroscopy in order to correlate its organic fraction rich in calcium with calcium containing samples. (author)

Study of calcium forms and their effect in carbon stabilization in fertile soils by FTIR and XPS

Energy Technology Data Exchange (ETDEWEB)

Araujo, J.R.; Assis, K.L.S.; Calil, V.L.; Souza, K.R.; Beltrao, M.S.S.; Sena, L.A.; Archanjo, B.S.; Achete, C.A., E-mail: jraraujo@inmetro.gov.br [Instituto Nacional de Metrologia, Qualidade e Tecnologia (INMETRO), Duque de Caxias, RJ (Brazil). Divisao de Materiais e Metrologia

2013-07-01

Organic matter or black carbon atoms of Terra Preta de Indio (Amazonian Dark Earth) soils are composed of oxidized carbon groups as phenols, epoxide, carbonyl and carboxyl groups in their surface. At the pH of soil, carboxylate groups are deprotonated generating carboxylate anions leaving the surface of these soils with negative charges. Calcium cations can interact with oxidized carbon groups by chemisorption interactions lowering the total system energy. In this work, Terra Preta de Indio was examined by X-ray photoelectron spectroscopy and Infrared spectroscopy in order to correlate its organic fraction rich in calcium with calcium containing samples. (author)

Preparation of Pd/γ- Al2O3 catalyst utilized in chemisorption of hydrogen isotopes

International Nuclear Information System (INIS)

David, Elena; Stefanescu, Doina; Stanciu, V.

1997-01-01

Separation and hydrogen isotope determination require packings with special properties, utilizable in separation columns. Consequently, such packings as catalysts using γ-aluminia and metallic palladium active component as holder were obtained. The γ-aluminia used as holder has been prepared starting from λ salts, easy soluble in water, such as Al 2 (NO 3 ) 3 ·9H 2 O, at a preset (6.2-6.4) controlled pH. At a first stage the Al(OH) 3 results which by calcination at controlled temperature transforms in γ-Al 2O3 . On this holder, in which the specific surface and porosity has been determined, metallic palladium has been deposed, using for impregnation a 2% PdCl 2 solution. The content of deposed palladium was determined as the difference between the content in the initial solution and solution remaining after holder impregnation. This content has been determined by atomic absorption and is within 0.5 - 1.2% Pd. After impregnation the catalyst has been dried, then granulated at the 0.16 mm size and activated by hydrogen at a flow rate of 300 vol H 2 /volume

Tuning the surface potential of Ag surfaces by chemisorption of oppositely-oriented thiolated carborane dipoles

Czech Academy of Sciences Publication Activity Database

Lübben, J.F.; Baše, Tomáš; Rupper, P.; Künniger, T.; Macháček, Jan; Guimond, S.

2011-01-01

Roč. 354, č. 1 (2011), s. 168-174 ISSN 0021-9797 R&D Projects: GA AV ČR(CZ) IAA400320901 Keywords : Adsorption * Thiolated carboranes * Silver surface * Surface potential * X-ray photoelectron spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 3.070, year: 2011

Coverage dependent photoelectron spectroscopy of CO chemisorption on Cu (111): evidence for two adsorption sites

International Nuclear Information System (INIS)

Jugnet, Y.; Tran, M.D.

1978-06-01

The ultraviolet photoelectron spectra (UPS) of CO adsorbed on (111) face of Cu are found to be dependent of coverage from exposure of 0.3L up to saturation. At lowest dose two intense molecular orbitals are observed at binding energies of 8.7 and 11.7 eV - phase I -. The intensity of two additional structures at 9.6 and 13.7 eV is fastly enhanced with increasing exposure - phase II -, more weakly bound, yielding at saturation coverage the complex four peak spectra usually reported for CO and Cu. We therefore reassign the levels at 11.7 and 8.7 eV to the 4SIGMA and overlap of molecular orbitals of CO adsorbed on top position and the levels at 13.7 and 9.6 eV to the same for CO adsorbed on bridge position

Adsorption of SO{sub 2} on Li atoms deposited on MgO (1 0 0) surface: DFT calculations

Energy Technology Data Exchange (ETDEWEB)

Eid, Kh.M., E-mail: Kheid98@hotmail.com [Physics Department, Faculty of Education, Ain Shams University, Cairo 11757 (Egypt); Ammar, H.Y. [Department of Physics, Faculty of Science, Najran University, Najran 1988 (Saudi Arabia)

2011-05-01

The adsorption of sulfur dioxide molecule (SO{sub 2}) on Li atom deposited on the surfaces of metal oxide MgO (1 0 0) on both anionic and defect (F{sub s}-center) sites located on various geometrical defects (terrace, edge and corner) has been studied using density functional theory (DFT) in combination with embedded cluster model. The adsorption energy (E{sub ads}) of SO{sub 2} molecule (S-atom down as well as O-atom down) in different positions on both of O{sup -2} and F{sub s} sites is considered. The spin density (SD) distribution due to the presence of Li atom is discussed. The geometrical optimizations have been done for the additive materials and MgO substrate surfaces (terrace, edge and corner). The oxygen vacancy formation energies have been evaluated for MgO substrate surfaces. The ionization potential (IP) for defect free and defect containing of the MgO surfaces has been calculated. The adsorption properties of SO{sub 2} are analyzed in terms of the E{sub ads}, the electron donation (basicity), the elongation of S-O bond length and the atomic charges on adsorbed materials. The presence of the Li atom increases the catalytic effect of the anionic O{sup -2} site of MgO substrate surfaces (converted from physisorption to chemisorption). On the other hand, the presence of the Li atom decreases the catalytic effect of the F{sub s}-site of MgO substrate surfaces. Generally, the SO{sub 2} molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F{sub s}-center.

Structural characterisation of Arquad 2HT-75 organobentonites: Surface charge characteristics and environmental application

Energy Technology Data Exchange (ETDEWEB)

Sarkar, Binoy; Megharaj, Mallavarapu; Xi, Yunfei [CERAR - Centre for Environmental Risk Assessment and Remediation, Building X, University of South Australia, Mawson Lakes, SA 5095 (Australia); CRC CARE - Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, P.O. Box 486, Salisbury, SA 5106 (Australia); Naidu, Ravi, E-mail: ravi.naidu@crccare.com [CERAR - Centre for Environmental Risk Assessment and Remediation, Building X, University of South Australia, Mawson Lakes, SA 5095 (Australia); CRC CARE - Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, P.O. Box 486, Salisbury, SA 5106 (Australia)

2011-11-15

Highlights: {yields} Arquad 2HT-75 is comparatively less toxic and inexpensive surfactant. {yields} Increasing Arquad 2HT-75 loadings give rise to various organobentonite structures. {yields} The organobentonites produce positive zeta potential at TOC contents above 28.1%. {yields} Zeta potential values decrease with increasing suspension pH. {yields} Multiple mechanisms of partitioning, physio-sorption and chemisorption control adsorption. - Abstract: Organoclays are increasingly being used to remediate both contaminated soils and waste water. The present study was attempted to elucidate the structural evolution of bentonite based organoclays prepared from a commercially available, low-cost alkyl ammonium surfactant Arquad 2HT-75. XRD, FTIR, SEM and zeta potential measurement were used to characterise the organoclays. In particular, the relationship between surface charge characteristics of the organoclays and their ability to remediate organic contaminants such as phenol and p-nitrophenol was investigated. The investigation revealed that the arrangement and conformation of surfactant molecules in the bentonite became more regular, ordered and solid-like as of Arquad 2HT-75 loading increased. This also led to the formation of a positive zeta potential on the surface of organobentonites prepared with 3.57:1 and 4.75:1 surfactant-clay (w/w) ratio. The zeta potential values decreased with increasing pH of the suspension. The adsorption data of phenol and p-nitrophenol were best fitted to Freundlich isotherm model. The adsorption was controlled by multiple mechanisms of partitioning, physico-sorption and chemisorption. The outcomes of this study are useful for the synthesis of low cost organobentonite adsorbents for the remediation of ionisable organic contaminants such as phenol and p-nitrophenol from waste water.

The glass block site radionuclide migration study

International Nuclear Information System (INIS)

Killey, R.W.D.; Champ, D.R.

1990-01-01

In 1960 25 nepheline syenite glass blocks containing 14 TBq of mixed fission products in 50 kg of glass were placed below the water table in a shallow sand aquifer at Chalk River Laboratories. Experimental studies undertaken at the site since 1960 have included detailed mapping of the plume of 90 Sr in 1963, 1966 and 1971. Mathematical modeling studies have employed the radiostrontium plume data in determining the split between ion exchange and chemisorption of 90 Sr, and in obtaining reaction rate data for chemisorption. The distribution of 137 Cs on downgradient soils was mapped in 1963 and 1979. An extended plume of low-level 137 Cs contamination observed in the 1979 study prompted an investigation of the role of particulate materials in radionuclide transport. IN 1983, large volume groundwater sampling and separation of cationic, anionic, and neutral dissolved species, as well as particulates, detected anionic and cationic dissolved europium isotopes (154 and 155), and again encountered particulate 137 Cs. A variety of investigations of cesium and strontium sorption have provided a data base on sediment mineralogy, particle surface features, and information on sorption sites and processes. The year 1990 saw the inauguration of a three-year program to update investigations of radionuclide release, transport, and sorption at the glass block site. The first stage of the program has been a detailed definition and simulation of the hydrogeologic setting. Plume mapping and aqueous speciation studies are in progress. This paper summarizes past investigations, reviews the status of the current program, and discusses components of future studies, including investigations of sediment sorption mechanisms. (Author) (17 refs., 8 figs.)

Protein–nanoparticle interaction in bioconjugated silver nanoparticles: A transmission electron microscopy and surface enhanced Raman spectroscopy study

Energy Technology Data Exchange (ETDEWEB)

Reymond-Laruinaz, Sébastien; Saviot, Lucien; Potin, Valérie; Marco de Lucas, María del Carmen, E-mail: delucas@u-bourgogne.fr

2016-12-15

Highlights: • Synthesis of protein-conjugated Ag nanoparticles (NPs) in absence of citrates. • NPs size and protein layer thickness determined by TEM. • SERS spectra showed the chemisorption of proteins on the surface of Ag-NPs. - Abstract: Understanding the mechanisms of interaction between proteins and noble metal nanoparticles (NPs) is crucial to extend the use of NPs in biological applications and nanomedicine. We report the synthesis of Ag-NPs:protein bioconjugates synthesized in total absence of citrates or other stabilizing agents in order to study the NP-protein interaction. Four common proteins (lysozyme, bovine serum albumin, cytochrome-C and hemoglobin) were used in this work. Transmission electron microscopy (TEM) and surface enhanced Raman spectroscopy (SERS) were mainly used to study these bioconjugated NPs. TEM images showed Ag NPs with sizes in the 5–40 nm range. The presence of a protein layer surrounding the Ag NPs was also observed by TEM. Moreover, the composition at different points of single bioconjugated NPs was probed by electron energy loss spectroscopy (EELS). The thickness of the protein layer varies in the 3–15 nm range and the Ag NPs are a few nanometers away. This allowed to obtain an enhancement of the Raman signal of the proteins in the analysis of water suspensions of bioconjugates. SERS results showed a broadening of the Raman bands of the proteins which we attribute to the contribution of different configurations of the proteins adsorbed on the Ag NPs surface. Moreover, the assignment of an intense and sharp peak in the low-frequency range to Ag–N vibrations points to the chemisorption of the proteins on the Ag-NPs surface.

Enhancement of photoelectric catalytic activity of TiO2 film via Polyaniline hybridization

International Nuclear Information System (INIS)

Wang Yajun; Xu Jing; Zong Weizheng; Zhu Yongfa

2011-01-01

A Polyaniline (PANI)/TiO 2 film coated on titanium foil was successfully prepared using the sol-gel method followed by a facile chemisorption. Compared with pristine TiO 2 , the photocatalytic (PC) and photoelectrocatalytic (PEC) degradation rates of 2,4-dichlorophenol (2,4-DCP) with the PANI/TiO 2 film were enhanced by 22.2% and 57.5%, respectively. 2,4-DCP can be mineralized more effectively in the presence of PANI/TiO 2 film. The best PEC degradation efficiency of 2,4-DCP with the PANI/TiO 2 film was acquired at an external potential of 1.5 V with a layer of 1 nm thick PANI. The PANI/TiO 2 film was characterized by Raman spectra, Fourier transform infrared spectra (FT-IR), Auger electron spectroscopy (AES), and electrochemical analysis. These results indicated that there was a chemical interaction on the interface of PANI and TiO 2 . This interaction may be of significance to promote the migration efficiency of carriers and induce a synergetic effect to enhance the PC and PEC activities. - Graphical abstract: The effect of PANI content on 2,4-DCP degradation with initial concentration of 50 mg/L, external potential=1.5 V. Inset: degradation rate constants of various PANI/TiO 2 films. Highlights: → Polyaniline/TiO 2 film was prepared using the sol-gel method followed by chemisorption. → Photoelectrocatalytic degradation rate of 2,4-dichlorophenol was enhanced by 57.5%. → The modification of Polyaniline to TiO 2 film caused a rapid charge separation. → Best degradation efficiency was acquired at 1.5 V with 1 nm thick PANI.

Fast response of sprayed vanadium pentoxide (V{sub 2}O{sub 5}) nanorods towards nitrogen dioxide (NO{sub 2}) gas detection

Energy Technology Data Exchange (ETDEWEB)

Mane, A.A. [Thin Film Nanomaterials Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004 (India); General Science and Humanities Department, Sant Gajanan Maharaj College of Engineering, Mahagaon, 416 503 (India); Suryawanshi, M.P. [Optoelectronics Convergence Research Center, Department of Materials Science and Engineering, Chonnam National University, 300, Yongbong-Dong, Buk-Gu, Gwangju 500-757 (Korea, Republic of); Kim, J.H., E-mail: jinhyeok@chonnam.ac.kr [Optoelectronics Convergence Research Center, Department of Materials Science and Engineering, Chonnam National University, 300, Yongbong-Dong, Buk-Gu, Gwangju 500-757 (Korea, Republic of); Moholkar, A.V., E-mail: avmoholkar@gmail.com [Thin Film Nanomaterials Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004 (India)

2017-05-01

Highlights: • Effect of solution concentration on physicochemical properties of sprayed V{sub 2}O{sub 5} nanorods is studied. • Good response and short response-recovery times of V{sub 2}O{sub 5} nanorods towards NO{sub 2} gas show it is potential material for fabrication of NO{sub 2} sensor. • The chemisorption mechanism of NO{sub 2} gas on the V{sub 2}O{sub 5} nanorods is discussed. - Abstract: The V{sub 2}O{sub 5} nanorods have been successfully spray deposited at optimized substrate temperature of 400 °C onto the glass substrates using vanadium trichloride (VCl{sub 3}) solution of different concentrations. The effect of solution concentration on the physicochemical and NO{sub 2} gas sensing properties of sprayed V{sub 2}O{sub 5} nanorods is studied at different operating temperatures and gas concentrations. The XRD study reveals the formation of V{sub 2}O{sub 5} having an orthorhombic symmetry. The FE-SEM micrographs show the nanorods-like morphology of V{sub 2}O{sub 5}. The AFM micrographs exhibit a well covered granular surface topography. For direct allowed transition, the band gap energy values are found to be decreased from 2.45 eV to 2.42 eV. The nanorods deposited with 30 mM solution concentration shows the maximum response of 24.2% for 100 ppm NO{sub 2} gas concentration at an operating temperature of 200 °C with response and recovery times of 13 s and 140 s, respectively. Finally, the chemisorption mechanism of NO{sub 2} gas on the V{sub 2}O{sub 5} nanorods is discussed.

Protein–nanoparticle interaction in bioconjugated silver nanoparticles: A transmission electron microscopy and surface enhanced Raman spectroscopy study

International Nuclear Information System (INIS)

Reymond-Laruinaz, Sébastien; Saviot, Lucien; Potin, Valérie; Marco de Lucas, María del Carmen

2016-01-01

Highlights: • Synthesis of protein-conjugated Ag nanoparticles (NPs) in absence of citrates. • NPs size and protein layer thickness determined by TEM. • SERS spectra showed the chemisorption of proteins on the surface of Ag-NPs. - Abstract: Understanding the mechanisms of interaction between proteins and noble metal nanoparticles (NPs) is crucial to extend the use of NPs in biological applications and nanomedicine. We report the synthesis of Ag-NPs:protein bioconjugates synthesized in total absence of citrates or other stabilizing agents in order to study the NP-protein interaction. Four common proteins (lysozyme, bovine serum albumin, cytochrome-C and hemoglobin) were used in this work. Transmission electron microscopy (TEM) and surface enhanced Raman spectroscopy (SERS) were mainly used to study these bioconjugated NPs. TEM images showed Ag NPs with sizes in the 5–40 nm range. The presence of a protein layer surrounding the Ag NPs was also observed by TEM. Moreover, the composition at different points of single bioconjugated NPs was probed by electron energy loss spectroscopy (EELS). The thickness of the protein layer varies in the 3–15 nm range and the Ag NPs are a few nanometers away. This allowed to obtain an enhancement of the Raman signal of the proteins in the analysis of water suspensions of bioconjugates. SERS results showed a broadening of the Raman bands of the proteins which we attribute to the contribution of different configurations of the proteins adsorbed on the Ag NPs surface. Moreover, the assignment of an intense and sharp peak in the low-frequency range to Ag–N vibrations points to the chemisorption of the proteins on the Ag-NPs surface.

Theoretical investigation on the alkali-metal doped BN fullerene as a material for hydrogen storage

International Nuclear Information System (INIS)

Venkataramanan, Natarajan Sathiyamoorthy; Belosludov, Rodion Vladimirovich; Note, Ryunosuke; Sahara, Ryoji; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

2010-01-01

Graphical abstract: First-principles calculations have been used to investigate hydrogen adsorption on alkali atom doped B 36 N 36 clusters. Adsorption of alkali atoms involves a charge transfer process, creating positively-charged alkali atoms and this polarizes the H 2 molecules and increases their binding energy. The maximum hydrogen storage capacity of Li doped BN fullerene is 8.9 wt.% in which 60 hydrogen atoms were chemisorbed and 12 H 2 were adsorbed in molecular form. - Abstract: First-principles calculations have been used to investigate hydrogen adsorption on alkali atom doped B 36 N 36 clusters. The alkali atom adsorption takes place near the six tetragonal bridge sites available on the cage, thereby avoiding the notorious clustering problem. Adsorption of alkali atoms involves a charge transfer process, creating positively charged alkali atoms and this polarizes the H 2 molecules thereby, increasing their binding energy. Li atom has been found to adsorb up to three hydrogen molecules with an average binding energy of 0.189 eV. The fully doped Li 6 B 36 N 36 cluster has been found to hold up to 18 hydrogen molecules with the average binding energy of 0.146 eV. This corresponds to a gravimetric density of hydrogen storage of 3.7 wt.%. Chemisorption on the Li 6 B 36 N 36 has been found to be an exothermic reaction, in which 60 hydrogen atoms chemisorbed with an average chemisorption energy of -2.13 eV. Thus, the maximum hydrogen storage capacity of Li doped BN fullerene is 8.9 wt.% in which 60 hydrogen atoms were chemisorbed and 12 hydrogen molecules were adsorbed in molecular form.

Insight into the adsorption of chloramphenicol on a vermiculite surface

Science.gov (United States)

Tri, Nguyen Ngoc; Carvalho, A. J. P.; Dordio, A. V.; Nguyen, Minh Tho; Trung, Nguyen Tien

2018-05-01

Four stable configurations were found upon adsorption of the chloramphenicol on a period slab model of the vermiculite surface, using the PBE and C09-vdW functionals in a projector-augmented wave (PAW) method approach. The adsorption is a strong chemisorption process, characterized by an adsorption energy of -106.5 kcal mol-1 at the most stable configuration. Stability of configurations contributed mainly by Mg⋯O/Cl attractive electrostatic interactions and C/Osbnd H⋯O hydrogen bonds. It is remarkable that the vermiculite is found to be a solid material with good potential to be used for adsorption and consequent removal of this type of antibiotic drugs.

Steam and CO2 reforming of methane over a Ru/ZrO2 catalyst

DEFF Research Database (Denmark)

Jakobsen, Jon Geest; Jørgensen, T.L.; Chorkendorff, Ib

2010-01-01

The kinetics of methane steam reforming over a Ru/ZrO2 catalyst was studied at 1.3 bar total pressure and in the temperature range 425-575 degrees C. These data were fitted by combining a reactor model with a series of kinetic models. The best fit was obtained by a model with methane dissociative...... adsorption as the rate limiting step and with CO and H adspecies partly blocking the active sites. The Ru/ZrO2 catalyst was characterized by TEM and H-2 chemisorption. By comparison of ex situ and in situ TEM, it is evident that Ru particles with diameters of...

Novel alternating polymer adsorption/surface activation self-assembled film based on hydrogen bond

Energy Technology Data Exchange (ETDEWEB)

Zhang Yongjun; Yang Shuguang; Guan Ying; Miao Xiaopeng; Cao Weixiao; Xu Jian

2003-08-01

By combining hydrogen bonding layer-by-layer self-assembly and the stepwise chemisorption method, a new alternating polymer adsorption/surface activation self-assembly method was developed. First a layer of diphenylamine-4-diazonium-formaldehyde resin (diazo resin or DR) is deposited on a substrate. In the following surface activation step, the diazonium groups on the surface couple with resorcin in the outside solution. The deposition of another layer of DR is feasible due to the formation of hydrogen bond between the diazonium group of DR and the hydroxy group of the resorcin moieties. The resulting film is photosensitive. After UV irradiation, the film becomes very stable towards polar organic solvents.

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.

Surface-Controlled Metal Oxide Resistive Memory

KAUST Repository

Ke, Jr-Jian

2015-10-28

To explore the surface effect on resistive random-access memory (ReRAM), the impact of surface roughness on the characteristics of ZnO ReRAM were studied. The thickness-independent resistance and the higher switching probability of ZnO ReRAM with rough surfaces indicate the importance of surface oxygen chemisorption on the switching process. Furthermore, the improvements in switching probability, switching voltage and resistance distribution observed for ReRAM with rough surfaces can be attributed to the stable oxygen adatoms under various ambience conditions. The findings validate the surface-controlled stability and uniformity of ReRAM and can serve as the guideline for developing practical device applications.

Energy storage device including a redox-enhanced electrolyte

Science.gov (United States)

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

2017-08-08

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

Analysis of the hydrogen permeation properties of TiN-TiC bilayers deposited on martensitic stainless steel

International Nuclear Information System (INIS)

Checchetto, R.; Horino, Y.; Benamati, G.

1996-01-01

The efficiency of TiN-TiC bilayer coatings, deposited by ion-beam-assisted deposition on martensitic steel, as a hydrogen permeation barrier was investigated by a gas phase method; the hydrogen permeability in the TiN-TiC bilayers is very low, at least 10 4 times lower than in the steel substrate in the temperature interval 470-570 K. Possible physical mechanisms, responsible for the reduced permeability of the ceramic bilayers, are discussed. In particular, from our experimental results, it can be concluded that chemisorption and/or hydrogen jumping from surface sites to the first subsurface atomic layer represents the hydrogen permeation limiting process. (orig.)

Factors determining the activity of catalysts of various chemical types in the oxidation of hydrogen. I. Oxidation and isotope exchange of hydrogen on cobalt monoxide-oxide

International Nuclear Information System (INIS)

Polgikh, L.Y.; Golodets, G.I.; Il'chenko, N.I.

1985-01-01

On the basis of data on the kinetics of the reaction 2H 2 + O 2 = 2H 2 O isotope exchange H 2 + D 2 = 2HD under the conditions of oxidative catalysis, and the kinetic isotope effect, a mechanism is proposed for the oxidation of hydrogen on cobalt monoxide-oxide. At low temperatures the reaction proceeds according to a mechanism of alternating reduction-reoxidation of the surface with the participation of hydrogen adsorbed in molecular form; at increased temperature and low P 02 /P /SUB H2/ ratios, a significant contribution to the observed rate is made by a mechanism including dissociative chemisorption of hydrogen

Sorption and desorption of remazol yellow by a Fe-zeolitic tuff

International Nuclear Information System (INIS)

Solache R, M. J.; Villalva C, R.; Diaz N, M. C.

2010-01-01

The adsorption of remazol yellow from aqueous solution was evaluated using a Fe-zeolitic tuff. The adsorbent was characterized by scanning electron microscopy, IR spectroscopy and X-ray diffraction. Sorption kinetic and isotherms were determined and the adsorption behavior was analyzed. Kinetic pseudo-second order and Langmuir-Freundlich models were successfully applied to the experimental results, indicating chemisorption on a heterogeneous material. The regeneration of the material was best accomplished by using a H 2 O 2 solution. The sorption capacity of the Fe-zeolitic tuff increased when the saturated samples were treated with a H 2O2 or FeCl 3 solution. (Author)

Sorption and desorption of remazol yellow by a Fe-zeolitic tuff

Energy Technology Data Exchange (ETDEWEB)

Solache R, M. J. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Villalva C, R.; Diaz N, M. C., E-mail: marcos.solache@inin.gob.m [Instituto Tecnologico de Toluca, Division de Estudios del Posgrado, Av. Tecnologico s/n, Ex-Rancho La Virgen, 52140 Metepec, Estado de Mexico (Mexico)

2010-07-01

The adsorption of remazol yellow from aqueous solution was evaluated using a Fe-zeolitic tuff. The adsorbent was characterized by scanning electron microscopy, IR spectroscopy and X-ray diffraction. Sorption kinetic and isotherms were determined and the adsorption behavior was analyzed. Kinetic pseudo-second order and Langmuir-Freundlich models were successfully applied to the experimental results, indicating chemisorption on a heterogeneous material. The regeneration of the material was best accomplished by using a H{sub 2}O{sub 2} solution. The sorption capacity of the Fe-zeolitic tuff increased when the saturated samples were treated with a H{sub 2O2} or FeCl{sub 3} solution. (Author)

Benzimidazole as corrosion inhibitor for heat treated 6061 Al- SiCp composite in acetic acid

International Nuclear Information System (INIS)

Chacko, Melby; Nayak, Jagannath

2015-01-01

6061 Al-SiCpcomposite was solutionizedat 350 °C for 30 minutes and water quenched. It was then underaged at 140 °C (T6 treatment). The aging behaviour of the composite was studied using Rockwell B hardness measurement. Corrosion behaviour of the underaged sample was studied in different concentrations of acetic acid and at different temperatures. Benzimidazole at different concentrations was used for the inhibition studies. Inhibition efficiency of benzimidazole was calculated for different experimental conditions. Thermodynamic parameters were found out which suggested benzimidazole is an efficient inhibitor and it adsorbed on to the surface of composite by mixed adsorption where chemisorption is predominant. (paper)

A DFT Structural Investigation of New Bimetallic PtSn_x Surface Alloys Formed on the Pt(110) Surface and Their Interaction with Carbon Monoxide

DEFF Research Database (Denmark)

Zheng, Jian; Busch, Michael; Artiglia, Luca

2016-01-01

desorbs from the PtSnx surfaces at about 415-425 K compared to 495 K on the clean Pt(110). The energetics and geometry of the CO chemisorption sites have been studied by DFT calculations, obtaining an adsorption energy of 0.7-0.86 eV on p(3 x 1) and 0.9-1.05 eV on p(6 x 1). Overall our theoretical...... spectroscopy. Based on the experimental results and density functional theory (DFT) calculations, we propose atomic models for these surface alloys, which both consist of a highly corrugated row structure with a very similar surface motif. CO temperature-programmed desorption (TPD) experiments indicate that CO...

Control of alkali species in gasification systems: Final report

Energy Technology Data Exchange (ETDEWEB)

Turn, S.; Kinoshita, C.; Ishimura, D. Zhou, J.; Hiraki, T.; Masutani, S.

2000-07-13

Gas-phase alkali metal compounds contribute to fouling, slagging, corrosion, and agglomeration problems in energy conversion facilities. One mitigation strategy applicable at high temperature is to pass the gas stream through a fixed bed sorbent or getter material, which preferentially absorbs alkali via physical adsorption or chemisorption. This report presents results of an experimental investigation of high-temperature alkali removal from a hot filtered gasifier product gas stream using a packed bed of sorbent material. Two getter materials, activated bauxite and emathlite, were tested at two levels of space time by using two interchangeable reactors of different internal diameters. The effect of getter particle size was also investigated.

Hydrogenation of hexene over platinum on alumina vs. platinum in a Na-Y zeolite

International Nuclear Information System (INIS)

Miner, R.S. Jr.; Ione, K.G.; Namba, S.; Turkevich, J.

1978-01-01

In order to study the efficacy of zeolites as supports, several platinum H--Y zeolites were prepared by ion exchanging an H--Y zeolite with Pt(NH 3 ) 4 Cl 2 and reducing these products with hydrazine hydrate (A, B, C). Another preparation was made by adsorbing 32-A platinum sol on the zeolite crystallites (D). These catalysts were studied for hydrogenation and isomerization of hexene-1, ethylene hydrogenation, hydrogen chemisorption, and poison titration. They were compared with monodisperse Pt (32 A diameter) on alumina. A marked difference was found between the behavior of hexene-1 with the platinum-in-zeolite and with the platinum-on-alumina

Chemisorption of H2O and CO2 on hydrotalcites for sorptionenhanced water-gas-shift processes

NARCIS (Netherlands)

Coenen, K.T.; Gallucci, F.; Cobden, P.; van Dijk, E; Hensen, E.J.M.; van Sint Annaland, M.

2017-01-01

Thermogravimetric analysis and breakthrough experiments in a packed bed reactor were used to validate a developed adsorption model to describe the cyclic working capacity of CO2 and H2O on a potassium-promoted hydrotalcite, a very promising adsorbent for sorption-enhanced water-gas-shift

Chemisorption of H2O and CO2 on hydrotalcites for sorptionenhanced water-gas-shift processes

NARCIS (Netherlands)

Coenen, K.T.; Gallucci, F.; Cobden, P.; van Dijk, E.; Hensen, E.J.M.; van Sint Annaland, M.

2016-01-01

Thermogravimetric analysis and breakthrough experiments in a packed bed reactor were used to validate a developed adsorption model to describe the cyclic working capacity of CO¬2 and H2O on a potassium-promoted hydrotalcite, a very promising adsorbent for sorption-enhanced water-gas-shift

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

Czech Academy of Sciences Publication Activity Database

Matunová, Petra; Jirásek, Vít; Rezek, Bohuslav

2016-01-01

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

Chemisorption of acetophenone on Si(111)-7 × 7. Polar aromatic molecule on electronically complex surface

Czech Academy of Sciences Publication Activity Database

Krejčí, Ondřej; Matvija, P.; Zimmermann, P.; Sobotík, P.; Ošt'ádal, I.; Kocán, P.

2016-01-01

Roč. 120, č. 17 (2016), s. 9200-9206 ISSN 1932-7447 Institutional support: RVO:68378271 Keywords : attachment * atoms * cycloaddition * adsorption * Si(001) * states * STM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.536, year: 2016

Numerical modeling of carbon dioxide chemisorption in sodium hydroxide solution in a micro-structured bubble column

NARCIS (Netherlands)

Jain, D.; Kuipers, J.A.M.; Deen, N.G.

2015-01-01

Gas-liquid flows with solid catalyst particles are encountered in many applications in the chemical, petrochemical, and pharmaceutical industries. Most commonly, two reactor types, slurry bubble column (SBC) and trickle bed (TB) reactors are applied for large scale in the industry. Both of these

Theoretical studies on chemisorption of oxygen on β-Mo2C catalyst and its surface oxidation

DEFF Research Database (Denmark)

Shi, Xue-Rong; Wang, Shengguang; Hu, Jia

2012-01-01

by O2 at PO2/P0 of 10−21–104 and temperature of 100–700K. For the (011) surface with O2 as the oxidant, the most stable structure is that with 1/2ML or 7/8ML oxygen coverage, depending on the temperature and PO2/P0 value. The increase of gaseous oxidant pressure or decrease of temperature can enhance...

The adsorption of oleate on powellite and fluorapatite: A joint experimental and theoretical simulation study

Energy Technology Data Exchange (ETDEWEB)

Zhen, Wang, E-mail: 544590553@qq.com

2017-07-01

Highlights: • Flotation of powellite from fluorapatite at pH 2–7 using 50–80 mg/L sodium oleate can be achieved. • Oleate chemisorbs on powellite by interaction of carboxylate group with lattice Ca atoms. • Calcium dioleate precipitates can also adsorb on powellite surface. - Abstract: Flotation and adsorption performance of sodium oleate(NaOl)on powellite and fluorapatite were investigated in this work through micro-flotation tests, work of adhesion calculations, molecular dynamics simulation, micro-topography studies and FTIR measurements. The micro-flotation results show a similar flotation behaviors of powellite and fluorapatite under alkaline conditions, but a considerable difference in mineral recoveries in the pH range 2–7, which demonstrates the possibilities for separating powillite from fluorapatite under acidic conditions. The great difference in mineral recovery displays a good accordance with the obvious difference in the work of adhesion of powellite and fluorapatite at NaOl dosage range of 40–80 mg/L, obtained from flotation and contact angle measurements, respectively. The more negative interaction energy (ΔE) between NaOl and powellite/water interface from molecular dynamics simulation reveals a more easily adsorption of NaOl onto powellite than onto fluorapatite, which excellently matches with the results of flotation and work of adhesion. The results of micro-topography study shows that the adsorption of NaOl on powellite is mainly ascribed to the chemisorption of oleate ions with Ca{sup 2+} on powellite lattice or the precipitation of calcium dioleate agglomerates on powellite surface when it was in the solution without or with Ca{sup 2+}, respectively. The FTIR measurements further confirm the chemisorption of oleate ions with Ca{sup 2+} active sites on powellite surface.

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

Science.gov (United States)

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

2012-03-01

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

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Low-Dimensional Materials for Optoelectronic and Bioelectronic Applications

Science.gov (United States)

Hong, Tu

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

Characterizing water-metal interfaces and machine learning potential energy surfaces

Science.gov (United States)

Ryczko, Kevin

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

The adsorption of oleate on powellite and fluorapatite: A joint experimental and theoretical simulation study

International Nuclear Information System (INIS)

Zhen, Wang

2017-01-01

Highlights: • Flotation of powellite from fluorapatite at pH 2–7 using 50–80 mg/L sodium oleate can be achieved. • Oleate chemisorbs on powellite by interaction of carboxylate group with lattice Ca atoms. • Calcium dioleate precipitates can also adsorb on powellite surface. - Abstract: Flotation and adsorption performance of sodium oleate(NaOl)on powellite and fluorapatite were investigated in this work through micro-flotation tests, work of adhesion calculations, molecular dynamics simulation, micro-topography studies and FTIR measurements. The micro-flotation results show a similar flotation behaviors of powellite and fluorapatite under alkaline conditions, but a considerable difference in mineral recoveries in the pH range 2–7, which demonstrates the possibilities for separating powillite from fluorapatite under acidic conditions. The great difference in mineral recovery displays a good accordance with the obvious difference in the work of adhesion of powellite and fluorapatite at NaOl dosage range of 40–80 mg/L, obtained from flotation and contact angle measurements, respectively. The more negative interaction energy (ΔE) between NaOl and powellite/water interface from molecular dynamics simulation reveals a more easily adsorption of NaOl onto powellite than onto fluorapatite, which excellently matches with the results of flotation and work of adhesion. The results of micro-topography study shows that the adsorption of NaOl on powellite is mainly ascribed to the chemisorption of oleate ions with Ca"2"+ on powellite lattice or the precipitation of calcium dioleate agglomerates on powellite surface when it was in the solution without or with Ca"2"+, respectively. The FTIR measurements further confirm the chemisorption of oleate ions with Ca"2"+ active sites on powellite surface.

Pb(II) removal from aqueous solution by a low-cost adsorbent dry desulfurization slag

Energy Technology Data Exchange (ETDEWEB)

Wu, Qiong; You, Ruirong [College of Materials Science and Engineering, Fuzhou University, New Campus, Minhou, Fujian Province 350108 (China); Clark, Malcolm [Marine Ecology Research Centre, School of Environment, Science and Engineering, Southern Cross University, P.O. Box 157, Lismore, NSW 2480 (Australia); Yu, Yan, E-mail: yuyan_1972@126.com [College of Materials Science and Engineering, Fuzhou University, New Campus, Minhou, Fujian Province 350108 (China)

2014-09-30

Highlights: • Dry desulfurization slag, solid waste, was an efficient adsorbent for lead removal. • The adsorption of Pb{sup 2+} onto dry desulfurization slag was generally monolayer. • The rate limiting step in the adsorption process of Pb{sup 2+} was chemisorption. • Pb{sup 2+} was absorbed onto the surface of the sample adsorbent only. • The adsorbent was low-cost and could be recycled. - Abstract: A collectable and non-sintered material prepared as hollow cylindrical shaped pellet from dry desulfurization slag (FGD ash) and ordinary Portland cement (OPC) for wastewater treatments is tested. The characteristic results of powder X-ray diffraction (XRD) and infrared absorption spectroscopy (IR) show that –OH, CO{sub 3}{sup 2−}, SO{sub 3}{sup 2−} and SO{sub 4}{sup 2−} are the possible functional groups responsible for Pb uptake. Adsorption data indicate that Pb removal is pH dependent and optimal at pH 6, with a very rapid initial removal that reaches equilibrium in about 90 min. A maximum removal of 99.2% is seen for 5 mg/L (pH of 6); higher initial Pb concentrations reduce overall removal efficiencies, but generate higher surface loadings. Adsorption process correlates well with both Langmuir and Freundlich models, although the Langmuir isotherm is more favored, providing a maximum adsorption capacity (Qm) of 130.2 mg/g (13 wt%). Pseudo-second order rate kinetic model best describes the Pb removal, and calculated R{sub L} values between 0 and 1, indicate a favored adsorption process that is chemisorption limited. SEM and EDAX analysis of the surface and fracture surface show that Pb occurs as surface precipitates and that Pb is not distributed to the inner core of the pellet. This study demonstrates that dry FGD ash could be successfully used for wastewater Pb removal.

Nanoscale Metal Oxide Semiconductors for Gas Sensing

Science.gov (United States)

Hunter, Gary W.; Evans, Laura; Xu, Jennifer C.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.

2011-01-01

A report describes the fabrication and testing of nanoscale metal oxide semiconductors (MOSs) for gas and chemical sensing. This document examines the relationship between processing approaches and resulting sensor behavior. This is a core question related to a range of applications of nanotechnology and a number of different synthesis methods are discussed: thermal evaporation- condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed, providing a processing overview to developers of nanotechnology- based systems. The results of a significant amount of testing and comparison are also described. A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. The TECsynthesized single-crystal nanowires offer uniform crystal surfaces, resistance to sintering, and their synthesis may be done apart from the substrate. The TECproduced nanowire response is very low, even at the operating temperature of 200 C. In contrast, the electrospun polycrystalline nanofiber response is high, suggesting that junction potentials are superior to a continuous surface depletion layer as a transduction mechanism for chemisorption. Using a catalyst deposited upon the surface in the form of nanoparticles yields dramatic gains in sensitivity for both nanostructured, one-dimensional forms. For the nanowire materials, the response magnitude and response rate uniformly increase with increasing operating temperature. Such changes are interpreted in terms of accelerated surface diffusional processes, yielding greater access to chemisorbed oxygen species and faster dissociative chemisorption, respectively. Regardless of operating temperature, sensitivity of the nanofibers is a factor of 10 to 100 greater than that of nanowires with the same catalyst for the same test condition. In summary, nanostructure appears critical to governing the reactivity, as measured by electrical

Developing nano-particles as radiopharmaceuticals

International Nuclear Information System (INIS)

Gambhir, S.

2013-01-01

The wide variety of core materials available, coupled with tunable surface properties, make nanoparticles an excellent platform for a broad range of biological and biomedical applications. The unique properties and utility of nanoparticles arise from a variety of attributes, including the similar size of nanoparticles and biomolecules such as proteins and polynucleic acids. Additionally, nanoparticles can be fashioned with a wide range of metal and semiconductor core materials that impart useful properties such as fluorescence and magnetic behavior. Bio-macromolecule surface recognition by nanoparticles as artificial receptors provides a potential tool for controlling cellular and extracellular processes for numerous biological applications such as transcription regulation, enzymatic inhibition, delivery and sensing. The size of nanoparticle cores can be tuned from 1.5 nm to more than 10 nm depending on the core material, providing a suitable platform for the interaction of nanoparticles with proteins and other biomolecules. The conjugation of nanoparticles with biomolecules such as proteins and DNA can be done by using two different approaches, direct covalent linkage and non-covalent interactions between the particle and bio-molecules.The most direct approach to the creation of integrated biomolecule-nanoparticle conjugates is through covalent attachment.This conjugation can be achieved either through chemisorptions of the biomolecule to the particle surface or through the use of hetero-bi-functional linkers. Chemisorption of proteins onto the surface of nanoparticles (usually containing a core of Au, ZnS, CdS, and CdSe/ZnS) can be done through cysteine residues that are present in the protein surface (e.g., oligo-peptide, serum albumin), or chemically using 2-iminothiolane (Traut's reagent). Bifunctional linkers provide a versatile means of bio-conjugation. Biomolecules are often covalently linked to ligands on the nanoparticle surface via traditional

Suppression of exchange bias effect in maghemite nanoparticles functionalized with H{sub 2}Y

Energy Technology Data Exchange (ETDEWEB)

Guivar, Juan A. Ramos, E-mail: juan.ramos5@unmsm.edu.pe [Faculty of Physical Sciences, National University of San Marcos, P. O. Box 14-0149, Lima, 14 Peru (Peru); Morales, M.A. [Departamento de Física Teórica e Experimental, UFRN, Natal, RN, 59078-970 Brazil (Brazil); Litterst, F. Jochen [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, Braunschweig, 38110 Germany (Germany)

2016-12-15

The structural, vibrational, morphological and magnetic properties of maghemite (γ-Fe{sub 2}O{sub 3}) nanoparticles functionalized with polar molecules EDTA(or H{sub 4}Y) and H{sub 2}Y are reported. The samples were functionalized before and after total synthesis of γ-Fe{sub 2}O{sub 3} nanoparticles. The molecules are anchored on the monodentate mode on the nanoparticles surface. Transmission electron microscopy (TEM) revealed the formation of maghemite nanoparticles with small diameter of 4 nm for the sample functionalized upon synthesis and 7.6 and 6.9 nm for the samples functionalized with EDTA and H{sub 2}Y after the formation of nanoparticles. Exchange bias phenomena were observed in some of the samples functionalized with EDTA at temperatures below 70 K. The presence of the bias effect was discussed in terms of the formation of a thin layer of a secondary phase like lepidocrocite, and the absence of this effect was explained in terms of the chemisorption of carboxylic groups from EDTA which suppressed the canting. Studies of Mössbauer spectroscopy as a function of temperature showed slow relaxation effects and allowed discussion of the secondary phase. In the M–T curves a maximum around 116 K was associated with this secondary phase also in agreement with the Mössbauer studies. The dynamic properties were studied by AC susceptibility, the out of phase signal revealed a spin glass like regime below 36.5 K. - Highlights: • Coprecipitation in alkaline medium was used for the synthesis of EDTA functionalized small maghemite nanoparticles. • Exchange bias effect was observed due to a thin layer of lepidocrocite like second phase. • The sample coprecipitated in a weak base did not show exchange bias effect. • The bias effect is discussed in terms of suppression of canting due to chemisorption of carboxylic groups from EDTA.

Study of 2D MXene Cr{sub 2}C material for hydrogen storage using density functional theory

Energy Technology Data Exchange (ETDEWEB)

Yadav, A. [Department of Physics and National Centre for Nanosciences & Nanotechnology, University of Mumbai, Vidyanagari, Santacruz (E), Mumbai 400 098 (India); Dashora, Alpa, E-mail: dashoralpa@gmail.com [UM-DAE Centre for Excellence in Basic Sciences, Vidyanagari, Santacruz (E), Mumbai 400 098 (India); Patel, N. [Department of Physics and National Centre for Nanosciences & Nanotechnology, University of Mumbai, Vidyanagari, Santacruz (E), Mumbai 400 098 (India); Dipartimento di Fisica, Università degli Studi di Trento, I-38123 Povo, Trento (Italy); Miotello, A. [Dipartimento di Fisica, Università degli Studi di Trento, I-38123 Povo, Trento (Italy); Press, M.; Kothari, D.C. [Department of Physics and National Centre for Nanosciences & Nanotechnology, University of Mumbai, Vidyanagari, Santacruz (E), Mumbai 400 098 (India)

2016-12-15

Highlights: • First-principles studies showed that Cr{sub 2}C MXene can store 7.6 wt.% of H{sub 2}. • 6.4 wt.% H{sub 2} can be reversibly stored at ambient temperature. • Charge transfer between H and Cr is responsible for the reversible H{sub 2} adsorption. • H-atom on hollow site between three Cr atoms is the most stable site. - Abstract: Hydrogen storage capacity of 2D MXene Cr{sub 2}C has been studied using density functional theory. Possibility to adsorb H{sub 2} molecule on Cr{sub 2}C surface at various sites has been studied. Among the studied adsorption sites on Cr{sub 2}C surface, few sites were found suitable for chemisorption and physisorption of H{sub 2} molecules. Few of the studied sites are also found to be suitable for Kubas-type interaction, which is useful for reversible hydrogen storage at ambient conditions. Electronic structure calculations and charge transfer analysis have been done to understand the interactions of adsorbed hydrogen with the Cr{sub 2}C layer. It has been found that the total hydrogen storage capacity of Cr{sub 2}C is 7.6 wt.% in which 1.2 wt.% of H is due to the chemisorption, 3.2 wt.% is bonded with Kubas-interaction and remaining 3.2 wt.% is bonded through weak electrostatic interactions (with binding energy of 0.26 eV/H{sub 2} and charge transfer of 0.09 e{sup −} to H atom from Cr atom). Thus the reversible hydrogen storage capacity at ambient conditions (controlled by hydrogen bonded with energies ranging from 0.1 to 0.4 eV/H{sub 2}, in the present case through Kubas and weak electrostatic interactions) is 6.4 wt.% which is greater than the 2017 DoE recommended target value of 5.5 wt.%.

A first principles study of the adsorption and dissociation of CO2 on the δ-Pu (111) surface

International Nuclear Information System (INIS)

Atta-Fynn, R.; Raya, A.K.

2009-01-01

A complete understanding of the nature of the 5f electrons has been and continues to be a major scientific problem in condensed matter physics. Bulk and surface electronic structure studies of the actinides as also atomic and molecular adsorptions on the actinide surfaces provide a path towards this understanding. In this work, ab initio calculations within the framework of density functional theory have been used to study the adsorption of molecular CO 2 and the corresponding partially dissociated (CO+O) and completely dissociated (C+O+O) products on the δ-Pu (111) surface. The completely dissociated C+O+O configurations exhibit the strongest binding with the surface (7.92 eV), followed by partially dissociated products CO+O (5.08 eV), with molecular CO 2 adsorption having the lowest binding energies (2.35 eV). For all initial vertically upright orientations, the CO 2 molecule physi-sorbs or do not bind to the surface and the geometry and orientation do not change. For all initial flat lying orientations chemisorption occurs, with the final state corresponding to a bent CO 2 molecule with bond angles of 117-130 degrees and the elongation of the CO bond. For CO+O co-adsorption, the stable configurations corresponded to CO dipole moment orientations of 100-172 degrees with respect to the surface normal and the elongation of the CO bond. The most stable chemisorption cases correspond to anomalously large rumpling of the top Pu layer. The interactions of the CO 2 and CO with the Pu surface have been analyzed using the energy density of states and difference charge density distributions. The nature and the behavior of the 5f electrons have also been discussed in detail in the context of this study. (authors)

A step towards molecular electronics. The ferrocene molecule on a metal-semiconductor system

Energy Technology Data Exchange (ETDEWEB)

Schmeidel, Jedrzej Piotr

2012-05-14

In the first part, the domain walls on Ag {radical}(3) x {radical}(3) are investigated and structural and electronic model are introduced and discussed. Furthermore, the temperature dependence is investigated, showing the Peierls-type transition along the domain wall chain. In the second part, the high resolution STM data of the local adsorption geometry of FDT on Ag {radical}(3)< x {radical}(3) are presented. The comparison of theoretical results obtained for the molecule, on Ag(lll) and Ag {radical}(3) x {radical}(3) surfaces, with STM measurement at RT, support the chemisorption with thiolate bonds to the Ag trimers on the HCT surface. The molecule is aligned with the Cp-Fe-Cp axis parallel to the surface, while the rotational freedom of the molecule is limited due to chemisorption. The presented adsorption model is supported by experiment and simulation. In the third part, the perfect Ag {radical}(3) x {radical}(3) is prepared and investigated by means of STM, focusing on structural and electronic characteristics. The different reconstructions and amounts of Ag on Si are investigated; the submonolayer amounts, Ag {radical}(3) x {radical}(3) wetting layers, perfect epitaxial layers and multilayer systems. The influence of wetting layer on electronic character of deposited Ag nanostructures is studied. The occurrence of effective single and double barriers in tunnelling microscopy and spectroscopy for the Ag {radical}(3) x <{radical}(3) system is investigated in the monolayer regime by varying the measurement and preparation conditions. The Coulomb Blockade oscillations are found for granular multilayer Ag films, whereas similar structures with existence of Ag {radical}(3) x {radical}(3) show only a single barrier characteristic. The vertical transport properties in this metal/ semiconductor system depend on the structure and bonding on the atomic scale and on the lateral two-dimensional properties of the interface.

Theory of the reaction dynamics of small molecules on metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

2016-09-09

The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H₂, H₂O and CH₄ on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

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

International Nuclear Information System (INIS)

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

2011-01-01

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

ACTIVATED ADSORPTION ON CLAY OF MICROPOLLUTANTS FROM PAPER PRINTING INDUSTRY

Directory of Open Access Journals (Sweden)

DIANA C. MIRILĂ

2018-03-01

Full Text Available The paper presents a preliminary study of chemisorption onto anionic and cationic clays, in order to reduce the content of pollutants from a paper printing effluent, collected after technological step named: printing of paper fabric manufacturing. The procedure of filtration fallowed by adsorption process is an effective, fast and low cost technique for treatment of black effluent resulting from paper printing industry. The key parameters tested to achieve a high efficiency for the movement of micropollutants from printing fluid were substrate dose and contact time. The highest treatment performance was obtained for cationic substrate at pH = 6.80, in contact and agitated magnetically for 30 respectively 90 minutes at room temperature.

Communication: Methane dissociation on Ni(111) surface: Importance of azimuth and surface impact site

International Nuclear Information System (INIS)

Shen, Xiangjian; Zhang, Zhaojun; Zhang, Dong H.

2016-01-01

Understanding the role of reactant ro-vibrational degrees of freedom (DOFs) in reaction dynamics of polyatomic molecular dissociation on metal surfaces is of great importance to explore the complex chemical reaction mechanism. Here, we present an expensive quantum dynamics study of the dissociative chemisorption of CH 4 on a rigid Ni(111) surface by developing an accurate nine-dimensional quantum dynamical model including the DOF of azimuth. Based on a highly accurate fifteen-dimensional potential energy surface built from first principles, our simulations elucidate that the dissociation probability of CH 4 has the strong dependence on azimuth and surface impact site. Some improvements are suggested to obtain the accurate dissociation probability from quantum dynamics simulations.

Positron annihilation spectroscopy for chemical analysis (PASCA). Chapter 9

International Nuclear Information System (INIS)

Cheng, K.L.; Jean, Y.C.

1988-01-01

This chapter gives an up to date overview of positron annihilation spectroscopy for chemical analysis (PASCA). As an in situ technique PASCA is especially suitable for studying processes occurring at surfaces. The in situ characteristics of PASCA are treated. The principes of positron annihilation life time spectroscopy (PAL) are discussed and some important analytical applications such as, in determining of total surface areas and cavity volumes in chemical reactions, in the study of chemisorption and catalytic reactions on porous surfaces, in the analysis of bulk materials, in determining molecular association constants in biological systems, in proton and neutron activation analysis, in thin layer chromatography and in tracer technology. 28 refs.; 15 figs.; 8 tabs

Kinetic Approach for the Adsorption of Organophosphorous Pesticides from Aqueous Solution Using “Waste” Jute Fiber Carbon

Directory of Open Access Journals (Sweden)

S. Senthilkumaar

2010-01-01

Full Text Available Chemically activated “Waste” Jute Fiber carbon has been effectively used for the removal of five organophosphorous pesticides (malathion, monocrotophos, methylparathion, phosphamidon and dimethoate from aqueous solutions. The prepared activated jute fiber carbon was characterized by using Elemental analyzer and proximate analysis methods. The adsorption equilibrium was examined at 28 ºC. Three different kinetic models, the pseudo first order, pseudo second order and Elovich kinetic models were selected to analyses the adsorption process. To compare the fitness of pseudo first order and pseudo second order, sum of the squares of the errors and correlation coefficient, r2 values were calculated. The Elovich model was used to confirm the chemisorptions.

Kinetic Characteristics of Hydrogen Transfer Through Palladium-Modified Membrane

Science.gov (United States)

Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

2018-01-01

The paper deals with hydrogen transfer through Pd-23%Ag alloy membrane, the surface of which is modified by the electrolytic deposition of highly dispersed palladium. The dependence between the density of hydrogen flow and its excess pressure on the input surface of membrane is well approximated by the first-order curve. This fact indicates that the process of hydrogen permeability is defined by its dissociation on the input surface. Activation energy of this process is 47.9 kJ/mol which considerably exceeds that of the process of hydrogen transfer through palladium (22-30 kJ/mol). This confirms the fact that the chemisorption is a rate-controlling step of the hydrogen transfer through membrane.

Activation and micropore structure of carbon-fiber composites

Energy Technology Data Exchange (ETDEWEB)

Jagtoyen, M.; Derbyshire, F.; Kimber, G. [Univ. of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

1997-12-01

Rigid, high surface area activated carbon fiber composites have been produced with high permeabilities for environmental applications in gas and water purification. The project involves a collaboration between the Oak Ridge National Laboratory (ORNL) and the Center for Applied Energy Research (CAER), University of Kentucky. The main focus of recent work has been to find a satisfactory means to uniformly activate large samples of carbon fiber composites to produce controlled pore structures. Processes have been developed using activation in steam and CO{sub 2}, and a less conventional method involving oxygen chemisorption and subsequent heat treatment. Another objective has been to explore applications for the activated composites in environmental applications related to fossil energy production.

Tungsten carbide and tungsten-molybdenum carbides as automobile exhaust catalysts

International Nuclear Information System (INIS)

Leclercq, L.; Daubrege, F.; Gengembre, L.; Leclercq, G.; Prigent, M.

1987-01-01

Several catalyst samples of tungsten carbide and W, Mo mixed carbides with different Mo/W atom ratios, have been prepared to test their ability to remove carbon monoxide, nitric oxide and propane from a synthetic exhaust gas simulating automobile emissions. Surface characterization of the catalysts has been performed by X-ray photoelectron spectroscopy (XPS) and selective chemisorption of hydrogen and carbon monoxide. Tungsten carbide exhibits good activity for CO and NO conversion, compared to a standard three-way catalyst based on Pt and Rh. However, this W carbide is ineffective in the oxidation of propane. The Mo,W mixed carbides are markedly different having only a very low activity. 9 refs.; 10 figs.; 5 tabs

Thermodynamics and vibrational study of hydrogenated carbon nanotubes: A DFT study

Science.gov (United States)

Khalil, Rana M. Arif; Hussain, Fayyaz; Rana, Anwar Manzoor; Imran, Muhammad

2018-02-01

Thermodynamic stability of the hydrogenated carbon nanotubes has been explored in the chemisorption limit. Statistical physics and density functional theory calculations have been used to predict hydrogen release temperatures at standard pressure in zigzag and armchair carbon nanotubes. It is found that hydrogen release temperatures decrease with increase in diameters of hydrogenated zigzag carbon nanotubes (CNTs) but opposite trend is noted in armchair CNTs at standard pressure of 1 bar. The smaller diameter hydrogenated zigzag CNTs have large values of hydrogen release temperature due to the stability of Csbnd H bonds. The vibrational density of states for hydrogenated carbon nanotubes have been calculated to confirm the Csbnd H stretching mode caused by sp3 hybridization.

Electronic-state-driven adsorption of O2 on a nanocrystalline TiO2 under 'dark' and UV-irradiation conditions: Ab initio study

Science.gov (United States)

Kevorkyants, R.; Sboev, M. N.; Chizhov, Yu. V.

2018-04-01

DFT study on O2 adsorption on a nanocrystalline titania is presented for the first time. The dioxide's nanoparticle is modeled via the nanocluster Ti8O16. According to the calculations, O2 physisorbs on the nanocluster Ti8O16 in S0 and T0 states and chemisorbs on the nanocluster in S1 state. The computed adsorption enthalpies, O2 vibrational frequencies, and O2-g-tensor agree well with available data. In contrast to the axial O2 orientation on a surface of titania with oxygen vacancies, in the chemisorption complex O2 is oriented laterally. We explain this by the sterical hindrance of the Ti3+ centers in the former case.

Theoretical Investigation of CO{sub 2} Adsorption on Graphene

Energy Technology Data Exchange (ETDEWEB)

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

2013-10-15

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

Electrochemical measurements for the corrosion inhibition of mild steel in 1 M hydrochloric acid by using an aromatic hydrazide derivative

Directory of Open Access Journals (Sweden)

P. Preethi Kumari

2017-07-01

Full Text Available The influence of an aromatic hydrazide derivative, 2-(3,4,5-trimethoxybenzylidene hydrazinecarbothioamide (TMBHC as corrosion inhibitor on mild steel in 1 M hydrochloric acid was studied by Tafel polarization and electrochemical impedance spectroscopy (EIS technique. The results showed that the inhibition efficiency (% IE of TMBHC increased with increasing inhibitor concentrations and also with increase in temperatures. TMBHC acted as a mixed type of inhibitor and its adsorption on mild steel surface was found to follow Langmuir’s adsorption isotherm. The evaluation of thermodynamic and activation parameters indicated that the adsorption of TMBHC takes place through chemisorption. The formation of protective film was further confirmed by scanning electron microscopy (SEM.

An investigation of Oxygen adsorption on W(110) using reflectance anisotropy spectroscopy

International Nuclear Information System (INIS)

Zeybek, O.

2004-01-01

The probe of metal surface electronic structure and results of the oxidation of a BCC material and the first Joint Density of States interpretation of the spectrum from same metal have been presented. The surface sensitivity of RAS has been exploited when applied to a cubic single crystal to study the surface electronic structure of W(110) and the resulting chemisorption-induced changes upon exposure to oxygen. Oxidation of the surface is monitored until a final exposure of 10 Langmuirs is reached. A decrease of reflectance anisotropy signal is obtained with increasing oxygen coverage on the substrate and a coverage of ∼0.75 ML results in zero anisotropy over the reflectance anisotropy energy range

An investigation of Oxygen adsorption on W(110) using reflectance anisotropy spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Zeybek, O [Department of Physics, Balikesir University, Balikesir (Turkey)

2004-07-01

The probe of metal surface electronic structure and results of the oxidation of a BCC material and the first Joint Density of States interpretation of the spectrum from same metal have been presented. The surface sensitivity of RAS has been exploited when applied to a cubic single crystal to study the surface electronic structure of W(110) and the resulting chemisorption-induced changes upon exposure to oxygen. Oxidation of the surface is monitored until a final exposure of 10 Langmuirs is reached. A decrease of reflectance anisotropy signal is obtained with increasing oxygen coverage on the substrate and a coverage of {approx}0.75 ML results in zero anisotropy over the reflectance anisotropy energy range.

On the inhibition of mild steel corrosion by 4-amino-5-phenyl-4H-1, 2, 4-trizole-3-thiol

International Nuclear Information System (INIS)

Musa, Ahmed Y.; Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Takriff, Mohd Sobri; Daud, Abdul Razak; Kamarudin, Siti Kartom

2010-01-01

The corrosion inhibition of mild steel in a 2.5 M H 2 SO 4 solution by 4-amino-5-phenyl-4H-1, 2, 4-trizole-3-thiol (APTT) was studied at different temperatures, utilising open circuit potential, potentiodynamic and impedance measurements. The results indicate that APTT performed as an excellent mixed-type inhibitor for mild steel corrosion in a 2.5 M H 2 SO 4 solution and that the inhibition efficiencies increased with the inhibitor concentration but decreased proportionally with temperature. The kinetic and thermodynamic parameters for adsorption of APTT on the mild steel surface were calculated. A chemisorption mechanism of APTT molecules on the mild steel surface was proposed based on the thermodynamic adsorption parameters.

Selective hydrogenation of furfural on Ir/TiO2 catalysts

Directory of Open Access Journals (Sweden)

Patricio Reyes

2010-01-01

Full Text Available Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

Effect of Y{sub 2}O{sub 3} addition to Rh/Al{sub 2}O{sub 3} catalysts on the autothermal reforming of methane; Efeito da adicao de Y{sub 2}O{sub 3} a catalisadores de Rh/Al{sub 2}O{sub 3} na reforma autotermica do metano

Energy Technology Data Exchange (ETDEWEB)

Ribeiro, Vanessa Monteiro; Cardoso, Gabriel Alexandre Lima; Coutinho, Ana Carla da S. Lomba S.; Passos, Fabio Barboza [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e de Petroleo. Lab. de Reatores, Cinetica e Catalise (RECAT)]. E-mail: vanessafisqui@yahoo.com.br

2008-07-01

In this work, the effect of the addition of Y{sub 2}O{sub 3} (with 2%, 5% and 10% weight content) on Rh/{alpha}-Al{sub 2}O{sub 3} catalysts in the autothermal reforming reaction of methane to the production of hydrogen for fuel cells was investigated. The catalysts were characterized by the following techniques: N{sub 2} adsorption, H{sub 2} chemisorption, X-ray diffraction (XRD) and cyclohexane dehydrogenation reaction. The catalysts were also evaluated in the reaction of autothermal reforming. The catalyst with higher Y{sub 2}O{sub 3} content showed the best results both in the cyclohexane dehydrogenation rate and in the conversion of methane. (author)

Electrochemical Synthesis of Ammonia from Water and Nitrogen using a Pt/GDC/Pt Cell

International Nuclear Information System (INIS)

Kim, Jong Nam; Yoo, Chung-Yul; Joo, Jong Hoon; Yu, Ji Haeng; Sharma, Monika; Yoon, Hyung Chul; Jeoung, Hana; Song, Ki Chang

2014-01-01

Electrochemical ammonia synthesis from water and nitrogen using a Pt/GDC/Pt cell was experimentally investigated. Electrochemical analysis and ammonia synthesis in the moisture-saturated nitrogen environment were performed under the operating temperature range 400-600 .deg. C and the applied potential range OCV (Open Circuit Voltage)-1.2V. Even though the ammonia synthesis rate was augmented with the increase in the operating temperature (i.e.. increase in the applied current) under the constant potential, the faradaic efficiency was decreased because of the limitation of dissociative chemisorption of nitrogen on the Pt electrode. The maximum synthesis rate of ammonia was 3.67x10 -11 mols -1 cm -2 with 0.1% faradaic efficiency at 600 .deg. C

Simulated structure and imaging of NTCDI on Si(1 1 1)-7 × 7 : a combined STM, NC-AFM and DFT study

Science.gov (United States)

Jarvis, S. P.; Sweetman, A. M.; Lekkas, I.; Champness, N. R.; Kantorovich, L.; Moriarty, P.

2015-02-01

The adsorption of naphthalene tetracarboxylic diimide (NTCDI) on Si(1 1 1)-7 × 7 is investigated through a combination of scanning tunnelling microscopy (STM), noncontact atomic force microscopy (NC-AFM) and density functional theory (DFT) calculations. We show that NTCDI adopts multiple planar adsorption geometries on the Si(1 1 1)-7 × 7 surface which can be imaged with intramolecular bond resolution using NC-AFM. DFT calculations reveal adsorption is dominated by covalent bond formation between the molecular oxygen atoms and the surface silicon adatoms. The chemisorption of the molecule is found to induce subtle distortions to the molecular structure, which are observed in NC-AFM images.

Chemisorption of oxygen and subsequent reactions on low index surfaces of β-Mo₂C

DEFF Research Database (Denmark)

Shi, Xue Rong; Wang, Shengguang; Wang, Jianguo

2016-01-01

to the carbon vacancy were identified. We examined the effect of oxygen coverage on the morphology of β-Mo2C by plotting the equilibrium crystal shape. Thermodynamic effect of temperature and reactant or product pressure on the CO/CO2 desorption were investigated. The CO/CO2 desorption is more favorable...... at the saturated oxygen coverage than the low oxygen coverage thermodynamically. The subsequent oxygen diffusion to the carbon vacancy after CO/CO2 desorption may happen depending on the surfaces and oxygen coverage....

Correlation of Chemisorption and Electronic Effects for Metal Oxide Interfaces: Transducing Principles for Temperature Programmed Gas Microsensors

International Nuclear Information System (INIS)

Semancik, Steve

2002-01-01

The spectrum of chemical monitoring problems faced by the Department of Energy at its hazardous waste sites is formidable. It is likely that a variety of existing types of instrumentation will be applied in the years ahead, with varying degrees of practicality and success. A tremendous impact could be realized, however, if instrumental methods could be supplemented by a low-cost, reliable sensing technology for continuous monitoring of a range of species, including, for example, volatile organics, chlorinated hydrocarbons, ammonia, and hydrogen. To meed the diverse gas and vapor monitoring needs at ODE hazardous waste sites, the sensing system must offer, inherently, and adaptability to match the wide variety of analytes and environmental conditions that well be encountered (in tank vapor spaces, and at locations with contaminated soil or groundwater.) The purpose of this project was to investigate scientific and technical concepts that could enable a MEMS-based chemical sensing technology (developed in its foundational form at NIST during early and mid 1990's) to be made tunable for multiple target analytes in differing types of backgrounds relevant to DOE waste storage and remediation

The chemisorption and reactions of formic acid on Cu films on ZnO (000 overline1)-O

Science.gov (United States)

Ludviksson, A.; Zhang, R.; Campbell, Charles T.; Griffiths, K.

1994-06-01

The adsorption and reactions of formic acid (HCOOD : HCOOH = 3:1) on the oxygen-terminated ZnO(0001¯)-O surface and on thin Cu films deposited on the ZnO(0001¯)-O surface have been studied with temperature programmed desorption (TPD) and XPS. Small amounts of formic acid dissociate at defect sites on clean ZnO(0001¯)-O to yield surface formate (HCOO). The acid D(H) from this dissociation does not reappear in TPD, and is lost to the ZnO bulk, as confirmed by nuclear reaction analysis. The surface HCOO decomposes to yield nearly simultaneous CO 2 (37%), CO (63%) and H 2 TPD peaks at 560 K. Substantial amounts of D (˜ 20%) are incorporated in this hydrogen TPD peak resulting from formate decomposition at ZnO defects, indicating that bulk D is readily accessible. Submonolayer and multilayer Cu films that are deposited at 130 K and partially cover the ZnO surface as 2D and 3D islands adsorb formic acid and decompose it into formate and hydrogen much like the Cu(110) surface. The surface formate from the Cu film decomposes at 470-500 K to give primarily CO 2 and H 2, also much like Cu(110), although atom-thin Cu islands also give ˜ 40% CO. Annealed Cu films give formate decomposition peaks at 25-50 K lower in temperature, attributed to thickening and ordering of the Cu islands to form Cu(111)-like sites. The acid D(H) atom from the formic acid is partially lost by hydrogen spillover from the Cu islands into the ZnO substrate, especially for thin Cu films. This effect partially desorbs and is enhanced upon preannealing the Cu layers, due to increased H diffusion rates across the annealed Cu islands, and/or the decrease in island size. Bulk D(H) is slowly removed as D 2, HD and H 2 above 400 K in diffusion-limited desorption, catalyzed by Cu.

Turbostratic carbon supported palladium as an efficient catalyst for reductive purification of water from trichloroethylene

Directory of Open Access Journals (Sweden)

Emil Kowalewski

2017-12-01

Full Text Available This work investigates the catalytic properties of turbostratic carbon supported Pd catalyst in hydrodechlorination of trichloroethylene (TCE HDC in aqueous phase. 1.57 wt% Pd/C was thoroughly characterized by BET, TPHD, CO chemisorption, PXRD, STEM, XPS and used as the catalyst in removal of trichloroethylene from drinking water in batch and continuous-flow reactors. The studies showed that catalytic performance of Pd/C depended on the hydrophobicity and textural properties of carbon support, which influenced noble metal dispersion and increased catalyst tolerance against deactivation by chlorination. Palladium in the form of uniformly dispersed small (~3.5 nm nanoparticles was found to be very active and stable in purification of water from TCE both in batch and continuous-flow operation.

Microstructural study of Ni/γ-Al2O3 catalyst: addition effects of CeO2 on carbon dioxide reforming of methane

International Nuclear Information System (INIS)

Valentini, Antoninho; Probst, Luiz Fernando Dias; Carreno, Neftali L. V.; Leite, Edson R.; Pontes, Fenelon M.; Longo, Elson; Schreiner, Wido H.; Lisboa-Filho, Paulo N.

2003-01-01

The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the γ-Al 2 O 3 /CeO 2 system prepared by wet impregnation. With the increase of the Co2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H 2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO 2 was observed to the Ni/CeO 2 sample after activation in a H 2 atmosphere above 300 deg C. Such behavior has a significantly influence on the catalytic activity. (author)

Estudo microestrutural do catalisador Ni/gama-Al2O3: efeito da adição de CeO2 na reforma do metano com dióxido de carbono Microstructural study of Ni/gamma-Al2O3 catalyst: addition effects of CeO2 on carbon dioxide reforming of methane

Directory of Open Access Journals (Sweden)

Antoninho Valentini

2003-10-01

Full Text Available The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the gamma-Al2O3/CeO2 system prepared by wet impregnation. With the increase of the CeO2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO2 was observed to the Ni/CeO2 sample after activation in a H2 atmosphere above 300 ºC. Such behavior has a significantly influence on the catalytic activity.

Investigation into interaction of CO/sub 2/ molecules with zeolites by infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Ignat' eva, L A; Levshin, L V; Chukin, G D; Efimenko, L V; Kozlova, T I [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Optiki

1975-07-01

Interaction of CO/sub 2/ molecules with zeolites, particularly with SrNaJ was studied by infrared-spectroscopy. To obtain infrared-spectra the zeolites were pressed into tablets and were calcinated at 500 deg. In the spectra the bands of chemisorbed CO/sub 2/ absorption were found in the range 1300 - 1600 cm/sup -1/. The CO/sub 2/ molecule was found to be strongly deformed due to chemisorption. In terms of electronic structure of the zeolite crystalline skeleton several types of CO/sub 2/ molecules interaction with different active zeolites were found. The position of the high-frequency band of CO/sub 2/ absorption in zeolites spectra was found to be a linear function of electrostatic field of the cations.

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

Science.gov (United States)

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

2013-01-01

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

Surface effects in metal oxide-based nanodevices

KAUST Repository

Lien, Der Hsien; Duran Retamal, Jose Ramon; Ke, Jr Jian; Kang, Chen Fang; He, Jr-Hau

2015-01-01

As devices shrink to the nanoscale, surface-to-volume ratio increases and the surface-environment interaction becomes a major factor for affecting device performance. The variation of electronic properties, including the surface band bending, gas chemisorption or photodesorption, native surface defects, and surface roughness, is called "surface effects". Such effects are ambiguous because they can be either negative or beneficial effects, depending on the environmental conditions and device application. This review provides an introduction to the surface effects on different types of nanodevices, offering the solutions to respond to their benefits and negative effects and provides an outlook on further applications regarding the surface effect. This review is beneficial for designing nano-enabled photodetectors, harsh electronics, memories, sensors and transistors via surface engineering.

Mechanism and Thermochemistry of Coal Char Oxidation and Desorption of Surface Oxides

DEFF Research Database (Denmark)

Levi, Gianluca; Causà, Mauro; Lacovig, Paolo

2017-01-01

The present study investigates the coal char combustion by a combination of thermochemical and X-ray photoemission spectroscopy (XPS) analyses. Thermoanalytical methods (differential thermogravimetry, differential scanning calorimetry, and temperature-programmed desorption) are used to identify...... the key reactive steps that occur upon oxidation and heating of coal char (chemisorption, structural rearrangement and switchover of surface oxides, and desorption) and their energetics. XPS is used to reveal the chemical nature of the surface oxides that populate the char surface and to monitor...... functionalities prevail. The rearrangement of epoxy during preoxidation goes together with activation of the more stable and less reactive carbon sites. Results are in good agreement with semi-lumped kinetic models of carbon oxidation, which include (1) formation of "metastable" surface oxides, (2) complex...

Surface effects in metal oxide-based nanodevices

KAUST Repository

Lien, Der Hsien

2015-10-29

As devices shrink to the nanoscale, surface-to-volume ratio increases and the surface-environment interaction becomes a major factor for affecting device performance. The variation of electronic properties, including the surface band bending, gas chemisorption or photodesorption, native surface defects, and surface roughness, is called "surface effects". Such effects are ambiguous because they can be either negative or beneficial effects, depending on the environmental conditions and device application. This review provides an introduction to the surface effects on different types of nanodevices, offering the solutions to respond to their benefits and negative effects and provides an outlook on further applications regarding the surface effect. This review is beneficial for designing nano-enabled photodetectors, harsh electronics, memories, sensors and transistors via surface engineering.

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

Science.gov (United States)

Frydel, Derek; Podgornik, Rudolf

2018-05-01

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

Adsorption of thiophene on a Si(0 0 1)-2 x 1 surface studied by photoelectron spectroscopy and diffraction

Energy Technology Data Exchange (ETDEWEB)

Shimomura, M. [Research Institute of Electronics, Shizuoka University, Johoku, Hamamatsu 432-8011 (Japan)]. E-mail: romshimo@rie.shizuoka.ac.jp; Ikejima, Y. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); Yajima, K. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); Yagi, T. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); Goto, T. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); Gunnella, R. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); UdR INFM, Department of Physics, University of Camerino, Camerino 62032 (Italy); Abukawa, T. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); Fukuda, Y. [Research Institute of Electronics, Shizuoka University, Johoku, Hamamatsu 432-8011 (Japan); Kono, S. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan)

2004-10-15

Chemisorption of thiophene on a Si(0 0 1) surface has been studied by synchrotron radiation induced photoelectron spectroscopy (SRPES). Two adsorption-related components in Si 2p and S 2p spectra are observed after exposure of thiophene. It is suggested that the two components of Si 2p are ascribed to silicon bonded to hydrocarbon and sulfur. The core-level shift resolved photoelectron diffraction (PED) result indicates that the low-kinetic-energy component of S 2p can be ascribed to 2,5-dihydrothiophehe (DHT)-like species. Another S 2p component could be assigned to dissociated sulfur based on the results of PED and time evolution of the spectrum under irradiation. These assignments are consistent with the core-level shift of S 2p.

Ligand substitution and selective surface coordination studies of iodine and 2,5-dihydroxythiophenol at platinum electrodes

International Nuclear Information System (INIS)

Berry, G.M.; Soriaga, M.P.

1989-01-01

The relative surface coordination strengths of 2,5-dihydroxythiophenol (DHT) and iodine at a smooth polycrystalline platinum electrode have been investigated by thin-layer electrochemical techniques. The competitive chemisorption was studied by exposing the Pt electrode to solutions of varying mole fractions of I and DHT. Studies of ligand substitution were carried out by the introduction of an iodine-coated Pt electrode into DHT solutions, and the introduction of a DHT-coated into I solutions. Surface coverage measurements indicated that DHT is preferentially adsorbed and will displace chemisorbed iodine at the Pt electrode. Chemisorbed DHT is not appreciably displaced by iodine. These results and their contribution to the trend in the selective surface coordination chemistry of platinum electrodes will be discussed

Catalytic oxidation of silicon by cesium ion bombardment

International Nuclear Information System (INIS)

Souzis, A.E.; Huang, H.; Carr, W.E.; Seidl, M.

1991-01-01

Results for room-temperature oxidation of silicon using cesium ion bombardment and low oxygen exposure are presented. Bombardment with cesium ions is shown to allow oxidation at O 2 pressures orders of magnitude smaller than with noble gas ion bombardment. Oxide layers of up to 30 A in thickness are grown with beam energies ranging from 20--2000 eV, O 2 pressures from 10 -9 to 10 -6 Torr, and total O 2 exposures of 10 0 to 10 4 L. Results are shown to be consistent with models indicating that initial oxidation of silicon is via dissociative chemisorption of O 2 , and that the low work function of the cesium- and oxygen-coated silicon plays the primary role in promoting the oxidation process

Characterization and potential application of pataua vegetable oil in apatite flotation

International Nuclear Information System (INIS)

Oliveira, P.S. de; Mansur, H.S.; Peres, A.E.C.

2016-01-01

The present research characterizes the Pataua palm (Oenocarpus bataua) oil regarding to its fatty acids profile and acidity index, and evaluates its use for apatite flotation. The Pataua oil evaluated is unsaturated e predominantly composed of cis-9-octadecenoic acid (oleic acid). The mineral sample characterization revealed a material composed by a fluoroapatite deficient in fluorine, a possibly result of isomorphic substitution, and with quartz and monazite inclusions. The analysis of the mineral after reagent conditioning, by Fourier Transform Infrared Spectroscopy (FTIR), pointed to the presence of characteristic bands of carbon chains and carboxylate group, suggesting the collector adsorption through the mechanisms of chemisorption and insoluble calcium salts precipitation. Thus, it is proposed the Pataua oil potential use in flotation systems aiming apatite recovery. (author)

Electrochemical Synthesis of Ammonia from Water and Nitrogen using a Pt/GDC/Pt Cell

Energy Technology Data Exchange (ETDEWEB)

Kim, Jong Nam; Yoo, Chung-Yul; Joo, Jong Hoon; Yu, Ji Haeng; Sharma, Monika; Yoon, Hyung Chul [Korea Institute of Energy Research, Daejeon (Korea, Republic of); Jeoung, Hana; Song, Ki Chang [Konyang University, Nonsan (Korea, Republic of)

2014-02-15

Electrochemical ammonia synthesis from water and nitrogen using a Pt/GDC/Pt cell was experimentally investigated. Electrochemical analysis and ammonia synthesis in the moisture-saturated nitrogen environment were performed under the operating temperature range 400-600 .deg. C and the applied potential range OCV (Open Circuit Voltage)-1.2V. Even though the ammonia synthesis rate was augmented with the increase in the operating temperature (i.e.. increase in the applied current) under the constant potential, the faradaic efficiency was decreased because of the limitation of dissociative chemisorption of nitrogen on the Pt electrode. The maximum synthesis rate of ammonia was 3.67x10{sup -11} mols{sup -1}cm{sup -2} with 0.1% faradaic efficiency at 600 .deg. C.

Contamination and decontamination of skin

International Nuclear Information System (INIS)

Severa, J.; Knajfl, J.

1983-01-01

In external contamination the beta radiation dose is the prevalent component of the total dose absorbed by the skin. There exist four types of radionUclide bonds to the skin: mechanical retention of solid particles or solution on the surface and in the pores, physical adsorption of nondissociated molecules or colloids, the ion exchange effect, and chemisorption. Radionuclides then penetrate the skin by transfollicular transfer. The total amount of radioactive substances absorbed into the skin depends on the condition of the skin. Skin is decontaminated by washing with lukewarm water and soap or with special decontamination solutions. The most widely used components of decontamination solutions are detergents, chelaton, sodium hexametaphosphate, oxalic acid, citric acid. The main principles of the decontamination of persons are given. (M.D.)

Studies on the Inhibition of Mild Steel Corrosion by Rauvolfia serpentina in Acid Media

Science.gov (United States)

Bothi Raja, P.; Sethuraman, M. G.

2010-07-01

Alkaloid extract of Rauvolfia serpentina was tested as corrosion inhibitor for mild steel in 1 M HCl and H2SO4 using weight loss method at three different temperatures, viz., 303, 313, and 323 K, potentiodynamic polarization, electrochemical impedance spectroscopy and scanning electron microscope (SEM) studies. It is evident from the results of this study that R. serpentina effectively inhibits the corrosion in both the acids through adsorption process following Tempkin adsorption isotherm. The protection efficiency increased with increase in inhibitor concentration and temperature. Free energy of adsorption calculated from the temperature studies also revealed the chemisorption. The mixed mode of action exhibited by the inhibitor was confirmed by the polarization studies while SEM analysis substantiated the formation of protective layer over the mild steel surface.

Adsorption of thiophene on a Si(0 0 1)-2 x 1 surface studied by photoelectron spectroscopy and diffraction

International Nuclear Information System (INIS)

Shimomura, M.; Ikejima, Y.; Yajima, K.; Yagi, T.; Goto, T.; Gunnella, R.; Abukawa, T.; Fukuda, Y.; Kono, S.

2004-01-01

Chemisorption of thiophene on a Si(0 0 1) surface has been studied by synchrotron radiation induced photoelectron spectroscopy (SRPES). Two adsorption-related components in Si 2p and S 2p spectra are observed after exposure of thiophene. It is suggested that the two components of Si 2p are ascribed to silicon bonded to hydrocarbon and sulfur. The core-level shift resolved photoelectron diffraction (PED) result indicates that the low-kinetic-energy component of S 2p can be ascribed to 2,5-dihydrothiophehe (DHT)-like species. Another S 2p component could be assigned to dissociated sulfur based on the results of PED and time evolution of the spectrum under irradiation. These assignments are consistent with the core-level shift of S 2p

Occlusion and storage of krypton in solids

International Nuclear Information System (INIS)

Vansant, E.F.; Thijs, A.; Peeters, G.; Bievre, P. de; Verhaert, I.

1984-01-01

The modification process in order to change in a controlled way the effective pore size of zeolites was optimized by investigating the reaction conditions such as degree of chemisorption, reaction temperature, extent of primary/secondary reactions, type of modifying agent, type of substrate, etc. Different reaction and adsorption conditions have been tested to increase the thermal stability of encapsulated krypton in modified zeolites. The possibilities for zeolite modification have been enlarged by combining boranation and silanation with a thermal treatment of sepiolite, and by the formation of boron-nitrogen compounds in zeolites. Screening experiments, on a semi-industrial scale, of the krypton removal from air were carried out. Two kinds of Kr/air separation have been tested suscessfully on modified mordenite

Applications of core level spectroscopy to adsorbates

International Nuclear Information System (INIS)

Nilsson, Anders

2002-01-01

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

Characterization and potential application of pataua vegetable oil in apatite flotation; Caracterizacao e potencial aplicacao do oleo vegetal de pataua na floracao de apatita

Energy Technology Data Exchange (ETDEWEB)

Oliveira, P.S. de; Mansur, H.S.; Peres, A.E.C., E-mail: eng.priscila.oliveira@gmail.com [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil)

2016-07-01

The present research characterizes the Pataua palm (Oenocarpus bataua) oil regarding to its fatty acids profile and acidity index, and evaluates its use for apatite flotation. The Pataua oil evaluated is unsaturated e predominantly composed of cis-9-octadecenoic acid (oleic acid). The mineral sample characterization revealed a material composed by a fluoroapatite deficient in fluorine, a possibly result of isomorphic substitution, and with quartz and monazite inclusions. The analysis of the mineral after reagent conditioning, by Fourier Transform Infrared Spectroscopy (FTIR), pointed to the presence of characteristic bands of carbon chains and carboxylate group, suggesting the collector adsorption through the mechanisms of chemisorption and insoluble calcium salts precipitation. Thus, it is proposed the Pataua oil potential use in flotation systems aiming apatite recovery. (author)

Dissociative and molecular oxygen chemisorption channels on reduced rutile TiO2(110): A high-resolution STM study

DEFF Research Database (Denmark)

Lira, Estephania; Hansen, Jonas Ørbæk; Huo, Peipei

2010-01-01

High-resolution scanning tunneling microscopy (STM) and temperature-programmed desorption (TPD) were used to study the interaction of O2 with reduced TiO2(110)–(1 × 1) crystals. STM is the technique of choice to unravel the relation between vacancy and non-vacancy assisted O2 dissociation channel...... in the near-surface region of reduced TiO2(110) crystals, the kinetics of the two O2 dissociation channels as well as the kinetics of the diffusion and reaction of Ti interstitials....

On the activation of Pt/Al2O3 catalysts in HC-SCR by sintering. Determination of redox-active sites using Multitrack

International Nuclear Information System (INIS)

Vaccaro, A.R.; Mul, G.; Moulijn, J.A.; Perez-Ramirez, J.

2003-01-01

A highly dispersed Pt/Al 2 O 3 catalyst was used for the selective catalytic reduction of NO x using propene (HC-SCR). Contact with the reaction gas mixture led to a significant activation of the catalyst at temperatures above 523K. According to CO chemisorption data and HRTEM analysis, Pt particles on the activated catalyst had sintered. The redox behavior of the fresh and sintered catalysts was investigated using Multitrack, a TAP-like pulse reactor. If Pt particles on the catalyst are highly dispersed (average size below =2nm), only a small part (=10%) of the total number of Pt surface sites as determined by CO chemisorption (Pt surf ) participates in H 2 /O 2 redox cycles (Pt surf,redox ) in Multitrack conditions. For a sintered catalyst, with an average particle size of 2.7nm, the number of Pt surf and Pt surf,redox sites are in good agreement. Similar results were obtained for both catalysts using NO as the oxidant. The low number of Pt surf,redox sites on highly dispersed Pt/Al 2 O 3 is explained by the presence of a kinetically more stable-probably ionic-form of Pt-O bonds on all surface sites of the smaller Pt particles, including corner, edge and terrace sites. When the average particle size shifts to =2.7nm, the kinetic stability of all Pt-O bonds is collectively decreased, enabling the participation of all Pt surface sites in the redox cycles. A linear correlation between the NO x conversion in HC-SCR, and the amount of Pt surf,redox was found. This suggests that redox-active Pt sites are necessary for catalytic activity. In addition, the correlation could be significantly improved by assuming that Pt surf,terrace sites of the particles larger than 2.7nm are mainly responsible for HC-SCR activity in steady state conditions. Implications of these results for the pathway of HC-SCR over Pt catalysts are discussed

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

IMPREGNATED FIBROUS CHEMOSORBENTS OF ACID GASES FOR RESPIRATORY PURPOSE

Directory of Open Access Journals (Sweden)

A. A. Ennan

2017-11-01

Full Text Available The present review is dedicated to the analysis of scientific works carried out in Physico- Chemical Institute of Environment and Human Protection (Odessa, Ukrainie and directed to the development of import-substituting sorption-filtering materials for respiratory purposes – impregnated fibrous chemisorbents (IFCS of acid gases, which are manufactured using standard equipment, as well as affordable and inexpensive chemical reagents and carriers of domestic origin. The process of chemisorption of sulphur dioxide by hexamethylenetetramine (HMTA modified nonwoven fibrous material resulted acid-catalyzed hydrolysis of HMTA to form aminomethanesulfonic acid and toxic formaldehyde. The IFCS with HMTA carried was recommended to use for air purification only from SiF4, HF, HCl and Cl2. Chemisorption of sulphur dioxide by fibrous materials impregnated by ethanolamines (monoethanolamine, diethanomamine, triethanomamine and N-methylethanolamine and polyethylenepolyamine (PEPA occurs only in the presence of “free” water with formation of “onium” sulphites, hydrosulphites and pyrosulphites. IFCS-PEPA (dynamic activity is 1,38 mmol(SO2/g are not inferior to the protective characteristics of IFCS with Na2CO3, HMTA, ethanolamines and the best foreign ionexchange fibrous chemisorbents brand VION and FIBAN (dynamic activity is 0,263 ÷0,422 mmol(SO2/g under conditions of respirators actual use (jAGM = 60 ÷ 90 %, TAGM = 297 K, VAGM = 2,0 sm/s, СSO2 = 20 ÷ 1000 mg/g3, QPEPA = 3,45 mmol/g. It is recommended to use the condensation products of primary alkylamines with formaldehyde (with large molar masses than the bases, complex compounds of amines with 3d-metals (Ni(II and Cu(II, salts of amine with aminoacids (glycine and polybasic acids (orthophosphoric acid (pKa1 = 2,12 and citric acid (pKa1 = 3,13 for manufacturing of IFCS of acid gases The IFCS with indication of dynamic absorptive capacity “wearing” (IVKS-I was developed.

A density functional study of NO{sub 2} adsorption on perfect and defective MgO (1 0 0) and Li/MgO (1 0 0) surfaces

Energy Technology Data Exchange (ETDEWEB)

Eid, Kh.M., E-mail: Khaled_eid@edu.asu.edu.eg [Physics Department, Faculty of Education, Ain Shams University, P.O. Box 11757, Cairo (Egypt); Ammar, H.Y. [Physics Department, Faculty of Education, Ain Shams University, P.O. Box 11757, Cairo (Egypt); Department of Physics, Faculty of Science, Najran University, Najran (Saudi Arabia)

2012-07-15

The density functional theory (DFT) in combination with embedded cluster model have been used to study the adsorption of nitrogen dioxide molecule (NO{sub 2}) on Li atom deposited on the surfaces of metal oxide MgO (1 0 0) on both anionic (O{sup 2-}) and defect (F{sub s} and F{sub s}{sup +}-centers) sites. The adsorption energy (E{sub ads}) of NO{sub 2} molecule (N-down as well as O-down) in different positions on O{sup -2}, F{sub s} and F{sub s}{sup +}-sites is considered. The geometrical optimizations have been done for the additive materials and MgO substrate surfaces. The formation energies have been evaluated for F{sub s} and F{sub s}{sup +} of MgO substrate surfaces. The ionization potential (IP) and electron affinity (eA) for defect free and defect containing surfaces have been calculated. The adsorption properties of NO{sub 2} are analyzed in terms of the adsorption energy, the electron donation (basicity), the elongation of N-O bond length and the atomic charges on adsorbed materials. The densities of states (DOS) have been calculated and used for examining the adsorption properties. The NO{sub 2} molecule is dissociated due to the interaction with the defective substrate surface (F{sub s}-site) producing an oxygen atom strongly chemisorbed to the vacancy of the substrate and gaseous NO far away from the surface. The presence of the Li atom increases the surface chemistry of the anionic O{sup 2-}-site of MgO substrate surfaces (converted from physisorption to chemisorption). On the other hand, the presence of the Li atom decreases the surface chemistry of the F{sub s} and F{sub s}{sup +}-sites of MgO substrate surfaces. Generally, the NO{sub 2} molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F{sub s} and F{sub s}{sup +}-centers.

Concurrent removal of elemental mercury and SO2 from flue gas using a thiol-impregnated CaCO3-based adsorbent: a full factorial design study.

Science.gov (United States)

Balasundaram, Karthik; Sharma, Mukesh

2018-03-22

Mercury (Hg) emitted from coal-based thermal power plants (CTPPs) can accumulate and bio-magnify in the food chain, thereby posing a risk to humans and wildlife. The central idea of this study was to develop an adsorbent which can concurrently remove elemental mercury (Hg 0 ) and SO 2 emitted from coal-based thermal power plants (CTPPs) in a single unit operation. Specifically, a composite adsorbent of CaCO 3 impregnated with 2-mercaptobenimidazole (2-MBI) (referred to as modified calcium carbonate (MCC)) was developed. While 2-MBI having sulfur functional group could selectively adsorb Hg 0 , CaCO 3 could remove SO 2 . Performance of the adsorbent was evaluated in terms of (i) removal (%) of Hg 0 and SO 2 , (ii) adsorption mechanism, (iii) adsorption kinetics, and (iv) leaching potential of mercury from spent adsorbent. The adsorption studies were performed using a 2 2 full factorial design of experiments with 15 ppbV of Hg 0 and 600 ppmV of SO 2 . Two factors, (i) reaction temperature (80 and 120 °C; temperature range in flue gas) and (ii) mass of 2-MBI (10 and 15 wt%), were investigated for the removal of Hg 0 and SO 2 (as %). The maximum Hg 0 and SO 2 removal was 86 and 93%, respectively. The results of XPS characterization showed that chemisorption is the predominant mechanism of Hg 0 and SO 2 adsorption on MCC. The Hg 0 adsorption on MCC followed Elovich kinetic model which is also indicative of chemisorption on heterogeneous surface. The toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) leached mercury from the spent adsorbent were within the acceptable levels defined in these tests. The engineering significance of this study is that the 2-MBI-modified CaCO 3 -based adsorbent has potential for concurrent removal of Hg 0 and SO 2 in a single unit operation. With only minor process modifications, the newly developed adsorbent can replace CaCO 3 in the flue-gas desulfurization (FGD) system.

Theory of molecular hydrogen sorption for hydrogen storage

Science.gov (United States)

Zhang, Shengbai

2011-03-01

Molecular hydrogen (H2) sorption has the advantage of fast kinetics and high reversibility. However, the binding strength is often too weak to be operative at near room temperatures. Research into such hydrogen sorption materials has branched into the study of pure van der Waals (vdW) physisorption and that of weak chemisorption (known to exist in the so-called Kubas complexes). In either case, however, theoretical tools to describe such weak interactions are underdeveloped with error bars that often exceed the strength of the interaction itself. We have used quantum-chemistry (QC) based approaches to benchmark the various available DFT methods for four classes of weak chemisorption systems [Sun et al., Phys. Rev. B 82, 073401 (2010)]. These involve complexes containing Li, Ca, Sc, and Ti with increased strength of H2 binding from predominantly vdW to mostly Kubas-like. The study reveals that most of the DFT functionals within the generalized gradient approximation underestimate the binding energy, oppose to overestimating it. The functionals that are easy to use yet yielding results reasonably close to those of accurate QC are the PBE and PW91. I will also discuss the effort of implementing vdW interaction into the currently available density functional methods [Sun, J. Chem. Phys. 129, 154102 (2008)]. The rationale is that while the true vdW is an electron-electron correlation, a DFT plus classical dispersion approach may be too simple and unnecessary within the DFT. A local pseudopotential approach has been developed to account for the core part of the polarizability of the elements. Applications to a number of benchmark systems yield good agreement with QC calculations. The application of this method and the QC methods to vdW hydrogen binding will also be discussed. Work supported by DOE/BES and DOE/EERE Hydrogen Sorption Center of Excellence under RPI subcontracts No. J30546/J90336.

Mechanistic studies of mercury adsorption and oxidation by oxygen over spinel-type MnFe{sub 2}O{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Yang, Yingju [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Jing, E-mail: liujing27@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Shenzhen Institute of Huazhong University of Science and Technology, Shenzhen 518000 (China); Zhang, Bingkai; Liu, Feng [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

2017-01-05

Highlights: • Hg adsorption and oxidation mechanisms on MnFe{sub 2}O{sub 4} were studied using DFT method. • Hg{sup 0} adsorption on Mn-terminated MnFe{sub 2}O{sub 4} (100) surface is a chemisorption process. • HgO shows high chemical reactivity for its adsorption on MnFe{sub 2}O{sub 4} surface. • The reaction between adsorbed Hg and surface oxygen is the rate-determining step. - Abstract: MnFe{sub 2}O{sub 4} has been regarded as a very promising sorbent for mercury emission control in coal-fired power plants because of its high adsorption capacity, magnetic, recyclable and regenerable properties. First-principle calculations based on density functional theory (DFT) were used to elucidate the mercury adsorption and oxidation mechanisms on MnFe{sub 2}O{sub 4} surface. DFT calculations show that Mn-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface is much more stable than Fe-terminated surface. Hg{sup 0} is physically adsorbed on Fe-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface. Hg{sup 0} adsorption on Mn-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface is a chemisorption process. The partial density of states (PDOS) analysis indicates that Hg atom interacts strongly with surface Mn atoms through the orbital hybridization. HgO is adsorbed on the MnFe{sub 2}O{sub 4} surface in a chemical adsorption manner. The small HOMO–LUMO energy gap implies that HgO molecular shows high chemical reactivity for HgO adsorption on MnFe{sub 2}O{sub 4} surface. The energy barriers of Hg{sup 0} oxidation by oxygen on Fe- and Mn-terminated MnFe{sub 2}O{sub 4} surfaces are 206.37 and 76.07 kJ/mol, respectively. Mn-terminated surface is much more favorable for Hg{sup 0} oxidation than Fe-terminated surface. In the whole Hg{sup 0} oxidation process, the reaction between adsorbed mercury and surface oxygen is the rate-determining step.

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

Science.gov (United States)

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

2017-04-01

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

Utilization of chemically modified citrus reticulata peels for biosorptive removal of acid yellow-73 dye from water

International Nuclear Information System (INIS)

Rehman, R.; Salman, M.; Mahmud, T.; Kanwal, F.; Zaman, W.

2013-01-01

Textile effluents contain several varieties of natural and synthetic dyes, which are non-biodegradable. Acid Yellow-73 is one of them. In this research work, adsorptive removal of this dye was investigated using chemically modified Citrus reticulata peels, in batch mode. It was noted that adsorption of dye on Citrus reticulata peels increased by increasing contact time and decreased in basic pH conditions. Langmuir and Freundlich isothermal models were followed by equilibrium data, but the first isotherm fitted the data better, showing that chemisorption occurred more as compared to physiosorption, showing maximum adsorption capacity 96.46 mg.g-1.L-1. The thermodynamic study showed that adsorption of Acid Yellow-73 on chemically modified Citrus reticulata peels was favorable in nature, following pseudo-second order kinetics. (author)

Graft polymerization of vynil monomers at carbon black surface (1)

International Nuclear Information System (INIS)

Haryono Arumbinang.

1976-01-01

Effect of aromatic condensates containing functional group on carbon black surface, effect of pH condensates on carbon black chemisorption, analysis and configuration of functional group, the crystal structure, property measurement standard, particle diameter measurement, oil adsorption, colour capacity, volatile acid content, electric resistence and the volume of the granular or carbon black dust, are given. Electron paramagnetic resonance determination of the amount of free radicals on carbon black surface, its oxidation and effects on the surface and inner structure of carbon black, and graft polymerization by radiation copolymerization, are discussed. Experiments on radiation graft copolymerization by acrylic acid, methacrylate, and glycidol methacrylate, in a vacuum condition, have been carried out. It is concluded that further research on the modification and configuration of carbon black should be developed. (author)

Investigating the adsorption of H2O on ZnO nanoclusters by first principle calculations

KAUST Repository

Al-Sunaidi, Abdullah A.

2011-04-01

The interaction of a single H2O molecule on selected ZnO nanoclusters is investigated by carrying out calculations based on the density-functional theory at the hybrid-GGA (B97-2) level. These clusters have ring, drum, tube and bubble shapes and their physical properties like the binding energy and the band gap energy depend strongly on the shape and size of the cluster. Depending on the stability of the cluster, H2O show both chemisorption and dissociation on the surfaces of the clusters. We analyzed the effect of H2O adsorption on the properties of clusters of size n = 12 via the density of state, HOMO-LUMO orbitals and the changes in the IR frequencies. © 2011 Elsevier B.V. All rights reserved.

Adsorption behavior of n-butanol molecules on negatively charged surfaces of electrodes of mercury, gallium, and alloys In-Ga and Tl-Ga

International Nuclear Information System (INIS)

Damskin, B.B.; Baturina, O.A.; Vasil'ev, S.Yu.; Emets, V.V.; Kazarinov, V.E.

1999-01-01

Curves of differential capacitance in the interfaces Hg/H 2 O, Ga/H 2 O, (In-Ga)/H 2 O and (Tl-Ga)H 2 O in 0.05 M Na 2 SO 4 solutions with different additions of n-butanol have been obtained by the bridge method at a frequency of 420 Hz and temperature of 32 deg C. The method of regression analysis of the curves permitted ascertaining the adsorption parameters of n-butanol for the range of charges q, where there is no chemisorption of H 2 O dipoles. The data obtained suggested that the difference in the adsorption behaviour of organic molecules on the metals studied in the range of higher negative charges is largely determined by different electron electrochemical work functions, the definition being given by S. Trasatti [ru

Influence of reaction products of K-getter fuel additives on commercial vanadia-based SCR catalysts

DEFF Research Database (Denmark)

Castellino, Francesco; Jensen, Anker Degn; Johnsson, Jan Erik

2009-01-01

, deactivation rates up to 3%/day have been measured. The spent catalysts have been characterized by bulk chemical analysis, Hg-porosimetry and SEM-EDX. NH3-chemisorption tests on the spent elements and activity tests on catalyst powders obtained by crushing the monoliths have also been carried out. The catalyst...... characterization has shown that poisoning by K is the main deactivation mechanism. The results show that binding K in K–P salts will not reduce the rate of catalyst deactivation....... as a K-getter additive. The formed aerosols have been characterized by using both a SMPS system and a low pressure cascade impactor, showing a dual-mode volume-based size distribution with a first peak at around 30 nm and a second one at diameters >1 μm. The different peaks have been associated...

Photoluminescence quenching of chemically functionalized porous silicon by a ruthenium cluster

Energy Technology Data Exchange (ETDEWEB)

Boukherroub, R.; Wayner, D.D.M. [Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario (Canada); Lockwood, D.J. [Institute for Microstructural Sciences, National Research Council of Canada, Ottawa, Ontario (Canada); Zargarian, D. [Chemistry Department, University of Montreal, C.P. 6128, succursale, Centre-ville, Montreal QC (Canada)

2003-05-01

This paper describes photoluminescence (PL) quenching of hydrogen-terminated and chemically derivatized porous silicon (PSi) nanostructures by a green ruthenium cluster (I). Chemisorption of freshly prepared PSi surfaces in a hexane solution of the Ru cluster for several days at room temperature led to a complete quenching of the PSi PL. The only visible PL was due to the original PL of the cluster. When the PSi surface functionalized with undecylenic acid was immersed in the same hexane solution of (I), the PSi PL was completely quenched and accompanied with a shift to a lower energy of the cluster PL. This shift was assigned to the formation of an ester linkage resulting from the nucleophilic attack of the PO anion of the cluster on the terminal acid functional group. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

Photoluminescence quenching of chemically functionalized porous silicon by a ruthenium cluster

Science.gov (United States)

Boukherroub, R.; Wayner, D. D. M.; Lockwood, D. J.; Zargarian, D.

2003-05-01

This paper describes photoluminescence (PL) quenching of hydrogen-terminated and chemically derivatized porous silicon (PSi) nanostructures by a green ruthenium cluster (I). Chemisorption of freshly prepared PSi surfaces in a hexane solution of the Ru cluster for several days at room temperature led to a complete quenching of the PSi PL. The only visible PL was due to the original PL of the cluster. When the PSi surface functionalized with undecylenic acid was immersed in the same hexane solution of (I), the PSi PL was completely quenched and accompanied with a shift to a lower energy of the cluster PL. This shift was assigned to the formation of an ester linkage resulting from the nucleophilic attack of the PO anion of the cluster on the terminal acid functional group.

Interaction of scandium sesquioxide with carbon

International Nuclear Information System (INIS)

Vodop'yanov, A.G.; Zakharov, R.G.

1986-01-01

In the range of 2350-2470 degrees K at a PCO = 0.0 MPa, interaction in Sc 2 O 3 with carbon mixtures initially occurs by CO chemisorption at the scandium oxide surface and disproportionation into CO 2 and C, with subsequent replacement of oxygen in the oxide anion sublattice by carbon to form ScC. The carbide melt, creating a contact between the reagents, then transforms the process to a diffusion-based one. At 1820-2220 K in vacuum, reduction of the studied mixtures occurs by dissociative vaporization of the oxide, with precipitation of ScC at the carbon surface and generation of CO. The appearance of CO in the vapors of mixture leads to formation of an oxycarbide phase and to the partial occurrence of oxide dissociation

Friction and wear studies of graphite and a carbon-carbon composite in air and in helium

International Nuclear Information System (INIS)

Li, C.C.; Sheehan, J.E.

1980-10-01

Sliding friction and wear tests were conducted on a commercial isotropic graphite and a carbon-carbon composite in air, purified helium, and a helium environment containing controlled amounts of impurities simulating the primary coolant chemistry of a high-temperature gas-cooled reactor (HTGR). The friction and wear characteristics of the materials investigated were stable and were found to be very sensitive to the testing temperature. In general, friction and wear decreased with increasing temperature in the range from ambient to 950 0 C. This temperature dependence is concluded to be due to chemisorption of impurities to form lubricating films and oxidation at higher temperatures, which reduce friction and wear. Graphite and carbon-carbon composites are concluded to be favorable candidate materials for high-temperature sliding service in helium-cooled reactors

Sorption Kinetics for the Removal of Cadmium and Zinc onto Palm Kernel Shell Based Activated Carbon

Directory of Open Access Journals (Sweden)

Muhammad Muhammad

2010-12-01

Full Text Available The kinetics and mechanism of cadmium and zinc adsorption on palm kernel shell based activated carbons (PKSAC have been studied. A series of batch laboratory studies were conducted in order to investigate the suitability of palm kernel shell based activated carbon (PKSAC for the removal of cadmium (cadmium ions and zinc (zinc ions from their aqueous solutions. All batch experiments were carried out at pH 7.0 and a constant temperature of 30+-1°C using an incubator shaker that operated at 150 rpm. The kinetics investigated includes the pseudo first order, the pseudo-second order and the intraparticle diffusion models. The pseudo-second order model correlate excellently the experimental data, suggesting that chemisorption processes could be the rate-limiting step. Keywords: adsorption, cadmium, kinetics, palm kernel shell, zinc

The Inhibitive Action Of Sodium Soya Sulphonate Towards The Corrosion Of Aluminium In Hydrochloric Acid

OpenAIRE

Mourad, M. Y.; Mead, A. I.; Seliman, S. A.

1993-01-01

The dissolution of aluminium in 2M hydrochloric acid in the presence of sodium soya sulphonate (SSS) as corrosion inhibitor has been studied using hydrogen evolution and thermometric methods. The two methods gave consistent results. The results obtained indicate that the inhibitive effect of the sulphonated mixture relates to chemisorption mechanism on the metal surface via the n electrons in the double bonds. تمت دراسة ذوبان الألمونيوم في محلول 2 مولارى من حمض الهيدروكلوريك في وجود سلفونا...

Vibrational relaxation and dissociation of D2(vj) on Cu(111)

International Nuclear Information System (INIS)

Cacciatore, M.; DeFelice, P.; Capitelli, M.

1992-01-01

The dissociative chemisorption of H 2 /D 2 with single crystal Cu surface has recently been the object of experimental and theoretical investigations. Here the authors present their results for the D 2 (vj)/Cu(111) system obtained within a semiclassical model developed for the interaction of molecules with non-rigid surfaces. The dissociation probability for D 2 in a specific initial (vj) state has been computed as a function of the impact energy and the surface temperature set to 300K. The quantum tunneling probability through the potential barriers has also been evaluated. The results show that the D 2 dissociation probability is smaller when compared to that of H 2 . The D 2 absorption probability, as well as the energy transferred to the surface phonons, is higher then that found for H 2

Creation of paired electron states in the gap of semiconducting carbon nanotubes by correlated hydrogen adsorption

International Nuclear Information System (INIS)

Buchs, Gilles; Krasheninnikov, Arkady V; Ruffieux, Pascal; Groening, Pierangelo; Foster, Adam S; Nieminen, Risto M; Groening, Oliver

2007-01-01

The specific, local modification of the electronic structure of carbon nanomaterials is as important for novel electronic device fabrication as the doping in the case of silicon-based electronics. Here, we report low temperature scanning tunneling microscopy and spectroscopy study of semiconducting carbon nanotubes subjected to hydrogen-plasma treatment. We show that plasma treatment mostly results in the creation of paired electronic states in the nanotube band gap. Combined with extensive first-principle simulations, our results provide direct evidence that these states originate from correlated chemisorption of hydrogen adatoms on the tube surface. The energy splitting of the paired states is governed by the adatom-adatom interaction, so that controlled hydrogenation can be used for engineering the local electronic structure of nanotubes and other sp 2 -bonded nanocarbon systems

Surface analysis by Fourier-transform infrared (FTIR) spectroscopy

International Nuclear Information System (INIS)

Powell, G.L.; Smyrl, N.R.; Fuller, E.L.

1981-01-01

A diffuse-reflectance capability for the Fourier transform infrared spectrometer at the Y-12 Plant Laboratory has been implemented. A sample cell with a 25 to 400 0 C temperature-controlled sample stage and an ultrahigh-vacuum-to-atmospheric pressure gas-handling capability has been developed. Absorbance of light from the spectrometer beam, resulting from the beam being scattered from a powder sample, can be measured. This capability of detecting molecular species on and in powders is to be used to study chemisorption on actinide and rare-earth metals, alloys, and compounds. Cell design is described along with experiments demonstrating its performance in detecting moisture absorption on uranium oxide, moisture and carbon dioxide absorption on the lithium hydride/hydroxide system, and carbon dioxide absorption on potassium borohydride. 13 figures

Catalisadores Ni/Al2O3 promovidos com molibdênio para a reação de reforma a vapor de metano Mo-Ni/AL2O3 catalysts for the methane steam reforming reaction

Directory of Open Access Journals (Sweden)

Silvia Sálua Maluf

2003-03-01

Full Text Available Mo-promoted Ni/Al2O3 catalysts for the methane steam reforming reaction were studied in this work. The Ni/Al2O3 catalysts were prepared by precipitation and molibdenum was added by impregnation up to 2%wt. The solids were tested using a micro-reactor under two H2Ov/C conditions and were characterized by ICP-OES, XRD, N2 adsoption, H2 chemisorption and TPR. NiO and NiAl2O4 phases were observed and the metallic area decreased with the increase of the Mo content. From the catalytic tests high stability was verified for H2Ov/C=4.0. On the other hand, only the catalyst containing 0,05% Mo stayed stable during 30 hours of the test at H2Ov/C=2.0.

BIOADSORPSI Hg(II OLEH PATI SAGU TAUT SILANG FOSFAT [Bioadsorption of Hg(II by Crosslinked Sago Starch Phosphate

Directory of Open Access Journals (Sweden)

Sri Sugiarti2

2012-12-01

Full Text Available Crosslinked-sago-starch-phosphate (SgP has been successfully synthesized from native sago starch (Sg and Na2HPO4-NaH2PO4 in an acidic condition. The compound was designed as bioadsorbent for removing Hg(II inside human digestion tract as shown by in vitro test. The bioadsorption followed pseudo-second order of reaction kinetic and Freundlich equation as chemisorption. As a result, 21% of Hg(II was removed at pH of 6.80 and reached the isothermal equilibrium of the bioadsorption at pH of 5.80 and 8.60 for 29.95% and 31.39%, respectively. The result showed that SgP is more feasible than activated carbon to be used as bioadsorbent in removing Hg(II in human digestion tract as proved by in vitro system.

Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

Energy Technology Data Exchange (ETDEWEB)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi [Dipartimento di Fisica e Astronomia, Università di Padova, via Marzolo 8, I–35131 Padova, Italy and DEMOCRITOS National Simulation Center of the Italian Istituto Officina dei Materiali (IOM) of the Italian National Research Council (CNR), Trieste (Italy)

2016-03-21

Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp{sup 2} hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

Anharmonic vibrational modes of chemisorbed H on the Rh(001) surface

International Nuclear Information System (INIS)

Hamann, D.R.; Feibelman, P.J.

1988-01-01

The potential for H atoms in the vicinity of the fourfold hollow chemisorption site on the Rh(001) surface at monolayer coverage is calculated using local-density-functional theory, and the linear-augmented-plane-wave method. The potential is found to contain important anharmonic components, one that couples parallel and perpendicular motion, and another producing azimuthal anisotropy. Variational solutions are found for the ground and low-lying excited states of H and D in this potential. The fundamental asymmetric- and symmetric-stretch H vibrational excitations are found to have energies of 67 and 92 meV. The latter agrees with recent experimental results, and higher-lying experimental modes are interpreted as mixed excitations. Comparisons are made with spring-constant models, calculated potentials for H on Ni and Pd(001), and theories of Bloch states for H on Ni

Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules

Science.gov (United States)

Rigoni, F.; Drera, G.; Pagliara, S.; Perghem, E.; Pintossi, C.; Goldoni, A.; Sangaletti, L.

2017-01-01

The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption.

Gas dynamics, optics and chemistry of an aircraft condensable wake

Energy Technology Data Exchange (ETDEWEB)

Grinats, E.S.; Kashevarov, A.V.; Stasenko, A.L. [Central Aerohydrodynamic Inst., Zhukovsky (Russian Federation)

1997-12-31

Prediction of the properties of a jet-and-vortex wake from an individual airplane is of great interest as the first step to assessment of the possible global changes in the atmosphere due to the world civil aviation. Several mathematical models of the different regions of an aircraft wake and corresponding numerical results are presented. The axisymmetric exhaust jet was simulated on the base of the well-known k-{epsilon} model of turbulence. Jet chemistry was investigated on the base of kinetic scheme of the gas phase reactions of enriched by including chemisorption by water droplets of several species and by taking into account of the photochemical processes. In the 3D far wake model, the numerical results for distribution of species exhausted by the engines and entrapped by the velocity field of two parallel vortices are shown. (R.P.) 7 refs.

CO chemistry/research trends in CO chemistry in the US

Energy Technology Data Exchange (ETDEWEB)

Cantacuzene, M

1978-10-01

Research trends in CO chemistry in the U.S. include the development of stable and selective homogeneous catalysts which would facilitate the removal of the heat of reaction and be resistant to sulfur poisoning for the methanation reaction, methanol synthesis, and Fischer-Tropsch synthesis; development of low-temperature homogeneous water gas shift catalysts; and research on the coordination chemistry and photochemical conversions of CO/sub 2/. In 1977, the National Science Foundation awarded 16 contracts for a total of $720,000 to promote the research in this field, including studies on chemisorption and heterogeneous catalysis (four contracts) and on transition metal complexes (ten contracts, of which seven are dedicated to metal clusters). Carbon monoxide-based processes, including water gas shift reactions, CO reduction to alkanes and alcohols, hydroformylation, and homogeneous carbonylation processes, recently developed in the U.S. are listed.

Thermodynamic and kinetic studies of As2O3 toxicological effects on human insulin in generation diabetes mellitus

Science.gov (United States)

Mohsennia, Mohsen; Motaharinejad, Atieh; Rafiee-Pour, Hossain-Ali; Torabbeigi, Marzieh

2017-12-01

The interaction of arsenic trioxide with human insulin was investigated by circular dichroism (CD), cyclic voltammetry and electrophoresis techniques. The interfacial behavior of insulin in presence of As2O3 onto the Ag electrode surface was studied at 310 K in phosphate buffer solution (PBS). According to Far-UV CD spectroscopy results, As2O3 caused to decrease in structural compactness and variety of alpha helix into beta structures. Near-UV CD indicated that As2O3 dissociates disulfide linkage in insulin structure. The kinetic parameters, including charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were also determined. The thermodynamic parameters of insulin denaturation in presence of arsenic trioxide were calculated and reported. The obtained results indicated strong adsorption of insulin in presence of arsenic trioxide onto the Ag surface via chemisorptions.

Gas dynamics, optics and chemistry of an aircraft condensable wake

Energy Technology Data Exchange (ETDEWEB)

Grinats, E S; Kashevarov, A V; Stasenko, A L [Central Aerohydrodynamic Inst., Zhukovsky (Russian Federation)

1998-12-31

Prediction of the properties of a jet-and-vortex wake from an individual airplane is of great interest as the first step to assessment of the possible global changes in the atmosphere due to the world civil aviation. Several mathematical models of the different regions of an aircraft wake and corresponding numerical results are presented. The axisymmetric exhaust jet was simulated on the base of the well-known k-{epsilon} model of turbulence. Jet chemistry was investigated on the base of kinetic scheme of the gas phase reactions of enriched by including chemisorption by water droplets of several species and by taking into account of the photochemical processes. In the 3D far wake model, the numerical results for distribution of species exhausted by the engines and entrapped by the velocity field of two parallel vortices are shown. (R.P.) 7 refs.

Effect of sp3-hybridized defects on the oscillatory behavior of carbon nanotube oscillators

International Nuclear Information System (INIS)

Guo, Taiyu; Ding, Tony Weixi; Pei, Qing-Xiang; Zhang, Yong-Wei

2011-01-01

Using molecular dynamics simulations, we investigate the oscillatory behaviors of carbon nanotube oscillators containing sp 3 -hybridized defects formed by hydrogen chemisorption. It is found that the presence of these defects significantly affects the kinetic and potential energies of the nanotube systems, which in turn affects their oscillation periods and frequencies. We have also studied the oscillatory characteristics of the oscillators containing sp 3 -hybridized Stone-Wales defects. Our results show that it is possible to control the motion of the inner nanotube by introducing sp 3 -hybridized defects on the outer nanotube, which provides a potential way to tune the oscillatory behavior of nanotube oscillators. -- Highlights: → sp 3 -hybridized defects increase energy dissipation. → sp 3 -hybridized defects arranged in a row have stronger effect than that in a ring. → sp 3 -hybridized defects reduces the effect of SW defects.

The effects of rare earths on activity and surface properties of Ru/γ-Al2O3 catalyst for water gas shift reaction

Directory of Open Access Journals (Sweden)

Laitao Luo

2007-04-01

Full Text Available A series of Ru-RE/γ- Al2O3 (RE = Ce, Pr, La, Sm, Tb or Gd and Ru/γ- Al2O3 catalysts were prepared by impregnation method. The influence of rare earths on the catalytic performance of Ru/γ- Al2O3 catalyst for the water gas shift reaction was studied. The catalysts were characterized by X-ray diffraction (XRD, temperature programmed reduction (TPR, temperature programmed desorption (TPD, and CO chemisorption. The results show that the addition of rare earths increases the catalytic activity of Ru based catalyst. Among these cerium is the most remarkably. The addition of cerium increases the active surface area, improves the dispersion of ruthenium, and weakens the interaction between ruthenium and the support. Cerium also affects the adsorption and reduction properties of Ru/γ-Al2O3 catalyst.

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

Science.gov (United States)

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

2005-12-15

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

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

Directory of Open Access Journals (Sweden)

Franziska Klitsche

2015-05-01

Full Text Available A common approach to generate tailored materials and nanoparticles (NPs is the formation of molecular monolayers by chemisorption of bifunctional anchor molecules. This approach depends critically on the choice of a suitable anchor group. Recently, bifunctional catecholates, inspired by mussel-adhesive proteins (MAPs and bacterial siderophores, have received considerable interest as anchor groups for biomedically relevant metal surfaces and nanoparticles. We report here the synthesis of new tripodal catecholates as multivalent anchor molecules for immobilization on metal surfaces and nanoparticles. The tripodal catecholates have been conjugated to various effector molecules such as PEG, a sulfobetaine and an adamantyl group. The potential of these conjugates has been demonstrated with the immobilization of tripodal catecholates on ZnO NPs. The results confirmed a high loading of tripodal PEG-catecholates on the particles and the formation of stable PEG layers in aqueous solution.

Evaluation of dum palm kernel activated carbon in chromium and lead adsorption from synthetic waste water

Directory of Open Access Journals (Sweden)

HI Mohammed

2016-09-01

Full Text Available This study aimed at the co-current removal of chromium and lead ions from synthetic waste water using dum palm kernel activated carbon. The adsorption experiment was conducted by varying time, pH and concentrations of the simulated solution. The data obtained were analyzed, and the best conditions for the uptake were at pH of 6, equilibrium time of 40 minutes. The two best isotherms models for the adsorption system were Sip, and Dubinin–Radushkevich, models respectively. Based on the Temkin adsorption energy calculated as 9.5793 and 0.4997 J/mol, the uptake of lead and chromium were chemisorption and physico-sorption, respectively. The maximum uptake calculated from Dubinin–Radushkevich plots were 14.1696 and 7.7191 mg/g, for lead and chromium, respectively.International Journal of Environment Vol.5(3 2016, pp.104-118

A nitride-based epitaxial surface layer formed by ammonia treatment of silicene-terminated ZrB{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Wiggers, F. B., E-mail: F.B.Wiggers@utwente.nl; Van Bui, H.; Schmitz, J.; Kovalgin, A. Y.; Jong, M. P. de [MESA+ Institute for Nanotechnology, University of Twente, 7500 AE Enschede (Netherlands); Friedlein, R.; Yamada-Takamura, Y. [School of Materials Science, Japan Advanced Institute of Science and Technology, Nomi, Ishikawa 923-1292 (Japan)

2016-04-07

We present a method for the formation of an epitaxial  surface layer involving B, N, and Si atoms on a ZrB{sub 2}(0001) thin film on Si(111). It has the potential to be an insulating growth template for 2D semiconductors. The chemical reaction of NH{sub 3} molecules with the silicene-terminated ZrB{sub 2}  surface was characterized by synchrotron-based, high-resolution core-level photoelectron spectroscopy and low-energy electron diffraction. In particular, the dissociative chemisorption of NH{sub 3} at 400 °C leads to surface  nitridation, and subsequent annealing up to 830 °C results in a solid phase reaction with the ZrB{sub 2} subsurface layers. In this way, a new nitride-based epitaxial  surface layer is formed with hexagonal symmetry and a single in-plane crystal orientation.

Anti-Corrosion Performance of 1,3-BENZOTHIAZOLE on 410 Martensitic Stainless Steel in H2SO4

Science.gov (United States)

Loto, Roland Tolulope

The corrosion inhibition effect of synthesized 1,3-benzothiazole at very low concentrations on 410 martensitic stainless steel in 3MH2SO4 solution was studied through potentiodynamic polarization and weight loss measurements. The observation showed that the organic compound performed effectively with average inhibition efficiencies of 94% and 98% at the concentrations studied from both electrochemical methods due to the inhibition action of protonated inhibitor molecules in the acid solution. The amine and aromatics functional groups of the molecules active in the corrosion inhibition reaction were exposed from Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) spectroscopic analysis. Thermodynamic calculations showed cationic adsorption to be chemisorption adsorption, obeying the Langmuir adsorption isotherm. Images from optical microscopy showed an improved morphology in comparison to images from corroded stainless steel. Severe surface deterioration and macro-pits were observed in the uninhibited samples.

Scanning Tunneling Microscopic Observation of Adatom-Mediated Motifs on Gold-Thiol Self-assembled Monolayers at High Coverage

DEFF Research Database (Denmark)

Wang, Yun; Chi, Qijin; Hush, Noel S.

2009-01-01

the structural motifs observed on surfaces at low coverage and on gold nanoparticles to the observed spectroscopic properties of high-coverage SAMs formed by methanethiol. However, the significant role attributed to intermolecular steric packing effects suggests a lack of generality for the adatom-mediated motif......Self-assembled monolayers (SAMs) formed by chemisorption of a branched-chain alkanethiol, 2-methyl-1-propanethiol, on Au(111) surfaces were studied by in situ scanning tunneling microscopy (STM) under electrochemical potential control and analyzed using extensive density functional theory (DFT...... two R−S−Au−S−R adatom-mediated motifs per surface cell, with steric-induced variations in the adsorbate alignment inducing the observed STM image contrasts. Observed pits covering 5.6 ± 0.5% of the SAM surface are consistent with this structure. These results provide the missing link from...

Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

International Nuclear Information System (INIS)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2016-01-01

Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp 2 hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

A Quantitative PCR-Electrochemical Genosensor Test for the Screening of Biotech Crops

Directory of Open Access Journals (Sweden)

Suely Moura-Melo

2017-04-01

Full Text Available The design of screening methods for the detection of genetically modified organisms (GMOs in food would improve the efficiency in their control. We report here a PCR amplification method combined with a sequence-specific electrochemical genosensor for the quantification of a DNA sequence characteristic of the 35S promoter derived from the cauliflower mosaic virus (CaMV. Specifically, we employ a genosensor constructed by chemisorption of a thiolated capture probe and p-aminothiophenol gold surfaces to entrap on the sensing layer the unpurified PCR amplicons, together with a signaling probe labeled with fluorescein. The proposed test allows for the determination of a transgene copy number in both hemizygous (maize MON810 trait and homozygous (soybean GTS40-3-2 transformed plants, and exhibits a limit of quantification of at least 0.25% for both kinds of GMO lines.

Prospects of Fe/MCM-41 as a Catalyst for Hydrocarbon Synthesis

International Nuclear Information System (INIS)

Cagnoli, Maria V.; Gallegos, Norma G.; Bengoa, Jose F.; Alvarez, Ana M.; Marchetti, Sergio G.; Moreno, Sergio M. J.; Roig, Anna; Mercader, Roberto C.

2005-01-01

We report the synthesis of cylindrical nanoparticles of metallic Fe entirely included in MCM-41 pores. Their dimensions are approx.3 nm diameter and approx. 3.8 nm length. We show that a coherent analysis of the results yielded by the various techniques is essential to obtain a catalyst supported on an MCM-41 matrix of ≅ 3 nm average pore diameter, which is active and selective toward olefins. The solids were characterized by low-angle x-ray diffraction, high-resolution transmission electron microscopy, high-resolution scanning transmission electron microscopy equipped with a high-angle annular dark-field, CO chemisorption, volumetric oxidation, and Moessbauer spectroscopy (in controlled atmosphere for the reduced catalysts). Catalytic results in the Fischer-Tropsch synthesis, as well as some unexpected results --like the inhomogeneous pore filling and discontinuous Fe particles-- are also discussed

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

Science.gov (United States)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

Science.gov (United States)

Birkner, Nancy; Navrotsky, Alexandra

2014-04-29

Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

Reactivity of non-stoichiometric black alumina; Reactivite des alumines noires non stoechiometriques

Energy Technology Data Exchange (ETDEWEB)

Arghiropoulos, B; Elston, J; Hilaire, P; Juillet, F; Teichner, S J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; [Lyon-1 Univ., 69 (France)

1960-07-01

Oxides such as alumina, when divided or poorly crystallized, show enhanced physico-chemical properties with respect to those of non-divided crystals of the same solids. A stoichiometric difference may even be produced in the alumina, which brings about a new modification of its properties. However its characteristics of hydrogen chemisorption or of catalytic activity in ethylene hydrogenation do not appear to depend on the stoichiometric difference. (author) [French] Les oxydes, comme l'alumine, divises ou mal cristallises, presentent des proprietes physico-chimiques exaltees par rapport a celles des memes solides en cristaux non divises. Un ecart a la stoechiometrie peut meme etre produit dans l'alumine, ce qui entraine une nouvelle modification de ses proprietes. Toutefois ses caracteristiques de chimisorption d'hydrogene ou d'activite catalytique d'hydrogenation d'ethylene ne semblent pas dependre de l'ecart a la stoechiometrie. (auteur)

A DFT-based genetic algorithm search for AuCu nanoalloy electrocatalysts for CO2 reduction

DEFF Research Database (Denmark)

Lysgaard, Steen; Mýrdal, Jón Steinar Garðarsson; Hansen, Heine Anton

2015-01-01

Using a DFT-based genetic algorithm (GA) approach, we have determined the most stable structure and stoichiometry of a 309-atom icosahedral AuCu nanoalloy, for potential use as an electrocatalyst for CO2 reduction. The identified core–shell nano-particle consists of a copper core interspersed....... This shows that the mixed Cu135@Au174 core–shell nanoalloy has a similar adsorption energy, for the most favorable site, as a pure gold nano-particle. Cu, however, has the effect of stabilizing the icosahedral structure because Au particles are easily distorted when adding adsorbates....... that it is possible to use the LCAO mode to obtain a realistic estimate of the molecular chemisorption energy for systems where the computation in normal grid mode is not computationally feasible. These corrections are employed when calculating adsorption energies on the Cu, Au and most stable mixed particles...

Association/dissociation in dense gases and adsorption/desorption on surfaces

International Nuclear Information System (INIS)

Flannery, M.R.

1984-01-01

A new comprehensive theory is described for the time evolution towards equilibrium of association and dissociation in a dense gas. Expressions are formulated and are illustrated for the net probabilities of association to stable vibrational levels and dissociation to the continuum from an arbitrary bound vibrational level via collision with the thermal gas bath. A general variational principle emerges: The rate which corresponds to the overall direction of the process always adjusts itself to a minimum and the time evolution towards equilibrium is hindered. Analogy is established with Kirchhoff's Laws and Tellegen's Theorem for electrical networks, and with the Principle of Least Dissipation basic to thermodynamics, heat conduction, and fluid mechanics. The theory can also be modified to provide the first basic microscopic account of Associative Desorption of atoms from and Dissociative Chemisorption of molecules to surfaces

Investigation of electronic band structure and charge transfer mechanism of oxidized three-dimensional graphene as metal-free anodes material for dye sensitized solar cell application

Science.gov (United States)

Loeblein, Manuela; Bruno, Annalisa; Loh, G. C.; Bolker, Asaf; Saguy, Cecile; Antila, Liisa; Tsang, Siu Hon; Teo, Edwin Hang Tong

2017-10-01

Dye-sensitized solar cells (DSSCs) offer an optimal trade-off between conversion-efficiency and low-cost fabrication. However, since all its electrodes need to fulfill stringent work-function requirements, its materials have remained unchanged since DSSC's first report early-90s. Here we describe a new material, oxidized-three-dimensional-graphene (o-3D-C), with a band gap of 0.2 eV and suitable electronic band-structure as alternative metal-free material for DSSCs-anodes. o-3D-C/dye-complex has a strong chemical bonding via carboxylic-group chemisorption with full saturation after 12 sec at capacity of ∼450 mg/g (600x faster and 7x higher than optimized metal surfaces). Furthermore, fluorescence quenching of life-time by 28-35% was measured demonstrating charge-transfer from dye to o-3D-C.

Adsorption-induced gap states of h-BN on metal surfaces

Science.gov (United States)

Preobrajenski, A. B.; Krasnikov, S. A.; Vinogradov, A. S.; Ng, May Ling; Käämbre, T.; Cafolla, A. A.; Mårtensson, N.

2008-02-01

The formation of hexagonal boron nitride (h-BN) monolayers on Ni(111), Rh(111), and Pt(111) has been studied by a combination of x-ray emission, angle-resolved valence band photoemission, and x-ray absorption in search for interface-induced gap states of h-BN . A significant density of both occupied and unoccupied gap states with N2p and B2p characters is observed for h-BN/Ni(111) , somewhat less for h-BN/Rh(111) and still less for h-BN/Pt(111) . X-ray emission shows that the h-BN monolayer is chemisorbed strongly on Ni(111) and very weakly on Pt(111). We associate the gap states of h-BN adsorbed on the transition metal surfaces with the orbital mixing and electron sharing at the interface because their density increases with the growing strength of chemisorption.

On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets

DEFF Research Database (Denmark)

Falsig, Hanne; Shen, Juan; Khan, Tuhin Suvra

2014-01-01

We present a study of the dissociative chemisorption of NO, O2, and N2 over close-packed, stepped, kinked, and open (fcc {111}, {211}, {311}, {532}, {100}, and {110}) transition metal facets using density functional theory (DFT). The offset of the Bronsted-Evans-Polanyi (BEP) relations suggest......} rate. The ordering of the maximum activity over the facets is: {110} > {100} similar to {532} > {311} similar to {211} > {111}, which is in general agreement with the offset in the BEP relations. We show that the top-point location and shape of the volcano relations are approximately independent...... for generally obtaining quantitative agreement between theory and experiments is for the simulations to address in detail the propensities of the various types of active sites. Finally, we show that the ordering of NO decomposition rates among metals and facets is essentially unaltered when using BEP...

Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

Science.gov (United States)

Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

2012-08-16

Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

KAUST Repository

Basset, Jean-Marie

2016-06-09

The design of novel heterogeneous catalysts with multiple adjacent functionalities is of high interest for heterogeneous catalysis. Herein, we report a method to obtain a majority bifunctional acid-base pairs on SBA15. Aniline reacts with SBA15 by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear polarization enhanced ²⁹Si and ¹⁵N spectra demonstrate both the close proximity between the two moieties and the formation of a covalent Si-N surface bond and confirm the design of vicinal acid-base pairs. This approach was successfully applied to the design of a series of aniline derivatives bifunctional SBA15. A correlation of the substituents effects on the aromatic ring (Hammet parameters) on the kinetics of the model reaction of Knoevenagel is observed.

Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

KAUST Repository

Basset, Jean-Marie; Hamzaoui, Bilel; Bendjeriou-Sedjerari, Anissa; Pump, Eva; Abou-Hamad, Edy; Sougrat, Rachid; Gurinov, Andrei; Huang, Kuo-Wei; Gajan, David; Lesage, Anne; Emsley, Lyndon

2016-01-01

by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear

Correlation of Chemisorption and Electronic Effects for Metal Oxide Interfaces: Transducing Principles for Temperature Programmed Gas Microsensors. Final Report

International Nuclear Information System (INIS)

Semancik, S.; Cavicchi, R. E.; DeVoe, D. L.; McAvoy, T. J.

2001-01-01

This Final Report describes efforts and results for a 3-year DoE/OST-EMSP project centered at NIST. The multidisciplinary project investigated scientific and technical concepts critical for developing tunable, MEMS-based, gas and vapor microsensors that could be applied for monitoring the types of multiple analytes (and differing backgrounds) encountered at DoE waste sites. Micromachined ''microhotplate'' arrays were used as platforms for fabricating conductometric sensor prototypes, and as microscale research tools. Efficient microarray techniques were developed for locally depositing and then performance evaluating thin oxide films, in order to correlate gas sensing characteristics with properties including composition, microstructure, thickness and surface modification. This approach produced temperature-dependent databases on the sensitivities of sensing materials to varied analytes (in air) which enable application-specific tuning of microsensor arrays. Mechanistic studies on adsorb ate transient phenomena were conducted to better understand the ways in which rapid temperature programming schedules can be used to produce unique response signatures and increase information density in microsensor signals. Chemometric and neural network analyses were also employed in our studies for recognition and quantification of target analytes

Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes.

Science.gov (United States)

Song, Jiangxuan; Gordin, Mikhail L; Xu, Terrence; Chen, Shuru; Yu, Zhaoxin; Sohn, Hiesang; Lu, Jun; Ren, Yang; Duan, Yuhua; Wang, Donghai

2015-03-27

Despite the high theoretical capacity of lithium-sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g(-1) after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm(-2)) with a high sulfur loading of approximately 5 mg cm(-2), which is ideal for practical applications of the lithium-sulfur batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cu-based metal–organic framework/activated carbon composites for sulfur compounds removal

Energy Technology Data Exchange (ETDEWEB)

Shi, Rui-Hua [State Key Laboratory of Coal Science and Technology, Co-founded by Shanxi Province and the Ministry of Science and Technology, Institute for Chemical Engineering of Coal, Taiyuan University of Technology, West Yingze Street Number 79, Taiyuan 030024 (China); Zhang, Zhen-Rong [Institute of Applied Chemical, Shanxi (China); Fan, Hui-Ling, E-mail: fanhuiling@tyut.edu.cn [State Key Laboratory of Coal Science and Technology, Co-founded by Shanxi Province and the Ministry of Science and Technology, Institute for Chemical Engineering of Coal, Taiyuan University of Technology, West Yingze Street Number 79, Taiyuan 030024 (China); Zhen, Tian [Deparment of Analysis and Service Center Micromertics instrumental Ltd, Shanghai (China); Shangguan, Ju; Mi, Jie [State Key Laboratory of Coal Science and Technology, Co-founded by Shanxi Province and the Ministry of Science and Technology, Institute for Chemical Engineering of Coal, Taiyuan University of Technology, West Yingze Street Number 79, Taiyuan 030024 (China)

2017-02-01

Highlights: • Incorporation of AC less than 2% in MOF-199 can increase micropores and BET surface area, as evidenced by N{sub 2} adsorption. • Lewis acid (unsaturated copper) sites could also be increased in the modified MOF-199, as revealed by Py-IR characterization. • Composite with 2% AC showed highest sulfur capacity with 8.46 and 8.53% for H{sub 2}S and CH{sub 3}SCH{sub 3}, respectively. • The adsorption of CH{sub 3}SCH{sub 3} on composite is reversible, physic-adsorption and weak chemisorption were involved. - Abstract: MOF-199 was modified by incorporating activated carbon (AC) during its synthesis under hydrothermal conditions to improve its performance in the removal of hydrogen sulfide (H{sub 2}S) and dimethyl sulfide (CH{sub 3}SCH{sub 3}). A variety of different characterization techniques including X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, nitrogen adsorption/desorption isotherms, scanning electron microscopy (SEM), pyridine adsorption infrared spectroscopy (Py-IR), thermogravimetric- mass spectroscopy (TG-MS) and X-ray photoelectron spectroscopy (XPS) were used to analyze the fresh and exhausted composites. It was found that the composites, which have an amount of AC of less than 2%, had the same morphology as those of pristine MOF-199, but exhibited a more ordered crystallinity structure as well as higher surface area. The composite with 2% AC incorporation showed highest sulfur capacity of 8.46 and 8.53% for H{sub 2}S and CH{sub 3}SCH{sub 3}, respectively, which increased by 51 and 41% compared to that of MOF-199. This improvement was attributed to the formation of more micropores and especially the increased number of unsaturated copper metal sites, as revealed by Py-IR. It is suggested the chemical reaction was apparent during adsorption of H{sub 2}S, which resulted in the formation of CuS and the collapse of the MOF structure. Whereas reversible chemisorption was found for CH{sub 3}SCH{sub 3} adsorption, as

Interaction of hydrogen and oxygen with bulk defects and surfaces of metals

International Nuclear Information System (INIS)

Besenbacher, F.

1994-05-01

The thesis deals with the interaction of hydrogen with defects in metals and the interaction of hydrogen and oxygen with metal surfaces studied by ion-beam techniques and scanning tunneling microscopy (STM), respectively. The first part of the thesis discusses the interaction of hydrogen with simple defects in transition metals. The trap-binding enthalpies and the lattice location of hydrogen trapped to vacancies have been determined, and an extremely simple and versatile picture of the hydrogen-metal interaction has evolved, in which the trap strength is mainly determined by the local electron density. Any dilution of the lattice will lead to a trap, vacancies and voids being the strongest trap. It is found that hydrogen trapped to vacancies in fcc metals is quantum-mechanically delocalized, and the excitation energies for the hydrogen in the vacancy potential are a few MeV only. The interaction of hydrogen with metal surfaces is studied by the transmission channeling (TC) technique. It is found that hydrogen chemisorbs in the highest-coordinated sites on the surfaces, and that there is a direct relationship between the hydrogen-metal bond length and the coordination number for the hydrogen. In the final part of the thesis the dynamics of the chemisorption process for oxygen and hydrogen on metal surfaces is studied by STM, a fascinating and powerful technique for exploring the atomic-scale realm of surfaces. It is found that there is a strong coupling between the chemisorption process and the distortion of the metal surface. The adsorbates induce a surface reconstruction, i.e. metal-metal bond breaks and metal-adsorbate bounds form. Whereas hydrogen interacts weakly with the metals and induces reconstructions where only nnn metals bonds are broken, oxygen interacts strongly with the metal, and the driving force for the O-induced reconstructions appears to be the formation of low-coordinated metal-O rows, formed by breaking of nn metal bonds. Finally it is shown

Direct Flotation of Niobium Oxide Minerals from Carbonatite Niobium Ores

Science.gov (United States)

Ni, Xiao

Currently the recovery of niobium oxide minerals from carbonatite niobium ores relies on the use of non-selective cationic collectors. This leads to complicated process flowsheets involving multiple desliming and multiple reverse flotation stages, and low niobium recovery. In this research, anionic collectors that are capable of strong chemisorption on the niobium minerals were studied with the objective of directly floating the niobium oxide minerals from the carbonatite ores. In the flotation of both high purity minerals and Niobec ores, it was shown that the combination of hydroxamic acid and sodium metaphosphate was an effective reagent scheme for the direct flotation of niobium oxide from its ores. Batch flotation on the Niobec Mill Feed showed that over 95% of niobium oxide was recovered into a rougher concentrate that was less than 47% of the original feed mass. Preliminary cleaning tests showed that the reagent scheme could also be used to upgrade the rougher concentrate, although the depression of iron oxide minerals required further study. X-ray photoelectron spectroscopic (XPS) measurement results confirm that OHA (octyl hydroxamic acid) could chemisorb on pyrochlore surface while only physically adsorb on calcite, judging by the chemical shifts of electron binding energies in the elements in both OHA and the mineral surfaces. When hydroxamic acid was adsorbed on calcite surface, the binding energies of the N 1s electrons, at 400.3 eV, did not shift. However, after adsorption on pyrochlore, the N 1s binding energy peak split into two peaks, one at a binding energy of around 399 eV, representing chemically adsorbed OHA, the other at between 400 and 401 eV. The experimental data suggested a strong chemisorption of the OHA on pyrochlore surface in the form of a vertical head-on orientation of the OHA molecules so that the pyrochlore was strongly hydrophobized even at low OHA concentrations, followed by possibly randomly oriented physisorbed OHA molecules

Interaction of tetraethoxysilane with OH-terminated SiO{sub 2} (0 0 1) surface: A first principles study

Energy Technology Data Exchange (ETDEWEB)

Deng, Xiaodi, E-mail: dixiaodeng@gmail.com [Department of Engineering Physics, Tsinghua University, Beijing 100084 (China); Song, Yixu, E-mail: songyixu@163.com [State Key Laboratory on Intelligent Technology and Systems, Tsinghua National Laboratory for Information Science and Technology, Department of Computer Science and Technology, Tsinghua University, Beijing 100084 (China); Li, Jinchun [Institute of Applied Physics, University of Science and Technology Beijing, Beijing 100083 (China); Pu, Yikang [Department of Engineering Physics, Tsinghua University, Beijing 100084 (China)

2014-06-01

First principles calculates have been performed to investigate the surface reaction mechanism of tetraethoxysilane (TEOS) with fully hydroxylated SiO{sub 2}(0 0 1) substrate. In semiconductor industry, this is the key step to understand and control the SiO{sub 2} film growth in chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes. During the calculation, we proposed a model which breaks the surface dissociative chemisorption into two steps and we calculated the activation barriers and thermochemical energies for each step. Our calculation result for step one shows that the first half reaction is thermodynamically favorable. For the second half reaction, we systematically studied the two potential reaction pathways. The comparing result indicates that the pathway which is more energetically favorable will lead to formation of crystalline SiO{sub 2} films while the other will lead to formation of disordered SiO{sub 2} films.

Effect of preparation method on catalytic activity of Ni/ γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Miranda Morales, Barbara

2017-01-01

The performance of catalysts was shown to be strongly dependent on their methods of preparation. A study to examine the relationship between catalyst preparation procedures and the structure, dispersion, activity, and selectivity of the finished catalyst is reported. 10 wt.%Ni/γ-Al 2 O 3 catalysts were prepared by incipient wetness impregnation and by wet impregnation. The catalysts were used in the conversion of glycerol in gas phase and atmospheric pressure. The selectivity and activity of the catalysts were affected by the preparation method employed. The catalysts were characterized by thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), N 2 -physorption, H 2 -chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and temperature-programmed oxidation (TPO). The Ni particle size and dispersion of the catalysts affected the selectivity to hydrogenolysis and dehydration routes, and the formation of carbon deposits was also affected. (author) [es

An AgI@g-C3N4 hybrid core@shell structure: Stable and enhanced photocatalytic degradation

Science.gov (United States)

Liu, Li; Qi, Yuehong; Yang, Jinyi; Cui, Wenquan; Li, Xingang; Zhang, Zisheng

2015-12-01

A novel visible-light-active material AgI@g-C3N4 was prepared by ultrasonication/chemisorption method. The core@shell structure AgI@g-C3N4 catalyst showed high efficiency for the degradation of MB under visible light irradiation (λ > 420 nm). Nearly 96.5% of MB was degraded after 120 min of irradiation in the presence of the AgI@g-C3N4 photocatalyst. Superior stability was also observed in the cyclic runs indicating that the as prepared hybrid composite is highly desirable for the remediation of organic contaminated wastewaters. The improved photocatalytic performance is due to synergistic effects at the interface of AgI and g-C3N4 which can effectively accelerate the charge separation and reinforce the photostability of hybrid composite. The possible mechanism for the photocatalytic activity of AgI@g-C3N4 was tentatively proposed.

Hemimorphite Flotation with 1-hydroxydodecylidene-1,1-diphosphonic acid and Its Mechanism

Directory of Open Access Journals (Sweden)

Wen Tan

2018-01-01

Full Text Available 1-hydroxydodecylidene-1,1-diphosphonic acid (HDDPA was prepared and first applied in flotation of hemimorphite. HDDPA exhibited superior flotation performances for recovery of hemimorphite in comparison with lauric acid, and it also possessed good selectivity against quartz flotation under pH 7.0–11.0. Contact angle results revealed that HDDPA preferred to attach on hemimorphite rather than quartz and promoted the hydrophobicity of hemimorphite surfaces. In the presence of HDDPA anions, the zeta potential of hemimorphite particles shifted to more negative value even if hemimorphite was negatively charged, inferring a strong chemisorption of hemimorphite to HDDPA. The Fourier transform infrared (FTIR recommended that HDDPA might anchor on hemimorphite surfaces through bonding the oxygen atoms of its P(=O–O groups with surface Zn(II atoms. X-ray photoelectron spectroscopy (XPS gave additional evidence that the Zn(II-HDDPA surface complexes were formed on hemimorphite.

Layered-Double-Hydroxide Nanosheets as Efficient Visible-Light-Driven Photocatalysts for Dinitrogen Fixation.

Science.gov (United States)

Zhao, Yufei; Zhao, Yunxuan; Waterhouse, Geoffrey I N; Zheng, Lirong; Cao, Xingzong; Teng, Fei; Wu, Li-Zhu; Tung, Chen-Ho; O'Hare, Dermot; Zhang, Tierui

2017-11-01

Semiconductor photocatalysis attracts widespread interest in water splitting, CO 2 reduction, and N 2 fixation. N 2 reduction to NH 3 is essential to the chemical industry and to the Earth's nitrogen cycle. Industrially, NH 3 is synthesized by the Haber-Bosch process under extreme conditions (400-500 °C, 200-250 bar), stimulating research into the development of sustainable technologies for NH 3 production. Herein, this study demonstrates that ultrathin layered-double-hydroxide (LDH) photocatalysts, in particular CuCr-LDH nanosheets, possess remarkable photocatalytic activity for the photoreduction of N 2 to NH 3 in water at 25 °C under visible-light irradiation. The excellent activity can be attributed to the severely distorted structure and compressive strain in the LDH nanosheets, which significantly enhances N 2 chemisorption and thereby promotes NH 3 formation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of Cd (II) from water using the waste of jatropha fruit ( Jatropha curcas L.)

Science.gov (United States)

Nacke, Herbert; Gonçalves, Affonso Celso; Coelho, Gustavo Ferreira; Schwantes, Daniel; Campagnolo, Marcelo Angelo; Leismann, Eduardo Ariel Völz; Junior, Élio Conradi; Miola, Alisson Junior

2017-10-01

The aim of this work was to evaluate the removal of Cd (II) from water using three biosorbents originated from the biomass of jatropha (bark, endosperm, and endosperm + tegument). For that, batch tests were performed to verify the effect of solution pH, adsorbent mass, contact time, initial concentration of Cd (II), and the temperature of the process. The adsorption process was evaluated by the studies of kinetics, isotherms, and thermodynamics. The ideal conditions of solution pH were 5.5 and 8 g L-1 of adsorbent mass of biosorbents by solution volume, with an equilibrium time of 60 min. According to the Langmuir model, the maximum adsorption capacity for bark, endosperm, and bark + endosperm of jatropha was, respectively, 29.665, 19.562, and 34.674 mg g-1, predominating chemisorption in monolayers. The biosorbents presented potential for the remediation of waters contaminated with Cd (II).

Ab initio modeling of Al adsorption on CaF2 surfaces

International Nuclear Information System (INIS)

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

2008-01-01

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

Trends in reactivity of oxides

DEFF Research Database (Denmark)

Toftelund, Anja

The results in this thesis are based on Density Functional Theory calculations. The catalytic activity of oxides and other compound materials are investigated. It is found that the adsorption energy of the molecules NH2, NH, OH and SH on transition metal nitride, oxide and sulfide surfaces scales......, and I) and OH on a wide range of rutile oxide surfaces. Furthermore, Brønsted-Evans-Polanyi (BEP) relations are found for the adsorption of a large number of molecules (including Cl, Br and I) on transition metal oxides. In these relations the activation energies scale linearly with the dissociative...... chemisorption energies. It turns out that the BEP relation for rutile oxides is almost coinciding with the dissociation line, i.e. no barrier exists for the reactive surfaces. The heterogeneous catalytic oxidation of hydrogen halides (HCl, HBr, and HI) is investigated. A micro-kinetic model is solved...

Hydrogen storage in N- and B-doped graphene decorated by small platinum clusters: A computational study

Science.gov (United States)

Chen, I.-Nan; Wu, Shiuan-Yau; Chen, Hsin-Tsung

2018-05-01

In this work, we perform density functional theory (DFT) calculations to investigate the hydrogen adsorption on Pt4 cluster supported on pristine, B-, and N-doped graphene sheets. It is found that the doping B or N atom in the graphene could enhance the interaction between the Pt4 cluster and the supporting substrate. The first H2 molecule is found to be dissociative chemisorption on the three substrates. Further, dissociative and molecular adsorption of multiple H2 molecules are co-adsorbed on the three substrates. In addition, the interaction between Pt4(H2)x and the substrate is illustrated for the stability of Pt4(H2)x on the substrate. AIMD simulation is also performed to verify the stability and hydrogen storage. Accordingly, the B-graphene is predicted to be the most potential materials for hydrogen storage among these three materials.

The inhibition effect and mechanism of L-cysteine on the corrosion of bronze covered with a CuCl patina

International Nuclear Information System (INIS)

Wang, Tianran; Wang, Julin; Wu, Yuqing

2015-01-01

Highlights: • CuCl patina was synthesized on bronze electrodes with electrochemical method. • L-cysteine was used as a green inhibitor for bronze covered with CuCl patina. • The inhibition efficiency reached above 90%. • The inhibition mechanism of L-cysteine on CuCl patina was investigated. - Abstract: CuCl patina was synthesized on bronze electrodes with electrochemical method. The inhibition effect and mechanism of L-cysteine (Cys) on bronze covered with CuCl patina have been studied with electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) techniques. The EIS results show that Cys stabilized the CuCl patina to a great extent. The hydrolysis reaction of CuCl was inhibited effectively and an inhibition efficiency of over 90% was achieved. The XPS analyses indicate that the chemisorption of Cys molecules on CuCl surface occurred through sulfur atom in thiol and nitrogen atom in amino group

Selective depression of titanaugite in the ilmenite flotation with carboxymethyl starch

Science.gov (United States)

Meng, Qingyou; Yuan, Zhitao; Yu, Li; Xu, Yuankai; Du, Yusheng; Zhang, Chen

2018-05-01

In order to intensify the flotation separation of ilmenite from titanaugite, surface modification of mineral particles was carried out using carboxymethyl starch (CMS) by microflotation experiments, zeta potential measurements, Fourier transform infrared (FTIR) and atomic force microscopy (AFM) analysis. Microflotation results showed that CMS was a selective depressant, and it effectively enhanced the floatability difference between ilmenite and titanaugite in the pH range from 6.0 to 10.0. As it was revealed by the zeta potential, FTIR and AFM analysis, the CMS adsorption occurred onto mineral surfaces through chemisorption and hydrogen bonding, while CMS exhibited a stronger interaction with titanaugite than ilmenite. After that, the CMS adsorption impeded the adsorption of sodium oleate collector on titanaugite surfaces, giving rise to a concomitant decrease in the floatability of titanaugite. These findings exhibit great potential for CMS application in the selective flotation of ilmenite.

Random and cooperative sequential adsorption

Science.gov (United States)

Evans, J. W.

1993-10-01

Irreversible random sequential adsorption (RSA) on lattices, and continuum "car parking" analogues, have long received attention as models for reactions on polymer chains, chemisorption on single-crystal surfaces, adsorption in colloidal systems, and solid state transformations. Cooperative generalizations of these models (CSA) are sometimes more appropriate, and can exhibit richer kinetics and spatial structure, e.g., autocatalysis and clustering. The distribution of filled or transformed sites in RSA and CSA is not described by an equilibrium Gibbs measure. This is the case even for the saturation "jammed" state of models where the lattice or space cannot fill completely. However exact analysis is often possible in one dimension, and a variety of powerful analytic methods have been developed for higher dimensional models. Here we review the detailed understanding of asymptotic kinetics, spatial correlations, percolative structure, etc., which is emerging for these far-from-equilibrium processes.

Removal of Lead Hydroxides Complexes from Solutions Formed in Silver/Gold: Cyanidation Process

Science.gov (United States)

Parga, José R.; Martinez, Raul Flores; Moreno, Hector; Gomes, Andrew Jewel; Cocke, David L.

2014-04-01

The presence of lead hydroxides in "pregnant cyanide solution" decreases the quality of the Dore obtained in the recovery processes of gold and silver, so it is convenient to remove them. The adsorbent capacity of the low cost cow bone powder was investigated for the removal of lead ions from a solution of lead hydroxide complexes at different initial metal ion concentrations (10 to 50 mg/L), and reaction time. Experiments were carried out in batches. The maximum sorption capacity of lead determined by the Langmuir model was found to be 126.58 mg/g, and the separation factor R L was between 0 and 1, indicating a significant affinity of bone for lead. Experimental data follow pseudo-second order kinetics suggesting chemisorption. It is concluded that cow bone powder can be successfully used for the removal of lead ions, and improves the quality of the silver-gold cyanides precipitate.

Modification of Ni(111) reactivity toward CH4, CO, and D2 by two-dimensional alloying

DEFF Research Database (Denmark)

Holmblad, Peter Mikal; Nielsen, Jane Hvolbæk; Chorkendorff, Ib

1996-01-01

. In TPD spectra of deuterium saturated surface alloys a new clearly resolved desorption state is observed at 180-220 K with maximum intensity around theta(Au)=0.3-0.4 ML. This state is clearly related to chemisorption sites involving both Au and Ni. A site model based on mean field statistics adequately......Alloying Au into the outermost atomic layer of Ni(111) significantly alters the physical and chemical properties of the surface. The reactivity is investigated by the use of seeded supersonic molecular beams of CH4 and it is found that the nobleness of Au reduces the overall reactivity toward CH4....... This is accounted for in an ensemble model resolving the sticking probability on Ni atoms having different nearest neighbor surroundings. Although a mean field description of site distributions is found to be a very good approximation it is improved by using experimentally determined ensemble statistics from STM...

In vitro behaviour of nanocrystalline silver-sputtered thin films

International Nuclear Information System (INIS)

Piedade, A P; Vieira, M T; Martins, A; Silva, F

2007-01-01

Silver thin films were deposited with different preferential orientations and special attention was paid to the bioreactivity of the surfaces. The study was essentially focused on the evaluation of the films by x-ray diffraction (XRD), atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), electron probe microanalysis (EPMA) and contact angle measurements. The deposited thin films were characterized before and after immersion in S-enriched simulated human plasma in order to estimate the influence of the preferential crystallographic orientation on the in vitro behaviour. Silver thin films with and without (111) preferential crystallographic orientation were deposited by r.f. magnetron sputtering to yield nanocrystalline coatings, high compact structures, very hydrophobic surfaces and low roughness. These properties reduce the chemisorption of reactive species onto the film surface. The in vitro tests indicate that silver thin films can be used as coatings for biomaterials applications

Balance of Nanostructure and Bimetallic Interactions in Pt Model Fuel Cell Catalysts

DEFF Research Database (Denmark)

Friebel, Daniel; Viswanathan, Venkatasubramanian; Miller, Daniel J.

2012-01-01

We have studied the effect of nanostructuring in Pt monolayer model electrocatalysts on a Rh(111) single-crystal substrate on the adsorption strength of chemisorbed species. In situ high energy resolution fluorescence detection X-ray absorption spectroscopy at the Pt L3 edge reveals characteristic...... changes of the shape and intensity of the “white-line” due to chemisorption of atomic hydrogen (Had) at low potentials and oxygen-containing species (O/OHad) at high potentials. On a uniform, two-dimensional Pt monolayer grown by Pt evaporation in ultrahigh vacuum, we observe a significant destabilization...... of both Had and O/OHad due to strain and ligand effects induced by the underlying Rh(111) substrate. When Pt is deposited via a wet-chemical route, by contrast, three-dimensional Pt islands are formed. In this case, strain and Rh ligand effects are balanced with higher local thickness of the Pt islands...

Insight into biosorption equilibrium, kinetics and thermodynamics of crystal violet onto Ananas comosus (pineapple) leaf powder

Science.gov (United States)

Chakraborty, Sagnik; Chowdhury, Shamik; Saha, Papita Das

2012-06-01

Biosorption performance of pineapple leaf powder (PLP) for removal of crystal violet (CV) from its aqueous solutions was investigated. To this end, the influence of operational parameters such as pH, biosorbent dose, initial dye concentration and temperature were studied employing a batch experimental setup. The biosorption process followed the Langmuir isotherm model with high correlation coefficients ( R 2 > 0.99) at different temperatures. The maximum monolayer biosorption capacity was found to be 78.22 mg g-1 at 293 K. The kinetic data conformed to the pseudo-second-order kinetic model. The activation energy of the system was calculated as 58.96 kJ mol- 1 , indicating chemisorption nature of the ongoing biosorption process. A thermodynamic study showed spontaneous and exothermic nature of the biosorption process. Owing to its low cost and high dye uptake capacity, PLP has potential for application as biosorbent for removal of CV from aqueous solutions.

Study on Selective Removal of Impurity Iron from Leached Copper-Bearing Solution Using a Chelating Resin

Directory of Open Access Journals (Sweden)

Yubiao Li

2016-10-01

Full Text Available In order to selectively remove iron from copper laden solution after leaching but prior to electrowinning, equilibrium, kinetic, and thermodynamic studies have been conducted on an a chelating resin of Rexp-501 at pH 1.0 and at various temperatures. Both Langmuir and Freundlich models were investigated, with the Langmuir model proving to be more suitable for fitting iron removal performance, with little influence from copper concentration. Compared with the pseudo first order kinetic model, the pseudo second order kinetic model fitted the dynamic adsorption process better, indicating a chemisorption mechanism. Fourier transform infrared spectroscopy (FT-IR results indicated that C=O from carbonyl group played a key role in combining with iron and can be regenerated and reused. However, the C=O of the acylamino group combining with iron was not able to be released after oxalic acid was applied.

Properties and efficiency of a Pt/Al2O3 catalyst applied in a solid fuel thermo-accumulating furnace

Directory of Open Access Journals (Sweden)

SRDJAN BELOSEVIC

2007-08-01

Full Text Available A prototype of a solid fuel thermo-accumulating furnace has been developed. In order to achieve a higher combustion efficiency, a Pt/Al2O3 catalyst in the form of 3 ± 0.3 mm spheres was applied, which enabled further combustion of flue gases within the furnace. Experimental investigation of the influence of the catalyst on the conversion of CO has been done for different operation regimes and positions of the catalyst. Paper presents selected results regarding CO emission during wood and coal combustion. Investigations suggest a considerable effect of the catalyst and a strong influence of the catalyst position to CO emission reduction. The microstructure of the catalyst beads, characterized by selective chemisorption of CO, has shown the decrease of the number of Pt sites as a consequence of blockage by coke deposits formed during the combustion of solid fuel.

Efficient electronic structure methods applied to metal nanoparticles

DEFF Research Database (Denmark)

Larsen, Ask Hjorth

of efficient approaches to density functional theory and the application of these methods to metal nanoparticles. We describe the formalism and implementation of localized atom-centered basis sets within the projector augmented wave method. Basis sets allow for a dramatic increase in performance compared....... The basis set method is used to study the electronic effects for the contiguous range of clusters up to several hundred atoms. The s-electrons hybridize to form electronic shells consistent with the jellium model, leading to electronic magic numbers for clusters with full shells. Large electronic gaps...... and jumps in Fermi level near magic numbers can lead to alkali-like or halogen-like behaviour when main-group atoms adsorb onto gold clusters. A non-self-consistent NewnsAnderson model is used to more closely study the chemisorption of main-group atoms on magic-number Au clusters. The behaviour at magic...

Laser Tailoring the Surface Chemistry and Morphology for Wear, Scale and Corrosion Resistant Superhydrophobic Coatings.

Science.gov (United States)

Boinovich, Ludmila B; Emelyanenko, Kirill A; Domantovsky, Alexander G; Emelyanenko, Alexandre M

2018-06-04

A strategy, combining laser chemical modification with laser texturing, followed by chemisorption of the fluorinated hydrophobic agent was used to fabricate the series of superhydrophobic coatings on an aluminum alloy with varied chemical compositions and parameters of texture. It was shown that high content of aluminum oxynitride and aluminum oxide formed in the surface layer upon laser treatment allows solving the problem of enhancement of superhydrophobic coating resistance to abrasive loads. Besides, the multimodal structure of highly porous surface layer leads to self-healing ability of fabricated coatings. Long-term behavior of designed coatings in "hard" hot water with an essential content of calcium carbonate demonstrated high antiscaling resistance with self-cleaning potential against solid deposits onto the superhydrophobic surfaces. Study of corrosion protection properties and the behavior of coatings at long-term contact with 0.5 M NaCl solution indicated extremely high chemical stability and remarkable anticorrosion properties.

Spatial, Hysteretic, and Adaptive Host-Guest Chemistry in a Metal-Organic Framework with Open Watson-Crick Sites.

Science.gov (United States)

Cai, Hong; Li, Mian; Lin, Xiao-Rong; Chen, Wei; Chen, Guang-Hui; Huang, Xiao-Chun; Li, Dan

2015-09-01

Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site-specific recognition takes advantage of cooperative spatial effects, as in local folding in protein-DNA binding. Herein, we report a new nucleobase-tagged metal-organic framework (MOF), namely ZnBTCA (BTC=benzene-1,3,5-tricarboxyl, A=adenine), in which the exposed Watson-Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson-Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host-guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine-thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manganese oxide as a promoter for C2-C4 olefin production in the hydrogenation of carbon dioxide

International Nuclear Information System (INIS)

Kim, C.; Chen, K.; Hanson, F.V.; Oblad, A.G.; Tsai, Y.

1986-01-01

A number of active research and development programs have been initiated to explore the potential of CO hydrogenation process as a source of low molecular weight (C 2 -C 4 ) olefins. Metal catalysts such as Co-Mn, Ni-zeolite, Rd and Mo have been evaluated for low molecular weight olefin selectivity. The coprecipitated Fe-Mn system (Mn/Fe=9/1) was reported to be highly olefin selective. Recently, many investigators reported supporting evidence for the promotional effect of Mn for precipitated Fe catalysts. In this study, Raney Fe promoted with Mn has been evaluated for C 2 -C 4 olefin selectivity in the hydrogenation of CO relative to coprecipitated Fe-Mn catalysts. Catalyst characterization, including BET surface area, X-ray diffraction, selective chemisorption and ESCA, has been carried to provide insight into the role of manganese in both the Coprecipitated and Raney catalyst systems

Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

Directory of Open Access Journals (Sweden)

David R. Sellick

2015-04-01

Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

Switching on/off the chemisorption of thioctic-based self-assembled monolayers on gold by applying a moderate cathodic/anodic potential.

Science.gov (United States)

Sahli, Rihab; Fave, Claire; Raouafi, Noureddine; Boujlel, Khaled; Schöllhorn, Bernd; Limoges, Benoît

2013-04-30

An in situ and real-time electrochemical method has been devised for quantitatively monitoring the self-assembly of a ferrocene-labeled cyclic disulfide derivative (i.e., a thioctic acid derivative) on a polycrystalline gold electrode under electrode polarization. Taking advantage of the high sensitivity, specificity, accuracy, and temporal resolution of this method, we were able to demonstrate an unexpectedly facilitated formation of the redox-active SAM when the electrode was held at a moderate cathodic potential (-0.4 V vs SCE in CH3CN), affording a saturated monolayer from only micromolar solutions in less than 10 min, and a totally impeded SAM growth when the electrode was polarized at a slightly anodic potential (+0.5 V vs SCE in CH3CN). This method literally allows for switching on/off the formation of SAMs under "soft" conditions. Moreover the cyclic disulfide-based SAM was completely desorbed at this potential contrary to the facilitated deposition of a ferrocene-labeled alkanethiol. Such a strikingly contrasting behavior could be explained by an energetically favored release of the thioctic-based SAM through homolytic cleavage of the Au-S bond followed by intramolecular cyclization of the generated thiyl diradicals. Moreover, the absence of a discernible transient faradaic current response during the potential-assisted adsorption/desorption of the redox-labeled cyclic disulfide led us to conclude in a potential-dependent reversible surface reaction where no electron is released or consumed. These results provide new insights into the formation of disulfide-based SAMs on gold but also raise some fundamental questions about the intimate mechanism involved in the facilitated adsorption/desorption of SAMs under electrode polarization. Finally, the possibility to easily and selectively address the formation/removal of thioctic-based SAMs on gold by applying a moderate cathodic/anodic potential offers another degree of freedom in tailoring their properties and in controlling their self-assembly, nanostructuration, and/or release.

RESEARCH OF THE ADSORPTION OF ORGANIC ACIDS IN SUGARCANE BAGASSE ASH

Directory of Open Access Journals (Sweden)

Julio Omar Prieto García

2017-07-01

Full Text Available In this research a study of the adsorption of acetic, benzoic, butanoic, fumaric, maleic and succinic acids on sugarcane baggase ash is made. The adsorber material is characterized through physical criteria such as apparent and pictometric density, compressibility, porosity, superficial area and tortuosity. The sample has been examined by X-rays Diffraction, thermal analysis, IR-quality analysis. The isotherm for the sorption process is determined, where it is shown that the Freundlich model is adjusted to benzoic acid, the Langmuir and Toth model to acetic acid, Bunauer- Emmett- Teller (BET model to succinic acid and the butiric, maleic and fumaric acids are adjusted to Langmoir model. It is established that the first-order model is adjusted to the adsorption kinetics of the acetic and benzoic acids; while the rest of the acids are adjusted to a second-order model, in the case of the butanoic, succinic and maleic acids it is possible the occurrence of chemisorption processes.

Electronic structure of disordered alloys, surfaces and interfaces

CERN Document Server

Turek, Ilja; Kudrnovský, Josef; Šob, Mojmír; Weinberger, Peter

1997-01-01

At present, there is an increasing interest in the prediction of properties of classical and new materials such as substitutional alloys, their surfaces, and metallic or semiconductor multilayers. A detailed understanding based on a thus of the utmost importance for fu­ microscopic, parameter-free approach is ture developments in solid state physics and materials science. The interrela­ tion between electronic and structural properties at surfaces plays a key role for a microscopic understanding of phenomena as diverse as catalysis, corrosion, chemisorption and crystal growth. Remarkable progress has been made in the past 10-15 years in the understand­ ing of behavior of ideal crystals and their surfaces by relating their properties to the underlying electronic structure as determined from the first principles. Similar studies of complex systems like imperfect surfaces, interfaces, and mul­ tilayered structures seem to be accessible by now. Conventional band-structure methods, however, are of limited use ...

Analytical applications of the 12C(d,p) reaction. Treatment of experimental spectra

International Nuclear Information System (INIS)

Engerran, J.-A.

1975-01-01

The nuclear (d,p) reaction induced on carbon and oxygen at medium energies (1 to 4MeV) has been used for the determination of very small quantities (less than a monolayer) as well as of the in-depth distribution. With respect to the first feature of this reaction, chemisorption study has been undertaken for the mixture CO/O 2 at the surface of a polycristalline sample of platinum. An adapted irradiation detection set-up is described. Obtaining the in-depth distribution leads to the more general case of treatment of experimental spectra. Owing to the results given by the classical methods of deconvolution or convolution, a joint procedure was chosen for our application. A trial function is determined by a convolutionprocess, to be used as initial function in an iterative method. Convergence is then easily achieved avoiding Gibbs phenomena. As a main application, carbon profile determination is obtained for a boron matrix [fr

Drying characteristics of thorium fuel corrosion products

Energy Technology Data Exchange (ETDEWEB)

Smith, R.-E. E-mail: rzl@inel.gov

2004-07-01

The open literature and accessible US Department of Energy-sponsored reports were reviewed for the dehydration and rehydration characteristics of potential corrosion products from thorium metal and thorium oxide nuclear fuels. Mixed oxides were not specifically examined unless data were given for performance of mixed thorium-uranium fuels. Thorium metal generally corrodes to thorium oxide. Physisorbed water is readily removed by heating to approximately 200 deg. C. Complete removal of chemisorbed water requires heating above 1000 deg. C. Thorium oxide adsorbs water well in excess of the amount needed to cover the oxide surface by chemisorption. The adsorption of water appears to be a surface phenomenon; it does not lead to bulk conversion of the solid oxide to the hydroxide. Adsorptive capacity depends on both the specific surface area and the porosity of the thorium oxide. Heat treatment by calcination or sintering reduces the adsorption capacity substantially from the thorium oxide produced by metal corrosion.

Sorption of diclofenac and naproxen onto MWCNT in model wastewater treated by H2O2 and/or UV.

Science.gov (United States)

Czech, Bożena; Oleszczuk, Patryk

2016-04-01

The application of oxidation processes such as UV and/or H2O2 will change the physicochemical properties of carbon nanotubes (CNT). It may affect the sorption affinity of CNT to different contaminants and then affect their fate in the environment. In the present study the adsorption of two very common used pharmaceuticals (diclofenac and naproxen) onto CNT treated by UV, H2O2 or UV/H2O2 was investigated. Four different adsorption models (Freundlich, Langmuir, Temkin, Dubinin-Radushkevich) were tested. The best fitting of experimental data was observed for Freundlich or Langmuir model. The significant relationships between Q calculated from Langmuir model with O% and dispersity were observed. Kinetics of diclofenac and naproxen followed mainly pseudo-second order indicating for chemisorption limiting step of adsorption. The data showed that the mechanism of sorption was physical or chemical depending on the type of CNT modification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Development and application of a quasi-continuously working system for measuring the immission of acid air pollutants like HCl, NO2 and SO2 using an absorber tube

International Nuclear Information System (INIS)

Weisweiler, W.; Creutznacher, H.; Wien, F.

1993-10-01

Main objective of this study during the report time is found to be the testing of different absorption materials for the simultaneous determination of acid gaseous pollutants like HCl, NO 2 and SO 2 . These materials - so-called active collectors - were examined in laboratory-scale experiments using gas mixtures with various concentrations of the pollutants which should be chemisorbed by the active collectors. After eluation of the active collector and ion chromatographical analysis of the solutions informations about the absorption/desorption rate are obtained. In most cases adsorption were tested on which amino-functional groups are deposited by chemical reaction. The amino-groups act as reactive sites for the chemisorption of the acid gases. It can be observed that all tested materials are suitable for the measurement of HCl and SO 2 . Additionally some types of absorption materials are effective for the simultaneous absorption of HCl, SO 2 and NO 2 . (orig.). 25 figs., 21 tabs., 66 refs

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.

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

Science.gov (United States)

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

2016-03-15

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

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.

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

International Nuclear Information System (INIS)

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

2009-01-01

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

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

Science.gov (United States)

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

2017-08-01

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

Post-synthetic halide conversion and selective halogen capture in hybrid perovskites† †Electronic supplementary information (ESI) available. CCDC 1048945–1048947. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01135c

Science.gov (United States)

Solis-Ibarra, D.; Smith, I. C.

2015-01-01

Reaction with halogen vapor allows us to post-synthetically exchange halides in both three- (3D) and two-dimensional (2D) organic–inorganic metal-halide perovskites. Films of 3D Pb–I perovskites cleanly convert to films of Pb–Br or Pb–Cl perovskites upon exposure to Br2 or Cl2 gas, respectively. This gas–solid reaction provides a simple method to produce the high-quality Pb–Br or Pb–Cl perovskite films required for optoelectronic applications. Reactivity with halogens can be extended to the organic layers in 2D metal-halide perovskites. Here, terminal alkene groups placed between the inorganic layers can capture Br2 gas through chemisorption to form dibromoalkanes. This reaction's selectivity for Br2 over I2 allows us to scrub Br2 to obtain high-purity I2 gas streams. We also observe unusual halogen transfer between the inorganic and organic layers within a single perovskite structure. Remarkably, the perovskite's crystallinity is retained during these massive structural rearrangements. PMID:29218171

Oxygen-containing coke species in zeolite-catalyzed conversion of methanol to hydrocarbons

KAUST Repository

Liu, Zhaohui

2016-10-06

Zeolites are the most commonly used catalysts for methanol-to-hydrocarbon (MTH) conversion. Here, we identified two oxygen-containing compounds as coke species in zeolite catalysts after MTH reactions. We investigated the possible influences of the oxygen-containing compounds on coke formation, catalyst deactivation, product selectivity, and the induction period of the MTH reaction through a series of controlled experiments in which one of the identified compounds (2,3-dimethyl-2-cyclopenten-1-one) was co-fed with methanol over a zeolite H-ZSM-5 catalyst. Our results allow us to infer that once produced, the oxygen-containing compounds block the Brønsted acid sites by strong chemisorption and their rapid conversion to aromatics expedites the formation of coke and thus the deactivation of the catalyst. A minor effect of the production of such compounds during the MTH reaction is that the aromatic-based catalytic cycle can be slightly promoted to give higher selectivity to ethylene.

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-01-01

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

Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

Directory of Open Access Journals (Sweden)

Yongfeng Tong

2016-02-01

Full Text Available This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon–chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon–chalcogen atom-bond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the π-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

Pronounced cluster-size effects: gas-phase reactivity of bare vanadium cluster cations V(n)+ (n = 1-7) toward methanol.

Science.gov (United States)

Feyel, Sandra; Schröder, Detlef; Schwarz, Helmut

2009-05-14

Mass spectrometric experiments are used to examine the size-dependent interactions of bare vanadium cluster cations V(n)(+) (n = 1-7) with methanol. The reactivity patterns exhibit enormous size effects throughout the range of clusters investigated. For example, dehydrogenation of methanol to produce V(n)OC(+) is only brought about by clusters with n > or = 3. Atomic vanadium cation V(+) also is reactive, but instead of dehydrogenation of the alcohol, expulsions of either methane or a methyl radical take place. In marked contrast, the reaction efficiency of the dinuclear cluster V(2)(+) is extremely low. For the cluster cations V(n)(+) (n = 3-7), complete and efficient dehydrogenation of methanol to produce V(n)OC(+) and two hydrogen molecules prevails. DFT calculations shed light on the mechanism of the dehydrogenation of methanol by the smallest reactive cluster cation V(3)(+) and propose the occurrence of chemisorption concomitant with C-O bond cleavage rather than adsorption of an intact carbon monoxide molecule by the cluster.

DFT simulation on H2 adsorption over Ni-decorated defective h-BN nanosheets

Science.gov (United States)

Zhou, Xuan; Chu, Wei; Zhou, Yanan; Sun, Wenjing; Xue, Ying

2018-05-01

Nickel doped defective h-BN nanosheets and their potential application on hydrogen storage were explored by density functional theory (DFT) calculation. Three types of defective h-BN (SW defect, VB and VN substrates) were modeled. In comparison with the SW defect, the B or N vacancy can improve the interaction between Ni atom and h-BN nanosheet strikingly. Furthermore, the Ni-doped SW defect sheet shows chemisorption on H2 molecules, and the Hsbnd H bond is partially dissociated. While on the VB sheet, Ni adatom interacts with H2 in the range of physisorption. However, the Ni-functionalized VN sheet exhibits a desirable adsorption on H2, and the corresponding energy varies from -0.40 to -0.51 eV, which is favorable for H2 adsorption and release at ambient conditions. As a result, the VN substrate is expected to a desirable support for H2 storage. Our work provides an insight into H2 storage on Ni-functionalized defective h-BN monolayer.

Accelerating the development of transparent graphene electrodes through basic science driven chemical functionalization.

Energy Technology Data Exchange (ETDEWEB)

Chan, Calvin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Beechem, III, Thomas Edwin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Ohta, Taisuke [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Brumbach, Michael T. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wheeler, David Roger [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Veneman, Alexander [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Gearba, I. Raluca [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stevenson, Keith J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2013-09-01

Chemical functionalization is required to adapt graphenes properties to many applications. However, most covalent functionalization schemes are spontaneous or defect driven and are not suitable for applications requiring directed assembly of molecules on graphene substrates. In this work, we demonstrated electrochemically driven covalent bonding of phenyl iodoniums onto epitaxial graphene. The amount of chemisorption was demonstrated by varying the duration of the electrochemical driving potential. Chemical, electronic, and defect states of phenyl-modified graphene were studied by photoemission spectroscopy, spatially resolved Raman spectroscopy, and water contact angle measurement. Covalent attachment rehybridized some of the delocalized graphene sp2 orbitals to localized sp3 states. Control over the relative spontaneity (reaction rate) of covalent graphene functionalization is an important first step to the practical realization of directed molecular assembly on graphene. More than 10 publications, conference presentations, and program highlights were produced (some invited), and follow-on funding was obtained to continue this work.

Eggshell Powder as an Adsorbent for Removal of Fluoride from Aqueous Solution: Equilibrium, Kinetic and Thermodynamic Studies

Directory of Open Access Journals (Sweden)

R. Bhaumik

2012-01-01

Full Text Available A new medium, eggshell powder has been developed for fluoride removal from aqueous solution. Fluoride adsorption was studied in a batch system where adsorption was found to be pH dependent with maximum removal efficiency at 6.0. The experimental data was more satisfactorily fitted with Langmuir isotherm model. The kinetics and the factor controlling adsorption process fully accepted by pseudo-second-order model were also discussed. Ea was found to be 45.98 kJmol-1 by using Arrhenius equation, indicating chemisorption nature of fluoride onto eggshell powder. Thermodynamic study showed spontaneous nature and feasibility of the adsorption process with negative enthalpy (∆H0 value also supported the exothermic nature. Batch experiments were performed to study the applicability of the adsorbent by using fluoride contaminated water collected from affected areas. These results indicate that eggshell powder can be used as an effective, low-cost adsorbent to remove fluoride from aqueous solution as well as groundwater.

Covalent functionalization of octagraphene with magnetic octahedral B6- and non-planar C6- clusters

Science.gov (United States)

Chigo-Anota, E.; Cárdenas-Jirón, G.; Salazar Villanueva, M.; Bautista Hernández, A.; Castro, M.

2017-10-01

The interaction between the magnetic boron octahedral (B6-) and non-planar (C6-) carbon clusters with semimetal nano-sheet of octa-graphene (C64H24) in the gas phase is studied by means of DFT calculations. These results reveal that non-planar-1 (anion) carbon cluster exhibits structural stability, low chemical reactivity, magnetic (1.0 magneton bohr) and semiconductor behavior. On the other hand, there is chemisorption phenomena when the stable B6- and C6- clusters are absorbed on octa-graphene nanosheets. Such absorption generates high polarity and the low-reactivity remains as on the individual pristine cases. Electronic charge transference occurs from the clusters toward the nanosheets, producing a reduction of the work function for the complexes and also induces a magnetic behavior on the functionalized sheets. The quantum descriptors obtained for these systems reveal that they are feasible candidates for the design of molecular circuits, magnetic devices, and nano-vehicles for drug delivery.

Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst

DEFF Research Database (Denmark)

Kuld, Sebastian; Moses, Poul Georg; Sehested, Jens

2014-01-01

Methanol has recently attracted renewed interest because of its potential importance as a solar fuel. Methanol is also an important bulk chemical that is most efficiently formed over the industrial Cu/ZnO/Al2O3 catalyst. The identity of the active site and, in particular, the role of ZnO as a pro......Methanol has recently attracted renewed interest because of its potential importance as a solar fuel. Methanol is also an important bulk chemical that is most efficiently formed over the industrial Cu/ZnO/Al2O3 catalyst. The identity of the active site and, in particular, the role of Zn......O as a promoter for this type of catalyst is still under intense debate. Structural changes that are strongly dependent on the pretreatment method have now been observed for an industrial-type methanol synthesis catalyst. A combination of chemisorption, reaction, and spectroscopic techniques provides a consistent...

Characterization of Rh films on Ta(110)

International Nuclear Information System (INIS)

Jiang, L.Q.; Ruckman, M.W.; Strongin, M.

1990-01-01

The surface and electronic structure of Rh films on Ta(110) up to several monolayers thick on Ta(110) are characterized by photoemission, Auger emission, low-energy electron diffraction (LEED) and low-energy ion scattering (LEIS). From the variation of the Rh Auger peak-to-peak intensity as a function of evaporation time, Rh appears to grow in the Stranski--Krastanov mode at room temperature. However, the LEIS data show that the Rh adatoms begin to cluster on Ta(110) before growth of the monolayer is completed. Diffuse LEED scattering suggests that the Rh films are disordered. Photoemission shows that Rh chemisorption on Ta(110) generates two peaks located at -1.5 and -2.5 eV binding energy during the initial phase of thin-film growth (0 3.7 ML). CO dissociates on the Rh/Ta(110) surface for Rh coverages<2.5 ML and the surface develops a site capable of molecular CO adsorption above 0.3-ML Rh coverage

Electron stimulated desorption study of oxygen adsorption on tungsten

International Nuclear Information System (INIS)

Prince, R.H.; Floyd, G.R.

1978-01-01

The adsorption of oxygen on a polycrystalline tungsten surface at approximately 800 K has been studied by means of electron stimulated desorption (ESD). Although precision gas dosing was not employed, the initial sticking probability for dissociative adsorption appears to be essentially unity, while the variation with coverage suggests that a high degree of order exists and that precursor state kinetics are significant. A most noticeable and reproducible discontinuity in ESD parameters occurs at a fractional coverage theta approximately 0.8 (exposure approximately 1.4 X 10 15 molecules/cm 2 incident) which is interpreted as an order-disorder transition within a single (β 1 ) chemisorption state, and results in an increase in the ionic desorption cross-section by a factor of approximately 1.26. A discussion of the adsorption kinetics and the disorder transition is given in terms of current models of dissociative adsoption which include the effects of nearest neighbour lateral interactions. (Auth.)

Influence of ɣ and ultrasonic irradiations on the physicochemical properties of CeO2-Fe2O3-Al2O3 for textile dyes removal applications

Science.gov (United States)

Ibrahim, Marwa M.; El-Molla, Sahar A.; Ismail, Sahar A.

2018-04-01

In this study highly effective adsorbent ternary mixed oxide CeO2-Fe2O3-Al2O3 was prepared by precipitation method. Various methods used to treat the mixed hydroxide like calcination, ultrasonic, hydrothermal and ɣ radiation with different doses to obtain the ternary mixed oxide. XRD, TEM, EDX, FTIR and SBET are used to study the physicochemical properties of nanoparticles. The CFAH and CFAɣ0.8 have the different morphologies and high surface area. Batch adsorption experiments were performed to remove anionic Remazol Red RB-133 dye. The experimental data showed that The CFAH and CFAɣ0.8 have high adsorption rate for removing of dye. The removal of dye is enhanced by ultrasonic radiation and high temperature. The adsorption process was fitted well for pseudo second order kinetics and followed the Freundlich isotherm model. In addition to, Thermodynamic results of adsorption process displayed that, the adsorption of dye on adsorbent was spontaneous, endothermic and chemisorptions process.

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.

Methane dissociation on the steps and terraces of Pt(211) resolved by quantum state and impact site

Science.gov (United States)

Chadwick, Helen; Guo, Han; Gutiérrez-González, Ana; Menzel, Jan Paul; Jackson, Bret; Beck, Rainer D.

2018-01-01

Methane dissociation on the step and terrace sites of a Pt(211) single crystal was studied by reflection absorption infrared spectroscopy (RAIRS) at a surface temperature of 120 K. The C—H stretch RAIRS signal of the chemisorbed methyl product species was used to distinguish between adsorption on step and terrace sites allowing methyl uptake to be monitored as a function of incident kinetic energy for both sites. Our results indicate a direct dissociation mechanism on both sites with higher reactivity on steps than on terraces consistent with a difference in an activation barrier height of at least 30 kJ/mol. State-specific preparation of incident CH4 with one quantum of antisymmetric (ν3) stretch vibration further increases the CH4 reactivity enabling comparison between translational and vibrational activation on both steps and terraces. The reaction is modeled with first principles quantum theory that accurately describes dissociative chemisorption at different sites on the surface.

Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu; Aliaga, Cesar; Hung, Ling-I; Somorjai, Gabor A.; Yang, Peidong

2009-03-02

Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H2 chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

Separation of acid blue 25 from aqueous solution using water lettuce and agro-wastes by batch adsorption studies

Science.gov (United States)

Kooh, Muhammad Raziq Rahimi; Dahri, Muhammad Khairud; Lim, Linda B. L.; Lim, Lee Hoon; Chan, Chin Mei

2018-05-01

Three plant-based materials, namely water lettuce (WL), tarap peel (TP) and cempedak peel (CP), were used to investigate their potentials as adsorbents using acid blue 25 (AB25) dye as a model for acidic dye. The adsorbents were characterised using Fourier transform infrared spectroscopy, X-ray fluorescence and scanning electron microscope. Batch experiments involving parameters such as pH, temperature, contact time, and initial dye concentration were done to investigate the optimal conditions for the adsorption of AB25 onto the adsorbents. Thermodynamics study showed that the uptake of AB25 by the three adsorbents was feasible and endothermic in nature. Both the Langmuir and Freundlich isotherm models can be used to describe the adsorption process of AB25 onto WL and CP while pseudo-second-order fitted the kinetics data, suggesting that chemisorptions were majorly involved. The use of 0.1 M of NaOH showed the best results in regenerating of the WL, TP and CP's adsorption ability after AB25 treatment.

Catalysts prepared by interaction of transition metal organometallic compounds with the surface of supporters

International Nuclear Information System (INIS)

Ryndin, Yu.A.; Kuznetsov, B.N.; Moroz, Eh.M.; Tripol'skij, A.A.; Ermakov, Yu.I.

1977-01-01

The phase composition and dispersion of the catalyst (W + Pt)/SiO 2 , subjected to oxidation and reduction at an elevated temperature was investigated by roentgenographic methods (radial distribution of atoms and broadening of X-ray lines). The X-ray data are compared with the results of chemisorption measurements of platinum dispersion in the specimens and their activity in reactions of benzene hydration and ethane hydrogenolysis. It has been established that catalysts reduced at 600 deg C and not subjected to oxidation, as well as catalysts oxidized at 200 deg C and then reduced at 600 deg C are characterized by a high platinum dispersion. The dispersion catalysts are noted for their activity in the reaction of benzene hydration and ethane hydrogenolysis. On the other hand, the activity of catalysts oxidized and reduced in rigid conditions (600 deg C, air) is much lower and is close to the activity of the coarsely dispersed PtSiO 2 catalyst

Adsorption characteristics of self-assembled thiol and dithiol layer on gold

International Nuclear Information System (INIS)

Tlili, A.; Abdelghani, A.; Aguir, K.; Gillet, M.; Jaffrezic-Renault, N.

2007-01-01

Monolayers of functional proteins are important in many fields related to pure and applied biochemistry and biophysics. The formation of extended uniform protein monolayers by single- or multiple-step self-chemisorption depends on the quality of the functionalized gold surface. The optical and the electrical properties of the 1-nonanethiol and 1,9-nonanedithiol deposited on gold with the self-assembled technique were investigated. We use cyclic voltammetry and impedance spectroscopy to characterize the insulating properties of the two layers. The analysis of the impedance spectra in terms of equivalent circuit of the gold/electrolyte and gold/SAM/electrolyte interface allows defining the thickness of the two thiols and the percentage of coverage area. Atomic force microscopy, contact angle measurement and Fourier transform infra-red spectroscopy have been used for homogeneity, hydrophobic properties and molecular structure of the formed thiols layer, respectively. The measured thickness with impedance spectroscopy fit well the results found with atomic force microscopy

SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

Science.gov (United States)

Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

2017-10-01

SeO2 adsorption mechanisms on CaO surface were firstly investigated by both density functional theory (DFT) calculations and adsorption experiments. Adsorption of multiple SeO2 on the CaO (001) surface was investigated using slab model. Based on the results of adsorption energy and surface property, a double-layer adsorption mechanisms were proposed. In experiments, the SeO2 adsorption products were prepared in a U-shaped quartz reactor at 200 °C. The surface morphology was investigated by field emission scanning electron microscopy (FE-SEM). The superficial and total SeO2 mass fractions were measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. The surface valence state and bulk structure are determined by XPS and X-Ray Diffraction (XRD). The experimental results are in good agreement with the DFT results. In conclusion, the fundamental SeO2 chemisorption mechanisms on CaO surface were suggested.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

Science.gov (United States)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

Science.gov (United States)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Study of Henna (Lawsonia inermis) as Natural Corrosion Inhibitor for Aluminum Alloy in Seawater

International Nuclear Information System (INIS)

Nik, W B Wan; Zulkifli, F; Sulaiman, O; Samo, K B; Rosliza, R

2012-01-01

Commercial henna (Lawsonia inermis) was investigated to inhibit the corrosion of aluminum alloy through immersion in seawater. The aluminum alloy (5083) was prepared in size of 25mm × 25mm × 3mm. The immersion test was conducted in seawater with different concentration of henna, 100ppm, 300ppm, 500ppm for duration of 60 days. Four characterizations were performed in this study which was weight loss study, Fourier Transform Infrared (FTIR), Electrochemical Impedance Spectroscopy (EIS) and adsorption isotherm. The results indicated that henna has major constituents of lawsone which contributed to the chemisorptions or adsorption process by forming an isolation layers on the aluminum alloy surface which follows the Langmuir adsorption isotherm. It was found that the protection layer attached on metal was not permanent and precipitation occurred as the time increases. The highest inhibition efficiency was found at 88% (500ppm). This research found that henna is an excellent natural inhibitor for aluminum alloy in seawater.

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

Science.gov (United States)

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

2017-03-23

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

Characterization of ZSM-5 modified with niobium pentoxide: the study of thiophene adsorption

Energy Technology Data Exchange (ETDEWEB)

Cavalcanti, Rodrigo M.; Barros, Ivoneide de C.L., E-mail: ibarros@ufam.edu.br [Universidade Federal do Amazonas (UFAM), Manaus, AM (Brazil). Inst. de Ciencias Exatas; Dias, Jose A.; Dias, Silvia C.L. [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica

2013-01-15

ZSM-5 adsorbents impregnated with Nb{sub 2}O{sub 5} were applied in the sulfur removal in the form of thiophene, refractory substance of difficult removal of liquid fuels. For this purpose, a model fuel containing iso-octane contaminated with thiophene in concentrations of 877.5 to 1155 ppmw was prepared. The samples were characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR) and Fourier transform-Raman (FT-Raman) spectroscopies for confirmation of the adsorbents, being prioritized the adsorption study with that containing 5 wt.% of niobium pentoxide, because it showed a greater capacity for removal of thiophene. The best results of adsorption were achieved at 353 K, a longer time to reach equilibrium was observed. Under these conditions, the best kinetic fitting was achieved using the equation of pseudo-second order, demonstrating the domain of the phenomenon of chemisorption. While under lower temperatures, the diffusion model presented a better approximation of the experimental results. Also, the increasing of temperature did enhance spontaneous processes. (author)

Growth of pentacene on Ag(1 1 1) surface: A NEXAFS study

International Nuclear Information System (INIS)

Pedio, M.; Doyle, B.; Mahne, N.; Giglia, A.; Borgatti, F.; Nannarone, S.; Henze, S.K.M.; Temirov, R.; Tautz, F.S.; Casalis, L.; Hudej, R.; Danisman, M.F.; Nickel, B.

2007-01-01

Thin films of pentacene (C 22 H 14 ) have become widely used in the field of organic electronics. Here films of C 22 H 14 of thickness ranging from submonolayer to multilayer were thermally deposited on Ag(1 1 1) surface. The determination of molecular geometry in pentacene films on Ag(1 1 1) studied by X-ray absorption at different stages of growth up to one monolayer is presented. XAS spectra at the C K-edge were collected as a function of the direction of the electric field at the surface. The different features of the spectra were assigned to resonances related to the various molecular unoccupied states by the comparison with the absorption coefficient of the pentacene gas phase. The transitions involving antibonding π states show a pronounced angular dependence for all the measured coverages, from submonolayer to multilayer. The spectra analysis indicates a nearly planar chemisorption of the first pentacene layer with a tilt angle of 10 o

Ruthenium-platinum bimetallic catalysts supported on silica: characterization and study of benzene hydrogenation and CO methanation

Energy Technology Data Exchange (ETDEWEB)

Chakrabarty, D.K.; Rao, K.M.; Sundararaman, N.; Chandavar, K.

1986-12-15

Ru-Pt/SiO/sub 2/ bimetallic catalysts with varying Ru:Pt ratio have been prepared and studied with the aim to establish if they contain coclusters or isolated ruthenium and platinum particles. X-ray diffraction studies show that individual crystallites of ruthenium and platinum are present and no coclusters are formed. Metal dispersion has been determined by hydrogen chemisorption and surface composition of the catalysts has been obtained from XPS. It was found that preoxidation of the catalysts prior to reduction is essential for good platinum dispersion. The experimental turnover number (TN) for benzene hydrogenation on the bimetallic catalysts agrees very well with that of the weighted average on the individual metal catalysts and this may be taken as a kinetic evidence for the absence of coclusters. Carbon monoxide methanation activity of the bimetallic catalysts is quite similar to that of the supported platinum catalyst. 6 refs., 6 figs., 2 tabs.

Diatomite Modified Immobilized Delftia sp. for the Bio-Abiotic Removal of Antibiotics Amoxicillin in the Aqueous System

Science.gov (United States)

Gao, Lijuan; Sun, Jing; Guan, Kai; Shen, Tingting; Wang, Xikui

2017-05-01

Diatomite modified sodium alginate (Si/SA) immobilized Delftia sp. A2(2011) (STT01) was applied to degrade amoxicillin. The immobilized pellets provided a direct and visual probe for the degradation process due to their intrinsic bright colour. The results demonstrated that 100% of amoxicillin and 68.5% of CODcr removal were achieved after 72 h, comparing with the cases of sodium alginate (SA) system (81.2%, 46.9%) and the free cells system (60.5%, 35.5%). The degradation kinetics was in good agreement with Michaelis-Menten equation. The maximum rate (Vm ) and Michaelis constant (Km ) were calculated as 9.09 mg L-1 h-1 and 228 mg L-1, respectively. The results further revealed that diatomite not only acted as immobilization support to improve the mechanical strength and lifetime of the pellets but also as absorbent to promote the treatment efficiency. Therefore, both enzymatic catalysis and chemisorption were responsible for the removal of amoxicillin.

Deactivation by carbon of iron catalysts for indirect liquefaction

Energy Technology Data Exchange (ETDEWEB)

Bartholomew, C.H.

1990-10-11

This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for Fischer-Tropsch (FT) synthesis, the objectives of which are: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; model the rates of deactivation of the same catalysts in fixed-bed reactors. During the thirteenth quarter design of software for a computer-automated reactor system to be used in the kinetic and deactivation studies was continued. Further progress was made toward the completion of the control language, control routines, and software for operating this system. Progress was also made on the testing of the system hardware and software. H{sub 2} chemisorption capacities and activity selectivity data were also measured for three iron catalysts promoted with 1% alumina. 47 refs., 8 figs., 1 tab.

Study on effective utilization of palm oil (Part 2). Extraction of carotenes from palm oil

Energy Technology Data Exchange (ETDEWEB)

Mamuro, Hideo; Kubota, Yasuhiko; Shiina, Hisako; Nakasato, Satoshi

1987-01-08

This report is a part of the result of an international cooperation project with Malaysia Palm Oil Research Institute. Extraction of carotenes from palm oil was carried out by means of molecular distillation or adsorption method. High recovery and enrichment of carotene was obtained from the sample treated with phosphoric acid or polyphosphoric acid. However, even the maximum enrichment was only 3.8 times of carotene concentration of the sample, which was far remote from the target value of 10. The yield of recovery was also as low as 40%. Adsorption of carotenes was found to be chemisorptive in nature. The highest enrichment and recovery were obtained in the caseof oil pretreated with the phosphorous pentoxide, the recovery was 34.3% and enrichment was 11.3 which exceeded the target of 10. This adsorption process may be commercialized if the demand for carotene will grow to justify it. (2 figs, 7 tabs, 18 refs)

The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian

International Nuclear Information System (INIS)

Mastromatteo, Michael; Jackson, Bret

2013-01-01

Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH 4 dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrational excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied

Controlled Oxygen Chemisorption on an Alumina Supported Rhodium Catalyst. The Formation of a New Metal-Metal Oxide Interface Determined with EXAFS.

NARCIS (Netherlands)

Koningsberger, D.C.; Martens, J.H.A.; Prins, R.

1989-01-01

An alumina-supported rhodium catalyst has been studied with EXAFS. After reduction and evacuation, oxygen was admitted at 100 and 300 K. EXAFS spectra of the catalyst after oxygen admission at 100 K indicated the beginning of oxidation. At 300 K only a small part of the rhodium particles remained

Effects of an iron-silicon material, a synthetic zeolite and an alkaline clay on vegetable uptake of As and Cd from a polluted agricultural soil and proposed remediation mechanisms.

Science.gov (United States)

Yao, Aijun; Wang, Yani; Ling, Xiaodan; Chen, Zhe; Tang, Yetao; Qiu, Hao; Ying, Rongrong; Qiu, Rongliang

2017-04-01

Economic and highly effective methods of in situ remediation of Cd and As polluted farmland in mining areas are urgently needed. Pot experiments with Brassica chinensis L. were carried out to determine the effects of three soil amendments [a novel iron-silicon material (ISM), a synthetic zeolite (SZ) and an alkaline clay (AC)] on vegetable uptake of As and Cd. SEM-EDS and XRD analyses were used to investigate the remediation mechanisms involved. Amendment with ISM significantly reduced the concentrations of As and Cd in edible parts of B. chinensis (by 84-94 % and 38-87 %, respectively), to levels that met food safety regulations and was much lower than those achieved by SZ and AC. ISM also significantly increased fresh biomass by 169-1412 % and 436-731 % in two consecutive growing seasons, while SZ and AC did not significantly affect vegetable growth. Correlation analysis suggested that it was the mitigating effects of ISM on soil acidity and on As and Cd toxicity, rather than nutrient amelioration, that contributed to the improvement in plant growth. SEM-EDS analysis showed that ISM contained far more Ca, Fe and Mn than did SZ or AC, and XRD analysis showed that in the ISM these elements were primarily in the form of silicates, oxides and phosphates that had high capacities for chemisorption of metal(loid)s. After incubation with solutions containing 800 mg L -1 AsO 4 2- or Cd 2+ , ISM bound distinctly higher levels of As (6.18 % in relative mass percent by EDS analysis) and Cd (7.21 % in relative mass percent by EDS analysis) compared to SZ and AC. XRD analysis also showed that ISM facilitated the precipitation of Cd 2+ as silicates, phosphates and hydroxides, and that arsenate combined with Fe, Al, Ca and Mg to form insoluble arsenate compounds. These precipitation mechanisms were much more active in ISM than in SZ or AC. Due to the greater pH elevation caused by the abundant calcium silicate, chemisorption and precipitation mechanisms in ISM treatments

First-principles study of SF_6 decomposed gas adsorbed on Au-decorated graphene

International Nuclear Information System (INIS)

Zhang, Xiaoxing; Yu, Lei; Gui, Yingang; Hu, Weihua

2016-01-01

Graphical abstract: - Highlights: • We theoretically investigated the decomposed gaseous components of sulfur hexafluoride (SF_6), namely, H_2S, SO_2, SOF_2, and SO_2F_2, adsorbed on pristine and Au-embedded graphene based on DFT-D, in which the van der Waals effect is considered. • H_2S, SO_2, SOF_2, and SO_2F_2 are chemisorption on Au-doped graphene, appreciably stronger than physisorption on pristine graphene in which the van der Waals dominates. • Only H_2S exhibits n-type doping to Au-graphene, whereas the rest gases exhibit p-type doping. The n-type and p-type sensing behaviors that Au-doped graphene displays to different gases play a crucial role in selective sensing application. • Magnetic moments fluctuate substantially in the original Au-graphene when H_2S and SO_2 are adsorbed. While the adsorption effects of SOF_2 and SO_2F_2 generate magnetism quenching. The different changes of magnetic moments in every adsorption system provide another approach to selective detection. • The charge transfer mechanism is deeply discussed in this paper. - Abstract: We theoretically investigated the decomposed gaseous components of sulfur hexafluoride (SF_6), namely, H_2S, SO_2, SOF_2, and SO_2F_2, adsorbed on pristine and Au-embedded graphene based on the revised Perdew–Burke–Ernzerhof calculation, which empirically includes a dispersion correction (DFT-D) for van der Waals interaction with standard generalized gradient approximation. Pristine graphene exhibits weak adsorption and absence of charge transfer, which indicates barely satisfactory sensing for decomposed components. The Au atom introduces magnetism to the pristine graphene after metal-embedded decoration as well as enhances conductivity. All four molecules induce certain hybridization between the molecules and Au-graphene, which results in chemical interactions. SOF_2 and SO_2F_2 exhibit a strong chemisorption interaction with Au-graphene, while H_2S and SO_2 exhibit quasi-molecular binding

Electronic energy transfer from molecules to metal and semiconductor surfaces, and chemisorption-induced changes in optical response of the nickel (111) surface

International Nuclear Information System (INIS)

Whitmore, P.M.

1982-10-01

The evolution of molecular excited states near solid surfaces is investigated. The mechanisms through which energy is transferred to the surface are described within a classical image dipole picture of the interaction. More sophisticated models for the dielectric response of the solid surface add important new decay channels for the energy dissipation. The predictions and applicability of three of these refined theories are discussed

Vibration atomic layer deposition for conformal nanoparticle coating

Energy Technology Data Exchange (ETDEWEB)

Park, Suk Won; Woo Kim, Jun; Jong Choi, Hyung; Hyung Shim, Joon, E-mail: shimm@korea.ac.kr [School of Mechanical Engineering, Korea University, Seoul 136-701 (Korea, Republic of)

2014-01-15

A vibration atomic layer deposition reactor was developed for fabricating a conformal thin-film coating on nanosize particles. In this study, atomic layer deposition of 10–15-nm-thick Al{sub 2}O{sub 3} films was conducted on a high-surface-area acetylene black powder with particle diameters of 200–250 nm. Intense vibration during the deposition resulted in the effective separation of particles, overcoming the interparticle agglomeration force and enabling effective diffusion of the precursor into the powder chunk; this phenomenon led to the formation of a conformal film coating on the nanopowder particles. It was also confirmed that the atomic layer deposition Al{sub 2}O{sub 3} films initially grew on the high-surface-area acetylene black powder particles as discrete islands, presumably because chemisorption of the precursor and water occurred only on a few sites on the high-surface-area acetylene black powder surface. Relatively sluggish growth of the films during the initial atomic layer deposition cycles was identified from composition analysis.

Adsorption of Congo red dye onto antimicrobial terephthaloyl thiourea cross-linked chitosan hydrogels.

Science.gov (United States)

El-Harby, Nouf F; Ibrahim, Shaimaa M A; Mohamed, Nadia A

2017-11-01

Adsorption capacity of three antimicrobial terephthaloyl thiourea cross-linked chitosan hydrogels for Congo red dye removal from its aqueous solution has been investigated for the first time in this work. These hydrogels were prepared by reacting chitosan with various amounts of terephthaloyl diisothiocyanate cross-linker. The effect of the hydrogel structural variations and several dye adsorption processing parameters to achieve the best adsorption capacity were investigated. The hydrogels' structural variations were obtained by varying their terephthaloyl thiourea moieties content. The processing variables included initial concentration of the dye solution, temperature and time of exposure to the dye. The adsorption kinetics and isotherms showed that the sorption processes were better fitted by the pseudo-second-order equation and the Langmuir equation, respectively. On the basis of the Langmuir analysis Congo red dye gave the maximum sorption capacity of 44.248 mg/g. The results obtained confirmed that the sorption phenomena are most likely to be controlled by chemisorption process. The adsorption reaction was endothermic and spontaneous according to the calculated results of adsorption thermodynamics.

Adsorptive removal of congo red and sunset yellow dyes from water systems by lady finger stem

International Nuclear Information System (INIS)

Abbas, A.; Murtaza, S.; Ayub, R.; Rehman, R.; Zahid, A.

2012-01-01

Summary: In this research work two anionic dyes, i.e. Congo Red and Sunset Yellow were removed successfully from aqueous media by Lady Finger stem in batch mode. Operational conditions optimization showed that agitation speed and particle size did not affect much in adsorption of these dyes; but contact time, pH, adsorbent dose and temperature of system effects the adsorption rate. Optimized conditions of adsorption for Congo Red dye were: 40 minute contact time, 8.0 pH, 0.5 g adsorbent dose, 40-60 microns mesh sized particles, 150 rpm agitation speed and 50 degree C temperature. Whereas for Sunset Yellow optimized conditions were: 30 minute contact time, 2.0 pH, 2.5 g adsorbent dose, 20-40 microns mesh sized particles, 50 rpm agitation speed and 30 degree C temperature. Suitability of equilibrium data was modulated with Langmuir, Freundlich and Temkin models and found that both physisorption and chemisorption processes play important role in adsorption of these dyes by Lady Finger stem. The results demonstrated that Lady Finger stem can be efficiently employed on larger scale wastewater treatment. (author)

Natural silica sand modified by calcium oxide as a new adsorbent for uranyl ions removal from aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Elhefnawy, O.A.; Elabd, A.A. [Nuclear and Radiological Regulatory Authority (NRRA), Cairo (Egypt). Nuclear Safeguards and Physical Protection Dept.

2017-07-01

Calcium oxide modified El-Zafarana silica sand (CMZS) was prepared as a new adsorbent for U(VI) removal from aqueous solutions in a series of batch experiments. The new adsorbent CMZS was characterized by different analysis techniques SEM, EDX, XRD, and FTIR. The influence of many parameters on the removal process like; effect of pH, contact time, U(VI) initial concentration and temperature on U(VI) removal were investigated. Kinetic experiments showed that U(VI) removal on CMZS followed pseudo-second-order kinetics model appropriately and the equilibrium data agreed well with the Langmuir isotherm model. Kinetics and isothermal data reveal the chemisorption process of U(VI) on CMZS. The thermodynamic parameters (ΔH {sup circle}, ΔS {sup circle}, ΔG {sup circle}) were evaluated from temperature dependent adsorption data and the U(VI) removal on CMZS was found to be endothermic and spontaneous in nature. U(VI) desorption from CMZS was studied by a simple acid treatment. The results indicate that CMZS is an effective adsorbent for U(VI) from aqueous solutions.

Assembly and luminescence properties of lanthanide-polyoxometalates/polyethyleneimine/SiO{sub 2} particles with core–shell structure

Energy Technology Data Exchange (ETDEWEB)

Wang, Jun, E-mail: junwang924@yahoo.com.cn; Fan, Shaohua; Zhao, Weiqian; Zhang, Hongyan

2013-01-01

In this paper, two lanthanide-polyoxometalate (LnW{sub 10}) complexes were bonded on the surface of the polyethyleneimine (PEI)-modified silica nanoparticles with different sizes, resulting in the formation of LnW{sub 10}/PEI/SiO{sub 2} particles. The hybrid core–shell particles were characterized by infrared, luminescent spectra, scanning electronic microscope, and transmission electronic microscope. The particles obtained exhibit the fine spherical core–shell structure and the excellent luminescence properties. The luminescence spectra studies revealed that the formation of LnW{sub 10}/PEI/SiO{sub 2} particles and the size of particle have an influence on the luminescence properties of lanthanide ions. - Highlights: ► SiO{sub 2}/polyethyleneimine (PEI) shows the chemisorption for Ln-polyoxometalates (LnW{sub 10}). ► The core-shell LnW{sub 10}/PEI/SiO{sub 2} nanoparticles with different sizes were fabricated. ► The hybrid particles exhibit the excellent luminescence properties. ► The sizes of particles affect the luminescence properties of lanthanide ions.