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Sample records for chemisorption

  1. Chemisorption And Precipitation Reactions

    Science.gov (United States)

    The transport and bioavailability of chemical components within soils is, in part, controlled by partitioning between solids and solution. General terms used to describe these partitioning reactions include chemisorption and precipitation. Chemisorption is inclusive of the suit...

  2. Refrigerator Based on Chemisorption

    Science.gov (United States)

    Jones, Jack A.

    1987-01-01

    Reversible chemical reaction generates pressurized oxygen for cooling. Concept for cryogenic refrigerator based on chemical absorption of oxygen by praseodymium/cerium oxide (PCO) compound. Refrigerator produces cryogenic liquid for cooling infrared sensors. Also used for liquefying air and separating oxygen from nitrogen in air. In chemisorption refrigerator, PCO alternately absorbs and desorbs oxygen depending on whether cooled or heated. One pair of compressors accepts oxygen while others releases it. Compressed oxygen liquefied when precooked and expanded.

  3. Oxygen chemisorption cryogenic refrigerator

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1987-01-01

    The present invention relates to a chemisorption compressor cryogenic refrigerator which employs oxygen to provide cooling at 60 to 100 K. The invention includes dual vessels containing an oxygen absorbent material, alternately heated and cooled to provide a continuous flow of high pressure oxygen, multiple heat exchangers for precooling the oxygen, a Joule-Thomson expansion valve system for expanding the oxygen to partially liquefy it and a liquid oxygen pressure vessel. The primary novelty is that, while it was believed that once oxygen combined with an element or compound the reaction could not reverse to release gaseous oxygen, in this case oxygen will indeed react in a reversible fashion with certain materials and will do so at temperatures and pressures which make it practical for incorporation into a cryogenic refrigeration system.

  4. The chemisorptive bond basic concepts

    CERN Document Server

    Clark, Alfred

    1974-01-01

    The Chemisorptive Bond: Basic Concepts describes the basic concepts of the chemisorptive bond on solid surfaces from the simple analogies with ordinary chemical bonds to the quantum-mechanical approaches.This book is composed of 10 chapters and begins with discussions of simple formulas for correlating measurable quantities in chemisorptions and catalysis. The succeeding chapters deal with theories based on quantum-mechanical principles that describe the mutual interactions of atoms of the solid and foreign atoms on the surface. The remaining chapters consider the possible arrangements

  5. Modified Technique For Chemisorption Measurements

    Science.gov (United States)

    Schryer, David R.; Brown, Kenneth G.; Schryer, Jacqueline

    1989-01-01

    In measurements of chemisorption of CO on Pt/SnO2 catalyst observed that if small numbers of relatively large volumes of adsorbate gas are passed through sample, very little removal of CO detected. In these cases little or no CO has been chemisorbed on Pt/SnO2. Technique of using large number of small volumes of adsorbate gas to measure chemisorption applicable to many gas/material combinations other than CO on Pt/SnO2. Volume used chosen so that at least 10 percent of adsorbate gas removed during each exposure.

  6. Chemisorptive electron emission versus sticking probability

    Science.gov (United States)

    Böttcher, Artur; Niehus, Horst

    2001-07-01

    The chemisorption of N2O on thin Cs films has been studied by monitoring the time evolution of the sticking probability as well as the kinetics of the low-energy electron emission. By combining the data sets, two time domains become distinguishable: the initial chemisorption stage is characterized by a high sticking probability (0.1exoemission and the chemisorption excludes the model of surface harpooning as the elementary process responsible for the electron emission in the late chemisorption stage. A long-term emission decay has also been observed after turning off the flux of chemisorbing molecules. A model is proposed that attributes both, the late chemisorptive and the nonchemisorptive electron emission to the relaxation of a narrow state originated from an oxygen vacancy in the Cs oxide layer terminating the surface. The presence of such a state has been confirmed by the metastable de-excitation spectroscopy [MDS, He*(21S)].

  7. Chemisorption on supported-metal catalysts

    Science.gov (United States)

    Davison, S. G.; Bose, S. M.; Sulston, K. W.

    1988-07-01

    A Gree-function formalism is developed to describe the electronic and chemisorption properties of a supported-metal composite substrate. Within the framework of the tight-binding approximation, the metal catalyst is represented by a finite chain of d-orbitals, while the semi-infinite semiconductor support is characterized by a linear chain of alternating s- and p-orbitals. The Anderson-Newns model is used to calculate the chemisorption energy and adatom charge transfer for hydrogen chemisorption on the Ni/ZnO composite system.

  8. N2 chemisorption to W-n nanoclusters : molecular versus dissociative chemisorption

    OpenAIRE

    Kim, Young Dok; Stolcic, Davor; Fischer, Matthias; Ganteför, Gerd

    2003-01-01

    Comparative studies on adsorption of atomic and molecular nitrogen indicate that in contrast to the previous results from tungsten bulk crystals, molecular chemisorption of N2 is more stable than dissociative ones on tungsten anion clusters consisting of 8 atoms or less. Our result provides a new aspect in chemisorption on metal clusters, namely the energetically preferred channel of chemisorption dissociative versus molecular might be different for metal clusters and bulk surfaces.

  9. CO Chemisorption at Metal Surfaces and Overlayers

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Morikawa, Y.; Nørskov, Jens Kehlet

    1996-01-01

    A database of ab initio calculations of the chemisorption energy of CO over Ni(111), Cu(111), Ru(0001), Pd(111), Ag(111), Pt(111), Au(111), Cu3Pt(111), and some metallic overlayer structures is presented. The trends can be reproduced with a simple model describing the interaction between the metal...... d states and the CO 2 pi* and 5 sigma states, renormalized by the metal sp continuum. Our model rationalizes the results by Rodriguez and Goodman [Science 257, 897 (1992)] showing a strong correlation between the CO chemisorption energy and the surface core level shift....

  10. Theory of hydrogen chemisorption on metals

    International Nuclear Information System (INIS)

    A theory of hydrogen chemisorption on metals is presented. Green's function is derived taking into account the coupling strength between metal and chemisorbed atom and the strength of the interatomic Coulomb repulsion, allowing the calculation of the local density of states at the adatom, especially for the limiting cases of strong and weak coupling

  11. Orbital-Specific Modeling of CO Chemisorption

    OpenAIRE

    Mason, Sara E.; Grinberg, Ilya; Rappe, Andrew M.

    2006-01-01

    We demonstrate that variations in molecular chemisorption energy on different metals, different surface terminations, and different strain conditions can be accounted for by orbital-specific changes in the substrate electronic structure. Our density functional theory data set, spanning three metals, two surface terminations, and five strain states, is fit to a single model based on tight binding. A crucial aspect of the model is decomposition of the $d$-band into contributions from the five $...

  12. CO Chemisorption at Metal Surfaces and Overlayers

    OpenAIRE

    Hammer, Bjørk; Morikawa, Y.; Nørskov, Jens Kehlet

    1996-01-01

    A database of ab initio calculations of the chemisorption energy of CO over Ni(111), Cu(111), Ru(0001), Pd(111), Ag(111), Pt(111), Au(111), Cu3Pt(111), and some metallic overlayer structures is presented. The trends can be reproduced with a simple model describing the interaction between the metal d states and the CO 2 pi* and 5 sigma states, renormalized by the metal sp continuum. Our model rationalizes the results by Rodriguez and Goodman [Science 257, 897 (1992)] showing a strong correlati...

  13. Reversible Chemisorption Gas-Gap Thermal Switch

    Science.gov (United States)

    Jones, Jack A.; Bard, Steven; Blue, Gary

    1991-01-01

    Gas/sorbent combinations provide means to turn heat-conduction paths on and off. Single-stage gas-gap thermal switch based on reversible chemisorption of hydrogen gas by ZrNiH. Two-stage gas-gap thermal switch based on reversible desorption of O2 from MnO2 in first stage, followed by absorption in Cu on zeolite in second stage. Requires relatively low power. Used in sorption refrigeration systems designed to operate for long times without maintenance.

  14. Chemisorption of Guanine on Cu(110)

    Science.gov (United States)

    Matos, Jeronimo; Kara, Abdelkader

    2011-03-01

    We use density functional theory (PBE) to calculate the adsorption of a guanine molecule on Cu(110). At saturation coverage, guanine adsorbs tilted with the oxygen atom strongly bound to one of the surface atoms at a height of 2.12 Å above this surface atom with a binding energy of 430 meV/molecule. The substrate top layer atoms show a buckling of 0.22 Å , while the molecule experiences a twist from the flat configuration in the gas phase. The dz 2 state of the copper atom -that is bound to the oxygen atom- presents an enhancement in its density near the Fermi level. We calculated a drop in the work function of 0.34 eV upon adsorption of guanine on Cu(110). These effects classify this system as chemisorption.

  15. Chemisorption of SO2 and Cl2 on indium oxide

    International Nuclear Information System (INIS)

    The mutual influence of SO2 and Cl2 during chemisorption on In2O3 surface has been studied. It is shown that SO2 molecules are adsorbed in a non-charged form and the amount of SO2 adsorbed decreases with temperature increase. Preliminary Cl2 chemisorption results in an abrupt decrease of SO2 sorption and change in SO2 bonding with indium oxide surface. In case of SO2 presorption a decrease in temperature of chloride formation during subsequent Cl2 chemisorption takes place. 8 refs.; 3 figs.; 1 tab

  16. Chemisorption of O and H on an Al-13 cluster

    Science.gov (United States)

    Patridge, H.; Bauschlicher, C. W., Jr.

    1986-01-01

    Chemisorption of oxygen and hydrogen atoms onto a 13 atom aluminum cluster is investigated theoretically. Oxygen atoms are found to remain on the outside of the cluster, and at low coverage, to expand the Al-Al bond length by 0.42 bohr. Hydrogen atoms penetrate into the cluster resulting in a sizeable, 0.57 bohr expansion at high coverage. The difference between chemisorption on aluminum and beryllium clusters is discussed.

  17. Summary Abstract: Chemisorption of water on Rh(111)

    OpenAIRE

    Zinck, J. J.; Weinberg, W. H.

    1980-01-01

    The chemisorption of H2O on the (111) surface of Rh has been studied by thermal desorption mass spectrometry and low-energy electron diffraction. In addition to the clean surface, the chemisorptive behavior of H2O has been examined when various coverages of oxygen, hydrogen, or carbon monoxide have been pre-adsorbed on the surface in the form of atomic oxygen, atomic hydrogen, and molecular CO.

  18. Direct dissociative chemisorption of propane on Ir(110)

    International Nuclear Information System (INIS)

    We have employed molecular beam techniques to investigate the initial probability of direct dissociative chemisorption, Pd, and the intrinsic trapping probability, ξ, of C3H8, C3D8, and (CH3)2CD2 on Ir(110) as a function of beam translational energy, Ei, from 1.5 to 59 kcal/mol. For C3H8 and (CH3)2CD2, a measurable (≥0.02) initial probability of direct dissociative chemisorption is observed above a beam energy of approximately 7 kcal/mol. For C3D8 this energy is roughly 10 kcal/mol. Above these energies the initial probability of direct chemisorption of each of the isotopomers of propane increases nearly linearly with Ei, approaching a value of approximately Pd=0.48 at Ei=52 kcal/mol for C3H8 and (CH3)2CD2, and Pd=0.44 at Ei=59 kcal/mol for C3D8. This kinetic isotope effect for the direct chemisorption of C3D8 relative to C3H8 is smaller than that expected for a mechanism of H (or D) abstraction by tunneling through an Eckart barrier, suggesting a contribution of C endash C bond cleavage to direct chemisorption. The lack of a kinetic isotope effect for the direct chemisorption of (CH3)2CD2 relative to C3H8 indicates that 1 degree C endash H bond cleavage dominates over 2 degree C endash H bond cleavage during the direct chemisorption of propane on Ir(110). The trapping behavior of each of these isotopomers of propane is approximately identical as a function of Ei, with ξ>0.9 at Ei=1.5 kcal/mol, ξ=0.3 at Ei=20 kcal/mol, and ξi=40 kcal/mol. copyright 1996 American Institute of Physics

  19. Wastewater centrate ammonia removal by chemisorption processes

    International Nuclear Information System (INIS)

    '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

  20. A model for nitrogen chemisorption in ion thrusters

    Science.gov (United States)

    Wilbur, P. J.

    1979-01-01

    A theoretical model describing the formation of nitrogen species subject to chemisorption on ion thruster discharge chamber surfaces is presented. Molecules, atoms, atomic ions and molecular ions are identified as the important species in the analysis. Current densities of the atomic and molecular ions predicted by the model are compared to current densities measured in the beam of a SERT II thruster. The predicted and measured values of these two current densities are shown to agree within about + or - 100%. The mechanisms involved in the erosion of a surface subjected to simultaneous nitrogen chemisorption and sputter erosion by high energy ions are also discussed.

  1. Nature of Chemisorption on Titanium Carbide and Nitride

    OpenAIRE

    Ruberto, Carlo; Vojvodic, Aleksandra; Lundqvist, Bengt I.

    2005-01-01

    Extensive density-functional calculations are performed to understand atomic chemisorption on the TiC(111) and TiN(111) surfaces, in particular the calculated pyramid-shaped trends in the adsorption energies for second- and third-period adatoms. Our previously proposed concerted-coupling model for chemisorption on TiC(111) is tested against new results for adsorption on TiN(111) and found to apply on this surface as well, thus reflecting both similarities and differences in electronic structu...

  2. Chemisorption-Induced Resonance Frequency Shift of a Microcantilever

    International Nuclear Information System (INIS)

    The autonomy and property of atoms/molecules adsorbed on the surface of a microcantilever can be probed by measuring its resonance frequency shift due to adsorption. The resonance frequency change of a cantilever induced by chemisorption is theoretically studied. Oxygen chemisorbed on the Si(100) surface is taken as a representative example. We demonstrate that the resonant response of the cantilever is mainly determined by the chemisorption-induced bending stiffness variation, which depends on the bond configurations formed by the adsorbed atoms and substrate atoms. This study is helpful for optimal design of microcantilever-based sensors for various applications. (condensed matter: structure, mechanical and thermal properties)

  3. Commensurate Registry and Chemisorption at a Hetero-organic Interface

    Science.gov (United States)

    Stadtmüller, Benjamin; Sueyoshi, Tomoki; Kichin, Georgy; Kröger, Ingo; Soubatch, Sergey; Temirov, Ruslan; Tautz, F. Stefan; Kumpf, Christian

    2012-03-01

    We present evidence for a partly chemisorptive bonding between single monolayers of copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) that are stacked on Ag(111). A commensurate registry between the two molecular layers and the substrate, i.e., a common crystallographic lattice for CuPc and PTCDA films as well as for the Ag(111) surface, indicates that the growth of the upper layer is dominated by the structure of the lower. Photoemission spectroscopy clearly reveals a gradual filling of the lowest unoccupied molecular orbital of PTCDA due to CuPc adsorption, which proves the chemisorptive character.

  4. Dissociative chemisorption of N2 on Rhenium

    DEFF Research Database (Denmark)

    Billing, Gert D.; Guldberg, Annette; Henriksen, Niels Engholm;

    1990-01-01

    The dissociative chemisorption of nitrogen on the (0001) rhenium surface is studied at low impact energies, where tunnelling processes are important. A quantum-classical model is used in which two coordinates, the distance from the surface and the vibrational coordinate, are treated quantum...

  5. Chemisorption Techniques for the Determination of Metal Dispersion

    International Nuclear Information System (INIS)

    Chemisorption is an effective and un expensive analytical technique for characterizing and titrating active centers of the catalyst surface and for evaluating its activity with good approximation. The paper describes experimental procedures and the nature of information that can be obtained about active metal dispersion and area, diameter of active particles and isosteric heat of dispersion

  6. Theoretical study of chemisorption of CO on copper clusters

    International Nuclear Information System (INIS)

    The cluster size oscillations of the chemisorption energies are strongly effected by the geometry optimization of the clusters. This is found to be true for the case of CO absorbed on copper clusters of which this paper investigated using a correlated quantum chemical model approach

  7. Chemisorption of uranium hexa-fluoride on sodium fluoride pellets

    International Nuclear Information System (INIS)

    This paper comprises kinetics of chemical reaction or rather chemisorption of uranium hexafluoride gas on sodium fluoride pellets. The chemisorption is essentially irreversible at room temperature, while the process reverses at high temperature above 280 deg C. This chemisorption process was experimentally conducted in static condition at room temperature and its kinetics was studied. In the experiments, practically pure UF6 was used and the effects of gas pressure and weight of NaF pellets, were studied. In this heterogenous reaction, in which diffusion through ash layer is followed by chemical reaction, the reaction part is instantaneous and is first order with respect to gas concentration. Since the process of chemisorption is not only pure chemical reaction but also gas diffusion through ash layer, the rate constant depreciates with the percentage loading of UF6 on NaF pellets. The kinetic equation for the above process has been established for a particular size of NaF pellets and pellet porosity. (author)

  8. Chemisorption of ordered atomic layers on a model transition metal

    International Nuclear Information System (INIS)

    The effect of chemisorption of ordered atomic layers with p(1x1), p(2x1), c(2x2), p(2x2), p(4x1), and c(4x2) structures on the (001) surface of a tight-binding (model transition) metal is investigated within the Newns-Anderson model using the Hartree-Fock Green's function formalism and the phase shift technique. The self-consistent adatom charge q, the heat of adsorption ΔE, and the change in the electronic density of states during chemisorption are calculated for the two binding sites (on-site and centered fourfold-site). Particular attention is paid to the H/W (001) system and the results are compared with the available experimental results. It is shown that the long-range order and adsorption geometry of the overlayers are of great importance for the electronic properties of the chemisorbed systems. (author)

  9. Studies on chemisorption of oxygen on copper orthovanadate

    International Nuclear Information System (INIS)

    Kinetics of chemisorption of oxygen has been measured by the constant volume method on copper orthovanadate (a) preheated at 350 deg C in vacuo and (b) preheated with hydrogen at 130 deg C. Arrhenius activation energy for the former increases with surface coverage at 138 deg C-239 deg C, while for the latter it generally decreases and becomes negative at higher coverages. An attempt has been made to explain the negative activation energy on the basis of the Knudsen diffusion. (author)

  10. Modified carbon nanoparticle-chitosan film electrodes: Physisorption versus chemisorption

    Energy Technology Data Exchange (ETDEWEB)

    Rassaei, Liza; Sillanpaeae, Mika [Laboratory of Applied Environmental Chemistry, Department of Environmental Sciences, University of Kuopio, Patteristonkatu 1, 50101 Mikkeli (Finland); Marken, Frank [Department of Chemistry, University of Bath, Bath BA2 7AY (United Kingdom)

    2008-08-01

    Surface functionalised carbon nanoparticles of ca. 8 nm diameter co-assemble with chitosan into stable thin film electrodes at glassy carbon surfaces. Robust electrodes for application in sensing or electrocatalysis are obtained in a simple solvent evaporation process. The ratio of chitosan binder backbone to carbon nanoparticle conductor determines the properties of the resulting films. Chitosan (a poly-D-glucosamine) has a dual effect (i) as the binder for the mesoporous carbon composite structure and (ii) as binding site for redox active probes. Physisorption due to the positively charged ammonium group (pK{sub A} {approx} 6.5) occurs, for example, with anionic indigo carmine (a reversible 2e{sup -}-2H{sup +} reduction system in aqueous media). Chemisorption at the amine functionalities is demonstrated with 2-bromo-methyl-anthraquinone in acetonitrile (resulting in a reversible 2e{sup -}-2H{sup +} anthraquinone reduction system in aqueous media). Redox processes within the carbon nanoparticle-chitosan films are studied and at sufficiently high scan rates diffusion of protons (buffer concentration depended) is shown to be rate limiting. The chemisorption process provides a much more stable interfacial redox system with a characteristic and stable pH response over a pH 2-12 range. Chemisorption and physisorption can be employed simultaneously in a complementary binding process. (author)

  11. Indication of a size-dependent transition from molecular to dissociative chemisorption on clusters

    OpenAIRE

    Burkart, Stefan; Blessing, Nico; Ganteför, Gerd

    1999-01-01

    We report experimental indications for a size-dependent change of the chemical nature of chemisorption on small atomic clusters. We studied chemisorption of atomic hydrogen on negatively charged Tin- clusters using mass and photoelectron spectroscopy. Our experimental data support the assumption that for clusters with up to four Ti atoms, adsorption of intact H2 molecules is the energetically preferred configuration. For larger Tin clusters with n>4, dissociative hydrogen chemisorption is the...

  12. Chemisorption kinetics of hydrogen on evaporated iron films

    Science.gov (United States)

    Shanabarger, M. R.

    1975-01-01

    An investigation is conducted of the kinetics of isothermal adsorption-desorption processes involving molecular hydrogen which is chemisorbed onto thin (20 to 50 A) polycrystalline Fe films at temperatures near 300 K. The results of the investigation indicate that chemisorption in the H2-Fe system occurs via a precursor state of molecularly adsorbed hydrogen. Contamination of the surface from unknown impurities in the gas phase is found to affect the number of available adsorption sites and to modify the prefactor for the absolute desorption rate constant for the precursor state.

  13. Chemisorption and catalytic decrease of sintering temperature for ceramics

    International Nuclear Information System (INIS)

    An explanation is suggested for a sintering temperature decrease in oxide ceramics (76%ZrO2, 19.8%Al2O3, 4.2Y2O3) during ceramic powder processing with carbon tetrachloride. It is shown that chemisorption on surface of powders to be compacted can affect both the density of compacts through a decrease of friction factor between powder particles and the kinetics of sintering through formation of additional vacancies in the process of chemisorbed substance dissolution over the bulk of particles. 6 refs

  14. Commensurate registry and chemisorptions at a hetero-organic interface

    OpenAIRE

    Stadtmüller, B; Sueyoshi, T; Kichin, G.; Kröger, I.; Soubatch, S.; Temirov, R.; Tautz, F. S.; Kumpf, C.

    2012-01-01

    We present evidence for a partly chemisorptive bonding between single monolayers of copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) that are stacked on Ag(111). A commensurate registry between the two molecular layers and the substrate, i.e., a common crystallographic lattice for CuPc and PTCDA films as well as for the Ag(111) surface, indicates that the growth of the upper layer is dominated by the structure of the lower. Photoemission spectroscopy c...

  15. Oxygen chemisorption compressor study for cryogenic J-T refrigeration

    Science.gov (United States)

    Jones, Jack A.; Blue, Gary D.

    1987-01-01

    Over twenty potentially reversible heat-powered oxide reactions have been studied and/or tested to determine their potential use as thermochemical oxygen compressors for cryogenic J-T LO2 refrigerators. One gas-solid compound family, Pr(1-n)Ce(n)O(x), proved to be completely reversible with fast kinetics for all pressure ranges tested below 650 C. With a heat-powered charcoal/methane physical adsorption upper stage and a Pr(1-n)Ce(n)O(x) chemisorption lower stage, temperatures should be attainable in the 55-80 K range for less power and over five times less weight than for charcoal/nitrogen sorption refrigeration systems. Total system power requirements with a hydride chemisorption lower stage (10 K to 7 K minimum) are about three times less than any mechanical refrigerator, and spacecraft refrigeration weights are about twenty times less. Due to the lack of wear-related moving parts in sorption refrigerators, life expectancy is at least ten years, and there essentially no vibration.

  16. Hydrogen chemisorption and oxidation of transition metal carbides

    International Nuclear Information System (INIS)

    A study was made of the catalytic activity of WC, focusing on the possible influence of point defects. The chemisorption of H on WC and titanium oxycarbides was studied with differential scanning calorimetry. The catalytic activity of these materials for oxidation of H was determined by potentiostatic steady-state and potentiodynamic measurements in acid electrolyte. Compositions of WC surfaces were determined by x-ray photoemission and related to the catalytic behavior. Titanium oxycarbide surfaces were analyzed by Auger electron spectroscopy. Of the carbides tested only one WC preparation was able to chemisorb H. Both WC powders investigated catalyzed H oxidation with similar specific activities. Spectroscopic studies showed that the active surface of WC was a mixture of WO3 and a carbon-deficient WC phase. This result indicates that carbon vacancies are the active sites in tungsten carbide. Theoretical models of a carbon vacancy surrounded by metal atoms suggested by calculations by other workers support this assignment and identify the important role of the W6s level. The measured value of the heat of chemisorption is consistent with the proposed model

  17. Modelling of a chemisorption refrigeration and power cogeneration system

    International Nuclear Information System (INIS)

    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

  18. Chemisorption and Reactions of Small Molecules on Small Gold Particles

    Directory of Open Access Journals (Sweden)

    Geoffrey C. Bond

    2012-02-01

    Full Text Available The activity of supported gold particles for a number of oxidations and hydrogenations starts to increase dramatically as the size falls below ~3 nm. This is accompanied by an increased propensity to chemisorption, especially of oxygen and hydrogen. The explanation for these phenomena has to be sought in kinetic analysis that connects catalytic activity with the strength and extent of chemisorption of the reactants, the latter depending on the electronic structure of the gold atoms constituting the active centre. Examination of the changes to the utilisation of electrons as particle size is decreased points to loss of metallic character at about 3 nm, as energy bands are replaced by levels, and a band gap appears. Detailed consideration of the Arrhenius parameters (E and ln A for CO oxidation points clearly to a step-change in activity at the point where metallic character is lost, as opposed to there being a monotonic dependence of rate on a physical property such as the fraction of atoms at corners or edges of particles. The deplorable scarcity of kinetic information on other reactions makes extension of this analysis difficult, but non-metallic behaviour is an unavoidable property of very small gold particles, and therefore cannot be ignored when seeking to explain their exceptional activity.

  19. X-Ray Absorption Characterization of Supported Palladium Catalysts : A Comparison with Hydrogen Chemisorption

    OpenAIRE

    Zhang, G.; Habib, M; Vittoratos, S.

    1997-01-01

    X-ray absorption spectroscopy was used to characterize the supported palladium hydrocracking catalysts. Results with regard to the percentage of metal exposed are compared with those from hydrogen chemisorption measurements. Results from XAS indicate that hydrogen chemisorption has underestimated the metal dispersion. Possible explanations for this discrepancy are discussed.

  20. Communication: Enhanced dissociative chemisorption of CO2 via vibrational excitation

    Science.gov (United States)

    Jiang, Bin; Guo, Hua

    2016-03-01

    A fully coupled global nine-dimensional potential energy surface for the dissociative chemisorption of CO2 on Ni(100) is constructed from ˜18 000 density functional points. It reveals a complex reaction pathway dominated by two near iso-energetic transition states. The dissociation probabilities obtained by quasi-classical trajectories on the potential energy surface reproduced experimental trends, and indicate that vibrational excitations of CO2 significantly promote the dissociation. Using the sudden vector projection model, the behavior of the reactivity is rationalized by couplings with the reaction coordinate at each transition state. These results offer plausible rationalization for the observed enhancement of CO2 dissociation in non-thermal plasmas by metal surfaces.

  1. Quantum modelling of hydrogen chemisorption on graphene and graphite

    International Nuclear Information System (INIS)

    The chemisorption of hydrogen on graphene or graphite is studied within a quantum formalism involving a subsystem coupled to a phonon bath. The subsystem includes the hydrogen atom approaching the surface perpendicularly right on top of a carbon atom which puckers out of the surface. The bath includes the acoustic and optical phonon modes vibrating perpendicularly to the surface. Couplings between subsystem and bath are obtained with a periodic density functional theory calculation. Trapping probabilities are obtained as a function of the hydrogen atom kinetic energy. These results are discussed in the light of the experimental hydrogenation studies performed on graphite by Zecho et al. [J. Chem. Phys. 117, 8486 (2002)] and on graphene by Haberer et al. [Adv. Mater. 23, 4497 (2011)

  2. Chemisorption of CO on particulate deposits of platinum

    Science.gov (United States)

    Doering, D. L.; Poppa, H.; Dickinson, J. T.

    1982-01-01

    Morphology and CO chemisorption properties are studied as a function of particle size for the case of particulate Pt films, vapor-deposited onto ultrahigh vacuum-cleaved and heat-treated mica surfaces at a 200 C substrate temperature. The particles were found to be mostly irregular in shape and randomly-oriented, with two desorption peaks after CO absorption at 60 C: (1) an alpha peak, at 120 C, attributed to smooth particle surfaces, and (2) a beta peak, at about 175 C, attributed to particle edges and steps. Transmission electron microscopy showed that major changes occur in particle morphology during absorption-desorption cycling, so that the decrease in CO desorption flux may be interpreted as due to particle restructuring, rather than contamination by CO decomposition as in the cases of Ni or Pd on mica. Auger electron spectroscopy corroborates the lack of CO decomposition, even for the case of very small Pt particles.

  3. Dissociative chemisorption dynamics of small molecules on metal surfaces

    Institute of Scientific and Technical Information of China (English)

    JIANG Bin; XIE DaiQian

    2014-01-01

    Much progress has been achieved for both experimental and theoretical studies on the dissociative chemisorption of molecules on surfaces.Quantum state-resolved experimental data has provided unprecedented details for these fundamental steps in heterogeneous catalysis,while the quantitative dynamics is still not fully understood in theory.An in-depth understanding of experimental observations relies on accurate dynamical calculations,in which the potential energy surface and adequate quantum mechanical implementation are desired.This article summarizes the current methodologies on the construction of potential energy surfaces and the quantum mechanical treatments,some of which are promising for future applications.The challenges in this field are also addressed.

  4. Formation of cavities in Si and their chemisorption of metals

    International Nuclear Information System (INIS)

    Nanometer-size cavities formed in Si by He+ implantation and annealing are examined with cross-section TEM. During annealing at 700 C or above, He degasses from the specimens, leaving uhv cavities with reactive Si bonds on their walls. Cavity microstructures have been characterized in detail for an implanted fluence of 1 x 1017 He/cm2: cavity volume remains approximately constant (0.75 lattice sites/He) for anneals from 700 to ∼1000 C, while surface area (3 to 7 times the wafer area) decreases with temperature as the cavities coarsen. The cavities are found to getter up to ∼1 monolayer of Cu or Au from solution in Si without second-phase formation, thus identifying the trapping mechanism as chemisorption on the cavity walls

  5. Nanocatalysis: size- and shape-dependent chemisorption and catalytic reactivity

    Science.gov (United States)

    Roldan Cuenya, Beatriz; Behafarid, Farzad

    2015-06-01

    In recent years, the field of catalysis has experienced an astonishing transformation, driven in part by more demanding environmental standards and critical societal and industrial needs such as the search for alternative energy sources. Thanks to the advent of nanotechnology, major steps have been made towards the rational design of novel catalysts. Striking new catalytic properties, including greatly enhanced reactivities and selectivities, have been reported for nanoparticle (NP) catalysts as compared to their bulk counterparts. However, in order to harness the power of these nanocatalysts, a detailed understanding of the origin of their enhanced performance is needed. The present review focuses on the role of the NP size and shape on chemisorption and catalytic performance. Since homogeneity in NP size and shape is a prerequisite for the understanding of structure-reactivity correlations, we first review different synthesis methods that result in narrow NP size distributions and shape controlled NPs. Next, size-dependent phenomena which influence the chemical reactivity of NPs, including quantum size-effects and the presence of under-coordinated surface atoms are examined. The effect of the NP shape on catalytic performance is discussed and explained based on the existence of different atomic structures on the NP surface with distinct chemisorption properties. The influence of additional factors, such as the oxidation state of the NPs and NP-support interactions, is also considered in the frame of the size- and shape-dependency that these phenomena present. Ultimately, our review highlights the importance of achieving a systematic understanding of the factors that control the activity and selectivity of a catalyst in order to avoid trial and error methods in the rational design of the new generation of nanocatalysts with properties tunable at the atomic level.

  6. Diffusion-controlled chemisorption transitions for (La,Sr)MnO3

    International Nuclear Information System (INIS)

    This paper considers the mechanism of oxygen interaction with the surface of oxide electrode materials, such as LSM, and surface related electrical properties. The mechanism involves rapid oxygen chemisorption, resulting in an increase of the surface charge, followed by slow oxygen incorporation, resulting in a shift of chemisorption equilibria and leading, in consequence, to a decrease of the surface charge. The latter process, involving transient chemisorption, is controlled by chemical diffusion. A good agreement between the chemical diffusion coefficient determined from work function and that determined by the manometric method is revealed. Copyright (1998) Australasian Ceramic Society

  7. The dissociative chemisorption of silane on the Si(111)7x7 surface

    International Nuclear Information System (INIS)

    Full text: The study of the interaction of silane with semiconducting substrates is of both fundamental and technological importance. This paper reports theoretical calculations of the initial stages of the dissociative chemisorption of silane on the Si(111)7x7 surface. The calculations have been performed within the periodic slab formalism using the extended Brenner empirical potential. The geometries and energetics of the different chemisorption structures are discussed, and compared with the existing experimental data

  8. Quantum-size effects on chemisorption properties: CO on Cu ultrathin films

    OpenAIRE

    Mouketo, L.; Binggeli, N.; M'Passi-Mabiala, B.

    2011-01-01

    We address, by means of ab-initio calculations, the origin of the correlation that has been observed experimentally between the chemisorption energy of CO on nanoscale Cu(001) supported films and quantum-size effects. The calculated chemisorption energy shows systematic oscillations, as a function of film thickness, with a periodicity corresponding to that of quantum-well states at the surface-Brillouin-zone center crossing the Fermi energy. We explain this trend based on the oscillations, wi...

  9. Molecular N-2 chemisorption-specific adsorption on step defect sites on Pt surfaces

    OpenAIRE

    Tripa, C. Emil; Zubkov, T.S.; Yates, John T.; Mavrikakis, Manos; Nørskov, Jens Kehlet

    1999-01-01

    Infrared reflection-absorption spectroscopy and density functional theory, within the generalized gradient approximation, were used to investigate both experimentally and theoretically N-2 chemisorption on stepped and smooth Pt surfaces. N-2 chemisorption was observed to occur only on the edge atoms of step defect sites in atop configuration by both methods. The calculated vibrational frequency of N-2 chemisorbed on Pt(112) step sites (2244 cm(-1)) is in good agreement with the frequency obse...

  10. Influence of chemisorption products of carbon dioxide and water vapour on radiolysis of tritium breeder

    International Nuclear Information System (INIS)

    Highlights: • Chemisorption products affect formation proceses of radiation-induced defects. • Radiolysis of chemisorption products increase amount of radiation-induced defects. • Irradiation atmosphere influence radiolysis of lithium orthosilicate pebbles. - Abstract: Lithium orthosilicate pebbles with 2.5 wt% excess of silica are the reference tritium breeding material for the European solid breeder test blanket modules. On the surface of the pebbles chemisorption products of carbon dioxide and water vapour (lithium carbonate and hydroxide) may accumulate during the fabrication process. In this study the influence of the chemisorption products on radiolysis of the pebbles was investigated. Using nanosized lithium orthosilicate powders, factors, which can influence the formation and radiolysis of the chemisorption products, were determined and described as well. The formation of radiation-induced defects and radiolysis products was studied with electron spin resonance and the method of chemical scavengers. It was found that the radiolysis of the chemisorption products on the surface of the pebbles can increase the concentration of radiation-induced defects and so could affect the tritium diffusion, retention and the released species

  11. Theoretical study of CO chemisorption on nickel and copper surfaces

    Science.gov (United States)

    Yu, H. L.

    1978-01-01

    A comparative study of the chemisorption of CO on Ni(001) and Cu(001) surfaces has been performed. The study is based on an analysis of the electronic structure of (M)5CO clusters obtained from self-consistent field X alpha scattered-wave calculations. The electron orbital formed principally by the 5 sigma orbital on CO was found to be mainly responsible for the bonding of the CO molecule to the metal surface for both the CO/Ni and CO/Cu systems. The different occupation of the antibonding 7 a sub 1 orbital in the two clusters is believed to be the major reason for the large difference observed in the measured heats of adsorption of CO on Ni and Cu surfaces. It was found also that metal atoms transfer electronic charge to the antibonding pi(asterisk)-like orbital of CO. A possible correlation between the amount of the charge transfered and the relative ease of dissociation of CO molecules on metal surfaces is discussed.

  12. 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.

  13. DETERMINATION OF THE METAL PARTICLE SIZE OF SUPPORTED Pt, Rh, AND Ir CATALYSTS. A CALIBRATION OF HYDROGEN CHEMISORPTION BY EXAFS

    OpenAIRE

    Zon, van, JBAD Hans; Kip, BJ; Koningsberger, DC Diek; Prins, R Roel

    1986-01-01

    Hydrogen chemisorption measurements of highly dispersed Pt, Rh, and Ir catalysts yielded H/M values exceeding unity. These results cannot be used straightforwardly to determine the average metal particle size, because the H/M stoichiometry on the surface is unknown. EXAFS measurements were performed to determine the metal particle size and thereby, to calibrate the hydrogen chemisorption results. The high hydrogen chemisorption values can be explained best by assuming H/M surface stoichiometr...

  14. An investigation of the kinetics of hydrogen chemisorption on iron metal surfaces

    Science.gov (United States)

    Shanabarger, M. R.

    1982-01-01

    The isothermal kinetics of H2, H2S, and O2 chemisorption onto epitaxially grown (III) oriented Fe films were studied. The measurements were made using the techniques of chemisorption induced resistance change and Auger electron spectroscopy (for adsorbed sulfur and oxygen). Also the origin of the chemisorption induced resistance change for these systems and its applicability to kinetic measurements were established. The chemisorption kinetics were interpreted as dissociative chemisorption via an adsorbed molecular species. The applicable rate constants were established. In none of the studies were the rate constants observed to be coverage dependent. By comparing the temperature dependence of the rate constants with absolute rate theory, the binding energies and activation energies of all the kinetic processes were obtained for the H2/Fe system. The initial sticking coefficient was pressure dependent for both the H2/Fe and H2S/Fe systems. This results from the step between the adsorbed molecular state and the dissociated chemisorbed state being the rate limiting step for absorption at certain pressures and temperatures. Estimates were obtained for the temperature dependence of the rate constants for the O2/Fe system.

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

    Science.gov (United States)

    Srivastava, Deepak; Dzegilenko, Fedor; Menon, Madhu

    2000-01-01

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

  16. Chemisorption of Al and Ga on the GaAs (110) surface

    OpenAIRE

    Swarts, C. A.; Barton, J J; Goddard, W. A.; T. C. Mcgill

    1980-01-01

    We have studied the initial stages of the chemisorption of Al and Ga on the clean GaAs (110) surface by applying quantum chemical methods to small clusters representing Al or Ga on GaAs (110). These calculations suggest that at smallest coverages Al or Ga bind to a surface Ga atom; for higher coverages Al and the surface Ga interchange positions. We have obtained the binding energy, the chemical shifts of the Ga–3d, As–3d and Al–2p states, and the microscopic dipole associated with chemisorpt...

  17. An investigation of the kinetics for hydrogen chemisorption on iron metal surfaces

    Science.gov (United States)

    Shanabarger, M. R.

    1980-01-01

    A quasi-isothermal approach was used to study the kinetics of hydrogen and hydrogen sulfide chemisorption onto iron film in an effort to understand the environmental degradation of steels. The coverage of chemisorbed hydrogen or chemisorbed sulfur was observed as a function of time for fixed conditions of substrate temperature. Auger electron spectroscopy was used to observe the sulfur and chemisorption-induced resistance change was employed to monitor hydrogen coverage. To compare the results obtained from studying the kinetics by two different techniques, the kinetics of oxygen chemisorption onto iron films was also studied. A reaction model utilized to interpret the H2/Fe2 chemisorption kinetics was applied to data from an earlier study on the desorption kinetics for H2 chemisorbed onto nicket films in the vicinity of the Curie temperature of the film. This analysis permitted a separation of the gross desorption process into individual components so that the influence of the magnetic phase transition on the rate constants could be determined.

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

    International Nuclear Information System (INIS)

    Both chemisorption and physisorption affect the electronic properties of two-dimensional materials, such as MoS2, but it remains a challenge to probe their respective roles experimentally. Through repeated in-situ electrical measurements of few-layer MoS2 field-effect transistors in an ultrahigh vacuum system with well-controlled oxygen partial pressure (6 × 10−8 mbar–3 × 10−7 mbar), we were able to study the effect of chemisorption on surface defects separately from physically adsorbed oxygen molecules. It is found that chemisorption of oxygen results in n-doping in the channel but negligible effect on mobility and on/off ratio of the MoS2 transistors. These results are in disagreement with the previous reports on p-doping and degradation of the device's performance when both chemisorption and physisorption are present. Through the analysis of adsorption-desorption kinetics and the first-principles calculations of electronic properties, we show that the experimentally observed n-doping effect originates from dissociative adsorption of oxygen at the surface defects of MoS2, which lowers the conduction band edge locally and makes the MoS2 channel more n-type-like as compared to the as-fabricated devices

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

    Science.gov (United States)

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

    2016-02-01

    Both chemisorption and physisorption affect the electronic properties of two-dimensional materials, such as MoS2, but it remains a challenge to probe their respective roles experimentally. Through repeated in-situ electrical measurements of few-layer MoS2 field-effect transistors in an ultrahigh vacuum system with well-controlled oxygen partial pressure (6 × 10-8 mbar-3 × 10-7 mbar), we were able to study the effect of chemisorption on surface defects separately from physically adsorbed oxygen molecules. It is found that chemisorption of oxygen results in n-doping in the channel but negligible effect on mobility and on/off ratio of the MoS2 transistors. These results are in disagreement with the previous reports on p-doping and degradation of the device's performance when both chemisorption and physisorption are present. Through the analysis of adsorption-desorption kinetics and the first-principles calculations of electronic properties, we show that the experimentally observed n-doping effect originates from dissociative adsorption of oxygen at the surface defects of MoS2, which lowers the conduction band edge locally and makes the MoS2 channel more n-type-like as compared to the as-fabricated devices.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-02-08

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

  1. CHEMISORPTIONS OF ATOMIC OXYGEN AND ITS REPLACEMENT BY HYDROGEN ON THE DIAMOND (100) SURFACE STUDIED BY FIRST PRINCIPLES

    OpenAIRE

    Wang, Z. G.; X. T. ZU; J. L. NIE; H. Y. XIAO

    2006-01-01

    The initial oxidation process of a clean diamond (100) surface was studied by first-principles calculations. The O-bridge with C–O–C bond chemisorption, O-on-dimer chemisorption with epoxy structure, and O-on-top chemisorption with C=O bond structure are found to be stable on the diamond (100) surfaces. The epoxy structure is more stable than the O-bridge structure. The calculation also shows that the oxygen atom can be replaced by hydrogen in the oxidized diamond (100) surface.

  2. DFT-GGA errors in NO chemisorption energies on (111) transition metal surfaces: Possible origins and correction schemes

    OpenAIRE

    Huang, Xu; Mason, Sara E.

    2013-01-01

    Here we investigate whether well-known DFT-GGA errors in predicting the chemisorption energy ($E_{\\rm chem}$) of CO on transition metal surfaces manifest in analogous NO chemisorption systems. To verify the occurrence of DFT-GGA overestimation of the back-donation mechanism in NO Chemisorption, we use electronic structure analysis to show that the partially filled molecular NO 2$\\pi^{*}$ orbital rehybridizes with the transition metal $d$-band to form new bonding and anti-bonding states. We re...

  3. HCl chemisorption-induced drastic magneto-structural transformation in a layered cobalt-phosphonotriazolate coordination polymer.

    Science.gov (United States)

    Zhang, Weiquan; Wang, Dianpeng; Zhu, Lin; Zhai, Fupeng; Weng, Linhong; Sun, Jinyu; Ling, Yun; Chen, Zhenxia; Zhou, Yaming

    2016-07-14

    The chemisorption of gaseous HCl molecules in a two-dimensional coordination polymer results in subtle changes in its structure and instigates a drastic modification from antiferro- to ferromagnetic properties. PMID:27294584

  4. The effect of CO chemisorption on the metal surface CO/Ni(100)

    Science.gov (United States)

    Bauschlicher, Charles, W., jr.; Nelin, Constance J.

    1986-01-01

    The chemisorption of CO on Ni(100) is studied with a cluster model. The calculations suggest that chemisorption changes the nature of the Ni 3d orbitals. The open shell Ni 3d accepts charge from the Ni valence 4s4p orbitals, reducing the open shell 3d character on the Ni. The closed shell Ni 3d orbitals also mix with the Ni valence 4s4p orbitals and donate charge to the CO; thus helping to maintain the Ni 3d population near 9. These changes should affect the density of 3d states near the Fermi level and the surface magnetic moment. The variation in the bonding with the size of cluster is also discussed.

  5. 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; Nørskov, Jens Kehlet

    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 three...... developed to extend the Hammer-Norskov surface reactivity model [Surf. Sci. 343, 211 (1995)] to the analysis of bimetallic Pd-Re alloyed systems. The hydrogen chemisorption energies are correlated linearly to the surface d-band center, which is weighted appropriately by the d-band coupling matrix elements...... for Pd and Re. The farther the weighted d-band center is shifted below the Fermi energy, the weaker is the interaction of atomic hydrogen with the alloyed Pd-Re surface. (C) 2000 American Institute of Physics....

  6. CHEMISORPTION OF CO AND METHANATION ON Rh SURFACES AT LOW TEMPERATURE AND LOW PRESSURE, AN ATOM-PROBE FIM STUDY

    OpenAIRE

    W. Liu; Ren, D.; Bao, C.; Tsong, T.

    1987-01-01

    Pulsed-laser imaging atom-probe and high resolution voltage pulsed atom-probe were employed to study the chemisorption behavior of CO on rhodium surfaces at low temperature and low pressure. The results are consistent and interesting. Our results support dissociative chemisorption on stepped surfaces of Rh and the effect of the surface structures. We also carried out methanation on Rh surfaces under adverse conditions and identified the intermediates of methanation with an isotope exchange te...

  7. A molecular-beam study of the dissociative chemisorption of O2 on Ir(110)-(1×2)

    OpenAIRE

    Mullins, C B; Wang, Y.; Weinberg, W. H.

    1989-01-01

    The zero-coverage probability of dissociative chemisorption of O2 on Ir(110)-(1×2) has been measured using molecular-beam techniques for a wide range of incident kinetic energies, incident angles, and surface temperatures. The data indicate that a trapping-mediated mechanism is responsible for dissociative chemisorption at low energies, whereas at high energies a direct mechanism accounts for dissociative adsorption. Total energy scaling approximately describes the dissociative dynamics on th...

  8. EXCHANGE-SPLITTING OF ADSORBATE-INDUCED BANDS IN CHEMISORPTION ON FERROMAGNETIC 3d-METALS

    OpenAIRE

    Schönhense, G.; Getzlaff, M.; Westphal, C; Heidemann, B.; Bansmann, J.

    1988-01-01

    The influence of the ferromagnetism of 3d-metal substrates upon the electronic states of "nonmagnetic" adsorbate overlayers like oxygen and sulphur has been investigated by means of photoelectron spinpolarization spectroscopy. The spectra reveal a substantial exchange splitting of the O 2p- and S 3p-derived bands in chemisorption on Fe and FeCo. This demonstrates the strong magnetic coupling of these species with the substrate.

  9. Chemisorption of atomic and molecular oxygen on Au and Ag cluster anions : discrimination of different isomers

    OpenAIRE

    Kim, Young Dok; Ganteför, Gerd; Sun, Qiang; Jena, Purusottam

    2004-01-01

    Structures of coinage metal clusters reacted with atomic and molecular oxygen were studied using Ultraviolet Photoelectron Spectroscopy and Density Functional Theory calculations. We show that O2 partially dissociates on Ag-2, and this dissociative chemisorption is a kinetically hindered step. For Au4O-2, in addition to the previously observed molecularly adsorbed oxygen, we are now able to synthesize a second isomer using atomic oxygen reagents, in which oxygen adsorbs dissociatively. We dem...

  10. Nanoparticle chemisorption printing technique for conductive silver patterning with submicron resolution

    OpenAIRE

    Yamada, Toshikazu; Fukuhara, Katsuo; Matsuoka, Ken; Minemawari, Hiromi; Tsutsumi, Jun'ya; Fukuda, Nobuko; Aoshima, Keisuke; Arai, Shunto; Makita, Yuichi; Kubo, Hitoshi; Enomoto, Takao; Togashi, Takanari; Kurihara, Masato; Hasegawa, Tatsuo

    2016-01-01

    Silver nanocolloid, a dense suspension of ligand-encapsulated silver nanoparticles, is an important material for printing-based device production technologies. However, printed conductive patterns of sufficiently high quality and resolution for industrial products have not yet been achieved, as the use of conventional printing techniques is severely limiting. Here we report a printing technique to manufacture ultrafine conductive patterns utilizing the exclusive chemisorption phenomenon of we...

  11. Evolution of ConAl clusters and chemisorption of hydrogen on ConAl clusters

    International Nuclear Information System (INIS)

    The growth behavior of ConAl (n = 1–15) and the chemisorptions of hydrogen on the ground state geometries have been studied using the density functional theory (DFT) within the generalized gradient approximation (GGA). The growth pattern for ConAl is Al-substituted Con+1 clusters, and it keeps the similar frameworks of the most stable Con+1 clusters except for n = 2, 3, and 6. The Al atom substitutes the surface atom of the Con+1 clusters for n ≤ 13. Starting from n = 14, the Al atom completely falls into the center of the Co-frame. The dissociation energy, the second-order energy differences, and the HOMO–LUMO gaps indicate that the magic numbers of the calculated ConAl clusters are 7, 9, and 13, corresponding to the high symmetrical structures. To my knowledge, this is the first time that a systematic study of chemisorption of hydrogen on cobalt aluminum clusters. The twofold bridge site is identified to be the most favorable chemisorptions site for one hydrogen adsorption on ConAl (n = 1–6, 8, 10), and two hydrogen adsorption on ConAl (n = 1–7), while threefold hollow site is preferred for one hydrogen adsorption on ConAl (n = 7, 9, 11–15) and two hydrogen adsorption on ConAl (n = 8–10, 12–15) clusters. The ground state structure of two hydrogen adsorption on Co11Al is exceptional. In general, the binding energy of both H and 2H of ConAl (n = 1–12) is found to increase with the cluster size. And the result shows that large binding energies of the hydrogen atoms and large fragmentation energies for Co11AlH and Co12AlH make these species behaving like magic clusters.

  12. Isotope effects in trapping-mediated chemisorption of ethane and propane on Ir(110)

    International Nuclear Information System (INIS)

    We compare here recent results of molecular beam investigations of the initial probability of trapping-mediated C endash H and C endash D bond cleavage of C2H6, C2D6, C3H8, and C3D8 on Ir(110) at low beam translational energy and surface temperatures, TS, from 85 to 800 K. Each of these systems is highly reactive at low TS and displays decreasing reactivity with increasing TS. Measurements of the initial probability of trapping-mediated chemisorption for both ethane and propane reveal an isotope effect, which we attribute to zero-point energy differences, with the perhydrido-species exhibiting greater reactivity at a given TS. A difference in activation energies for desorption vs reaction (C endash D bond cleavage) for C2D6 has been found to be Ed endash Er=1.8±0.3 kcal/mol, cf. Ed endash Er=2.2 kcal/mol for C endash H bond cleavage of C2H6. For the trapping-mediated dissociative chemisorption of propane on Ir(110), Ed endash Er=4.2 kcal/mol for C endash H bond cleavage of C3H8, and Ed endash Er=3.2 kcal/mol for C endash D bond cleavage of C3D8. A quantitative analysis of the initial probability of trapping-mediated dissociative chemisorption of ethane and propane on Ir(110), within the context of a classical kinetic model of barrier crossing from the physically adsorbed state to the dissociatively chemisorbed state, provides the most reasonable description of the observed adsorption behavior. copyright 1996 American Institute of Physics

  13. Ca chemisorption on Cu(100) in the submonolayer regime: Metastable and stable adsorption phases

    OpenAIRE

    Rudolf, P.; Astaldi, C.; Bianco, A.; Modesti, S.

    1993-01-01

    Ca adsorption on Cu(100) has been studied by high-resolution electron energy-loss spectroscopy, work-function measurements, and low-energy electron diffraction as a function of coverage, up to one monolayer, at 110 and 300 K. At each coverage a condensed phase is formed at 110 K that irreversibly transforms into a dispersed phase upon heating. The 300-K data suggest that Ca occupies substitutional sites at this temperature. A comparison with the chemisorption of alkali metals is presented.

  14. Molecular cluster theory of CO chemisorption on a nickel /100/ surface

    Science.gov (United States)

    Ellis, D. E.; Baerends, E. J.; Adachi, H.; Averill, F. W.

    1977-01-01

    Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of carbon monoxide on a (100) transition metal surface are presented. Energy levels and charge distribution for the CO:Ni5 cluster in C sub 4v symmetry are obtained, and the variation of binding energies with height of the CO molecule above the surface of nickel is studied in detail. Comparison is made with experimental binding energy spectra and with the multiple-scattering results of Batra and Bagus. The redistribution in energy of free-atom valence levels is studied by means of local-densities-of-states diagrams.

  15. Molecular cluster theory for chemisorption of first row atoms on nickel /100/ surfaces

    Science.gov (United States)

    Ellis, D. E.; Adachi, H.; Averill, F. W.

    1976-01-01

    Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of first-row atoms on Ni(100) surfaces are presented. Energy levels and ground-state charge distributions are given for XNi5 clusters with the adatom X = H, C, N, O located in C4V symmetry at a fixed height of 2.0 au above the surface. The variation of properties with height was studied in detail for the case of oxygen. Theoretical results compare rather well with experimental photoelectron and energy-loss data. Local-densities-of-states diagrams are used to clarify the interaction between adsorbate levels and metal conduction bands.

  16. Tunneling electron induced chemisorption of copper phthalocyanine molecules on the Cu(111) surface

    International Nuclear Information System (INIS)

    The adsorption of up to one monolayer (ML) of copper phthalocyanine (CuPc) molecules on a room temperature Cu(111) surface has been studied using scanning tunneling microscopy (STM). Below 1 ML the molecules are in a fluid state and are highly mobile on the surface. At 1 ML coverage the molecules coalesce into a highly ordered 2D crystal phase. At sub-ML coverages, chemisorption of individual CuPc molecules can be induced through exposure to tunneling electrons at a tunneling bias voltage exceeding a threshold value. This tunneling electron induced effect has been exploited to perform molecular STM lithography

  17. 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

    2016-01-01

    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. PMID:27213387

  18. Absorption and Chemisorption of Small Levitated Single Bubbles in Aqueous Solutions

    OpenAIRE

    Alexander Tollkötter; Norbert Kockmann

    2014-01-01

    The absorption and chemisorption of small bubbles with N2 or CO2 were investigated experimentally in aqueous and alkaline solutions. Different bubble sizes were studied ranging from 0.1 to 2.5 mm in alkaline concentrations of 0.1 mM to 1 M NaOH. The experiments were conducted in a device consisting of a converging microchannel with a down flowing liquid. Levitation positions of single bubbles were optically characterized. A correlation was developed for the drag force coefficient, CD, includi...

  19. Chemisorption of hydrogen and oxygen atoms on a cobalt surface: A quantum chemical cluster model study

    International Nuclear Information System (INIS)

    The chemisorption of atomic hydrogen and oxygen on a cobalt surface has been studied on a five-atom cluster model using one-electron effective core potential (le- ECP) and all-electron calculations at the ab initio SCF and MCPF levels. Also, density functional calculations have been carried out. The different approaches are evaluated. The le- ECP has been compared to similar ECPS for nickel and copper. Our results indicate that this approach is valid also for cobalt. Different contributions to the cluster-adsorbate bonding energy are discussed. 31 refs., 1 fig., 1 tab

  20. Characteristics of synthesis and morphology of globular filtration-chemisorption membranes

    International Nuclear Information System (INIS)

    Conditions of synthesis, morphology and sorption properties towards iodine of globular filtration-chemisorption membranes produced by means of fast photo-induced copolymerization of compositions containing bifunctional cross-linker, vinylamide monomer and organic solvent are studied. Kinetic studied on iodine sorption, when aqueous solution containing 0.2 g of I2 and 8 g of KI in 200 ml of water is passed through the membrane permitted ascertaining that the adsorption complex consisted of two statistic segments of polyvinylamide and I3- ion

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

    Directory of Open Access Journals (Sweden)

    Andrea Calvi

    2016-05-01

    Full Text Available 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.

  2. Chemisorption and catalytic reactivity of cobalt and sulfur monolayers on ordered molybdenum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Knight, C.C.

    1992-03-01

    Complex Co/Mo sulfide catalysts are modelled by the chemisorption of layers on Mo single crystal surfaces. Growth and structure of overlayers on flat, stepped and kinked surfaces were investigated. Growth of Co overlayers on clean and S covered Mo surfaces was studied using AES and CO chemisorption; results reveal that Co grows as a flat monolayer on clean Mo surfaces. Co multilayers then form 3-D islands. When Co is deposited on S covered surfaces, the S overlayer migrates to the top; this topmost overlayer reduces CO adsorption capacity. While growth mode of Co overlayers are similar on flat and stepped surfaces, the number and type of ordered Co and S structures on flat and stepped surfaces are different. In the case of Co, an ordered (3 {times} 1) structure is formed on Mo(910) and (28,4,1) surfaces; this structure does not develop on clean (100) surface. Only one of two possible (3 {times} 1) Co domains are formed on Mo(910) and Mo(28,4,1) surfaces. These domains have one side of (3 {times} 1) unit cell parallel to the step edges, suggesting that Co adsorbs at the step edges. The (3 {times} 1) structure does not form on Mo(911) surface, indicating that step orientation can restrict formation of ordered overlayers. For chemisorbed S, only a subset of ordered overlayers on flat (100) surface nucleate on (910) and (911) and (28,4,1) surfaces. Ordered S overlayers also form domains that maximize the number of sulfur-step atom bonds. The adsorption and ordering of S overlayers on stepped and kinked Mo surfaces lead to doubling of step height and terrace width. Thiophene hydrodesulfurization (HDS) reactions were performed over Mo crystal surfaces modified by chemisorption of S, Co, C, and S + Co. The stepped and kinked Mo surfaces have reactivities greater than low Miller index (100) surface. Chemisorption of adsorbates decreased the thiophene HDS reactivity. Deposition of Co on Mo single crystal surfaces did not lead to increased HDS activity.

  3. The mechanism of chemisorption of hydrogen atom on graphene: Insights from the reaction force and reaction electronic flux

    International Nuclear Information System (INIS)

    At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows that hydrogen chemisorption is driven by charge transfer processes through four electronic events taking place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a sp3 hybridization to form the σC-H bond; and (d) spontaneous intermolecular charge transfer to reach the final chemisorbed state

  4. Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity.

    Science.gov (United States)

    Jiang, Bin; Yang, Minghui; Xie, Daiqian; Guo, Hua

    2016-06-27

    Dissociative chemisorption is the initial and often rate-limiting step in many heterogeneous processes. As a result, an in-depth understanding of the reaction dynamics of such processes is of great importance for the establishment of a predictive model of heterogeneous catalysis. Overwhelming experimental evidence has suggested that these processes have a non-statistical nature and excitations in various reactant modes have a significant impact on reactivity. A comprehensive characterization of the reaction dynamics requires a quantum mechanical treatment on a global potential energy surface. In this review, we summarize recent progress in constructing high-dimensional potential energy surfaces for polyatomic molecules interacting with transition metal surfaces based on the plane-wave density functional theory and in quantum dynamical studies of dissociative chemisorption on these potential energy surfaces. A special focus is placed on the mode specificity and bond selectivity in these gas-surface collisional processes, and their rationalization in terms of the recently proposed Sudden Vector Projection model. PMID:26100606

  5. Reversibility of hydrogen chemisorption on a ceria-supported rhodium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Bernal, S.; Calvino, J.J.; Cifredo, G.A.; Izquierdo, J.M. Rodriguez (Univ. de Cadiz, Perto Real (Spain)); Perrichon, V.; Laachir, A. (Inst. de Recherches sur la Catalyse (France))

    1992-09-01

    Cerium dioxide is an important component of the so-called three-way catalysts. This work reports on some new aspects of the chemistry of hydrogen-ceria systems. It is shown that, at room temperature, in the presence of highly dispersed rhodium, ceria chemisorbs large amounts of hydrogen. As deduced from magnetic measurements carried out in situ, this spillover process leads to the reduction of ceria to an extent of 21% of the total amount of cerium ions present in the sample, which is roughly equivalent to the complete surface reduction of the oxide. It is found that over a highly hydroxylated sample the reduction of ceria induced by the spillover process is partly reversible even at 295 K. If the sample is pumped off at 773 K, the initial oxidation state of ceria is almost completely recovered. Both the rate and extent of hydrogen chemisorption on ceria were found to be sensitive to the specific pretreatment applied to the catalyst. Over bare ceria, hydrogen chemisorption at 298 K was negligible, temperatures as high as 473 K being necessary to activate the process. In contrast to the rhodium-containing catalyst, over pure ceria the desorption of hydrogen leads to a much larger extent to water formation, thus revealing a deeper irreversible reduction of the oxide.

  6. Particle size effect for cobalt Fischer-Tropsch catalysts based on in situ CO chemisorption

    Science.gov (United States)

    Yang, Jia; Frøseth, Vidar; Chen, De; Holmen, Anders

    2016-06-01

    The cobalt particle size effect on activity and selectivity for CO hydrogenation was revisited on cobalt catalysts supported on a large variety of supports at 483 K, 1.85 bar, and H2/CO/Ar = 15/1.5/33.5 Nml/min. The size dependence of the activity and selectivity was analyzed in terms of site coverage and rate constants based on SSITKA experimental results. It was found that the Co particle size index estimated by the conventional method, namely, ex situ hydrogen chemisorption, could not correlate well the activity and selectivity as a function of the particle size index. The same holds for the site coverage of CO and intermediates leading to methane formation. However, the cobalt particle size index based on in situ CO chemisorption measured at 373 K provides a good correlation for turnover frequencies (TOFs) at reaction conditions. It was observed that TOF for CO conversion (TOFCO) increased with increasing particle size index of cobalt and SSITKA experiments showed that this was possibly due to increased site coverage of CO. The TOF for methane formation (TOFCH4) increased with particle size and remained constant at higher particle sizes possibly due to combined effect from the site coverage of intermediates leading to methane (θCHx) and the pseudo-first-order rate constant (kt). The results suggest that the support can play an important role for the size dependence of the activity and selectivity of CO hydrogenation on Co catalysts.

  7. Ab initio investigation of the SCN− chemisorption of single-walled boron nitride nanotubes

    International Nuclear Information System (INIS)

    Highlights: ► We explored the adsorption behavior of the SCN− on outer surface BNNTs via DFT. ► We reported the NBO charge distribution of SCN− on BNNTs surface. ► Chemisorptions are observed for SCN− on Al- and Ga-doped BNNTs. ► Notable changes are observed in the electronic properties of BNNT after doping. - Abstract: The thiocyanate anion (SCN−) adsorption capacity of zigzag single-walled boron nitride nanotubes (SWBNNTs) is studied via first-principles theory. Binding energy corresponding to the most stable configuration of SCN−/BNNT is found to be −148.42 kJ mol−1, which is typical for the chemisorptions. Our results indicate that both aluminum and gallium doping can significantly enhance the adsorption energy of SCN−/BNNTs complexes. Our electronic results reveal that there is a significant orbital hybridization between two species in adsorption process being an evidence of strong interaction. Thus, we arrive at the prediction that the BNNTs nanocage can be implemented as suitable sensor for practical applications.

  8. Chemisorption of group-III metals on the Si(111) and Ge(111) surfaces: An ab initio study

    OpenAIRE

    Ricart, J M; Rubio Martínez, Jaime; Illas i Riera, Francesc

    1990-01-01

    Chemisorption of group-III metal adatoms on Si(111) and Ge(111) has been studied through the ab initio Hartree-Fock method including nonempirical pseudopotentials and using cluster models to simulate the surface. Three different high-symmetry sites (atop, eclipsed, and open) have been considered by using X4H9, X4H7, and X6H9 (X=Si,Ge) cluster models. In a first step, ideal surface geometries have been used. Metal-induced reconstruction upon chemisorption has also been taken into account. Equi...

  9. Impact-induced chemisorption of C2H2 on diamond(0 0 1) surfaces: a molecular dynamics simulation

    International Nuclear Information System (INIS)

    This paper reports some new observations in studying the interaction between hyperthermal C2H2 and diamond (0 0 1)-2x1 surface at room temperature by means of molecular dynamics simulations with the many-body hydrocarbon potential. Six types of chemisorption configurations have been observed, some of these are reported for the first time. Also, we have observed threshold effect and hydrogen atom dissociation in the chemisorption processes. All these facts are expected to be useful in setting experimental condition in diamond synthesis

  10. Decrease in the tension at the electrode-solution interface caused by a chemisorption interaction between solvent and metal

    International Nuclear Information System (INIS)

    On the basis of experimental data the values of decrease in liquid electrode interface tension in the maximum of electric capillary curve stemming from chemisorption interaction between water molecules and electrodes made of In-Ga and Cd-Ga alloys in reference to mercury electrode, were determined. The values obtained, equal to 0.59 and 0.65 μJ/cm2 respectively, are energy characteristic of a metal hydrophility. It is shown that chemisorption interaction of water molecules with In, Cd and Ga can not actually effect the composition of the surface layer in the above-mentioned alloys

  11. Chemisorption interaction between solvents and the gallium subgroup metals: a relationship with the ionization potential of the solvent molecules

    International Nuclear Information System (INIS)

    Experimental data characterizing chemisorption metal-solvent interaction on Ga-, (In-Ga)-, (Tl-Ga) - and Hg - electrodes in various solvents have been considered from the viewpoint of quantum-chemical notions of chemical bond formation. It is shown that there is a correlation between parameters characterizing chemisorption metal-solvent interaction on the electrodes and the change in the value of the first adiabatic ionization potential of the solvent molecule, as well as the change in electron energy on the metal Fermi level

  12. DFT-GGA errors in NO chemisorption energies on (111) transition metal surfaces: Possible origins and correction schemes

    CERN Document Server

    Huang, Xu

    2013-01-01

    Here we investigate whether well-known DFT-GGA errors in predicting the chemisorption energy ($E_{\\rm chem}$) of CO on transition metal surfaces manifest in analogous NO chemisorption systems. To verify the occurrence of DFT-GGA overestimation of the back-donation mechanism in NO Chemisorption, we use electronic structure analysis to show that the partially filled molecular NO 2$\\pi^{*}$ orbital rehybridizes with the transition metal $d$-band to form new bonding and anti-bonding states. We relate the back-donation charge transfer associated with chemisorption to the promotion of an electron from the 5$\\sigma$ orbital to the 2$\\pi^{*}$ orbital in the gas-phase NO G$^{2}\\Sigma^{-}\\leftarrow \\rm{X}^{2}\\Pi$ excitation. We establish linear relationships between $E_{\\rm chem}$ and $\\Delta E_{\\rm G\\leftarrow X}$ and go on to formulate an $E_{\\rm chem}$ correction scheme in the style of Mason {\\it et al.}, {[Physical Review B {\\bf 69}, 161401(R)]}. We apply the NO $E_{\\rm chem}$ correction method to the (111) surface...

  13. 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

    Oxygen chemisorption on β-Mo2C surface and its oxidation have been investigated by using the density functional theory with the periodic models. Two surfaces of (011) and (101) were chosen to perform the calculations and the most stable surface structures together with the energetics of oxygen...

  14. A tight-binding model of CO chemisorption on Pd/Ta(110) and similar systems

    International Nuclear Information System (INIS)

    Chemisorption of an isolated CO molecule at various adsorption sites above the epitaxial Pd overlayer on Ta(110), and on related systems, is studied by using a self-consistent tight-binding scheme. Basic assumptions of the model are discussed in detail. The σ donation and especially the π backdonation are generally a good deal reduced at the bimetallic surface as compared with the pure Pd(111) surface. Simultaneously, the bond between CO and the surface becomes weaker. However, for CO in the atop position the effect is considerably smaller than for sites with twofold or threefold coordination and the atop site can therefore become preferred. A simple bonding picture explaining the gross trends is suggested. Core-level shifts induced in surface atoms by the adsorption are briefly discussed. (authors)

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

    Science.gov (United States)

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

    2016-04-01

    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 D2O 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 D2O 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.

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

    International Nuclear Information System (INIS)

    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.

  17. Electrocatalytic conversion of products of chemisorption of simple iodoaromatic molecules on smooth platinum

    International Nuclear Information System (INIS)

    The role of iodine atom in electrocatalytic transformations of iodinated aromatic hydrocarbons, as well as the reasons of catalytic activity of hyper valent of iodinated aromatic hydrocarbons in various oxidizing processes were investigated. The curves of electrooxidation of the resulting chemisorption products in the C6H5I and C6H5IO solutions of the different concentration are presented. The oxidation product of C6H5IO is reduced easiest, than the oxidation product of C6H5I. It is noted that the reduction of the chemisorbed products of C6H5I is not available in the 0 - 0.4 V range of potentials. In the similar experiments with C6H5OI changing nature of the previously chemisorbed product occurs. It is proposed that break of the C-I bond is possible during the adsorption of C6H5IO

  18. Molecular Adsorption Changes the Quantum Structure of Oxide-Supported Gold Nanoparticles: Chemisorption versus Physisorption.

    Science.gov (United States)

    Stiehler, Christian; Calaza, Florencia; Schneider, Wolf-Dieter; Nilius, Niklas; Freund, Hans-Joachim

    2015-07-17

    STM conductance spectroscopy and mapping has been used to analyze the impact of molecular adsorption on the quantized electronic structure of individual metal nanoparticles. For this purpose, isophorone and CO2, as prototype molecules for physisorptive and chemisorptive binding, were dosed onto monolayer Au islands grown on MgO thin films. The molecules attach exclusively to the metal-oxide boundary, while the interior of the islands remains pristine. The Au quantum well states are perturbed due to the adsorption process and increase their mutual energy spacing in the CO2 case but move together in isophorone-covered islands. The shifts disclose the nature of the molecule-Au interaction, which relies on electron exchange for the CO2 ligands but on dispersive forces for the organic species. Our experiments reveal how molecular adsorption affects individual quantum systems, a topic of utmost relevance for heterogeneous catalysis. PMID:26230817

  19. Nanoparticle chemisorption printing technique for conductive silver patterning with submicron resolution

    Science.gov (United States)

    Yamada, Toshikazu; Fukuhara, Katsuo; Matsuoka, Ken; Minemawari, Hiromi; Tsutsumi, Jun'ya; Fukuda, Nobuko; Aoshima, Keisuke; Arai, Shunto; Makita, Yuichi; Kubo, Hitoshi; Enomoto, Takao; Togashi, Takanari; Kurihara, Masato; Hasegawa, Tatsuo

    2016-04-01

    Silver nanocolloid, a dense suspension of ligand-encapsulated silver nanoparticles, is an important material for printing-based device production technologies. However, printed conductive patterns of sufficiently high quality and resolution for industrial products have not yet been achieved, as the use of conventional printing techniques is severely limiting. Here we report a printing technique to manufacture ultrafine conductive patterns utilizing the exclusive chemisorption phenomenon of weakly encapsulated silver nanoparticles on a photoactivated surface. The process includes masked irradiation of vacuum ultraviolet light on an amorphous perfluorinated polymer layer to photoactivate the surface with pendant carboxylate groups, and subsequent coating of alkylamine-encapsulated silver nanocolloids, which causes amine-carboxylate conversion to trigger the spontaneous formation of a self-fused solid silver layer. The technique can produce silver patterns of submicron fineness adhered strongly to substrates, thus enabling manufacture of flexible transparent conductive sheets. This printing technique could replace conventional vacuum- and photolithography-based device processing.

  20. Nanoparticle chemisorption printing technique for conductive silver patterning with submicron resolution

    Science.gov (United States)

    Yamada, Toshikazu; Fukuhara, Katsuo; Matsuoka, Ken; Minemawari, Hiromi; Tsutsumi, Jun'ya; Fukuda, Nobuko; Aoshima, Keisuke; Arai, Shunto; Makita, Yuichi; Kubo, Hitoshi; Enomoto, Takao; Togashi, Takanari; Kurihara, Masato; Hasegawa, Tatsuo

    2016-01-01

    Silver nanocolloid, a dense suspension of ligand-encapsulated silver nanoparticles, is an important material for printing-based device production technologies. However, printed conductive patterns of sufficiently high quality and resolution for industrial products have not yet been achieved, as the use of conventional printing techniques is severely limiting. Here we report a printing technique to manufacture ultrafine conductive patterns utilizing the exclusive chemisorption phenomenon of weakly encapsulated silver nanoparticles on a photoactivated surface. The process includes masked irradiation of vacuum ultraviolet light on an amorphous perfluorinated polymer layer to photoactivate the surface with pendant carboxylate groups, and subsequent coating of alkylamine-encapsulated silver nanocolloids, which causes amine–carboxylate conversion to trigger the spontaneous formation of a self-fused solid silver layer. The technique can produce silver patterns of submicron fineness adhered strongly to substrates, thus enabling manufacture of flexible transparent conductive sheets. This printing technique could replace conventional vacuum- and photolithography-based device processing. PMID:27091238

  1. Absorption and Chemisorption of Small Levitated Single Bubbles in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Alexander Tollkötter

    2014-02-01

    Full Text Available The absorption and chemisorption of small bubbles with N2 or CO2 were investigated experimentally in aqueous and alkaline solutions. Different bubble sizes were studied ranging from 0.1 to 2.5 mm in alkaline concentrations of 0.1 mM to 1 M NaOH. The experiments were conducted in a device consisting of a converging microchannel with a down flowing liquid. Levitation positions of single bubbles were optically characterized. A correlation was developed for the drag force coefficient, CD, including wall effects based on the force equilibrium. A linear decrease of bubble diameters was identified with and without chemical reaction, which is referred to as a rigid bubble surface area. Measured Sherwood numbers agree well with the literature values for the investigated Reynolds number range.

  2. Direct dissociative chemisorption of alkanes on Pt(111): Influence of molecular complexity

    International Nuclear Information System (INIS)

    The direct dissociative chemisorption of ethane, propane, n-butane, isobutane, and neopentane on Pt(111) was investigated as a function of the initial translational energy, ET, polar angle of incidence, θi, initial vibrational temperature, and surface temperature using supersonic molecular beam techniques. For each alkane, the initial probability for direct dissociative chemisorption scales with the initial normal energy of the alkanes, En=ET cos2 θi, and is independent of both the surface temperature and initial vibrational energy of the alkanes under the experimental conditions employed. Above initial normal energies of approximately 125 kJ/mol, at constant En, the dissociation probability decreases with increasing chain length of the C2-C4 linear alkanes; however, the dissociation probability of neopentane is greater than that of isobutane, and both isobutane and neopentane are more reactive than n-butane. By assuming that cleavage of primary C-H bonds is the dominant reaction pathway for all of the alkanes investigated here, the trends in reactivity are best explained by considering the differences in the steric factors for primary C-H bond cleavage for these alkanes. Secondary C-H bond cleavage does appear to contribute to the reactivity of propane and n-butane but only at the highest energies examined. Additionally, the reaction probabilities of each of these alkanes were estimated using a statistical model recently proposed by Ukrainstev and Harrison [J. Chem. Phys. 101, 1564 (1994)]. Assuming cleavage of only primary C-H bonds, the trends in reactivity for ethane, propane, n-butane, and isobutane were qualitatively reproduced by the statistical model; however, except for ethane, which was used to obtain the necessary parameters for the theory, there was poor quantitative agreement, and the predictions for neopentane were significantly lower than the measured values. The model also predicts that the dissociation probability is enhanced by increasing the

  3. A study of the chemisorption of a series of aminophenols on plasma-grown aluminium and magnesium oxides by IETS

    Science.gov (United States)

    Brown, N. M. D.; Taggart, G. M.

    Inelastic electron tunnelling spectroscopy (IETS) has been applied to study the adsorption of a series of aminophenols on plasma-grown aluminium and magnesium oxides. Vapour-phase doping of these surfaces was used and spectra recorded for 1,2-aminophenol, 1,3-aminophenol and 1,4-aminophenol. The tunnel spectra of the 1,2- and 1,3-aminophenols show that their chemisorption at both oxide surfaces is via reaction between phenolic and surface hydroxyl groups. For the 1,4-aminophenol example, adsorbate chemisorption involves transfer of surface-bound protons from the oxide in amino-group protonation. Some of these protons are replaced by deprotonation of the phenol at surface oxide ions. Observed band intensities for all three systems on aluminium oxide are held to be indicative of an adsorbate orientation on the surface which is close to the vertical. In contrast, those for magnesium oxide are more consistent with a non-vertical configuration.

  4. Effect of particle size on the chemisorption and decomposition of carbon monoxide by palladium and nickel clusters

    Science.gov (United States)

    Doering, D. L.; Poppa, H.; Dickinson, J. T.

    1981-01-01

    The chemisorption of gases on well-defined, supported metal particles is a model for basic processes in heterogeneous catalysis. In this study, the chemisorption and decomposition of carbon monoxide on palladium and nickel particles was examined as a function of particle size. Particulate films with average particle sizes ranging from 1 to 10 nm were grown by vapor deposition on UHV-cleaved mica. Successive CO adsorption-desorption cycles resulted in the accumulation of carbon on the particles, which suppressed CO adsorption. The rate of carbon accumulation was strongly dependent on particle size and was higher for Ni than for Pd over the same size range. Carbon was removed from both metals by oxygen treatments at elevated temperatures. However, a mixture of CO and O2 was effective for monitoring the removal of carbon from palladium.

  5. Adsorbate-adsorbate interactions and chemisorption at different coverage studied by accurate {\\em ab initio} calculations: CO on transition metal surfaces

    OpenAIRE

    Mason, Sara E.; Grinberg, Ilya; Rappe, Andrew M.

    2005-01-01

    We use density functional theory (DFT) with the generalized gradient approximation (GGA) and our first-principles extrapolation method for accurate chemisorption energies {[Mason {\\em et al.}, Phys. Rev. B {\\bf 69}, 161401R (2004)]} to calculate the chemisorption energy for CO on a variety of transition metal surfaces for various adsorbate densities and patterns. We identify adsorbate through-space repulsion, bonding competition, and substrate-mediated electron delocalization as key factors d...

  6. A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorption on the Relaxed (0001) Surface of Double Hexagonal Close Packed Americium

    OpenAIRE

    Dholabhai, P. P.; Atta-Fynn, R.; A.K. Ray

    2009-01-01

    Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorption on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals method. Chemisorption energies were optimized with respect to the distance of the adatom from the relaxed surface for three adsorption sites, namely top, bridge, and hollow hcp sites, the adlayer str...

  7. Synthesis of vanadium-phosphorus oxide systems by joint chemisorption of phosphorus and vanadium oxychlorides on silica surface

    International Nuclear Information System (INIS)

    A new method of synthesis on silica of multilayer vanadium-phosphorus oxide systems containing vanadium in oxidation state (+4), which consists in joint chemisorption of phosphorus and vanadium oxychlorides, hydrolysis of surface chlorine-containing compounds by water steam and vanadium reduction by ammonia vapors, was suggested. The samples prepared were characterized by the method of ESR, IR spectroscopy and electron spectroscopy of diffuse reflection

  8. The chemisorption of H2O, HCOOH and CH3COOH on thin amorphous films of Al2O3

    Science.gov (United States)

    Lewis, B. F.; Weinberg, W. H.; Mosesman, M.

    1974-01-01

    Investigation of the irreversible chemisorption of water, formic acid and acetic acid on a thin amorphous aluminum oxide film, using inelastic tunneling spectroscopy. All of the tunnel junctions employed were Al-Al2O3-Pb junctions with the adsorbate on the Al2O3 surface between the Al2O3 and the Pb electrode. The results obtained include the finding that all Al2O3 surfaces prepared by oxidation of Al have free CH groups present on them.

  9. A Computational NMR Study for Chemisorption of Oxygen-doped on the Surface of Single-Walled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    A. Ghasemi

    2012-08-01

    Full Text Available In this study computational Nuclear Magnetic Resonance (NMR study and chemisorptions are performed to investigate the electronic structure properties of arm-chair (4, 4 and zig-zag (5, 0 Single-Wall Carbon Nanotubes (SWCNTs. First-principles of Density Function Theory (DFT have applied in calculations on properties of molecular oxygen-doped (O-doped SWCNTs. The results show dramatic differences between two types, (5, 0 zigzag and (4, 4 arm chair, of carbon nano-tubes. Structural models are optimized and chemisorption energies are obtained to investigate the Nuclear Magnetic Resonance (NMR parameters for Odoped (5, 0 zigzag and (4, 4 armchair single-walled carbon nanotubes based on calculations using DFT. The chemical-shielding (σιι tensors were converted to isotropic chemical-shielding (iso and anisotropic chemicalshielding (Δσ and asymmetric (μj parameters of 17O and 13C atom for the optimized structures. We found that introduction oxygen does significantly change the structure of the SWCNT and thus the bonding mode of the structure is remarkably altered. Comparing the results of the zigzag and armchair models and calculated chemical shielding, electric filed gradient tensors at the sites of carbon reveal that O2 chemisorption has a dramatic effect on the electronic structure of SWCNTs.

  10. Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

    International Nuclear Information System (INIS)

    We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. On the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces

  11. Theoretical calculations of the Si(111)√3x√3R30 deg - B chemisorption system

    International Nuclear Information System (INIS)

    Full text: The plane wave pseudopotential density functional theory package fhi98md has been used to study the Si(111)√3x√3R30 deg - B chemisorption system. The minimum energy structure has been shown to be the B(S5) configuration in which the boron atoms occupy the second layer (S5) sites below the silicon surface. The calculated geometry for this B(S5) topology has been found to be in excellent agreement with recent experimental results. The electronic structure has also been calculated using the fhi98md program. By carefully analysing the nature of the wavefunctions in the vicinity of the Fermi energy we have been able to identify the surface states along the various symmetry directions of the Surface Brillouin Zone. We have found that there are two surface state bands below the Fermi energy with a splitting at the M point of 0.35 eV. This prediction, and the overall dispersion of the surface state bands, is in excellent agreement with the angle-resolved photoemission data. We also predict the occurrence of two surface state bands at the Γ-point. Only the upper of these two bands has so far been observed experimentally

  12. Water Chemisorption on aSputter Deposited Uranium Dioxide Film – Effect of Defects

    International Nuclear Information System (INIS)

    Uranium Dioxide (UO2) is mainly used as fuel for nuclear power plants for electricity generation and in the manufacturing of radioisotopes. Today more than ∼440 nuclear power plants are operating,generating a total capacity of ∼0.4 TW. Therefore,UO2 surface structure and reactions have been studied extensively(1). The two main corrosion threats to UO2 aremoisture and hydrogen. Moisture is mostly effective in atmospheric conditions (endless supply), and its reactivity can be further increased by radiation damage and radiolysis during long term storage.The enhanced oxidation and hydrogen formation can lead to a buildup of pressure and eventually a threat of breaching the storage container and a release of radioactive materials. Therefore, the safe disposal of UO2 spent fuel is crucial to environment safety. Previousstudies(2,3)had measured the effects of water adsorption on single crystal and thin film UO2 surfaces with high resolution X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). In the present study, the characteristics of water vapor chemisorption on a UO2 film, obtained by reactive sputter deposition, were studied over a temperature range of 300-500 K by combined measurements of direct recoil spectrometry (DRS) and XPS

  13. Scattering and recoiling imaging spectrometry (SARIS) study of chlorine chemisorption on Ni(1 1 0)

    International Nuclear Information System (INIS)

    The clean and chlorine chemisorbed Ni(1 1 0) surface has been investigated by scattering and recoiling imaging spectrometry (SARIS). Rare gas ion beams at 4 keV were scattered at different incident (α) and exit (β) angles along different azimuthal directions of the surface. The LEED pattern changed from a sharp (1x1) to a weak (3x1) after exposure to Cl2. The He+ images from the Cl/Ni surface exhibited very little differences compared to those of the clean surface. This is due to the high penetration depth of the He+ ions, which results in low surface sensitivity. The images obtained from the Cl/Ni surface with the heavier ions exhibited obvious changes due to their low penetration depths, which facilitates high surface sensitivity. Scattering and Recoiling Imaging Code (SARIC) simulations were carried out in order to interpret the perturbations induced by the chlorine adatoms. Different chemisorption sites for chlorine were tested. The results of the experiments and simulations agree that Cl atoms are chemisorbed in the short-bridge sites above the [1 1-bar 0] rows

  14. 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...

  15. Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111)

    Science.gov (United States)

    Guo, Han; Jackson, Bret

    2016-05-01

    A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, 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 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 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 1v3 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.

  16. Chemisorption of isocyanate (NCO) on the Pd(1 0 0) surface at different coverages

    Science.gov (United States)

    Belelli, Patricia G.; Branda, María M.; Garda, Graciela R.; Ferullo, Ricardo M.; Castellani, Norberto J.

    2010-02-01

    The chemisorption of isocyanate (NCO) species on Pd(1 0 0) was studied within the density functional formalism (DFT) using a periodic slab model. The NCO was adsorbed on top, bridge and hollow sites of the metal surface at different coverages. At low coverages, the adsorption energies are in the range of -2.5/-3.0 eV, indicating an important adsorbate-substrate interaction for the three sites studied. The lateral repulsive interaction between neighboring NCO species is almost negligible or weak at lower and intermediate coverages, and very strong at complete monolayer. At low coverages, both bridge and hollow sites are energetically preferred; yet the bridge site becomes the only favoured site at intermediate and complete coverages. Work function and dipole moment calculations can be interpreted by an important charge transfer from the metal surface to NCO. Interestingly, while on hollow site the charge taken by NCO is essentially the same over all the range of coverage, an increasing depolarization is observed on bridge and top sites as the coverage increases. Symmetric and asymmetric NCO stretching modes were also calculated and compared with recent infrared spectroscopy measurements.

  17. Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

    Science.gov (United States)

    Sermon, Paul A.; Self, Valerie A.; Vong, Mariana S. W.; Wurie, Alpha T.

    1990-01-01

    The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

  18. A First Principle Comparative Study on Chemisorption of H2 on C60, C80, and Sc3N@C80 in Gas Phase and Chemisorption of H2 on Solid Phase C60

    OpenAIRE

    Hongtao Wang; Lijuan Chen; Yongkang Lv; Jianwen Liu; Gang Feng

    2014-01-01

    The chemisorptions of H2 on fullerenes C60 and C80, endofullerene Sc3C@C80 and solid C60 were comparatively studied. A chain reaction mechanism for dissociative adsorption of H2 on solid C60 is proposed under high pressure. The breaking of H–H bond is concerted with the formation of two C–H bonds on two adjacent C60 in solid phase. The adsorption process is facilitated by the application of high pressure. The initial H2 adsorption on two adjacent C60 gives a much lower barrier 1.36 eV in comp...

  19. Methane dissociative chemisorption and detailed balance on Pt(111): Dynamical constraints and the modest influence of tunneling

    International Nuclear Information System (INIS)

    A dynamically biased (d-) precursor mediated microcanonical trapping (PMMT) model of the activated dissociative chemisorption of methane on Pt(111) is applied to a wide range of dissociative sticking experiments, and, by detailed balance, to the methane product state distributions from the thermal associative desorption of adsorbed hydrogen with coadsorbed methyl radicals. Tunneling pathways were incorporated into the d-PMMT model to better replicate the translational energy distribution of the desorbing methane product from the laser induced thermal reaction of coadsorbed hydrogen and methyl radicals occurring near Ts = 395 K. Although tunneling is predicted to be inconsequential to the thermal dissociative chemisorption of CH4 on Pt(111) at the high temperatures of catalytic interest, once the temperature drops to 395 K the tunneling fraction of the reactive thermal flux reaches 15%, and as temperatures drop below 275 K the tunneling fraction exceeds 50%. The d-PMMT model parameters of (E0 = 58.9 kJ/mol, s = 2, ηv = 0.40) describe the apparent threshold energy for CH4/Pt(111) dissociative chemisorption, the number of surface oscillators involved in the precursor complex, and the efficacy of molecular vibrational energy to promote reaction, relative to translational energy directed along the surface normal. Molecular translations parallel to the surface and rotations are treated as spectator degrees of freedom. Transition state vibrational frequencies are derived from generalized gradient approximation-density functional theory electronic structure calculations. The d-PMMT model replicates the diverse range of experimental data available with good fidelity, including some new effusive molecular beam and ambient gas dissociative sticking measurements. Nevertheless, there are some indications that closer agreement between theory and experiments could be achieved if a surface efficacy less than one was introduced into the modeling as an additional dynamical

  20. Chemisorption of molecular oxygen on Cu(1 0 0): a Hartree¿Fock and density functional study

    OpenAIRE

    Torras Costa, Juan; Lacaze-Dufaure, C.; Russo, Beniamino; Ricart Pla, Josep Manel

    2001-01-01

    The interaction of molecular oxygen with the Cu(1 0 0) surface has been studied by using both Hartree–Fock and density functional methods in the framework of the cluster model approach. In this study, we have used the Cu8(6,2) cluster in order to simulate the O2 molecular adsorption on different high symmetry chemisorption sites (top–top, bridge–fourfold, bridge–top, fourfold–fourfold) on the Cu(1 0 0) surface. High level non-local density functional (NLSD) computations indicate that the more...

  1. XPS study of the chemisorption induced surface segregation in LaNi5 and ThNi5

    OpenAIRE

    Schlapbach, L.; Brundle, C. R.

    1981-01-01

    Surface segregation with the disproportionation into La and Th oxide plus precipitations of elemental Ni play an important role in the understanding of the easy hydrogen absorption of LaNi5 and of the catalytic properties of ThNi5. By means of core-level X-ray photoelectron spectroscopy we show that the chemisorption of O2, H2O, and H2 on LaNi 5 surfaces induces a strong, weak and no surface segregation, resp. Precoverage with SO2 blocks further segregation, whereas exposure to H2S does not. ...

  2. Bond Lengths and Bond Strengths in Weak and Strong Chemisorption: N2, CO, and CO/H on Nickel Surfaces

    OpenAIRE

    Sayago, David I.; Hoeft, Jon T.; Polcik, Martin; Kittel, Martin; Toomes, Rachel L.; Robinson, J.; Woodruff, David Phillip; Pascal, Mathieu; Lamont, Christine L. A.; Nisbet, Gareth

    2003-01-01

    New chemical-state-specific scanned-energy mode photoelectron diffraction experiments and density functional theory calculations, applied to CO, CO/H, and N2 adsorption on Ni(100), show that chemisorption bond length changes associated with large changes in bond strength are small, but those associated with changes in bond order are much larger, and are similar to those found in molecular systems. Specifically, halving the bond strength of atop CO to Ni increases the Ni-C distance by 0.06 Å...

  3. Hydrogen atom chemisorption and diffusion on neutral and charged polycyclic aromatic hydrocarbon (PAH) flakes in the interstellar media

    Science.gov (United States)

    Sánchez, Morella; Ruette, Fernando

    2015-11-01

    Hydrogen atoms diffusion on a hydrocarbon flake is studied using PM6 and DFT programs using as models neutral and positive charged coronene. Chemisorption and potential energy surfaces and diffusion paths were calculated. Results show that diffusion occurs through Csbnd C bonds. Edge effects are very important because the most stable adsorptions occur on hydrogenated border sites, so the diffusion is biased toward edge sites. Charged coronene has stronger adsorption energies than neutral systems. A large difference between barriers in neutral and charged systems was not observed in most of the cases. A discussion of modeling diffusion processes is presented.

  4. First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111).

    Science.gov (United States)

    Zhang, Zhaojun; Liu, Tianhui; Fu, Bina; Yang, Xueming; Zhang, Dong H

    2016-01-01

    Despite significant progress made in the past decades, it remains extremely challenging to investigate the dissociative chemisorption dynamics of molecular species on surfaces at a full-dimensional quantum mechanical level, in particular for polyatomic-surface reactions. Here we report, to the best of our knowledge, the first full-dimensional quantum dynamics study for the dissociative chemisorption of H2O on rigid Cu(111) with all the nine molecular degrees of freedom fully coupled, based on an accurate full-dimensional potential energy surface. The full-dimensional quantum mechanical reactivity provides the dynamics features with the highest accuracy, revealing that the excitations in vibrational modes of H2O are more efficacious than increasing the translational energy in promoting the reaction. The enhancement of the excitation in asymmetric stretch is the largest, but that of symmetric stretch becomes comparable at very low energies. The full-dimensional characterization also allows the investigation of the validity of previous reduced-dimensional and approximate dynamical models. PMID:27283908

  5. Use of carbon-14 for the study of elementary carbon exchange between methane and its chemisorption residues on metallic films

    International Nuclear Information System (INIS)

    After giving the results of the most recent work done with a view to providing a rational account of the exchanges between two gases in contact with a catalyst, the authors, using C14, proceed to study elementary exchange between methane and its chemisorption residues on molybdenum films. The surface is labelled in two ways: by chemisorption of C14H4 at different temperatures; or by exchange between C14H4 with a high specific activity and a metallic film previously treated with inactive methane. The C14 is counted in the form of CO2 in the Geiger region. The results show that the exchange rate is measurable from about 100o C onwards and that it reaches a maximum at about 250o C. Furthermore, the exchange is governed by laws which vary according to the prior treatment of the surface. On the basis of the results discussed, the authors suggest a methane displacement pattern which they compare with the CH4 and D2 exchange mechanisms suggested by Kemball. (author)

  6. Physisorption to chemisorption transition of NO2 on graphene induced by the interplay of SiO2 substrate and van der Waals forces: A first principles study

    International Nuclear Information System (INIS)

    Highlights: ► New mechanism of NO2 chemisorption on graphene is proposed. ► SiO2 changes the structures of graphene and enhances the NO2 adsorption. ► The physisorption to chemisorption transition can be induced by the interplay of substrate and van der Waals interactions. -- Abstract: The effect of SiO2 substrate and van der Waals interactions on the adsorption of NO2 molecule on graphene is studied using density functional theory. Contrary to physisorption on suspended graphene, both physisorption and chemisorption phenomena can be found, which are mainly caused by the covalent C–O bonds, the broken symmetry, and the local corrugations induced by SiO2. The electronic structures of the system are significantly influenced after NO2 adsorption, enhancing the detection of NO2. Interestingly, NO2 induces magnetization into graphene, and the spin polarization locates mainly on carbon atoms of graphene. The barrier of the transition from physisorption to chemisorption is about 0.05 eV, and this “pseudo barrier” can be overcome by van der Waals interactions. This work explains the experiments of graphene as gas sensors with high sensitivity, and supports new applications for electronic, spintronic devices.

  7. Empirical potential study of the dissociative chemisorption of Si2H6 on the Si(001)2x1 surface

    International Nuclear Information System (INIS)

    Full text: Two models have been proposed for the epitaxial growth of silicon on the Si(001)2x1 surface from the dissociation of disilane (Si2H6). Molecular dynamics simulations and potential energy calculations have been performed to investigate this dissociative chemisorption process. These calculations have been carried out using the extended Brenner (XB) empirical potential. The minimum energy atomic configurations for SiH3, SiH2 and H-Si-Si-H (Si2H2) species chemisorbed on the Si(001)2x1 surface have been determined. The chemisorption of SiH3 radicals has been observed to occur predominantly at the dangling bond sites of the Si(001) surface. The most stable SiH2 configurations are found to be the on-dimer and intra-row structures. Seven different Si2H2 chemisorption structures have been investigated and the on-dimer-B structure found to be the most energetically favourable. These theoretically predicted structures are discussed in the light of recent experimental studies and the proposed models for silicon epitaxial growth. Comparison of the results of these XB potential energy calculations with all-electron ab initio cluster calculations has also been made for a number of these different chemisorption structures

  8. A molecular dynamics study of the dissociative chemisorption Si2H6 on the Si(001):2x1 surface

    International Nuclear Information System (INIS)

    Full text: Molecular dynamics simulations have been carried out to investigate the dissociative adsorption of disilane (Si2H6) on the Si(001):2x1 surface using the improved empirical Brenner potential (IXB). A number of chemisorption sites and atomic configurations of the SiH, SiH2, SiH3 species chemisorbed on the Si(001):2x1 surface have been identified. The chemisorption of the SiH3, radicals was observed to occur predominantly on the dangling bond sites of the Si(001) surface. The chemisorption of the SiH2 species result in forming on-dimer and intra-row structures which were found to be most energetic and thermodynamic stable configurations. The three-fold bonding structure has been identified to be the most energetically favourable configuration for the chemisorption of the SiH radicals on Si(001). The comparison between the empirical molecular dynamics simulations and all electron ab initio cluster calculations for some of the atomic configurations discussed above is also presented

  9. Chemisorption of a thiol-functionalized ruthenium dye on zinc oxide nanoparticles: Implications for dye-sensitized solar cells

    Science.gov (United States)

    Singh, Jagdeep; Im, Jisun; Whitten, James E.; Soares, Jason W.; Steeves, Diane M.

    2010-09-01

    ZnO is an alternative to TiO 2-based dye-sensitized solar cells (DSSCs). Adsorption of cis-ruthenium-bis[2,2'-bipyridine]-bis[4-thiopyridine] onto ZnO nanorods has been studied using X-ray and ultraviolet photoelectron spectroscopies (XPS and UPS). XPS indicates chemisorption with a surface density of ca. 1 × 10 15 molecules/cm 2, confirming the possibility of using thiol-terminated dyes for ZnO-based DSSC devices. The energy level diagram, based on UPS and absorbance spectroscopy, indicates that the LUMO of this dye is lower in energy than the ZnO conduction band edge, providing minimal enthalpic driving force for photovoltaic electron injection. However, optimization of thiol-functionalized Ru dyes could result in competitive ZnO-based DSSCs.

  10. Atomic and electronic structure of the Si(001)2x1-K chemisorption system at monolayer coverage

    International Nuclear Information System (INIS)

    Full text: It has been well established that the chemisorption of potassium on the Si (001) 2x1 surface leads to the so-called 'double-layer model' at one monolayer coverage. The plane wave pseudopotential density functional programs VASP and fhi98md have been used to optimise the geometry of this double-layer model. The resulting geometry has been found to be in excellent agreement with the experimental results. To identify the surface states of this double-layer model in the vicinity of the Fermi energy we have calculated the modulus squared of each wavefunction integrated over the surface unit cell. We have also calculated charge density contour plots over various planes containing the surface silicon and potassium atoms. The theoretically predicted dispersion of both the occupied and unoccupied surface states has been found to be in excellent agreement with the experimental data

  11. Chemisorption of sulfur on (100)Mo: growth of surface and volume sulfides, absolute calibration, thermodesorption of sulfur

    International Nuclear Information System (INIS)

    Physico-chemical processes following the chemisorption of sulfur on (100)Mo, that is: growth of the surface and volume sulfides, their thermo-stability, variation of emission and catalytic properties of the surface are studied using high resolution (δ E/E ≤ 0.1%) EOS with recording of spectra directly from the specimen highly heated up to T = 2000 K. The work of yield and bound energy of sulfur atom depending on the level of Mo surface population by S atoms are determined. It is shown that Mo exposure in H2S atmosphere under T = 300-2000 K does not result in accumulation of S atoms within the specimen volume. The absolute concentration of sulfur atoms in the surface sulfide is determined and it is shown that its stoichiometry is MoS. 31 refs., 5 figs

  12. Ab initio modeling of glass corrosion: Hydroxylation and chemisorption of oxalic acid at diopside and akermanite surfaces

    International Nuclear Information System (INIS)

    Using ab initio density functional theory, we have performed a systematic study of corrosion processes at pure and at hydroxylated surfaces of the silicate minerals diopside (CaMgSi2O6) and akermanite (Ca2MgSi2O7), serving as model systems for multicomponent glasses. The tendency of the cations to assume their ideal bulk coordination was identified as the driving force behind spontaneous surface relaxation and hydroxylation in an aqueous environment. Surface complexes formed after exposing the glass surfaces to oxalic acid form a protective hydrophobic layer on the surface and thus prevent the leaching of metal cations from the glass surface. This provides a description of the mechanism of glass corrosion inhibition at the atomic level: as the chemisorption energy of oxalic acid is larger than the physisorption energy of water, the former is the process that will actually occur.

  13. Density functional theory study of the chemisorption of CO on Ir/MgO(1 0 0)

    International Nuclear Information System (INIS)

    Density functional theory calculations have been used to study the adsorption of CO on the Ir/MgO(1 0 0). Substrate and adsorbate geometry relaxation, adsorption, energy and density of states are computed. Top and bridge adsorption sites for iridium atom deposition have been considered. The result indicated that the energetically most favorable sites are the top sites of the O atoms. CO adsorption on the Ir atom is then studied. Different adsorbate arrangements, perpendicular and parallel to the surface have been considered. Among them, the most stable CO chemisorption geometry, is that corresponding to the adsorbate perpendicular to the surface iridium atom and C-down oriented. Density of states and the CO stretching frequency analysis further found that the obvious charge transfer from adsorbate to the substrate.

  14. Six-dimensional potential energy surface of the dissociative chemisorption of HCl on Au(111) using neural networks

    Institute of Scientific and Technical Information of China (English)

    LIU TianHui; FU BiNa; ZHANG Dong H

    2014-01-01

    We constructed a six-dimensional potential energy surface(PES)for the dissociative chemisorption of HCl on Au(111)using the neural networks method based on roughly 70000 energies obtained from extensive density functional theory(DFT)calculations.The resulting PES is accurate and smooth,based on the small fitting errors and good agreement between the fitted PES and the direct DFT calculations.Time-dependent wave packet calculations show that the potential energy surface is very well converged with respect to the number of DFT data points,as well as to the fitting process.The dissociation probabilities of HCl initially in the ground rovibrational state from six-dimensional quantum dynamical calculations are quite diferent from the four-dimensional fixed-site calculations,indicating it is essential to perform full-dimensional quantum dynamical studies for the title molecule-surface interaction system.

  15. 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

    Oxygen chemisorption on β-Mo2C surfaces, the subsequent CO/CO2 desorption and oxygen diffusion to the carbon vacancy have been investigated by density-functional theory. The most stable structures together with the energetics of oxygen stepwise adsorption, CO/CO2 desorption and oxygen diffusion...... 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....

  16. Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Hyung Chul, E-mail: hchahm@kist.re.kr [Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712 (United States); Fuel Cell Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Manogaran, Dhivya [Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712 (United States); Hwang, Gyeong S., E-mail: gshwang@che.utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712 (United States); Han, Jonghee; Kim, Hyoung-Juhn; Nam, Suk Woo; Lim, Tae Hoon [Fuel Cell Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2015-03-30

    Graphical abstract: - Highlights: • Pd ensembles greatly reduce CO adsorption energy as compared to Pt ensembles. • The steeper potential energy surface of CO adsorption in Pd(1 1 1) than in Pt(1 1 1). • Switch of binding site preference in ensembles is key to determining CO adsorption. • Opposite electronic (ligand) effect in Pd and Pt ensemble. - Abstract: Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state.

  17. Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Pd ensembles greatly reduce CO adsorption energy as compared to Pt ensembles. • The steeper potential energy surface of CO adsorption in Pd(1 1 1) than in Pt(1 1 1). • Switch of binding site preference in ensembles is key to determining CO adsorption. • Opposite electronic (ligand) effect in Pd and Pt ensemble. - Abstract: Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state

  18. Interaction of cyclobutane with the Ru(001) surface: Low-temperature molecular adsorption and dissociative chemisorption at elevated surface temperature

    International Nuclear Information System (INIS)

    We have studied the interaction of cyclobutane with the hexagonally close-packed Ru(001) surface. High-resolution electron energy loss spectroscopy (HREELS) has been used to identify the vibrational modes of both c-C4H8 and c-C4D8 adsorbed at 90 K as a function of cyclobutane exposure. We have observed a vibrational mode not observed in the gas phase at 2600 cm-1 (2140 cm-1) which is attributed to the strong interaction of the cyclobutane C endash H (C endash D) bonds with the ruthenium surface. Two different adsorption geometries for cyclobutane on Ru(001) have been proposed based on the dipolar activity of this softened C endash H mode. We have also measured the trapping-mediated dissociative chemisorption of both c-C4H8 and c-C4D8 at surface temperatures between 190 and 1200 K. The measured activation energies with respect to the bottom of the physically adsorbed well for c-C4H8 and c-C4D8 are 10thinsp090±180 and 10thinsp180±190 cal/mol, respectively. The trapping-mediated chemisorption of cyclobutane is believed to occur via C endash C bond cleavage, as judged by the absence of a kinetic isotope effect. The measured ratios of the preexponential factors for desorption relative to reaction of 21±2 and 47±4 for c-C4H8 and c-C4D8 respectively, are in the expected range considering the greater entropy gain associated with the transition state for desorption relative to the transition state for C endash C bond cleavage. copyright 1999 American Institute of Physics

  19. Investigation of the doped transition metal promotion effect on CO2 chemisorption on Ni (1 1 1)

    International Nuclear Information System (INIS)

    The chemisorption of CO2 on the pure Ni (1 1 1) and doped Ni (1 1 1) by transition metal (Co, Rh, Cr, Ce, La) were investigated by using the generalized gradient approximation (GGA) and the Perdew-Burke-Emzerhof (PBE) functional. The optimized structure of doped metal surface showed that Rh, Cr, Ce, La atoms upward shift from the surface of Ni (1 1 1) plane, while the atom radius of Co is the minimum offset which lead to the height is -0.03 Å. The ability of CO2 chemisorption follows the order of La/Ni (1 1 1) > Ce/Ni (1 1 1) > Cr/Ni (1 1 1) > Co/Ni (1 1 1) > pure Ni (1 1 1). It is exothermic when CO2 chemisorbed on Cr/Ni (1 1 1) Ce/Ni (1 1 1) and La/Ni (1 1 1), while it is endothermic on the Co/Ni (1 1 1) and pure Ni (1 1 1). CO2 molecular chemisorbed on all the metal surfaces are negatively charged, result from the electron transfer between the metal surfaces and the CO2 molecular. The transition metals La, Ce and Cr can promote the transformation of electron and make the C-O bonds longer than the pure Ni (1 1 1). We also analyzed the dissociation of CO2 on the Ni-based surface and found that the La/Ni (1 1 1) surface is the preference surface for the dissociation of CO2, which improved the ability to hinder carbon deposition.

  20. Chemisorption of single fluorine atoms on the surface of zigzag single-walled carbon nanotubes: A model calculation

    Energy Technology Data Exchange (ETDEWEB)

    Margulis, Vl.A. [Department of Physics, N.P. Ogarev Mordovian State University, Saransk 430000 (Russian Federation)]. E-mail: 612033@inbox.ru; Muryumin, E.E. [Department of Chemistry, N.P. Ogarev Mordovian State University, Saransk 430000 (Russian Federation)

    2007-03-01

    We report a model calculation of the chemisorption energies {delta}E{sub ads} of single fluorine atoms on the outer surface of zigzag single-walled carbon nanotubes (Z-SWCNTs) (p,0) with p ranging from 11 to 21. A simplified model based on an effective-mass theory is adopted to describe the electronic structure of the nanotubes. Chemisorption is treated within the Anderson-Newns approach, which takes account of Coulomb interaction between adsorbate electrons. Considering adsorption of an adatom directly on top of a surface carbon atom, we find that in the case of a fluorine atom bonded to the sidewall of the nanotubes, the absolute values of {delta}E{sub ads} are in the range 4.3-5.5eV for Z-SWCNTs with typical diameters of 0.86-1.66nm, larger {delta}E{sub ads} values being associated with semiconducting tubes. For the latter ones, {delta}E{sub ads} decreases rather significantly as the radius R of the tubes increases, tending towards the ''infinite'' radius graphene case, whereas for metallic tubes {delta}E{sub ads} slightly increases with increasing R. The localized acceptor states induced by a fluorine atom in the band gap of the semiconducting tubes are found to be responsible for such difference in the behaviour of {delta}E{sub ads} for the two above-mentioned types of tubes. The results obtained shed light on the possible mechanism of the atomic fluorine adsorption-induced hole-doping of the semiconducting tubes, which might significantly affect the transport properties of these tubes.

  1. Difference between potentials of zero charge in the absence of the metal-solvent chemisorption interaction of mercury and metals of the gallium subgroup

    International Nuclear Information System (INIS)

    The modern solution of the Volt problem is introduced. The difference values of the zero-charge potentials between Hg- and Ga-(In-Ga)- and (Tl-Ga)-electrodes in six solvents in the absence of the metal-solvent chemisorption interaction of mercury and the gallium subgroup metals are calculated. The errors of the calculated values and the possibility of their minimization are evaluated. It is shown, that the values obtained are determined by the metal nature alone

  2. Use of charge sensitivity analysis in diagnosing chemisorption clusters: Minimum-energy coordinate and Fukui function study of model toluene-[V2O5] systems

    International Nuclear Information System (INIS)

    Charge sensitivity analysis (CSA) is carried out for model toluene-vanadium pentoxide chemisorption complexes involving the two-pyramidal model of the active site on the (010)-V2O5 surface. Maps of the electrostatic potential around the adsorbate and the substrate cluster are used to rationalize energetical preferences of alternative perpendicular and parallel arrangements of the toluene ring relative to the pyramid bases, known from previous SCF MO studies. The minimum-energy coordinates (MEC) in the electron population space are determined from the CSA semiempirical, finite difference atomic hardness matrix for the actual SCF MO charges in the chemisorption clusters. They represent collective charge displacements which minimize the system energy per unit change in the oxidation state of a specified atom, thus providing a convenient diagnostic tool for testing the alternative charge rearrangements and range of perturbations due to the chemisorption bond or changes in the cluster environment. The MEC relaxed hardnesses diagnose mode stabilities and together with the MEC relaxed hardnesses diagnose mode stabilities and together with the MEC topologies identify the most probable locations of the adsorbate activation. Finally, the atomic Fukui function indices are used to explore trends in the distribution of the external charge transfer due to the system environment. 14 refs., 4 figs

  3. Theoretical studies of chemisorption on transition-metal surfaces: interaction of hydrogen with titanium. Final report, June 1, 1977-August 31, 1982

    International Nuclear Information System (INIS)

    The research concerns the theory of chemisorption of molecules on solid surfaces: the development of a general formalism, and specific applications to the hydrogen-titanium system. The objective is to develop a suitable formalism for treating electronic interactions at an ab initio level when both localized and delocalized interactions occur, as in the case of molecular adsorption on a metallic surface. For H2 and CO adsorption on titanium, the goal is a determination of the energetics of adsorption and molecular dissociation as a function of surface site. The first phase of the research concerned primarily the formalism and the second the modeling of the titanium surface, preparatory to the chemisorption studies. The final phase of the research has dealt with applications of the chemisorption theory to several systems: H2 on Ti(0001), CO on Ti(0001), interstitial H in titanium, H on Cu(100) and H2 dissociation on Cu(100). Work on stepped copper surfaces and CO interactions with Ni(100) was also begun. With the exception of the latter two projects now underway, the results of all studies have been published. Brief summaries of the individual projects are included in this report

  4. In situ analysis of CO during chemisorption and oxidation on graphite: Supported Pt by FTIR-microspectrometry

    Science.gov (United States)

    Self, Valerie A.; Sermon, Paul A.

    1990-01-01

    For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.

  5. Energy window effect in chemisorption of C36 on diamond (0 0 1)-(2x1) surface

    International Nuclear Information System (INIS)

    In this paper, the collision of a C36, with D6h symmetry, on diamond (0 0 1)-(2x1) surface was investigated using molecular dynamics (MD) simulation based on the semi-empirical Brenner potential. The incident kinetic energy of the C36 ranges from 20 to 150 eV per cluster. The collision dynamics was investigated as a function of impact energy Ein. The C36 cluster was first impacted towards the center of two dimers with a fixed orientation. It was found that when Ein was lower than 30 eV, C36 bounces off the surface without breaking up. Increasing Ein to 30-45 eV, bonds were formed between C36 and surface dimer atoms, and the adsorbed C36 retained its original free-cluster structure. Around 50-60 eV, the C36 rebounded from the surface with cage defects. Above 70 eV, fragmentation both in the cluster and on the surface was observed. Our simulation supported the experimental findings that during low-energy cluster beam deposition small fullerenes could keep their original structure after adsorption (i.e. the memory effect), if Ein is within a certain range. Furthermore, we found that the energy threshold for chemisorption is sensitive to the orientation of the incident C36 and its impact position on the asymmetric surface

  6. Dissociative chemisorption of methane on metal surfaces: Tests of dynamical assumptions using quantum models and ab initio molecular dynamics

    International Nuclear Information System (INIS)

    The dissociative chemisorption of methane on metal surfaces is of great practical and fundamental importance. Not only is it the rate-limiting step in the steam reforming of natural gas, the reaction exhibits interesting mode-selective behavior and a strong dependence on the temperature of the metal. We present a quantum model for this reaction on Ni(100) and Ni(111) surfaces based on the reaction path Hamiltonian. The dissociative sticking probabilities computed using this model agree well with available experimental data with regard to variation with incident energy, substrate temperature, and the vibrational state of the incident molecule. We significantly expand the vibrational basis set relative to earlier studies, which allows reaction probabilities to be calculated for doubly excited initial vibrational states, though it does not lead to appreciable changes in the reaction probabilities for singly excited initial states. Sudden models used to treat the center of mass motion parallel to the surface are compared with results from ab initio molecular dynamics and found to be reasonable. Similar comparisons for molecular rotation suggest that our rotationally adiabatic model is incorrect, and that sudden behavior is closer to reality. Such a model is proposed and tested. A model for predicting mode-selective behavior is tested, with mixed results, though we find it is consistent with experimental studies of normal vs. total (kinetic) energy scaling. Models for energy transfer into lattice vibrations are also examined

  7. Observing the Transition from Equatorial to Axial CO Chemisorption: Infrared Photodissociation Spectroscopy of Yttrium Oxide-Carbonyls.

    Science.gov (United States)

    Xie, Hua; Liu, Zhiling; Zhao, Zhi; Kong, Xiangtao; Fan, Hongjun; Tang, Zichao; Jiang, Ling

    2016-06-01

    A series of yttrium oxide-carbonyls are prepared via a laser vaporization supersonic cluster source in the gas phase and identified by mass-selected infrared photodissociation (IRPD) spectroscopy in the C-O stretching region and by comparing the observed IR spectra with those from quantum chemical calculations. For YO(CO)4(+), all four CO ligands prefer to occupy the equatorial site of the YO(+) unit, leading to a quadrangular pyramid with C4v symmetry. Two energetically nearly degenerate isomers are responsible for YO(CO)5(+), in which the fifth CO ligand is either inserted into the equatorial plane of YO(CO)4(+) or coordinated opposite the oxygen on the C4 axis. YO(CO)6(+) has a pentagonal bipyramidal structure with C5v symmetry, which includes five equatorial CO ligands and one axial CO ligand. The present IRPD spectroscopic and theoretical study of YO(CO)n(+) extends the first shell coordination number of CO ligands in metal monoxide carbonyls to six. The transition from equatorial to axial CO chemisorption in these yttrium oxide-carbonyls is fortunately observed at n = 5, providing new insight into ligand interactions and coordination for the transition metal oxides. PMID:27158889

  8. The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

    International Nuclear Information System (INIS)

    A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H2O, HOD, and D2O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D2O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate

  9. The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-21

    A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H{sub 2}O, HOD, and D{sub 2}O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D{sub 2}O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate.

  10. Ab initio cluster-model study of the on-top chemisorption of F and Cl on Si(111) and Ge(111) surfaces

    OpenAIRE

    Illas i Riera, Francesc; Rubio Martínez, Jaime; Ricart, J M

    1985-01-01

    The interaction of atomic F and Cl with Si4H9 and Ge4H9 cluster models has been studied by using ab initio pseudopotentials and basis sets of increasing complexity. The results show that the effect of d orbitals is important in order to reproduce the experimental findings. However, the use of polarization functions in the atoms which are directly involved in the chemisorption bond leads to results which are very close to those obtained using extended basis sets. The local nature of the chemis...

  11. An ab initio full potential fully relativistic study of atomic carbon, nitrogen, and oxygen chemisorption on the (111) surface of delta-plutonium

    OpenAIRE

    Atta-Fynn, Raymond; Ray, Asok K.

    2007-01-01

    Adsorption of carbon, nitrogen, and oxygen on the (111) surface of delta-Plutonium has been studied within the framework of density functional theory using the full-potential linear augmented plane wave plus local basis (FP-LAPW+lo) method. All adatoms prefer to bind at the higher coordinated hollow sites, with the chemisorption energies for C, N, and O being 6.539 eV, 6.714 eV, and 8.2 eV respectively. The work function and the surface Pu magnetic moments respectively increased and decreased...

  12. An ab initio cluster study of atomic oxygen chemisorption on Ga-rich GaAs(100) (2x1) and beta(4x2) surfaces

    OpenAIRE

    Mayo, Michael L.; Ray, Asok K.

    2003-01-01

    Ab initio self-consistent total energy calculations using second order Moller-Plesset perturbation theory and Hay-Wadt effective core potentials for gallium and arsenic have been used to investigate the chemisorption of atomic oxygen on the Ga-rich GaAs (100) (2 x 1) and beta(4 x 2) surfaces. Finite sized hydrogen saturated clusters with the experimental zinc-blende lattice constant of 5.654 angstroms and the energy optimized surface Ga dimer bond length of 2.758 angstroms have been used to m...

  13. Bond Lengths and Bond Strengths in Weak and Strong Chemisorption: N2, CO, and CO/H on Nickel Surfaces

    OpenAIRE

    Sayago, D.; Hoeft, J.; Polcik, M.; Kittel, M; Toomes, R.; Robinson, J.; Woodruff, D.; Pascal, M.; LaMont, C.; Nisbet, G.

    2003-01-01

    New chemical-state-specific scanned-energy mode photoelectron diffraction experiments and density functional theory calculations, applied to CO, CO/H, and N2 adsorption on Ni(100), show that chemisorption bond length changes associated with large changes in bond strength are small, but those associated with changes in bond order are much larger, and are similar to those found in molecular systems. Specifically, halving the bond strength of atop CO to Ni increases the Ni-C distance by 0.06 Å, ...

  14. Validity of the site-averaging approximation for modeling the dissociative chemisorption of H2 on Cu(111) surface: A quantum dynamics study on two potential energy surfaces

    International Nuclear Information System (INIS)

    A new finding of the site-averaging approximation was recently reported on the dissociative chemisorption of the HCl/DCl+Au(111) surface reaction [T. Liu, B. Fu, and D. H. Zhang, J. Chem. Phys. 139, 184705 (2013); T. Liu, B. Fu, and D. H. Zhang, J. Chem. Phys. 140, 144701 (2014)]. Here, in order to investigate the dependence of new site-averaging approximation on the initial vibrational state of H2 as well as the PES for the dissociative chemisorption of H2 on Cu(111) surface at normal incidence, we carried out six-dimensional quantum dynamics calculations using the initial state-selected time-dependent wave packet approach, with H2 initially in its ground vibrational state and the first vibrational excited state. The corresponding four-dimensional site-specific dissociation probabilities are also calculated with H2 fixed at bridge, center, and top sites. These calculations are all performed based on two different potential energy surfaces (PESs). It is found that the site-averaging dissociation probability over 15 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability for H2 (v = 0) and (v = 1) on the two PESs

  15. 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

    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...... binding energies of atomic hydrogen adsorbed in the fee hollow site, at 100% surface coverage, on the Pd(111), Re(0001), Pd-ML/Re(0001), and Re-ML/Pd(111) surfaces, are -2.66, -2.82, -2.25, and -2.78 eV, respectively. Formal chemisorption theory was used to correlate the predicted binding energy...... 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]....

  16. A low temperature oxygen chemisorption study of (VO/sub 2/P/sub 2/O/sub 7/ and V/sub 2/ O/sub 5/ catalysts

    International Nuclear Information System (INIS)

    Low temperature oxygen chemisorption (LTOC) has been applied to (VO)sub 2/P/sub 2/O/sub 7/ and V/sub 2/O/sub 5/ catalysts following reduction carbon monoxide as a means of determining the surface population of chemisorbed molecular oxygen. This latter measurement is taken to be equivalent to the surface population of anion vacancies, the oxygen being chemisorbed at the vacancies as O/sub 2/. The desorption activation energies for the molecular oxygen obtained for both catalysts were in the range 24-31 kJ mol showing the bonding to be in the lower limit of chemisorption. (author)

  17. Immobilization of bovine serum albumin on TiO 2 film via chemisorption of H 3PO 4 interface and effects on platelets adhesion

    Science.gov (United States)

    Weng, Y. J.; Hou, R. X.; Li, G. C.; Wang, J.; Huang, N.; Liu, H. Q.

    2008-02-01

    In the present study, bovine serum albumin (BSA) was successfully covalently immobilized on the surface of anatase TiO 2 film by a three-step method, i.e. application of H 3PO 4 chemisorption to increase surface -OH, which increases the amount of coupling 3-aminopropyl-triethoxylsilane (APTES), thus linking with BSA by imide bond using EDC/NHS/MES. There is no significant -OH group increase on rutile film when using the same method of phosphoric acid treatment, which suggest it is difficult for further chemical modification of the rutile film. After covalent immobilization of BSA on anatase film, an improved hemocompatibility of anti-platelet adhesion and aggregation in vitro could be recognized by LDH and SEM analysis. This study suggests BSA-immobilized anatase surface can serve as hemocompatibility material in vivo.

  18. Mode specificity for the dissociative chemisorption of H2O on Cu(111): a quantum dynamics study on an accurately fitted potential energy surface.

    Science.gov (United States)

    Liu, Tianhui; Zhang, Zhaojun; Fu, Bina; Yang, Xueming; Zhang, Dong H

    2016-03-16

    The mode-specific dynamics for the dissociative chemisorption of H2O on Cu(111) is first investigated by seven-dimensional quantum dynamics calculations, based on an accurately fitted potential energy surface (PES) recently developed by neural network fitting to DFT energy points. It is indicated that excitations in all three vibrational modes have a significant impact on reactivity, which are more efficacious than increasing the translational energy in promoting the reaction, with the largest enhancement for the excitation in the asymmetric stretching mode. There is large discrepancy between the six-dimensional reactivities with fixed azimuthal angles and seven-dimensional results, revealing that the 6D "flat surface" model cannot accurately characterize the reaction dynamics. The azimuthal angle-averaging approach is validated for vibrational excited states of the reactant, where the 7D mode-specific probability can be well reproduced by averaging the 6D azimuthal angle-fixed probabilities over 18 angles. PMID:26941197

  19. Chemisorption Mechanism of DNA on Mg/Fe Layered Double Hydroxide Nanoparticles: Insights into Engineering Effective SiRNA Delivery Systems.

    Science.gov (United States)

    Lu, Mingsheng; Shan, Zhi; Andrea, Kori; MacDonald, Bruce; Beale, Stefanie; Curry, Dennis E; Wang, Li; Wang, Shujun; Oakes, Ken D; Bennett, Craig; Wu, Wenhui; Zhang, Xu

    2016-03-22

    Layered double hydroxide nanoparticles (LDH NPs) have attracted interest as an effective gene delivery vehicle in biomedicine. Recent advances in clinic trials have demonstrated the efficacy of Mg/Fe LDHs for hyperphosphatemia treatment, but their feasibility for gene delivery has not been systematically evaluated. As a starting point, we aimed to study the interaction between oligo-DNA and Mg/Fe LDH NPs. Our investigation revealed the chemisorption mechanism of DNA on Mg/Fe LDH surfaces, wherein the phosphate backbone of the DNA polymer coordinates with the metal cations of the LDH lattice via the ligand-exchange process. This mechanistic insight may facilitate future gene delivery applications using Mg/Fe LDH NPs. PMID:26919981

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

    International Nuclear Information System (INIS)

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

  1. 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)

    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 H2, the effects and the bimetallic interactions are discussed that frequently happen in the supported catalysts. Starting from the studies of chemical adsorption of H2 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 H2 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

  2. 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.

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

    International Nuclear Information System (INIS)

    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 CuN(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

  4. Model catalyst studies of SMSI and the role of D-electrons in chemisorption and catalysis. Progress report, January 15, 1985-January 14, 1986

    International Nuclear Information System (INIS)

    Electron spectroscopic studies of the surface composition, electronic structure and chemisorption properties of model Rh/TiO2 catalysts fabricated on well characterized single-crystal supports have provided evidence that argues strongly against the simple charge transfer model of strong metal-support interaction that involves the transfer of electrons from surface Ti3+ ions that are created by high temperature reduction. The presence of surface Ti3+ ions does appear to be necessary in order to facilitate the migration of sub-oxides over the catalyst particles in the SMSI state, but hydrogen is not necessary if Ti3+ defect sites exist prior to high temperature annealing. A newly constructed electron beam evaporation source is now being used for in situ deposition of Rh onto TiO2 supports, giving greater control over catalyst loading and particle size. TEM studies of catalyst morphology, performed in parallel with the electron spectroscopic studies, are continuing. 3 figs

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

    Science.gov (United States)

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

    2016-03-01

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

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

    International Nuclear Information System (INIS)

    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. (paper)

  7. Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

    Science.gov (United States)

    Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

    2014-03-01

    We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material.

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

    Science.gov (United States)

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

    2016-03-01

    We measured the electronic and the molecular surface structure of pentacene deposited on the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy (UPS) and low-energy electron diffraction (LEED). Pentacene is almost flat-lying in monolayers on all three substrates and highly ordered on Au(1 1 1) and on Cu(1 1 1). On Ag(1 1 1), however, weak chemisorption leads to almost disordered monolayers, both, at room temperature and at 78 K. On Cu(1 1 1) pentacene is strongly chemisorbed and the lowest unoccupied molecular orbital becomes observable in UPS by a charge transfer from the substrate. On Ag(1 1 1) and Cu(1 1 1) multilayers adopt a tilted orientation and a high degree of crystallinity. On Au(1 1 1), most likely, also in multilayers the molecular short and long axes are parallel to the substrate, leading to a distinctively different electronic structure than on Ag(1 1 1) and Cu(1 1 1). Overall, it could be demonstrated that the substrate not only determines the geometric and electronic characteristics of molecular monolayer films but also plays a crucial role for multilayer film growth. PMID:26870881

  9. Especiação e quimissorção de Pb(II em rejeito de caulim Speciation and chemisorption of Pb(II on kaolin waste

    Directory of Open Access Journals (Sweden)

    Marta Helena Tavares Pinheiro

    2013-01-01

    Full Text Available This study assesses the adsorption of Pb(II on natural kaolin waste (KRnatural and on that treated with 3 mol L-1 H2SO4 and HCl. Equilibrium and thermodynamic parameters were determined. The results indicate that the values of CEC, specific area and SiO2/Al2O3 ratio (4.6-6.0 cmol kg-1, 14.0-16.0 m² g-1 and 1.16-1.30, respectively vary only slightly for the adsorbents; the concentration of Pb2+ is much higher than that of other species (PbOH+ and Pb(OH2. The values of R L, ΔGº, ΔHº and ΔSº are typical of feasible, spontaneous, exothermic and ordered adsorption. The chemisorption on KRnatural is more feasible and ordered.

  10. Study on Chemisorption and Desorption of Hydrogen and Nitrogen on Ru-based Ammonia Synthesis Catalyst%钌基氨合成催化剂氢氮吸附性能的研究

    Institute of Scientific and Technical Information of China (English)

    祝一锋; 李小年; 高冬梅; 周春晖; 刘化章

    2003-01-01

    The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen,dispersion of metallic Ru and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammoniasynthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activitytest. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, andparticularly, potassium exhibited the best promotion on the activity because of the strong electronic donation tometallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activityof Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could beascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit theadsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 showsthe best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of activesites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the correspondingamount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energyfor nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm,just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst iscontrolled by the step of dissociation of nitrogen.

  11. Solventless supramolecular chemistry via vapor diffusion of volatile small molecules upon a new trinuclear silver(I)-nitrated pyrazolate macrometallocyclic solid: an experimental/theoretical investigation of the dipole/quadrupole chemisorption phenomena.

    Science.gov (United States)

    Galassi, Rossana; Ricci, Simone; Burini, Alfredo; Macchioni, Alceo; Rocchigiani, Luca; Marmottini, Fabio; Tekarli, Sammer M; Nesterov, Vladimir N; Omary, Mohammad A

    2013-12-16

    cavities. Density functional theory simulation results are also consistent with the chemisorption model, explain the experimental adsorption selectivity for 1, and attribute the lack of similar adsorption by 2 to significantly less polarizable electrostatic potential and also to strong argentophilic bonding whose energy is even higher than the quadrupole-dipole adduct bond energy upon proper selection of the density functional. PMID:24256298

  12. Sauerstoff- und Stickstoff-Chemisorption an Metallclustern

    OpenAIRE

    Stolcic, Davor

    2003-01-01

    Anion Photoelectron Spectroscopy is a powerful tool for the investigation of the electronic structure of clusters. In this work three investigations are carried out with this method: Using photoelectron spectroscopy and first principle molecular orbital calculations the first observation of a metal-semiconductor transition with increasing number of Oxygen atoms in Tungsten oxide is observed. Tungsten oxide clusters with up to six Tungsten atoms and up to twelve Oxygen atoms were investigated....

  13. 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. PMID:27243042

  14. Regularities in aluminium and indium chemisorption on chelating polymeric sorbents

    International Nuclear Information System (INIS)

    Complexation properties of synthesized polymer chelate sorbents: substituted of polystyrene-azo-pyrocatechol are investigated and correlations between pK'OH of functional groups of sorbents as well as pH50 values of chelation and constants of stability (lgKstab) are established for studying regularities of effect of structure and acid-base properties of functional groups of sorbents on the parameters of Al3+ and In3+ chemical sorption. Established correlations make it possible to predict the physicochemical parameters of sorbents and sorption of metal ions with the aim of separation and concentration of aluminium and indium micro account from the objects of different origin

  15. Sorption J-T refrigeration utilizing manganese nitride chemisorption

    Science.gov (United States)

    Jones, Jack; Lund, Alan

    1990-01-01

    The equilibrium pressures and compositions have been measured for a system of finely powdered manganese nitride and nitrogen gas at 650, 700, 800, and 850 C for various nitrogen loadings. Pressures ranged from less than 0.02 MPa at 650 C to 6.38 MPa at 850 C. Analysis of the test results has shown that under certain conditions Mn(x)N(y) could potentially be used in a triple regenerative sorption compressor refrigeration system, but the potential power savings are small compared to the increased complexity and reliability problems associated with very high temperature (above 950 C) pressurized systems.

  16. Chemisorption and reactions on clusters of nickel atoms

    Science.gov (United States)

    Waber, J. T.; Adachi, H.; Yu, T.

    1982-01-01

    The nucleation and growth of metallic clusters on a substantially amorphous substrate are discussed with emphasis on the geometrical and electronic structure of the clusters. Several clusters of different symmetry containing five to nine nickel atoms were studied. It was found that the energy range of primary d-like states is not significantly different from the width of the d-band states in nickel metal, as long as the interatomic distance is comparable to that in the bulk metal. The approach of one or more molecules to the cluster is examined using at the hydrogenation of acetylene and the dehydrogenation of ethylene as examples.

  17. Sequential oxygen atom chemisorption on surfaces of small iron Clusters

    International Nuclear Information System (INIS)

    We report photoelectron spectra of iron oxide clusters, FexOy- (x=1 endash 4, y=1 endash 6). For a given x, we find that the electron affinity increases with the number of O atoms, consistent with an increasing degree of oxidation. The results are interpreted based on charge transfer interactions between the Fex clusters and the O atoms, and provide key information about the oxide cluster structures, in which each O atom is suggested to locate on the surface of the clusters for the x=3 and 4 series. These clusters provide novel model systems to understand the electronic structure of bulk iron oxides. copyright 1996 The American Physical Society

  18. Electronic shell structure and chemisorption on gold nanoparticles

    OpenAIRE

    Larsen, Ask Hjorth; Kleis, Jesper; Thygesen, Kristian Sommer; Nørskov, J. K.; Jacobsen, Karsten Wedel

    2013-01-01

    We use density functional theory (DFT) to investigate the electronic structure and chemical properties of gold nanoparticles. Different structural families of clusters are compared. For up to 60 atoms we optimize structures using DFT-based simulated annealing. Cluster geometries are found 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 t...

  19. Chemisorption of CO on Pd particles supported on mica

    Science.gov (United States)

    Thomas, M.; Poppa, H.; Dickinson, J. T.; Pound, G. M.

    1978-01-01

    A UHV technique is presented for evaluating the adsorption-desorption properties of UHV vapor-deposited metal particles supported on insulating substrates. Desorption studies of CO from particulate and continuous Pd films supported on mica were performed. The desorption results indicate that: the CO desorption energies from the deposited metals are much lower than those from bulk single crystals; two desorption states exist for the vapor-deposited films; and the lower energy desorption peak of the vapor-deposited films is coverage dependent. Possible reasons for the difference between previously reported CO desorption studies on bulk substrates and the present results are discussed.

  20. Physisorption versus chemisorption of oxygen molecules on Ag(100)

    Science.gov (United States)

    Mehlhorn, Michael; Morgenstern, Karina

    2016-04-01

    We compare the adsorption of oxygen molecules on Ag(100) at 60 K and at 100 K. At both temperatures, the molecules form islands. Differences between the species adsorbed at the two temperatures in both low-temperature scanning tunneling microscopy and inelastic electron tunneling spectroscopy are attributed to two different adsorption states, a chemisorbed state after 100 K adsorption and a physisorbed state after 60 K adsorption.

  1. Role of Amine Functionality for CO2 Chemisorption on Silica.

    Science.gov (United States)

    Hahn, Maximilian W; Jelic, Jelena; Berger, Edith; Reuter, Karsten; Jentys, Andreas; Lercher, Johannes A

    2016-03-01

    The mechanism of CO2 adsorption on primary, secondary, and bibasic aminosilanes synthetically functionalized in porous SiO2 was qualitatively and quantitatively investigated by a combination of IR spectroscopy, thermogravimetry, and quantum mechanical modeling. The mode of CO2 adsorption depends particularly on the nature of the amine group and the spacing between the aminosilanes. Primary amines bonded CO2 preferentially through the formation of intermolecular ammonium carbamates, whereas CO2 was predominantly stabilized as carbamic acid, when interacting with secondary amines. Ammonium carbamate formation requires the transfer of the carbamic acid proton to a second primary amine group to form the ammonium ion and hence two (primary) amine groups are required to bind one CO2 molecule. The higher base strength of secondary amines enables the stabilization of carbamic acid, which is thereby hindered to interact further with nearby amine functions, because their association with Si-OH groups (either protonation or hydrogen bonding) does not allow further stabilization of carbamic acid as carbamate. Steric hindrance of the formation of intermolecular ammonium carbamates leads to higher uptake capacities for secondary amines functionalized in porous SiO2 at higher amine densities. In aminosilanes possessing a primary and a secondary amine group, the secondary amine group tends to be protonated by Si-OH groups and therefore does not substantially interact with CO2. PMID:26700549

  2. Surface studies of Cl2 chemisorption on CVD diamond

    International Nuclear Information System (INIS)

    The technique of X-ray photoelectron spectroscopy has been used to study the interactions of molecular chlorine with CVD diamond surfaces. Chlorine is found to adsorb onto the clean surface with a sticking probability of ∼0.001 at 25 deg C, although this can be enhanced by prehydrogenation of the surface. Adsorbed chlorine desorbs from the surface over a wide temperature range below 500 deg C. It can also be very efficiently etched away by atomic hydrogen. In this paper we present results obtained in the investigation, and discuss their implications in diamond growth mechanisms, in particular to the development of low temperature growth models using halogen-based precursors

  3. Surface electronic structure and chemisorption of plutonium and uranium

    International Nuclear Information System (INIS)

    This paper reports that for the early actinides, uranium through plutonium, the direct overlap of the 5f orbitals and their hybridization with the s and d orbital give rise to narrow banding behavior for the 5f electrons. For the heavier actinides (from americium onward) the 5f electrons of the elemental solids remain localized and do not form a band. As the proportion of 5f to 6d and 7s electrons increases, the itinerant behavior of the 5f electrons gradually disappears. The change to localization is more dramatic between plutonium and americium. Surface f electrons tend to be somewhat more localized than those in the interior because of decreased opportunity for overlap and hybridization. It follows that the degree of localized f-electron behavior will be more conspicuous at the surface for any of the light actinides. Several experimentally accessible surface properties such as the work function are quite sensitive monitors of the degree of f-electron localization

  4. Electronic shell structure and chemisorption on gold nanoparticles

    DEFF Research Database (Denmark)

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

    2011-01-01

    We use density functional theory (DFT) to investigate the electronic structure and chemical properties of gold nanoparticles. Different structural families of clusters are compared. For up to 60 atoms we optimize structures using DFT-based simulated annealing. Cluster geometries are found to...

  5. Adsorbed hydrogen detection on a surface by slow electron energy loss, physisorption, chemisorption

    International Nuclear Information System (INIS)

    The use of Electron Energy Loss Spectroscopy (EELS) for the detection of hydrogen adsorbed on a surface is discussed. The principle of EELS is reminded and the experimental set up described. An overwiew of experimental results obtained on various substrates is given. It is shown that this method is able to determine the chemical form of hydrogen (physisorbed, chemisorbed, etc...). Furthermore the role of the surface dipole moment on hydrogen physisorption is outlined

  6. H2 recombination on interstellar grains. [due to hydrogen atom chemisorption on graphite grains

    Science.gov (United States)

    Barlow, M. J.; Silk, J.

    1976-01-01

    From a consideration of relevant theoretical and experimental data it is concluded that H atoms (but not H2 molecules) will be chemisorbed on interstellar graphite grains, with H2 formation proceeding efficiently for graphite grain temperatures less than 70 K. It is argued that graphite grains will act as the principal sites for H2 formation, with a formation rate of about 4 to the minus 17th cu cm per sec. Heating by H2 molecules formed by surface recombination is analyzed in the context of the available experimental data, and a heating rate is derived and compared with other suggested cloud heating mechanisms. It is concluded that H2 recombination will provide the largest heat source in diffuse clouds if the albedo of interstellar dust in the 912-1200 A region is high (about 0.9), whereas if the albedo in this wavelength region is lower (about 0.5), photoelectron ejection from grains will tend to predominate, and can explain observed cloud temperatures with a carbon depletion factor of approximately 2, a factor attributable to a normal interstellar abundance of graphite grains.

  7. A proposal for the proper use of pseudopotentials in molecular orbital cluster model studies of chemisorption

    Science.gov (United States)

    Bagus, P. S.; Bauschlicher, C. W., Jr.; Nelin, C. J.; Laskowski, B. C.; Seel, M.

    1984-01-01

    The interaction of CO with Cu5, Ni5, and Al4 are treated as model systems for molecular adsorption on metal surfaces. The effect of the use of pseudopotentials for the metal atoms is studied by considering three types of clusters. In the first case, all of the metal electrons are explicitly included in the wave function; an all electron (AE) treatment. In the second case, the metal atom which directly interacts with the CO is described by AE but the remaining metal atoms include a pseudopotential for their core electrons. Finally, in the third case, all of the metal atoms in the cluster have a pseudopotential treatment for the core electrons. The AE cluster results are taken as reference values for the two pseudopotential treatments. The mixed cluster results are in excellent agreement with those of the all AE clusters; however, the results for the all pseudopotential cluster of Ni5CO or of Cu5CO are qualitatively different. The pseudopotential treatment for all of the metal atoms often leads to results that contain serious errors and it is not a reliable approach.

  8. Influence of hydrogen chemisorption kinetics on the interpretation of hydrogen transport through iron membranes

    Science.gov (United States)

    Shanabarger, M. R.; Taslami, A.; Nelson, H. G.

    1981-01-01

    The influence of a specific surface reaction on the transport of gas-phase hydrogen through iron membranes has been investigated on the basis of model calculations. The surface reaction involves an adsorbed molecular hydrogen precursor between the gas phase and the dissociated chemisorbed state. The calculations demonstrate that the surface reaction for the H2/Fe system makes significant contributions to the time delay associated with the transient hydrogen transport through iron membranes, even under conditions where the steady-state hydrogen transport is independent of the surface reaction. These contributions to the time delay are interpreted in terms of an effective diffusivity, which is a function of the pressure on the entrance side and the thickness of the membrane.

  9. The effects of cations and anions on hydrogen chemisorption at Pt

    Science.gov (United States)

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

    1977-01-01

    Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

  10. Molecular Orbital Studies for Na Chemisorption on the Ga-stabilized GaAs(100) Surface

    International Nuclear Information System (INIS)

    Using the ASED-MO total energy calculations of the model clusters, we have investigated the adsorption site and the corresponding adsorption bond length of Na on the Ga-stabilized GaAs(100) surface. The bridge site (III) is the most stable site for the adsorption, and the distance between Na and the surface is 1.47 A. Our calculations suggest that this bridge site (III), the furthest one from the As atoms, is the most effective adsorption site of Na. It suggests that Na may interact more effectively with Ga than with As in the low Na coverage

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

    International Nuclear Information System (INIS)

    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

  12. Lewis Basicity of Nitrogen-Doped Graphite Observed by CO2 Chemisorption

    Science.gov (United States)

    Kiuchi, Hisao; Shibuya, Riku; Kondo, Takahiro; Nakamura, Junji; Niwa, Hideharu; Miyawaki, Jun; Kawai, Maki; Oshima, Masaharu; Harada, Yoshihisa

    2016-03-01

    The characteristics of CO2 adsorption sites on a nitrogen-doped graphite model system (N-HOPG) were investigated by X-ray photoelectron and absorption spectroscopy and infrared reflection absorption spectroscopy. Adsorbed CO2 was observed lying flat on N-HOPG, stabilized by a charge transfer from the substrate. This demonstrated that Lewis base sites were formed by the incorporation of nitrogen via low-energy nitrogen-ion sputtering. The possible roles of twofold coordinated pyridinic N and threefold coordinated valley N (graphitic N) sites in Lewis base site formation on N-HOPG are discussed. The presence of these nitrogen species focused on the appropriate interaction strength of CO2 indicates the potential to fine-tune the Lewis basicity of carbon-based catalysts.

  13. Long-range surface faceting induced by chemisorption of PTCDA on stepped Ag(111) surfaces

    Science.gov (United States)

    Schmitt, Stefan; Schöll, Achim; Umbach, Eberhard

    2016-01-01

    The organic molecule PTCDA preferentially adsorbs on steps of vicinal Ag(111) surfaces and bunches them to well defined facet planes. These depend on coverage and annealing temperature and are independent of the nominal step direction and angle of inclination of the unreconstructed initial surface. We study the development of the facets and present a map of all 16 types of facets in a stereographic triangle of 35° off the [111]-direction. The faceting mechanism is interpreted as orientational phase separation originating from different bonding strengths of PTCDA on various facets. The faceting drives the system to the minimum of its surface free energy.

  14. Carbon Monoxide Chemisorption and Disproportionation on Thin Palladium Layers, Supported by Niobium and Niobium Pentoxide

    Czech Academy of Sciences Publication Activity Database

    Plšek, Jan; Nikolajenko, Vladimír; Thiam, Michel Malick; Knor, Zlatko

    2003-01-01

    Roč. 68, č. 10 (2003), s. 1833-1847. ISSN 0010-0765 R&D Projects: GA ČR GV202/98/K002; GA ČR GA202/02/0618 Institutional research plan: CEZ:AV0Z4040901 Keywords : thermally programmed desorption * energy dissipation * carbon monoxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.041, year: 2003

  15. sup 1 H NMR studies of hydrogen and carbon monoxide chemisorption on the EUROPt-1 catalyst

    CERN Document Server

    Bouyssy, P X

    2001-01-01

    possible carbon monoxide-induced reorganisation of the surface sites available for hydrogen, following a carbon monoxide precoverage above a critical level. It also shows that carbon monoxide blocks hydrogen adsorption but not in the manner expected. No desorption of carbon monoxide was observed with gas phase infrared experiments even at hydrogen coverages approaching saturation. Secondly, to further the understanding of the dynamics of adsorbed hydrogen exchanging between the strongly bound and the weakly bound sites, proton relaxation NMR experiments were undertaken. T sub 1 and T sub 1 subrho measurements were carried out as a function of hydrogen coverage at room temperature and as a function of temperature at fixed hydrogen coverage. These experiments proved to be experimentally challenging and the data obtained do not show a clear enough trend to reach a significant conclusion as was firstly expected. A specially designed sup 1 H NMR probe, capable of holding a large quantity of catalyst sample for in ...

  16. NO Chemisorption on Cu/SSZ-13: a Comparative Study from Infrared Spectroscopy and DFT Calculations

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Renqin; McEwen, Jean-Sabin; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2014-11-07

    The locations and energies of Cu ions in a Cu/SSZ-13 zeolite catalyst were investigated by density functional theory (DFT) calculations. For 'naked' Cu2+ ions (i.e., Cu2+ ions with no ligands in their coordination spheres other than zeolite lattice oxygen atoms), the more energetically favorable sites are within a 6-membered ring. However, with the presence of various adsorbates, the energy difference between 6- and 8-membered ring locations greatly diminishes. Specifically, Cu2+ ions are substantially stabilized by -OH ligands (as [CuII(OH)]+), making the extra-framework sites in an 8-membered ring energetically more favorable than 6-membered ring sites. Under fully dehydrated high vacuum conditions with different Si/Al and Cu/Al ratios, three chemisorbed NO species coexist upon exposure of NO to Cu/SSZ-13: NO+, Cu2+-NO and Cu+-NO. The relative signal intensities for these bands vary greatly with Si/Al ratios. The vibrational frequency of chemisorbed NO was found to be very sensitive to the location of Cu2+ ions. On the one hand, with the aid from DFT calculations, the nature for these vibrations can be assigned in detail. On the other hand, the relative intensities for various Cu2+-NO species provide a good measure of the nature of Cu2+ ions as functions of Si/Al and Cu/Al ratios and the presence of humidity. These new findings cast doubt on the generally accepted proposal that only Cu2+ ions located in 6-membered rings are catalytically active for NH3-SCR.

  17. Lewis Basicity of Nitrogen-Doped Graphite Observed by CO2 Chemisorption.

    Science.gov (United States)

    Kiuchi, Hisao; Shibuya, Riku; Kondo, Takahiro; Nakamura, Junji; Niwa, Hideharu; Miyawaki, Jun; Kawai, Maki; Oshima, Masaharu; Harada, Yoshihisa

    2016-12-01

    The characteristics of CO2 adsorption sites on a nitrogen-doped graphite model system (N-HOPG) were investigated by X-ray photoelectron and absorption spectroscopy and infrared reflection absorption spectroscopy. Adsorbed CO2 was observed lying flat on N-HOPG, stabilized by a charge transfer from the substrate. This demonstrated that Lewis base sites were formed by the incorporation of nitrogen via low-energy nitrogen-ion sputtering. The possible roles of twofold coordinated pyridinic N and threefold coordinated valley N (graphitic N) sites in Lewis base site formation on N-HOPG are discussed. The presence of these nitrogen species focused on the appropriate interaction strength of CO2 indicates the potential to fine-tune the Lewis basicity of carbon-based catalysts. PMID:26951127

  18. Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

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

    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-18O2-16O2 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 relevantO2 activation steps involve directO2* (or O2) reactions with CO* to form reactive O*-O-C*dO intermediates that decompose to form CO2 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 unassistedO2 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 equilibriumconstants 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.

  19. 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.

  20. Chemisorption of aromatic molecules on Si(100)-2x1. An HREELS study

    Energy Technology Data Exchange (ETDEWEB)

    Alkunshalie, T

    1998-07-01

    HREELS has been used to investigate the growth of ultra-thin organic film on Si(100)-2x1 by reactive coupling of polyimide precursors. 1,4- phenylenediamine and pyromelltic dianhydride were sequentially dosed on clean Si(100)-2x1 under ultra high vacuum conditions. The interfacial imidisation was initiated by thermal curing at 200 deg C. To simplify the analysis of the vibrational data, model compounds benzoic acid, aniline and phthalic anhydride were characterised first. HREEL spectra show that the model compounds absorb through dissociation of the functional group. The spectra also show that an oligimide chain has been formed which stands upright on the surface. The oligomer chain bonds to the silicon surface via a Si-(NH)-C linkage. (author)

  1. Chemisorption of NCO on Cu(1 0 0): A density functional theory study

    Science.gov (United States)

    Garda, Graciela R.; Ferullo, Ricardo M.; Castellani, Norberto J.

    2005-12-01

    The isocyanate group adsorption on sites of different coordination of Cu(1 0 0) was theoretically studied considering the cluster approach. The site of four-fold symmetry is the most favored. When NCO adsorbs on Cu, it charges negatively. This electron transfer from the substrate is greater for the site of lowest coordination. The projected DOS curves for the most important valence molecular orbitals of isocyanate group indicate a strong mixing between its 2π orbital and 3d xz and 3d yz AOs of Cu. The predicted asymmetric mode at 2187 cm -1 for NCO adsorbed on the hollow site agrees very well with the experimental observed values of 2162-65 cm -1.

  2. CHEMISORPTION OF SULFUR (IV) OXIDE BY WATER UNDER STATIC CONDITIONS. HENRY’S CONSTANT

    OpenAIRE

    Khoma, R. E.; Dlubovskiy, R. M.

    2015-01-01

    The absorption of sulfur (IV) oxide by water and aqueous solutions has the practical relevance as well as the theoretical interest. The mathematical model showing the relationship of effective Henry’s constant (HS(IV)*, М/Pa) with Henry’s constant (HSO2, М/Pа), and mole fractions of SO2-H2O, HSO3-, S2O5 (2-)  and SO32- is: where K1and K2– dissociation constants of “sulphurous acid” for the first and second degrees, respectively; K*– dimerization constant of hydrogensulfite ions; [H+] – hydrog...

  3. Study of atomic and molecular oxygen chemisorption on BC3 nanotubes with Stone–Wales defects using density functional theory

    International Nuclear Information System (INIS)

    Highlights: • Atomic and molecular oxygen adsorption on BC3 nanotubes is studied by DFT methods. • Perfect BC3 nanotubes and four types of Stone-Wales defects are considered. • Adsorption of O is always exothermic, but for O2 it is sometimes endothermic. • Molecular oxygen is chemisorbed and produces spin-singlet states. • O2 adsorption on SW-CC-c system results in a half-metallic antiferromagnet. - Abstract: Density functional theory calculations are used to study the adsorption of chemical species including oxygen atom and oxygen molecule on the perfect and defective BC3 nanotubes. Stone–Wales topological defects with four different bond rotations have been examined. The adsorption of atomic oxygen is exothermic in all cases, while for the molecular oxygen, some sites showed endothermic adsorption. Comparative studies on the adsorption of these chemical species shows the maintenance of semiconductive behavior of nanotubes, except for one of the systems, the defected nanotube with a circumferential C–C bond rotation. In this system, the adsorption of molecular oxygen generates a half-metallic antiferromagnet. The results obtained in this paper are relevant for chemical sensing and spintronics applications

  4. Determination of the structural and chemisorption characteristics of granulated active charcoal on the basis of coconut shell

    Directory of Open Access Journals (Sweden)

    Milenković Dragan D.

    2004-01-01

    Full Text Available Wastewater purification and the acquirement of drinking water from water streams that are in most cases recipients of various industrial plants, present a significant problem nowadays. The structural characteristics of granulated active charcoal (GAC obtained by the carbonization of coconut shells and activated by steam are presented in this paper. The established kinetics of suspending cyanide from aqueous solution using GAC impregnated with copper(II acetate were studied and a mathematical model estabkusged by a regression - correlation analysis.

  5. FINAL REPORT. CORRELATION OF CHEMISORPTION AND ELECTRONIC EFFECTS FOR METAL OXIDE INTERFACES: TRANSDUCING PRINCIPLES FOR TEMPERATURE PROGRAMMED GAS MICROSENSORS

    Science.gov (United States)

    The spectrum of chemical monitoring problems faced by the Department of Energy (DOE) 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. ...

  6. CORRELATION OF CHEMISORPTION AND ELECTRONIC EFFECTS FOR METAL/OXIDE INTERFACES: TRANSDUCING PRINCIPLES FOR TEMPERATURE-PROGRAMMED GAS MICROSENSORS

    Science.gov (United States)

    The range of chemical monitoring problems faced by the Department of Energy (DOE) 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...

  7. Isotope effect in the study of H-W(100) and O-W(100) chemisorption systems using SIMS

    International Nuclear Information System (INIS)

    Large isotope effects were observed in the secondary ion yields when chemisorbed layers of H, D, 16O, and 18O on W(100) were sputtered with low energy Ne+ ions. Higher isotopic mass in general lowered both the atomic ion yields (H-, D-, O+ and O-) and the molecular ion yield (WO2-), except for H+(D+) where the converse was true

  8. Chemisorption studies on Cs/Cu(110): Model studies of cesium promoters on copper-based catalysts

    International Nuclear Information System (INIS)

    The adsorption of CO, CO2, and H2 O, the coadsorption of oxygen and H2 O, and the coadsorption of CO and surface hydroxyl (OH/sub a/)= on clean and cesium-covered Cu(110) surfaces have been studied with thermal desorption mass spectroscopy, x-ray photoelectron spectroscopy, Auger electron spectroscopy, and work function measurements. We review here results which show that the presence of preadsorbed cesium dramatically affects the adsorption behavior and surface chemistry of CO, CO2, and H2 O on Cu(110). We also present new results which show that surface formate (HCOO/sub a/) is not produced in any observable amount upon heating coadsorbed CO/sub a/ and OH/sub a/ on clean or Cs-dosed Cu(110). The implication of these results to Cs promotion of the catalytic water--gas shift and methanol synthesis reactions over Cu will be discussed

  9. Research of the behaviour of O chemisorption on the (110) surface of Rhx-Pt1-x alloy

    Institute of Scientific and Technical Information of China (English)

    Zhang Hui; Zhang Guo-Ying; Wang Rui-Dan; Zhong Bo

    2006-01-01

    An atomic group model of the disordered binary alloy Rhx-Pt1-x has been constructed to investigate surface segregation. According to the model, we have calculated the electronic structure of the Rhx-Pt-x alloy surface by using the recursion method when O atoms are adsorbed on the Rhxx(110) surface under the condition of coverage 0.5. The calculation results indicate that the chemical adsorption of O changes greatly the density of states near the Fermi level, and the surface segregation exhibits a reversal behaviour. In addition, when x<0.3, the surface on which O is adsorbed displays the property of Pt; whereas when x> 0.3 it displays the property of Rh.

  10. Effect of substrate preparation on the structure and chemisorption properties of Pd/MgO model catalyst

    Science.gov (United States)

    Henry, C. R.; Poppa, H.

    1988-01-01

    Pd/MgO model catalysts are prepared by vapor deposition of Pd particles on MgO thin films which are deposited, at different temperatures, on UHV cleaved mica. MgO films and Pd particles are characterized in situ by Auger electron spectroscopy and energy-loss spectroscopy and ex situ by transmission electron microscopy. Succesive temperature programmed desorption (TPD) of CO shows a different evolution of the morphology of the Pd particles deposited on MgO films prepared at low and high temperature. In addition, on MgO prepared at low temperature, the smallest particles show a continuous decay of CO adsorption during TPD due to contamination by support species.

  11. Correlation of Chemisorption and Electronic Effects for Metal Oxide Interfaces: Transducing Principles for Temperature Programmed Gas Microsensors (Final Report)

    Energy Technology Data Exchange (ETDEWEB)

    S. Semancik; R. E. Cavicchi; D. L. DeVoe; T. J. McAvoy [National Institute of Standards and Technology (US)]|[University of Maryland (US)

    2001-12-21

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Steve Semancik

    2002-01-03

    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

  13. DFT study of isocyanate chemisorption on Cu(100): Correlation between substrate-adsorbate charge transfer and intermolecular interactions

    Science.gov (United States)

    Belelli, Patricia G.; Garda, Graciela R.; Ferullo, Ricardo M.

    2011-07-01

    The adsorption of isocyanate (- NCO) species on Cu(100) was studied using the density functional theory (DFT) and the periodic slab model. The calculations indicate that at low and intermediate coverages NCO adsorbs preferentially on bridge and hollow sites. Work function and dipole moment changes show a significant negative charge transfer from Cu to NCO. The resulting charged NCO species interact repulsively among themselves being these dipole-dipole interactions particularly intensive when they are adsorbed in adjacent sites. Consequently, isocyanates tend to be separated from each other generating the vacant sites required for the dissociation to N and CO. This condition for NCO dissociation has been suggested in the past from experimental observations. A comparison was also performed with the NCO adsorption on Pd(100). In particular, the calculated minimal energy barrier for NCO dissociation was found to be higher on Cu(100) than on Pd(100) in accord with the well known higher NCO stability on Cu(100).

  14. Influence of the chemisorption state on the charge distribution of low energy Si scattered from I adatoms

    Czech Academy of Sciences Publication Activity Database

    Chen, X.; Šroubek, Zdeněk; Yarmoff, J. A.

    2007-01-01

    Roč. 264, č. 1 (2007), s. 23-28. ISSN 0168-583X R&D Projects: GA AV ČR IAA1067401 Grant ostatní: KONTAKT National Science Foundation(US) CHE-0091328 Institutional research plan: CEZ:AV0Z20670512 Source of funding: V - iné verejné zdroje Keywords : surface collisions * ion-surface impact Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.997, year: 2007

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

    International Nuclear Information System (INIS)

    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

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

    International Nuclear Information System (INIS)

    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

  17. Calculations of chemisorption and the elementary acts of catalytic reactions within the framework of a cluster model. XI. Dehydration of ethyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Senchenya, I.N.; Mikheikin, I.D.; Zhidomirov, G.M.; Kazanskii, V.B.

    1980-09-01

    Within the framework of the CNDO/BW method and of a cluster model, this article discusses the energetics of the intermediate structures in the dehydration of ethyl alcohol over alumino-silicate catalysts. It is shown that during coordination there ia a selective weakening of the C - O and C..beta.. - H bonds, which promotes the dehydration of ethyl alchol to an unsaturated hydrocarbon. The calculation argues in support of the possibility of a synchronous mechanism of the reaction in question.

  18. Quantum and classical dynamics of water dissociation on Ni(111): A test of the site-averaging model in dissociative chemisorption of polyatomic molecules

    International Nuclear Information System (INIS)

    Recently, we reported the first highly accurate nine-dimensional global potential energy surface (PES) for water interacting with a rigid Ni(111) surface, built on a large number of density functional theory points [B. Jiang and H. Guo, Phys. Rev. Lett. 114, 166101 (2015)]. Here, we investigate site-specific reaction probabilities on this PES using a quasi-seven-dimensional quantum dynamical model. It is shown that the site-specific reactivity is largely controlled by the topography of the PES instead of the barrier height alone, underscoring the importance of multidimensional dynamics. In addition, the full-dimensional dissociation probability is estimated by averaging fixed-site reaction probabilities with appropriate weights. To validate this model and gain insights into the dynamics, additional quasi-classical trajectory calculations in both full and reduced dimensions have also been performed and important dynamical factors such as the steering effect are discussed

  19. Thermoelectric properties of nano-granular indium-tin-oxide within modified electron filtering model with chemisorption-type potential barriers

    Science.gov (United States)

    Brinzari, V.; Nika, D. L.; Damaskin, I.; Cho, B. K.; Korotcenkov, G.

    2016-07-01

    In this work, an approach to the numerical study of the thermoelectric parameters of nanoscale indium tin oxide (ITO, Sn contentchemisorption effect, and this can be observed despite of the degeneracy of the conduction band (CB). This hypothesis and the corresponding calculations are in good agreement with recent experimental studies [Brinzari et al. Thin Solid Films 552 (2014) 225].

  20. Practical method for highly accurate large-scale surface calculations. [of linearized muffin-tin orbital technique for chemisorption and magnetism

    Science.gov (United States)

    Fernando, G. W.; Cooper, B. R.; Ramana, M. V.; Krakauer, H.; Ma, C. Q.

    1986-01-01

    An accurate and efficient film linearized muffin-tin orbital (FLMTO) technique for surface electronic-structure calculations is presented which uses only 60-70 basis functions, as opposed to the 300 functions used in the linear augmented plane-wave method. Calculations for three different (3d and 4d) transition-metal films resulted in high quality results for five-layer slabs of Cu(001), Fe(001), and Ru(001), in addition to good results for the work functions and projected density of states. By retaining the LMTO small basis size, computer time and memory are reduced, making practical the study of systems with a larger number of atoms in the two-dimensional unit cell.

  1. Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium–Sulfur Battery Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Song, Jiangxuan; Gordin, Mikhail; 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.

  2. Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium-Sulfur Battery Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Song, Jiangxuan [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Gordin, Mikhail L. [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Xu, Terrence [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Chen, Shuru [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Yu, Zhaoxin [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Sohn, Hiesang [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering; Lu, Jun [Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.; Ren, Yang [Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Div.; Duan, Yuhua [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Wang, Donghai [Pennsylvania State Univ., State College, PA (United States). Dept. of Mechanical and Nuclear Engineering

    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 mAhg-1after 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 mAhcm-2) with a high sulfur loading of approximately 5 mgcm-2, which is ideal for practical applications of the lithium–sulfur batteries.

  3. Quantum and classical dynamics of water dissociation on Ni(111): A test of the site-averaging model in dissociative chemisorption of polyatomic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Bin [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2015-10-28

    Recently, we reported the first highly accurate nine-dimensional global potential energy surface (PES) for water interacting with a rigid Ni(111) surface, built on a large number of density functional theory points [B. Jiang and H. Guo, Phys. Rev. Lett. 114, 166101 (2015)]. Here, we investigate site-specific reaction probabilities on this PES using a quasi-seven-dimensional quantum dynamical model. It is shown that the site-specific reactivity is largely controlled by the topography of the PES instead of the barrier height alone, underscoring the importance of multidimensional dynamics. In addition, the full-dimensional dissociation probability is estimated by averaging fixed-site reaction probabilities with appropriate weights. To validate this model and gain insights into the dynamics, additional quasi-classical trajectory calculations in both full and reduced dimensions have also been performed and important dynamical factors such as the steering effect are discussed.

  4. Chemisorptions effect of oxygen on the geometries, electronic and magnetic properties of small size Ni(n) (n = 1-6) clusters.

    Science.gov (United States)

    Bandyopadhyay, Debashis

    2012-02-01

    The present study reports the effect of oxygen addition on small size Ni(n) (n = 1-6) clusters in different spin states within the framework of linear combination of atomic orbital (LCAO) density functional theory (DFT) under spin polarized generalized gradient approximation (GGA) functional. Relative stabilities of the optimized clusters are discussed on the basis of the calculated parameters, such as, binding energy (BE), embedding energy (EE) and fragmentation energy (FE). Other parameters, like ionization potential (IP), electron affinity (EA), etc. show that though the additions of oxygen can affect the chemical properties of Ni(n) clusters with an additional stability to Ni(n)O. In most of the cases the magnetic moment of the stable isomers are geometry dependent for a particular size both in pure and oxidized clusters. Calculated magnetic moments of Ni(n)O (n = 1-6) clusters reveal that the magnetic moment of ground state Ni(4)O isomers in different geometries is same as in pure Ni(4) isomers. Present study also explains the cause of stable magnetic moment in Ni(4)O cluster through the distribution of electrons in different orbitals. PMID:21567288

  5. Synergistically Enhanced Polysulfide Chemisorption Using a Flexible Hybrid Separator with N and S Dual-Doped Mesoporous Carbon Coating for Advanced Lithium-Sulfur Batteries.

    Science.gov (United States)

    Balach, Juan; Singh, Harish K; Gomoll, Selina; Jaumann, Tony; Klose, Markus; Oswald, Steffen; Richter, Manuel; Eckert, Jürgen; Giebeler, Lars

    2016-06-15

    Because of the outstanding high theoretical specific energy density of 2600 Wh kg(-1), the lithium-sulfur (Li-S) battery is regarded as a promising candidate for post lithium-ion battery systems eligible to meet the forthcoming market requirements. However, its commercialization on large scale is thwarted by fast capacity fading caused by the Achilles' heel of Li-S systems: the polysulfide shuttle. Here, we merge the physical features of carbon-coated separators and the unique chemical properties of N and S codoped mesoporous carbon to create a functional hybrid separator with superior polysulfide affinity and electrochemical benefits. DFT calculations revealed that carbon materials with N and S codoping possess a strong binding energy to high-order polysulfide species, which is essential to keep the active material in the cathode side. As a result of the synergistic effect of N, S dual-doping, an advanced Li-S cell with high specific capacity and ultralow capacity degradation of 0.041% per cycle is achieved. Pushing our simple-designed and scalable cathode to a highly increased sulfur loading of 5.4 mg cm(-2), the Li-S cell with the functional hybrid separator can deliver a remarkable areal capacity of 5.9 mAh cm(-2), which is highly favorable for practical applications. PMID:27225061

  6. 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)

    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

  7. 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.

  8. Covalent functionalization of strained graphene

    OpenAIRE

    Boukhvalov, Danil W.; Son, Young-Woo

    2012-01-01

    Enhancement of the chemical activity of graphene is evidenced by first-principles modelling of chemisorption of the hydrogen, fluorine, oxygen and hydroxyl groups on strained graphene. For the case of negative strain or compression, chemisorption of the single hydrogen, fluorine or hydroxyl group is energetically more favourable than those of their pairs on different sublattices. This behaviour stabilizes the magnetism caused by the chemisorption being against its destruction by the pair form...

  9. Stanovení velikosti specifického povrchu palladia v hydrogenačních katalyzátorech chemisorpcí oxidu uhelnatého

    OpenAIRE

    Patera, J.; Krupka, J.; Pašek, J.; Paterová, I.; Jirátová, K.; Murafa, N. (Nataliya)

    2012-01-01

    An apparatus for dynamic chemisorption measurement was built and a reliable experimental methodology based on determination of the specific surface area of Pd (SPd) and the average particle size of Pd (dAV) in hydrogenation catalysts was developed using chemisorption of CO. Experimental conditions necessary for providing reproducibility of measured values were defined. The accuracy of the determination was verified by independent characterization techniques and by comparing chemisorption meas...

  10. 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...

  11. Hydrogen adsorption on boron doped graphene: an {\\it ab initio} study

    OpenAIRE

    Miwa, R. H.; Martins, T B; Fazzio, A.

    2007-01-01

    The electronic and structural properties of (i) boron doped graphene sheets, and (ii) the chemisorption processes of hydrogen adatoms on the boron doped graphene sheets have been examined by {\\it ab initio} total energy calculations.

  12. Stanovení velikosti specifického povrchu palladia v hydrogenačních katalyzátorech chemisorpcí oxidu uhelnatého

    Czech Academy of Sciences Publication Activity Database

    Patera, J.; Krupka, J.; Pašek, J.; Paterová, I.; Jirátová, Květa; Murafa, Nataliya

    2012-01-01

    Roč. 106, č. 12 (2012), s. 1122-1128. ISSN 0009-2770 Institutional support: RVO:67985858 ; RVO:61388980 Keywords : chemisorption * catalysts * experiments Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.453, year: 2012

  13. Photoactive hybrid material based on kaolinite intercalated with a reactive fluorescent silane

    Czech Academy of Sciences Publication Activity Database

    Sas, S.; Danko, M.; Lang, Kamil; Bujdák, J.

    2015-01-01

    Roč. 108, MAY (2015), s. 208-214. ISSN 0169-1317 Institutional support: RVO:61388980 Keywords : Chemisorption * Interfaces * Luminescence * Kaolinite * Optical materials * Rhodamines Subject RIV: CA - Inorganic Chemistry Impact factor: 2.467, year: 2014

  14. Reaction of tungsten anion clusters with molecular and atomic nitrogen

    OpenAIRE

    Kim, Young Dok; Stolcic, Davor; Fischer, Matthias; Ganteför, Gerd

    2003-01-01

    Ultraviolet photoelectron spectra for WnN-2 (n=1 8) clusters produced by addition of atomic and molecular nitrogen on W anion clusters are presented. Evidence is provided that molecular chemisorption of N2 is more stable than the dissociative one on tungsten anion clusters consisting of eight atoms or less, which is completely different from the results on tungsten bulk surfaces. A general tendency toward molecular chemisorption for small clusters can be explained by reduced charge transfer f...

  15. A New Activation Method for Electroless Metal Plating:Palladium Laden via Bonding with Self—Assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    LiNaXU; JianHuiLIAO; 等

    2002-01-01

    A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.

  16. A New Activation Method for Electroless Metal Plating: Palladium Laden via Bonding with Self-Assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition. A closely packed electroless copper film with strong adhesion is successfully fonned by AFM observation. XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.

  17. 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.

  18. Immobilization of Polymeric Luminophor on Nanoparticles Surface

    Science.gov (United States)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-04-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor.

  19. Some problems in adsorption and calorimetric studies of the steps of catalytic processes

    Institute of Scientific and Technical Information of China (English)

    Victor E. Ostrovskii

    2004-01-01

    Principal side factors as well as technical and procedural peculiarities capable of distorting the results of measurements of adsorbed and desorbed amounts, of falsifying the nature of the processes proceeding in the systems under study, and of promoting artifacts in calorimetric and other studies of gas chemisorption on powders are considered. Modified techniques and procedures allowing the elimination of sources of side phenomena and artifacts and freeing traditional glass static adsorption apparatuses and experimental procedures from undesirable factors and peculiarities are proposed.Some available chemisorption and calorimetric data representing artifacts and also some data that are not artifacts but,due to imperfections of chemisorption techniques, show up as artifacts are presented and discussed. Several applications of the improved techniques and procedures to calorimetric and adsorption studies of the steps of catalytic processes proceeding on the basis of natural gas and of products of its processing are presented and discussed.

  20. On adsorption of aluminium and methyl groups on silica for TMA/H2O process in atomic layer deposition of aluminium oxide nano layers

    Indian Academy of Sciences (India)

    Anu Philip; K Rajeev Kumar

    2010-04-01

    A detailed chemisorption mechanism is proposed for the atomic layer deposition (ALD) of aluminium oxide nano layers using trimethyl aluminum (TMA) and water as precursors. Six possible chemisorption mechanisms, complete ligand exchange, partial ligand exchange, simple dissociation, complete dissociation via ligand exchange, complete dissociation and association, are proposed and related parameters like ligand to metal ratio (L/M), concentrations of metal atoms and methyl groups adsorbed are calculated and compared against reported values. The maximum number of methyl groups that can get attached on the surface is calculated in a different way which yields a more realistic value of 6.25 per nm2 substrate area. The dependence of the number of metal atoms adsorbed on OH concentration is explained clearly. It is proposed that a combination of complete ligand exchange and complete dissociation is the most probable chemisorption mechanism taking place at various OH concentrations.

  1. Magnetism induced by single-atom defects in nanographites.

    OpenAIRE

    Yazyev, Oleg V.; Helm, Lothar

    2007-01-01

    We study from first principles the magnetism in graphene induced by single carbon atom defects. For two types of defects considered in our study, the hydrogen chemisorption defect and the vacancy defect, the magnetism due to the defect-induced extended states has been observed. Calculated magnetic moments are equal to 1 μB per hydrogen chemisorption defect and ∼1.5 μB per vacancy defect. The magnetic ordering is either ferromagnetic or antiferromagnetic, depending on whether the defects corre...

  2. 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...

  3. Dependence of CO2 absorption on particle size ferroelectric materials

    International Nuclear Information System (INIS)

    We have studied the interaction of carbon dioxide with the surface of ferroelectric oxides such as barium titanate (BaTiO3), potassium niobate (KNb=3) and lithium niobate (LiNbO3). The chemisorption states of CO2 on the surface of KnbO3 and LiNbO3 change when the particles of this material are smaller than 100 microns. The structure of the particles has been defined by x-ray diffraction and Raman spectroscopy, by size. Good correlation was found for the chemisorption properties and for the structural changes for particles smaller than 100 microns. (C.W)

  4. 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

  5. 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...

  6. 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...

  7. Efficient Methanol Synthesis Catalysts: Long-Term Stability and Deactivation Phenomena

    OpenAIRE

    Fichtl, Matthias

    2014-01-01

    In this thesis the deactivation mechanism on different coprecipitated Cu/ZnO/Al2O3 methanol synthesis catalysts is evaluated. Transmission electron microcopy, X-ray diffraction, chemisorption methods and modeling techniques are applied to correlate the deactivation behavior with structural changes in the active catalyst. Updated models for the catalyst microstructure and deactivation behavior are presented.

  8. Electrochemical reactions at surfaces. 1976-September, 1980 (citations from the NTIS Data Base). Report for 1976-September 1980

    Energy Technology Data Exchange (ETDEWEB)

    Cavagnaro, D.M.

    1980-10-01

    This bibliography covers electrode processes in aqueous solutions. The citations discuss battery electrode reactions, fuel cell reactions, electrochemical corrosion studies, catalyst reactions, chemisorption, theoretical analysis, electrical double layer, and measurement techniques. Also included are some molten salt processes. (This updated bibliography contains 148 citations, 23 of which are new entries to the previous edition.)

  9. 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.

  10. Environmental chemistry of radioactive waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Duffield, J.R.; Williams, D.R.

    1986-09-01

    In this review the environmental chemistry problems associated with radioactive waste disposal are considered from the point of view of the threat to man of waste disposal, contamination pathways, the chemistry of waste containment, speciation of radio-isotopes, chemisorption, risk assessment and computerized simulation of waste disposal phenomena. A strategy for the future is discussed.

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

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  12. 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

  13. Interaction of hydrogen with samaria supported rhodium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bernal, S.; Botana, F.J.; Calvino, J.J.; Cifredo, G.A.; Rodriguez-Izquierdo, J.M.

    1991-01-01

    Hydrogen chemisorption on several samaria supported rhodium catalysts has been studied. The TPD diagrams were broad and rather complex. Adsorption on both, rhodium and support phases was observed. The occurrence of spill over, as well as of metal decoration phenomena, restricts very much the use of apparent H/Rh data to estimate metallic dispersions.

  14. 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 at...

  15. Interactions of hydrogen with alkali promoted Ru/SiO{sub 2} catalysts: A proton NMR study

    Energy Technology Data Exchange (ETDEWEB)

    Ozbay, U.D.

    1994-05-10

    Role of H spillover to the silica support was studied using chemisorption; a strongly bound component of spilled over H was found in the silica support which interfered with accurate measurements of active metal sites via volumetric strong H chemisorption. The volumetric chemisorption technique was modified so that measurement times were reduced from 12--36 h to 1 h. The active Ru surface was characterized means of changes in proton spin counts and NMR Knight shifts vs alkali loading. Na, K blocked the active surface of Ru metal, but Cs was pushed off by H chemisorption. The alkali promoters restricted H mobility on both metal surface and at the metal support interfaces; this is consistent with effects on Fischer-Tropsch synthesis. {sup 1}H NMR was used to study the effect of the active metal and promoter on support hydroxyl groups. The OH group density in the silica support decreased with metal and/or promoter loading, but not on a one-to-one basis; the exchange efficiency of the hydroxyls decreased with atomic size of the alkali metal. An additional downfield proton resonance was detected which was assigned to the alkali hydroxide species in the support.

  16. 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

    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...

  17. 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

  18. Guanine adsorption on the Cu(110) surface

    Czech Academy of Sciences Publication Activity Database

    Feyer, V.; Plekan, O.; Šutara, F.; Cháb, Vladimír; Matolín, V.; Prince, K. C.

    2011-01-01

    Roč. 605, 3-4 (2011), s. 361-365. ISSN 0039-6028 R&D Projects: GA AV ČR IAA100100905 Institutional research plan: CEZ:AV0Z10100521 Keywords : guanine * copper * chemisorption * hydrogen bond Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.994, year: 2011

  19. Hydrogen atomic pair-ion production on catalyst surface

    International Nuclear Information System (INIS)

    To generate a hydrogen pair-ion plasma consisting of only hydrogen atomic pair ions, i.e., H+ and H- ions, the efficient production of pair ions is required. When discharged hydrogen plasma is irradiated to a Ni catalyst, pair ions are produced on the catalyst surface. It is clarified that hydrogen chemisorption on the catalyst affects pair-ion production.

  20. The concentration dependence of Co sorption on corrosion product oxide layers on austenitic steel at 368 K (95 0C)

    International Nuclear Information System (INIS)

    The Co sorption on corrosion products of stainless steel is a chemisorption process of hydroxocation Co(OH)+. Its dependence upon concentration and pH may be described quantitatively by an absorption equation of Freundlich-type. A relation for the concentration of the monolayer was derived and the value calculated from measuring data. (author)

  1. 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

  2. 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

  3. Kinetics of the Low Pressure Chemical Vapor Deposition of Polycrystalline Germanium-Silicon Alloys from SiH4 and GeH4

    NARCIS (Netherlands)

    Holleman, J.; Kuiper, A.E.T.; Verweij, J.F.

    1993-01-01

    A Langmuir-Hinshelwood growth-rate equation is presented for the germanium-silicon (GeSi) alloy deposition fromGeH4 and SiH4 assuming dissociative chemisorption on a heterogeneous GeSi surface. Model parameters for the depositionkinetics have been extracted from measurements. The fit for the bond-en

  4. 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.

  5. 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 of a...

  6. 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...

  7. Interaction of hydrogen with samaria supported rhodium catalysts

    International Nuclear Information System (INIS)

    Hydrogen chemisorption on several samaria supported rhodium catalysts has been studied. The TPD diagrams were broad and rather complex. Adsorption on both, rhodium and support phases was observed. The occurrence of spill over, as well as of metal decoration phenomena, restricts very much the use of apparent H/Rh data to estimate metallic dispersions

  8. Photocatalytic oxidation mechanism of alkanes in contact with titanium dioxide

    Science.gov (United States)

    Formenti, M.; Juillet, F.; Teichner, S. J.

    1977-01-01

    Isobutane was photooxidized on titanium dioxide between -16 and +180 C in tertiary butanol and acetone. The formation of tertiary butanol preceded the formation of acetone. Above 20 C the latter compound became clearly predominant. The reaction kinetics obeyed a steady state model of oxygen chemisorption with the involvement of isobutane in the physisorbed phase.

  9. Density-functional study of oxidation at the Mn-Co interface

    Czech Academy of Sciences Publication Activity Database

    Pick, Štěpán; Demangeat, C.

    2005-01-01

    Roč. 584, 2-3 (2005), s. 146-152. ISSN 0039-6028 Grant ostatní: European Commission(XE) HPRN-CT-2000-00143 Institutional research plan: CEZ:AV0Z40400503 Keywords : density -functional calculations * chemisorption * magnetic phenomena * cobalt * manganese Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.780, year: 2005

  10. H{sub 2} formation in diffuse clouds: A new kinetic Monte Carlo study

    Energy Technology Data Exchange (ETDEWEB)

    Iqbal, Wasim; Acharyya, Kinsuk [S. N. Bose National Centre for Basic Sciences, Salt Lake, Kolkata 700098 (India); Herbst, Eric [Departments of Chemistry, Astronomy, and Physics, University of Virginia, Charlottesville, VA 22904 (United States)

    2014-04-01

    We used the continuous-time random-walk Monte Carlo technique to study anew the formation of H{sub 2} on the surfaces of interstellar dust grains in diffuse interstellar clouds. For our study, we considered three different grain materials, olivine (a polycrystalline silicate), amorphous silicate, and amorphous carbon, as well as a grain temperature that depends on granular size. For some runs, we included temperature fluctuations. Four different granular surfaces were used, one 'flat' with one type of binding site due to physisorption, one 'rough' with five different types of physisorption binding sites due to lateral forces, and two with sites for chemisorption, one in which chemisorption sites are entered through precursor physisorption sites, and one in which chemisorption is direct but occurs with a barrier for the adsorption of the first hydrogen atom. We found that on flat and rough olivine surfaces, molecular hydrogen is formed at low efficiencies, with smaller grains contributing very little despite their large numbers due to high temperatures. For flat amorphous carbon and amorphous silicate surfaces, the efficiency increases, reaching unity for the largest grains. For models with barrierless chemisorption, the efficiency of formation of H{sub 2} is near unity at all grain sizes considered, while for direct chemisorption via a barrier, we found efficiencies of 0.13-0.6 depending upon the barrier, but independent of grain size. Treating the flat olivine and amorphous silicate surfaces with temperature fluctuations increases the efficiency of H{sub 2} formation.

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

    International Nuclear Information System (INIS)

    Highlights: • Both physisorption and chemisorption of Hg0 occurred on the surface of M6WN5. • Chemisorption process was an absolute predominant route for Hg0 removal by M6WN5. • The effect of NO, H2O, SO2 and O2 on Hg0 removal by M6WN5 was investigated. • M6WN5 demonstrated to be a promising Hg0 sorbent in flue gas. - Abstract: Pyrolyzed biochars from an industrial medicinal residue waste were modified by microwave activation and NH4Cl impregnation. Mercury adsorption of different modified biochars was investigated in a quartz fixed-bed reactor. The results indicated that both physisorption and chemisorption of Hg0 occurred on the surface of M6WN5 which was modified both microwave and 5 wt.% NH4Cl loading, and exothermic chemisorption process was a dominant route for Hg0 removal. Microwave activation improved pore properties and NH4Cl impregnation introduced good active sites for biochars. The presence of NO and O2 increased Hg0 adsorption whereas H2O inhibited Hg0 adsorption greatly. A converse effect of SO2 was observed on Hg0 removal, namely, low concentration of SO2 promoted Hg0 removal obviously whereas high concentration of SO2 suppressed Hg0 removal. The Hg0 removal by M6WN5 was mainly due to the reaction of the C−Cl with Hg0 to form HgCl2, 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 Hg0 sorbent in flue gas when compared with other sorbents

  12. 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.)

  13. Effect of method of preparation on hydrodesulphurization activity of Co- or Ni-promoted MoS2/SBA-15 catalysts

    Indian Academy of Sciences (India)

    Shelu Garg; Kapil Soni; V V D N Prasad; Manoj Kumar; Thallada Bhaskar; J K Gupta; G Murali Dhar; C S Gopinath

    2014-03-01

    Ordered mesoporous material SBA-15 was synthesized and used as a support for the preparation of molybdenum sulphide catalysts through precipitation from homogeneous solution (PFHS) technique with the Mo content varying from 2-12 wt%. The prepared catalysts were evaluated for thiophene hydrodesulphurization catalytic activities at 400°RC. Catalysts prepared through PFHS method resulted in highly dispersed MoS2 catalysts, which were inferred from powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low temperature oxygen chemisorptions (LTOC) and BET surface area analysis. The relationship between XPS intensity ratio, oxygen chemisorption and catalytic activities is discussed in terms of highly dispersed nano particles of MoS2 and its consequence in accommodating more promoted atoms at the edge sites.

  14. Adsorption of polyiodobenzene molecules on the Pt(111) surface using van der Waals density functional theory

    Science.gov (United States)

    Johnston, Karen; Pekoz, Rengin; Donadio, Davide

    2016-02-01

    Adsorption of aromatic molecules on surfaces is widely studied due to applications in molecular electronics. In this work, the adsorption of iodobenzene molecules on the Pt(111) surface has been studied using density functional theory. Iodobenzene molecules, with various numbers of iodine atoms, have two non-dissociative adsorption minima. One structure exhibits chemisorption between the ring and the surface (short-range) and the other structure exhibits chemisorption between the iodine ions and the surface (long-range). Both structures have a strong van der Waals interaction with the surface. In general, the adsorption energy increases as the number of iodine atoms increases. The dissociated structure of monoiodobenzene was investigated, and the dissociation barrier and the barrier between the short- and long-range states were compared.

  15. First-principles cluster expansion study of functionalization of black phosphorene via fluorination and oxidation

    Science.gov (United States)

    Nahas, Suhas; Ghosh, Barun; Bhowmick, Somnath; Agarwal, Amit

    2016-04-01

    Predicting the ground states for surface adsorption is a challenging problem because the number of degrees of freedom involved in the process is very high. Most of the studies deal with some specific arrangements of adsorbates on a given surface, but very few of them actually attempt to find the ground states for different adatom coverage. In this work, we show the effectiveness of the cluster expansion method to predict the "ground states" resulting from chemisorption of oxygen and fluorine atom on the surface of monolayer black phosphorus or phosphorene. For device applications, we find that in addition to band-gap tuning, controlled chemisorption can change the unique anisotropic carrier effective mass for both the electrons and holes and even rotate them by 90∘, which can be useful for exploring unusual quantum Hall effect and electronic devices based on phosphorene.

  16. The surface chemistry of metal-oxygen interactions

    DEFF Research Database (Denmark)

    Stokbro, Kurt; Baroni, Stefano

    1997-01-01

    We report on a computational study of the clean and oxygen-covered Rh(110) surface, based on density-functional theory within the local-density approximation. We have used plane-wave basis sets and Vanderbilt ultra-soft pseudopotentials. For the clean surface, we present results for the equilibrium...... structure, surface energy and surface stress of the unreconstructed and (1 x 2) reconstructed structures. For the oxygen-covered surface we have performed a geometry optimization at 0.5, 1, and 2 monolayer oxygen coverages, and we present results for the equilibrium configurations, workfunctions and oxygen...... chemisorption energies. At half monolayer coverage, we find that oxygen induces a (1 x 2) reconstruction of the surface, while at one monolayer coverage the chemisorption energy is highest for the unreconstructed surface. Our results are rationalized by a simple tight-binding description of the interaction...

  17. Production of high-quality ZnO films by the two-step annealing method

    Science.gov (United States)

    Ye, J. D.; Gu, S. L.; Zhu, S. M.; Qin, F.; Liu, S. M.; Liu, W.; Zhou, X.; Hu, L. Q.; Zhang, R.; Shi, Y.; Zheng, Y. D.

    2004-11-01

    In this study, a two-step annealing method is advanced to produce high-quality ZnO films with excellent structural, electrical, and optical properties. The effects of oxygen and nitrogen annealing on the properties of undoped ZnO films are reversible to each other and are attributed to the creation and annihilation of extrinsic trap states of antisite oxygen OZn and oxygen vacancies VO, which result from the chemisorption and desorption of oxygen, respectively. Moreover, annealing in nitrogen causes slight nitrogen incorporation, subsequently increasing the resistivity and inducing compressive stress in the film. The key to this two-step method is to keep the chemisorption and desorption of oxygen in equilibrium. Due to the similarity of annealing ambient with the growth condition, this process can be transplanted and employed in the in situ preparation of high-quality ZnO epilayers.

  18. Gaseous iodine trapping on mineral solid filters. I - Isotherms and kinetics

    International Nuclear Information System (INIS)

    In the nuclear spent fuel reprocessing plants, solid filters are the last device to trap iodine-129 in the gaseous effluents before atmospheric discharge. Molecular iodine is fixed by chemisorption on silver nitrate deposited in the porosity of a catalyst support. Within the framework of the researches on enhanced separation of LLFP, a program was undertaken aiming at identifying the trap properties controlling the iodine retention. Two industrial substrates were investigated to determine the influence of their physicochemical characteristics, successively on the reactive deposit and iodine trapping. The isotherms showed two quite distinct successive stages: chemisorption prevails as long as the silver nitrate is not completely converted and, then only, physi-sorption takes place controlled by the porous texture. The kinetics can be treated according to the LDF model which gives access to the kinetics constant for a given gas-solid equilibrium; the variation of this constant was assessed in a wide range of P/P0. (authors)

  19. Adsorption of oxygen on a nickel covered SrTiO3(100) surface studied by means of Auger electron spectroscopy and work function measurements

    International Nuclear Information System (INIS)

    The interaction of oxygen with evaporated Ni films on an Fe-doped SrTiO3(100) substrate was investigated by means of LEED, AES and work function measurements (WF) at room temperature. The adsorption of oxygen takes place on the nickel overlayer firstly by chemisorption on nickel step sites, accompanied by a reduction of the WF, and secondly on terrace sites, followed by a WF increase. After the chemisorption phase, the oxidation of the nickel overlayer starts with NiO island formation followed by bulk NiO development, which is marked by a second WF reduction. The adsorption phases of oxygen correspond closely to those of oxygen on single crystals of nickel. This indicates that the character of the Ni predeposited layers on strontium titanate seems to be metallic

  20. Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

    Science.gov (United States)

    Zhang, Ning; Li, Xiyu; Ye, Huacheng; Chen, Shuangming; Ju, Huanxin; Liu, Daobin; Lin, Yue; Ye, Wei; Wang, Chengming; Xu, Qian; Zhu, Junfa; Song, Li; Jiang, Jun; Xiong, Yujie

    2016-07-20

    Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials. PMID:27351805

  1. Elucidation of behavior of sulfur on nickel-based hot gas cleaning catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hepola, Jouko [VTT Energy, Energy Production Technologies, Espoo (Finland); McCarty, Jon; Wong, Victor [Catalytica, Inc., Mountain View, CA (United States); Krishnan, Gopala [SRI International, Menlo Park, CA (United States)

    1999-03-08

    A closed-loop gas-recirculation system was used to measure the isosteric heat of sulfur chemisorption on supported nickel catalysts in hot gas cleaning conditions of gasification gas. During sulfur adsorption, reconstruction of the catalysts occurred. In addition, probably the enormous increase in surface diffusion due to sulfur adsorption on some nickel catalysts with high flow rates resulted in melt formation of adsorbed species on the surfaces of catalyst particles. Heat of sulfur adsorption on nickel decreased when sulfur coverage was increased. However, the enthalpy of adsorption decreased even below the heat of formation of bulk Ni{sub 3}S{sub 2}, indicating most likely multi-layer or subsurface sulfur formation on catalyst surfaces. The structural properties of the catalysts had a great influence on sulfur adsorption behavior. The effect of sulfur on ammonia decomposition in synthetic gasification gas tests was explained by the change of heat of sulfur chemisorption on nickel

  2. Molecular Simulation Study on Interaction of Thiophene Sulfides with Transition Metals

    Institute of Scientific and Technical Information of China (English)

    Liu Yujian; Long Jun; Zhou Han; Zhu Yuxia; Da Zhijian

    2003-01-01

    The computer molecular simulation technique was applied to study the chemisorption of thiophene and tetramethylthiophene as the model sulfides on the simple oxides and complex oxides of some transition metals as the catalytic materials. The study disclosed that the thiophene sulfides could enter into chemisorption with metal oxides such as VO, ZnO, NiO and Zn-Al-spinel. This interaction could lead to thiophene molecular structure deformation to be in an activated adsorption state, which could help to promote the conversion of thiophene sulfides in the course of catalytic cracking. The VO with a valence of 2 could provide relatively strong selective adsorption sites for the conversion of thiophene sulfides to apparently transform the molecular structures and electron cloud states of such heterocyclic sulfur compounds such as thiophene and tetramethylthiophene into an activated adsorption state. The effect of this interaction was more pronounced with respect to tetramethylthiophene.

  3. 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.

  4. Low metal loading catalysts used for the selective hydrogenation of styrene

    OpenAIRE

    Juan Badano; Cecilia Lederhos; Mónica Quiroga; Pablo L'Argentière; Fernando Coloma-Pascual

    2010-01-01

    A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence o...

  5. Reactivity of non-stoichiometric black alumina

    International Nuclear Information System (INIS)

    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)

  6. Visible-light-induced water oxidation by a hybrid photocatalyst consisting of bismuth vanadate and copper(II) meso-tetra(4-carboxyphenyl)porphyrin.

    Science.gov (United States)

    Nakashima, Shu; Negishi, Ryo; Tada, Hiroaki

    2016-03-01

    Copper(II) meso-tetra(4-carboxyphenyl)porphyrin surface-modified monoclinic scheelite bismuth vanadate (CuTCPP/BiVO4) has been synthesized via a two-step route involving chemisorption of TCPP on BiVO4 and successive Cu(II) ion incorporation into the TCPP, and the surface modification drastically enhances the water oxidation to oxygen (O2) under visible-light irradiation (λ > 430 nm). PMID:26853997

  7. A Density Functional Study of O2 Adsorption on (100) Surface of gamma-Uranium

    OpenAIRE

    Huda, M. N.; A.K. Ray

    2004-01-01

    We have studied the chemisorption processes of O2 on the (100) surface of uranium using generalized gradient approximation to density functional theory. Dissociative adsorptions of O2 are significantly favored compared to molecular adsorptions. We found interstitial adsorption of molecular oxygen to be less probable, as no bound states were found in this case. Upon oxygen adsorption, O 2p orbitals is found to hybridize with U 5f bands, and part of the U 5f electrons become more localized. Als...

  8. The Role of the Coprecipitation Sequence of Salt Precursors on the Genesis of Cu-ZnO-Al2O3 Catalysts: Synthesis, Characterization and Activity for Low Temperature Shift Reaction

    OpenAIRE

    1998-01-01

    Cu-ZnO-Al2O3 catalysts for the low-temperature water-gas shift reaction were prepared using methods of direct and reverse coprecipitation. The catalysts obtained were characterized by DRX, TPR, XPS, N2O chemisorption, Hg-Porosimetry and BET surface area. It was observed that the precipitation sequence of the precursors led to significant differences in values of copper dispersion and consequently in the activity of the catalyst for the water-gas shift reaction.

  9. 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

  10. Dipole formation at metal/PTCDA interfaces: Role of the Charge Neutrality Level

    OpenAIRE

    Vazquez, H.; Oszwaldowski, R.; Pou, P.; Ortega, J.; Perez, R.; F. Flores; Kahn, A.

    2004-01-01

    The formation of a metal/PTCDA (3, 4, 9, 10-perylenetetracarboxylic dianhydride) interface barrier is analyzed using weak-chemisorption theory. The electronic structure of the uncoupled PTCDA molecule and of the metal surface is calculated. Then, the induced density of interface states is obtained as a function of these two electronic structures and the interaction between both systems. This induced density of states is found to be large enough (even if the metal/PTCDA interaction is weak) fo...

  11. Surface stress and large-scale self-organization at organic-metal interfaces

    OpenAIRE

    Pollinger, Florian

    2009-01-01

    Anhand von Modellsystemen wurde in dieser Arbeit die Bedeutung elastischer Wechselwirkungen an Organik-Metall Grenzflächen, insbesondere für die Selbstorganisierte Ausbildung periodisch facettierter Strukturen, untersucht. Die Änderung der Oberflächenspannung während der Ausbildung der Grenzfläche zwischen 3,4,9,10-Perylentetracarbonsäuredianhydrid (PTCDA) und Ag(111) wurde mit der Biegekristalltechnik gemessen. Es ist bekannt, dass dieses System durch eine chemisorptive Bindung bestimmt wird...

  12. Equilibrium Isotherm Modeling, Kinetics and Thermodynamics Study for Removal of Lead from Waste Water

    OpenAIRE

    Chowdhury, Z.; S. M. Zain; Rashid, A K

    2011-01-01

    The low cost adsorbent palm oil fuel ash (POFA) derived from an agricultural waste material was investigated as a replacement of current expensive methods for treating wastewater contaminated by Pb(II) cation. Adsorption studies were carried out to delineate the effect of contact time, temperature, pH and initial metal ion concentration. The experimental data followed pseudo second order kinetics which confirms chemisorptions. The values of Langmuir dimensionless constant, RL and Freundlich c...

  13. 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

  14. Thermal Emissivity-Based Chemical Spectroscopy through Evanescent Tunneling.

    Science.gov (United States)

    Poole, Zsolt L; Ohodnicki, Paul R

    2016-04-01

    A new spectroscopic technique is presented, with which environmentalchemistry-induced thermal emissivity changes of thin films are extracted with high isolation through evanescent tunneling. With this method the hydrogen-induced emissivity changes of films of TiO2 , Pd-TiO2 , and Au-TiO2 , with properties of high conductivity, hydrogen chemisorption, and plasmonic activity, are characterized in the UV-vis and NIR wavelength ranges, at 1073 K. PMID:26901747

  15. Ni adatoms on Al{sub 2}O{sub 3} film probed by NO adsorption: a RAIRS study

    Energy Technology Data Exchange (ETDEWEB)

    Magkoev, T.T. [State Univ. of North Ossetia, Vladikavkaz (Russian Federation). Dept. of Physics; Murata, Y. [Univ. of Electro-Communications, Tokyo (Japan). Div. of Natural Sciences

    2001-01-01

    In this note we present an experimental result on reflection absorption infrared spectroscopy (RAIRS) of nitric oxide (NO) molecules adsorbed on nickel (Ni) adatoms on Al{sub 2}O{sub 3} film grown on Mo(110) crystal, which we interpret as the evidence for the formation of the chemisorption bond between Ni adatoms and Al{sub 2}O{sub 3} dominated by the oxide oxygen ion, rather than the aluminum ion. (orig.)

  16. ИЗМЕНЕНИЕ ШИРИНЫ HOMO-LUMO ЩЕЛИ ОДНОСТЕННЫХ УГЛЕРОДНЫХ НАНОТРУБОК ТИПА «ЗИГЗАГ» ПРИ ХЕМОСОРБЦИИ ВОДОРОДА

    OpenAIRE

    Богданова, Дарья; Булярский, Сергей

    2014-01-01

    Background. The main interest in carbon nanotubes in the field of microand nanoelectronics is associated with their potential applications in creating various metal-semiconductor and semiconductor-semiconductor structures. To implement such structures in practice it is necessary to have a mechanism of effective control over the width of HOMO-LUMO energy gap of nanotubes. One of the most promising among these mechanisms is the hydrogen chemisorption on the nanotubes, which can be considered as...

  17. A Theoretical Simulation of Deformed Carbon Nanotubes with Adsorbed Metal Atoms: Enhanced Reactivity by Deformation

    OpenAIRE

    Hosoya, Naoki; Kusakabe, Koichi; Maheswari, S. Uma

    2010-01-01

    First-principles simulations were performed to investigate reaction of carbon nanotubes with adsorbed metal atoms. Mechanical modification of their structures enhances chemical reactivity of carbon nanotubes. Adsorption of a tungsten, tantalum, or niobium atom on a (5, 0) nanotube with a Stone-Wales defect was shown to have characteristically strong chemisorption. Bond-breaking in the carbon-carbon network and formation of a local metal-carbon complex were observed during the simulation. Adso...

  18. Purification of ethanol for highly sensitive self-assembly experiments

    OpenAIRE

    Kathrin Barbe; Martin Kind; Christian Pfeiffer; Andreas Terfort

    2014-01-01

    Ethanol is the preferred solvent for the formation of self-assembled monolayers (SAMs) of thiolates on gold. By applying a thin film sensor system, we could demonstrate that even the best commercial qualities of ethanol contain surface-active contaminants, which can compete with the desired thiolates for surface sites. Here we present that gold nanoparticles deposited onto zeolite X can be used to remove these contaminants by chemisorption. This nanoparticle-impregnated zeolite does not only ...

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

    International Nuclear Information System (INIS)

    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

  20. Surface thermodynamics

    International Nuclear Information System (INIS)

    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

  1. Carboranedithiols: Building Blocks for Self-Assembled Monolayers on Copper Surfaces

    Czech Academy of Sciences Publication Activity Database

    Baše, Tomáš; Bastl, Zdeněk; Havránek, Vladimír; Macháček, Jan; Langecker, Jens; Malina, Václav

    2012-01-01

    Roč. 28, č. 34 (2012), s. 12518-12526. ISSN 0743-7463 R&D Projects: GA ČR GAP205/10/0348; GA AV ČR KAN100400702 Institutional support: RVO:61388980 ; RVO:61388955 ; RVO:61389005 ; RVO:67985882 Keywords : copper surfaces * carboranethiols * cluster * chemisorption * self-assembled monolayer Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 4.187, year: 2012

  2. Tin dioxide materials chemically modified with trialkynylorganotins: functional nanohybrids for photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Vilaca, G.; Jousseaume, B.; Mahieux, C.; Toupance, T. [Laboratoire de Chimie Organique et Organometallique, UMR 5802-CNRS, Universite Bordeaux 1, 351 Cours de la Liberation, 33405 Talence Cedex (France); Belin, C. [Laboratoire de Physico-Chimie Moleculaire, UMR 5803-CNRS, Universite Bordeaux 1, 351 Cours de la Liberation, 33405 Talence Cedex (France); Cachet, H.; Bernard, M.C.; Vivier, V. [Laboratoire des Interfaces et Systemes Electrochimiques, UPR 15-CNRS, Universite Pierre et Marie Curie, 4 Place Jussieu, CP 133, 75252 Paris Cedex 05 (France)

    2006-04-18

    Surface modification of nanoporous tin dioxide materials with fluorinated or perylene units is achieved with trialkynylorganotin compounds. Irreversible chemisorption occurs in solution at room temperature, yielding an organic layer at the oxide surface via the cleavage of the three tin-alkynide bonds of the precursor and the formation of Sn{sub bulk}-O-Sn-C linkages. The dye-sensitized nanohybrids are suitable for solar-energy conversion devices. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  3. Halbleiternanopartikel-modifizierte Elektrode zum Nachweis von Substraten von NADH-abhängigen Enzymreaktionen

    OpenAIRE

    Schubert, Kirsten; Khalid, Waqas; Zhao, Yue; J. Parak, Wolfgang; Lisdat, Fred

    2010-01-01

    Es wurde ein Elektrodensystem entwickelt, das aufbauend auf Halbleiternanopartikeln (so genannte Quantenpunkte) die sensitive Detektion des Enzymkofaktors NADH (nicotinamide adenine dinucleotide) erlaubt. Kolloidale halbleitende CdSe/ZnS-Nanokristalle sind durch ein Dithiol über Chemisorption an Gold gebunden. Das Stromsignal kann durch die Beleuchtung der Quantenpunkt modifizierten Oberfläche beeinflusst werden. Durch Photoanregung entstehen Elektron-Loch- Paare in den Nanopartikeln, die als...

  4. Off-Site Regeneration of Hydroprocessing Catalysts Régénération hors-site de catalyseurs d'hydrotraitement

    OpenAIRE

    Dufresne P.; Brahma N.; Girardier F.

    2006-01-01

    This paper describes the basic phenomena occurring during oxidative regeneration of hydroprocessing catalysts, as well as laboratory experiments studying the removal of carbon and sulfur as a function of temperature. In addition, the evolution of Surface Area (SA) and Dynamic Oxygen Chemisorption (DOC) values versus regeneration temperature applied is discussed. DOC is used to evaluate the dispersion of the active metal-sulfide phase. DOC and SA measurements are complementary techniques for q...

  5. Washcoated Pd/Al2O3 monoliths for the liquid phase hydrodechlorination of dioxins

    OpenAIRE

    Cobo, Martha; Orrego, Andrés; Conesa Ferrer, Juan Antonio

    2012-01-01

    The catalytic activity and durability of 2 wt.% Pd/Al2O3 in powder and washcoated on cordierite monoliths were examined for the liquid phase hydrodechlorination (LPHDC) of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs), also known as dioxins. NaOH was employed as a neutralizing agent, and 2-propanol was used as a hydrogen donor and a solvent. Fresh and spent powder and monolith samples were characterized by elemental analysis, surface area, hydrogen chemisorption, s...

  6. Hydrogen on graphene: Electronic structure, total energy, structural distortions, and magnetism from first-principles calculations

    OpenAIRE

    2007-01-01

    Density functional calculations of electronic structure, total energy, structural distortions, and magnetism for hydrogenated single-layer, bilayer, and multi-layer graphene are performed. It is found that hydrogen-induced magnetism can survives only at very low concentrations of hydrogen (single-atom regime) whereas hydrogen pairs with optimized structure are usually nonmagnetic. Chemisorption energy as a function of hydrogen concentration is calculated, as well as energy barriers for hydrog...

  7. Nanoplasmonic structures for biophotonic applications: SERS overview

    International Nuclear Information System (INIS)

    Various nanoplasmonic devices were fabricated using top-down method such as electron beam lithography, electroplating and focused ion beam techniques. These substrates were investigated after depositing the molecules from dye to protein, using chemisorptions techniques. Theoretical simulations were also performed on these model nanostructures in order to understand the electrical field distribution. Furthermore, the future prospects of these nanostructures were also mentioned in this report. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Molecular dynamics simulation of gaseous atomic hydrogen interactions with hydrocarbon grains

    OpenAIRE

    Papoular, Renaud

    2004-01-01

    Semi-empirical molecular dynamics is used to simulate several gaseous atomic hydrogen interactions with hydrocarbon grains in space: recoil, adsorption, diffusion, chemisorption and recombination into molecular hydrogen. Their probabilities are determined by multiple numerical experiments, as a function of initial velocity of gas atoms. The equilibrium hydrogen coverage of free grains is then derived. These data can be used in calculations of material and energy balance as well as rates of hy...

  9. Tuning the composition of metastable CoxNiyMg100−xy(OH)(OCH3) nanoplates for optimizing robust methane dry reforming catalyst

    DEFF Research Database (Denmark)

    Fan, Xiaoli; Liu, Zhiting; Zhu, Yi-An;

    2015-01-01

    Finding controllable, low-cost, and scalable ways to generate Ni-based catalysts is the bottleneck for methane dry reforming catalyst design. A new method for generating trimetallic CoxNiyMg100−x−yO solid solution platelets enclosed by (111) facets has been developed from the topotactic pyrolysis...... enhances the chemisorption of oxygen and reduces the activation energy for methane fragmentation, which is the rate-determining step for the overall reaction....

  10. Desulphurization of flue gases

    International Nuclear Information System (INIS)

    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 Ca2+ concentration of the lime suspensions. It is shown that chemisorption is twice as effective in sulphur dioxide removal than absorption in water. (author)

  11. (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.

  12. Evidence of structural isomerism in small niobium clusters

    International Nuclear Information System (INIS)

    The reactivity of Nb clusters with nitrogen and deuterium was studied using a pulsed laser vporization source coupled to a fast flow reactor. The relative reactivity of the various clusters was determined by monitoring the depletion of the cluster ion signal as a function of reactant flow rate. A kinetic analysis of the chemisorption is given. The geometrical isomerism of the cluster ions and its relationship to reactivity is discussed

  13. Adsorption of Acetylene on a Pd-Pb Bimetallic Surface — a Theoretical Study

    Science.gov (United States)

    Ferullo, R. M.; Touroude, R.; Castellani, N. J.

    A semiempirical molecular orbital study of acetylene adsorption over Pd(111) and Pd3Pb(111) has been performed. A strong negative effect of Pb atoms on Pd chemisorptive strength was observed in the alloy. This behavior is related to a lower hybridization between acetylene π* and Pd orbitals when this mental interacts with Pb. Moreover this negative effect of Pb is of a strong local character.

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

    OpenAIRE

    Mudigere Krishnegowda Pavithra; Thimmappa Venkatarangaiah Venkateha; Mudigere Krishnegowda Punith Kumar; Nanjanagudu Subba Rao Anantha

    2015-01-01

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

  15. Modelling of Surface Catalytic Reaction Systems using the Concept of Extents

    OpenAIRE

    Chhabra, Vibhuti

    2014-01-01

    Gas-solid catalytic reaction systems depend on a combination of several dynamic eects, such as mass transfer, chemisorption and surface reactions taking place simultaneously. In this master thesis, the extension of the method of extent-based model identication is proposed for catalytic reaction systems which involves the transformation of the number of moles in the gas and solid phases into decoupled state variables called (vessel) extents. This transformation computes extents of inlet, outle...

  16. Coupling Noble Metals and Carbon Supports in the Development of Combustion Catalysts for the Abatement of BTX Compounds in Air Streams

    OpenAIRE

    Sergio Morales-Torres; Francisco Carrasco-Marín; Agustín F. Pérez-Cadenas; Francisco José Maldonado-Hódar

    2015-01-01

    The catalytic combustion of volatile organic compounds (VOCs) is one of the most important techniques to remove these pollutants from the air stream, but it should be carried out at the lowest possible temperature, saving energy and avoiding the simultaneous formation of nitrogen oxides (NOx). Under these experimental conditions, the chemisorption of water generated from VOCs combustion may inhibit hydrophilic catalysts. Nowadays, a wide variety of carbon materials is available to be used in ...

  17. Aqueous-phase reforming of xylitol over Pt/C and Pt/TiC-CDC catalysts : catalyst characterization and catalytic performance

    OpenAIRE

    Kirilin, Alexey V.; Hasse, Benjamin; Tokarev, Anton V.; Kustov, Leonid M.; Baeva, Galina N.; Bragina, Galina O.; Stakheev, Aleksandr Yu.; Rautio, Anne-Riikka; Salmi, Tapio; Etzold, Bastian J.M.; Mikkola, Jyri-Pekka; Murzin, Dmitry Yu

    2014-01-01

    The aqueous phase reforming (APR) of xylitol was studied over five Pt/C catalysts. The correlation between physico-chemical properties of the catalysts and catalytic performance was established. The Pt/C catalysts have different textural properties as well as different mean Pt cluster sizes and surface acidity. The average Pt cluster size was investigated by means of CO chemisorption as well as by TEM. The reaction was found to be structure sensitive and TOF linearly increases with increasing...

  18. Hydrogen on graphene: Electronic structure, total energy, structural distortions and magnetism from first-principles calculations

    OpenAIRE

    Boukhvalov, D W; Katsnelson, M. I.; Lichtenstein, A. I.

    2008-01-01

    Density functional calculations of electronic structure, total energy, structural distortions, and magnetism for hydrogenated single-layer, bilayer, and multi-layer graphene are performed. It is found that hydrogen-induced magnetism can survives only at very low concentrations of hydrogen (single-atom regime) whereas hydrogen pairs with optimized structure are usually nonmagnetic. Chemisorption energy as a function of hydrogen concentration is calculated, as well as energy barriers for hydrog...

  19. Background, phenomenology, and motivation

    International Nuclear Information System (INIS)

    The authors discuss the background to the kinetics of adsorption and desorption after an elementary introduction to the problem of chemisorption in two limiting cases. Other topics discussed include the thermodynamics of adsorption, reaction mechanisms outside surfaces, and a case history of catalytic hydrogenation of carbon monoxide. Figures show the potential energy barrier as a function of an appropriate reaction coordinate, and bonding of carbon monoxide to platinum metal

  20. Effect of Solution pH on the Removal of Paracetamol by Activated Carbon of Dende Coconut Mesocarp

    OpenAIRE

    Ferreira, R C; Couto Junior, O. M.; K. Q. Carvalho; P.A. Arroyo; M. A. S. D. Barros

    2015-01-01

    Activated carbon of dende coconut mesocarp was used to investigate the removal of paracetamol from water by adsorption. The results indicated that the retention of paracetamol was favored in activated carbon with neutral surface properties. The textural features and presence of a transport pores network contributed to ensuring the accessibility to the inner porosity, and the microporosity must be large enough to accommodate the paracetamol molecule. Chemisorption and mainly physisorption are ...

  1. Characterization, deactivation, and stabilization of cobalt oxide--molybdenum oxide--alumina

    International Nuclear Information System (INIS)

    The specific surface area of molybdena in reduced, alumina-supported catalysts of molybdena and cobalt-molybdena has been measured by the selective chemisorption of oxygen at low temperature on catalysts pre-reduced at high temperature. The amount of chemisorption was obtained from determining successive oxygen adsorption isotherms, at -1950C, on catalysts reduced and pumped at 5000C. The oxygen adsorption on pre-reduced (at 3500C), unsupported MoO3, 13.6 m2/ml(STP)O2 was used as calibrating standard for pre-reduced supported molybdena. For three supported catalysts, all of which contained about 15 percent MoO3 as prepared, the apparent fractional surface coverage was within the narrow range 0.24 to 0.28. The selective chemisorption of O2 (-1950C) and BET (-1950, N2) measurements on pre-sulfided and used synthoil catalyst showed lower values of total surface area as well as active area

  2. Biomolecular Interactions and Biological Responses of Emerging Two-Dimensional Materials and Aromatic Amino Acid Complexes.

    Science.gov (United States)

    Mallineni, Sai Sunil Kumar; Shannahan, Jonathan; Raghavendra, Achyut J; Rao, Apparao M; Brown, Jared M; Podila, Ramakrishna

    2016-07-01

    The present work experimentally investigates the interaction of aromatic amino acids viz., tyrosine, tryptophan, and phenylalnine with novel two-dimensional (2D) materials including graphene, graphene oxide (GO), and boron nitride (BN). Photoluminescence, micro-Raman spectroscopy, and cyclic voltammetry were employed to investigate the nature of interactions and possible charge transfer between 2D materials and amino acids. Graphene and GO were found to interact strongly with aromatic amino acids through π-π stacking, charge transfer, and H-bonding. Particularly, it was observed that both physi and chemisorption are prominent in the interactions of GO/graphene with phenylalanine and tryptophan while tyrosine exhibited strong chemisorption on graphene and GO. In contrast, BN exhibited little or no interactions, which could be attributed to localized π-electron clouds around N atoms in BN lattice. Lastly, the adsorption of amino acids on 2D materials was observed to considerably change their biological response in terms of reactive oxygen species generation. More importantly, these changes in the biological response followed the same trends observed in the physi and chemisorption measurements. PMID:27281436

  3. Predictive morphology, stoichiometry and structure of surface species in supported Ru nanoparticles under H2 and CO atmospheres from combined experimental and DFT studies.

    Science.gov (United States)

    Comas-Vives, Aleix; Furman, Karol; Gajan, David; Akatay, M Cem; Lesage, Anne; Ribeiro, Fabio H; Copéret, Christophe

    2016-01-21

    Further understanding of the chemisorption properties towards CO and H2 on silica-supported Ru nanoparticles is crucial in order to rationalize their high activity towards methanation, Fischer Tropsch and Water Gas Shift reactions. Ru nanoparticles having the same chemisorption properties towards CO and H2 were synthesized on different silica-based supports in order to combine various analytical techniques and obtain complimentary detailed information on their structure; while silica spheres were used in order to obtain high-resolution TEM images of the Ru nanoparticles, high surface area silica-based material (SBA) allowed CO chemisorption to be monitored by (13)C NMR spectroscopy. In addition, a model of the hcp-based Ru nanoparticles observed by HR-TEM was used to predict by ab initio calculations the CO and H2 coverages on the Ru nanoparticle under different conditions of interest in catalysis. For both adsorbates we show and quantify how the adsorption properties of the nanoparticle differ from the commonly used slab models. For the case of CO we show how the top, bridge and hollow sites can be present on the Ru nanoparticle, providing a description at atomistic level in good agreement with the IR spectroscopy measurements. PMID:26686546

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

    International Nuclear Information System (INIS)

    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)

  5. Characterization and functionalities of Pd/hydrotalcite catalysts

    Science.gov (United States)

    Naresh, Dhachapally; Kumar, Vanama Pavan; Harisekhar, Mitta; Nagaraju, Nekkala; Putrakumar, Balla; Chary, Komandur V. R.

    2014-09-01

    A series of palladium supported on calcined hydrotalcite (CHT) catalysts with varying palladium (Pd) loadings (1.0-8.0 wt%) were prepared by impregnation method. Their catalytic performance was evaluated for the reductive amination of phenol to aniline that showed a tremendous interest in the chemical industry. The catalysts were characterized by BET surface area, XRD, TEM, XPS, TPR of H2, TPD of CO2 and CO chemisorption. BET surface area decreased continuously with increase in Pd content. XRD results confirmed the changes in the crystalline phases with altering Pd content. TEM results showed the formation of fine particles at lower loadings and agglomerates at higher loadings. TPR profiles revealed that the reducibility increases with increase of Pd loading. CO2 TPD results illustrate the catalysts basicity increases with increase of Pd loading up to 4.0 wt% and decreases at higher loadings. Pd dispersion, metal area and crystallite sizes were determined by CO chemisorption method. Pd dispersion and metal area decreases with increase of Pd content and crystallite sizes. The results demonstrated that the Pd dispersion and basic properties are depending on the Pd loading. The catalytic performance clearly showed that the increase Pd loading the conversion of phenol increased up to 2.0 wt% and level off beyond the loading. The catalytic properties are well correlated with the active Pd sites determined by CO chemisorption, dispersion and basicity.

  6. Ga and As competition for thiolate formation at p-GaAs(1 1 1) surfaces

    International Nuclear Information System (INIS)

    Highlights: • SAMs of 4,4′-thio-bis-benzene-thiolate were formed at p-GaAs(1 1 1) surfaces. • Both As and Ga are involved in thiolate formation. • Only one SH group participates in the chemisorption bond. • Thiolate layer formed at GaAs(1 1 1)B is more stable than that formed at GaAs(1 1 1)A. • Terminal atoms control the chemisorption-and packing-forces joint action. -- Abstract: Self-assembled layers of 4,4′-thio-bis-benzene-thiolate spontaneously adsorbed on p-doped GaAs(1 1 1)A and GaAs(1 1 1)B electrodes were examined by EIS, XPS, and AFM investigations. XPS data provide evidence that (i) both As and Ga atoms are involved in the thiolate formation no matter which one is prevailing on the semiconducting surface and (ii) only one of the two thiol groups participates in the chemisorption bond. EIS and AFM results point to a more stable thiolate layer formed on the As-terminated surface than that formed on the Ga-terminated surface due to stronger self-assembling effects developed between the adsorbed species

  7. Immobilization of Polymeric Luminophor on Nanoparticles Surface.

    Science.gov (United States)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-12-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor. PMID:27090657

  8. 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.

  9. Synthesis of Ag/ZnO nanostructures by different methods and investigation of their photocatalytic efficiency for 4-nitrophenol degradation

    Science.gov (United States)

    Divband, B.; Khatamian, M.; Eslamian, G. R. Kazemi; Darbandi, M.

    2013-11-01

    In this paper, Ag/ZnO photocatalysts with different Ag loadings were prepared by photo reduction, chemical reduction and polyacrylamide-gel methods. The Ag/ZnO photocatalysts were characterized by XRD, SEM, TEM, EDS and DRUV-vis methods. The results of the photocatalytic degradation of 4-NP in aqueous suspensions showed that silver ions doping greatly improved the photocatalytic efficiency of ZnO nanocrystallites. The enhancement of photocatalytic activity is due to the fact that the modification of ZnO with an appropriate amount of Ag can increase the separation efficiency of photogenerated electrons and holes in ZnO, and the improvement of photo stability of ZnO is attributed to a considerable decrease of the surface defect sites of ZnO after the Ag loading. The chemisorptions of molecular oxygen and the chemisorption of atomic oxygen on Ag in the Ag/ZnO photocatalysts were observed. It was found that the metallic Ag in the Ag/ZnO photocatalysts does play a new role of O2 chemisorption sites except for electron acceptor, by which chemisorbed molecular oxygen reacts with photogenerated electrons to form active oxygen species, and thus facilitates the trapping of photogenerated electrons and further improves the photocatalytic activity of the Ag/ZnO photocatalysts. Also the method of preparation is regarded as important factors for determining photocatalysis. The best photocatalytic performance was exhibited for Ag/ZnO prepared by polyacrylamide gel method in comparison with chemical reduction and photo reduction method and the optimum Ag content was approximately 0.5%.

  10. Correlation between the acid-base properties of the La2O3 catalyst and its methane reactivity.

    Science.gov (United States)

    Chu, Changqing; Zhao, Yonghui; Li, Shenggang; Sun, Yuhan

    2016-06-28

    Density functional theory and coupled cluster theory calculations were carried out to study the effects of the acid-base properties of the La2O3 catalyst on its catalytic activity in the oxidative coupling of methane (OCM) reaction. The La(3+)-O(2-) pair site for CH4 activation is considered as a Lewis acid-Brönsted base pair. Using the Lewis acidity and the Brönsted basicity in the fluoride affinity and proton affinity scales as quantitative measures of the acid-base properties, the energy barrier for CH4 activation at the pair site can be linearly correlated with these acid-base properties. The pair site consisting of a strong Lewis acid La(3+) site and a strong Brönsted base O(2-) site is the most reactive for CH4 activation. In addition, the basicity of the La2O3 catalyst was traditionally measured by temperature-programmed desorption of CO2, but the CO2 chemisorption energy is better regarded as a combined measure of the acid-base properties of the pair site. A linear relationship of superior quality was found between the energy barrier for CH4 activation and the CO2 chemisorption energy, and the pair site favorable for CO2 chemisorption is also more reactive for CH4 activation, leading to the conflicting role of the "basicity" of the La2O3 catalyst in the OCM reaction. The necessity for very high reaction temperatures in the OCM reaction is rationalized by the requirement for the recovery of the most reactive acid-base pair site, which unfortunately also reacts most readily with the byproduct CO2 to form the very stable CO3(2-) species. PMID:27265027

  11. Fundamental studies of H2 interaction with MAl3 clusters [M = Li, Sc, Ti, Zr

    International Nuclear Information System (INIS)

    Highlights: • A first-principles calculation on H2 interaction and saturation on stable MAl3 clusters [M = Li, Sc, Ti, Zr] is performed. • Transition metals have negative electron charge density while Al atom has positive in MAl3 from NBO charge analysis. • H2 undergoes dissociative chemisorption on the M atop site resulting in M–H–Al bridge bond. • H2 saturation on M atop site results initially chemisorption and then physisorption with 3-centered Kubas interaction. • External electric field applied on TiAl3H4 leads to more polarization, H2 bond elongation and increased adsorption energy. -- Abstract: Complex metal hydride is a promising hydrogen storage material for automobile applications due to its reversible storage capacity. The presence of transition metal halide is found to improve significantly the kinetics of H2 adsorption and desorption processes. Experimental studies have indicated the formation of distorted MAl3 phase where M = Sc, Ti, Zr. In this study, a first-principles density functional study has been performed to investigate the hydrogen interaction and saturation on stable tetrahedral MAl3 clusters [M = Li, Sc, Ti, and Zr] by employing spin-polarized hybrid and non-local density functionals. On saturation, the first H2 molecule undergoes chemisorption in the transition metals while further loading results in physisorption with the Kubas-type H2 interaction. Activation energy barrier for the H2 dissociation over the cluster is calculated to be ∼0.2 eV for the transition metals. Effect of external electric field on the MAl3H4 cluster with molecular H2 is studied which leads to polarization of physisorbed H2 and the cluster. The results offer an explanation for catalysts role in improving the kinetics of H2 sorption process in complex metal hydrides

  12. DFT study of NH 3 dissociation on Si(1 1 1)-7 × 7. The role of intermolecular interactions

    Science.gov (United States)

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

    2007-04-01

    The adsorption of NH 3 molecule on the Si(1 1 1)-7 × 7 surface modelled with a cluster has been studied using density functional theory (DFT). The results indicate the existence of a precursor state for the non-dissociative chemisorption. The active site for the molecular chemisorption is the adatom; while the NH 3 molecule adsorbs on the Si restatom via this preadsorbed state, the adsorption on the Si adatom is produced practically without an energy barrier. The ammonia adsorption on the adatom induces an electron transfer from the dangling bond of this atom to the dangling bond of the adjacent Si restatom, hindering this site for the adsorption of a second NH 3 incoming molecule. However, this second molecule links strongly by means of two H-bonds. The dissociative chemisorption process was studied considering one and two ammonia molecules. For the dissociation of a lonely NH 3 molecule an energy barrier of ˜0.3 eV was calculated, yielding NH 2 on the adatom and H on the restatom. When two molecules are adsorbed, the NH 3-NH 3 interaction yields the weakening of a N-H bond of the ammonia molecule adsorbed closer the Si surface. As a consequence, the dissociation barrier practically disappears. Thus, the presence of a second NH 3 molecule at the adatom-restatom pair of the Si(1 1 1)-7 × 7 surface makes the dissociative reaction self-assisted, the total adsorption process elapsing with a negligible activation barrier (less than 0.01 eV).

  13. Synthesis of Ag/ZnO nanostructures by different methods and investigation of their photocatalytic efficiency for 4-nitrophenol degradation

    Energy Technology Data Exchange (ETDEWEB)

    Divband, B., E-mail: baharakdivband@yahoo.com [Inorganic Chemistry Department, Faculty of Chemistry, University of Tabriz, C.P. 51664 Tabriz (Iran, Islamic Republic of); Khatamian, M., E-mail: khatamian@tabrizu.ac.ir [Inorganic Chemistry Department, Faculty of Chemistry, University of Tabriz, C.P. 51664 Tabriz (Iran, Islamic Republic of); Eslamian, G.R. Kazemi [Food Science and Technology Department, International Aras Campus, University of Tabriz (Iran, Islamic Republic of); Darbandi, M. [Experimental Physics, Faculty of Physics, Lotharstr. 1, University of Duisburg-Essen, Duisburg (Germany)

    2013-11-01

    In this paper, Ag/ZnO photocatalysts with different Ag loadings were prepared by photo reduction, chemical reduction and polyacrylamide-gel methods. The Ag/ZnO photocatalysts were characterized by XRD, SEM, TEM, EDS and DRUV–vis methods. The results of the photocatalytic degradation of 4-NP in aqueous suspensions showed that silver ions doping greatly improved the photocatalytic efficiency of ZnO nanocrystallites. The enhancement of photocatalytic activity is due to the fact that the modification of ZnO with an appropriate amount of Ag can increase the separation efficiency of photogenerated electrons and holes in ZnO, and the improvement of photo stability of ZnO is attributed to a considerable decrease of the surface defect sites of ZnO after the Ag loading. The chemisorptions of molecular oxygen and the chemisorption of atomic oxygen on Ag in the Ag/ZnO photocatalysts were observed. It was found that the metallic Ag in the Ag/ZnO photocatalysts does play a new role of O{sub 2} chemisorption sites except for electron acceptor, by which chemisorbed molecular oxygen reacts with photogenerated electrons to form active oxygen species, and thus facilitates the trapping of photogenerated electrons and further improves the photocatalytic activity of the Ag/ZnO photocatalysts. Also the method of preparation is regarded as important factors for determining photocatalysis. The best photocatalytic performance was exhibited for Ag/ZnO prepared by polyacrylamide gel method in comparison with chemical reduction and photo reduction method and the optimum Ag content was approximately 0.5%.

  14. Novel Effective Catalyst for Elemental Mercury Removal from Coal-Fired Flue Gas and the Mechanism Investigation.

    Science.gov (United States)

    Chen, Wanmiao; Pei, Yang; Huang, Wenjun; Qu, Zan; Hu, Xiaofang; Yan, Naiqiang

    2016-03-01

    Mercury pollution from coal-fired power plants has drawn attention worldwide. To achieve efficient catalytic oxidation of Hg(0) at both high and low temperatures, we prepared and tested novel IrO2 modified Ce-Zr solid solution catalysts under various conditions. It was found that the IrO2/Ce0.6Zr0.4O2 catalyst, which was prepared using the polyvinylpyrrolidone-assisted sol-gel method, displayed significantly higher catalytic activity for Hg(0) oxidation. The mechanism of Hg(0) removal over IrO2/Ce0.6Zr0.4O2 was studied using various methods, and the Hg(0) oxidation reaction was found to follow two possible pathways. For the new chemisorption-regeneration mechanism proposed in this study, the adsorbed Hg(0) was first oxidized with surface chemisorbed oxygen species to form HgO; the HgO could desorb from the surface of catalysts by itself or react with adsorbed HCl to be release in the form of gaseous HgCl2. O2 is indispensable for the chemisorption process, and the doping of IrO2 could facilitate the chemisorption process. In addition, the Deacon reaction mechanism was also feasible for Hg(0) oxidation: this reaction would involve first oxidizing the adsorbed HCl to active Cl species, after which the Hg(0) could react with Cl to form HgCl2. Additionally, doping IrO2 could significantly improve the Cl yield process. In summary, the novel IrO2 modified catalyst displayed excellent catalytic activity for elemental mercury oxidation, and the proposed reaction mechanisms were determined reasonably. PMID:26815147

  15. Electric propulsion and its applications to space missions

    Science.gov (United States)

    Finke, R. C.

    1981-01-01

    Consideration is given the NASA, Air Force and European electric propulsion programs, the characteristics of primary electric propulsion systems, nuclear electric orbit transfer vehicles, and such topics in the fundamental processes of electrostatic thrusters as sputtering in mercury ion thrusters, the screen hole plasma sheath of an ion accelerator system, and the modelling of ion beam neutralization and nitrogen chemisorption. Also considered are electrostatic thruster components and systems, electromagnetic thrusters such as MPD and RIT systems, electric rail guns and mass drivers, power sources which include solar and nuclear alternatives, power conversion systems and their cooling apparatus, and the environmental interactions between spacecraft and their electric propulsion systems.

  16. Trends in reactivity of oxides

    DEFF Research Database (Denmark)

    Toftelund, Anja

    linearly with the adsorption energy of their central N, O and S atoms. It is also found that they follow the same trend as in the case of adsorption of the same molecules on transition metals. The same type of scaling relations are also established between the adsorption energies of the halides (Cl, Br...... 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 and the...

  17. Electrochemical study of corrosion inhibition and adsorption behaviour for pure iron by polyacrylamide in H2SO4: Synergistic effect of iodide ions

    International Nuclear Information System (INIS)

    Corrosion inhibition and adsorption behaviour for pure iron in 0.5 M H2SO4 by polyacrylamide (PA) were investigated using electrochemical techniques. The effect of iodide ion additives was also studied. It was found that inhibition efficiency increased with PA concentration. Corrosion inhibition was afforded by adsorption of PA onto the metal following El-Awady kinetic-thermodynamic adsorption isotherm model via chemisorption mechanism. A mixed inhibition mechanism is proposed for the inhibitive effects of PA as revealed by potentiodynamic polarization technique. A synergistic effect was observed between PA and KI as evident from the values of synergism parameter found to be greater than unity.

  18. 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)

  19. Pt-Rh/g Al2O3 Benzene Hydrogenation Reaction as a Characterization Technique

    Directory of Open Access Journals (Sweden)

    N.M. da Fonseca

    1998-06-01

    Full Text Available Pt-Rh/Al2O3 catalysts prepared by successive incipient impregnations and coimpregnation were characterized by H2 chemisorption, temperature programmed reduction and benzene hydrogenation reaction in the vapor phase. The results showed that Rh plays the role of Pt reducting agent, which is very different from the effects of metal-metal interaction which appear mainly in solids with the highest metal contents. The most important parameter that results in bimetallic particles in the catalyst prepared by successive impregnation is the sequence of metal addition.

  20. Surface reactions of metal clusters. II. Reactivity surveys with D2, N2, and CO

    OpenAIRE

    Morse, M. D.; Gausic, M. E.; Heath, J. R.; Smalley, R. E.

    1985-01-01

    Reactions on the surface of a variety of transition metal clusters have been studied in the gas phase at near room temperature using a newly developed fast-flow reaction device. Initial examples of the use of this device are provided by survey studies of the reactivity of iron, cobalt, nickel, copper, and niobium clusters in contact with low concentrations of D2, N2 and CO. Dissociative chemisorption of D2 is found to occur with dramatic sensitivity to cluster size in the cases of iron, cobal...

  1. 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.

  2. Linen Fire as Biosorbent to Remove Heavy Metal Ions From Wastewater Modeling

    Directory of Open Access Journals (Sweden)

    Ildar G. Shaikhiev

    2014-03-01

    Full Text Available The possibility of using linen fires – lnopererabotk i waste as a sorption material for the extraction of heavy metal ions from wastewater modeling. It is shown that treatment with acid solutions linen fires a low concentration increases the surface area of linen fires and thus sorption capacity for heavy metal ions. The values of the maximum sorption capacity ions Fe (III, Co (II, Ni (II and Zn (II under static and dynamic conditions. IR spectroscopy shows that along with the physical sorption process proceeds chemisorption.

  3. Kinetic for Adsorption of Dye Methyl Orange by the Modified Activated Carbon from Rice Husk

    Directory of Open Access Journals (Sweden)

    Muqing Qiu

    2015-08-01

    Full Text Available In this study, the modified activated carbon from rice husk is used as the low cost material to absorb dye Methyl Orange in aqueous solution. The effects of different process parameters like pH, initial dye concentration and contact time on the adsorption of dye are investigated. The kinetic data of adsorption studies are discussed by the pseudo first-order, pseudo second-order and intraparticle diffusion. The results were shown that the adsorption process is chemisorption, which involves a sharing of electrons between the adsorbate and the surface of the adsorbent.

  4. Sequential desorption energy of hydrogen from nickel clusters

    Energy Technology Data Exchange (ETDEWEB)

    Deepika,; Kumar, Rakesh, E-mail: rakesh@iitrpr.ac.in [Department of Physics, Indian Institute of Technology Ropar, Rupnagar-140001 (India); R, Kamal Raj. [Indian Institute of Science Education and Research Kolkata, Mohanpur-741246 (India); Kumar, T. J. Dhilip [Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar-140001 (India)

    2015-06-24

    We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage and regeneration of Hydrogen as a clean energy carrier.

  5. 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; Thygesen, Kristian Sommer

    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...

  6. Sequential desorption energy of hydrogen from nickel clusters

    International Nuclear Information System (INIS)

    We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage and regeneration of Hydrogen as a clean energy carrier

  7. Roles of Lewis and Brnsted acid sites in NO reduction with ammonia on CeO_2-ZrO_2-NiO-SO_4~(2-) catalyst

    Institute of Scientific and Technical Information of China (English)

    司知蠢; 翁端; 吴晓东; 江洋

    2010-01-01

    Nickel and sulfate co-modified CeO2-ZrO2 catalysts were prepared by sol-gel method. The catalysts were characterized by XRD, FTIR, XPS, NH3 chemisorption and NH3-SCR activity tests. The results showed that the enhanced acidity of CeO2-ZrO2 catalysts by nickel and sulfate co-modification was responsible for the broadened temperature window and improved the selectivity to N2 in NH3-SCR deNOx. The introduction of nickel to CeO2-ZrO2 solid solutions resulted in more Ce3+ on surface of catalyst, leading to an in...

  8. Quantum chemistry and scientific calculus

    International Nuclear Information System (INIS)

    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

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

    International Nuclear Information System (INIS)

    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

  10. Effects of Cerium Oxide on Ni/Al2O3 Catalysts for Decomposition of CH4 and C2H4

    Institute of Scientific and Technical Information of China (English)

    杨咏来; 李文钊; 徐恒泳

    2003-01-01

    Characteristics of carbon deposition of CH4 and C2H4 decomposition over supported Ni and Ni-Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal-semiconductor interaction (MScI) in the Ni-Ce catalyst, and the effect of MScI on the carbon deposition of CH4 decomposition is opposite to that of C2H4. A novel model of carbon deposition of CH4 or C2H4 decomposition was proposed.

  11. Impact dynamics of water droplets on chemically modified WOx nanowire arrays

    Science.gov (United States)

    Kwak, Geunjae; Lee, Mikyung; Senthil, Karuppanan; Yong, Kijung

    2009-10-01

    The effects of surface energy on the wetting transition for impinging water droplets were investigated on the chemically modified WOx nanowire surfaces. We could modify the surface energy of the nanowires through chemisorption of alkyltrichlorosilanes with various carbon chain lengths and also by the ultraviolet-enhanced decomposition of self assembled monolayer molecules. Three surface wetting states could be identified through the balance between antiwetting and wetting pressures. This approach establishes a simple strategy for design of the water-repellent surface to impinging droplets.

  12. Trends in Atomic Adsorption on Titanium Carbide and Nitride

    OpenAIRE

    Vojvodic, Aleksandra; Ruberto, Carlo; Lundqvist, Bengt I.

    2005-01-01

    Extensive density-functional calculations on atomic chemisorption of H, B, C, N, O, F, Al, Si, P, S, and Cl on the polar TiC(111) and TiN(111) yield similar adsorption trends for the two surfaces: (i) pyramid-like adsorption-energy trends along the adatom periods; (ii) strongest adsorption for O, C, N, S, and F; (iii) large adsorption variety; (iv) record-high adsorption energy for O (8.4-8.8 eV). However, a stronger adsorption on TiN is found for elements on the left of the periodic table an...

  13. Bioaccumulation of the 65 Zn2+ radioactive ions

    International Nuclear Information System (INIS)

    The paper investigates the possibility of using some microbiological collectors as Calothrix marchica Lemn. sp. 1 and 2, Porphyridium cruentum (Ag.) Nag. and Spirulina platensis CNM CB-02 for purification of effluents which are contaminated with 65 Zn2+ radioactive ions in simulated conditions. It was found that the degree of reaction between these radioactive ions with the algae diminished as follows: Spirulina sp.>Porphyridium cruentum(Ag.) Nag>Calothrix sp.2>Calothrix sp.1. The complete retention of ions is achieved in 1-5 min after the contact between the algae and radioactive suspension by a chemisorption process. (authors)

  14. Aging of the nanosized photochromic WO3 films and the role of adsorbed water in the photochromism

    Science.gov (United States)

    Gavrilyuk, A. I.

    2016-02-01

    Here it has been reported on aging of the nanosized WO3 film, which is revealed is continuous reduction of the photochromic sensitivity over time. Water molecules physically adsorbed on the film surface from ambient air form donor-acceptor and hydrogen bonds, changing gradually the adsorption state to chemisorption which prevents an access of organic molecules that serve as hydrogen donors by the photochromism. The mechanism of the process has been investigated and discussed. The role of water in the photochromism has been highlighted. The difference in the efficiency for being of a hydrogen donor in the photochromic process between water and organic molecules is discussed.

  15. Deactivation and Coke Accumulation during CO2/CH4 Reforming over Pt Catalysts

    OpenAIRE

    Bitter, J.H.; Seshan, K.; Lercher, J.A.

    2001-01-01

    The Deactivation of Pt catalysts used in the generation of synthesis gas via CO2/CH4 reforming depends strongly on the support and the metalparticle size. Methods of Physicochemical characterization such as X-ray absorption spectroscopy and hydrogen chemisorption suggest that carbon formation (most likely from methane) rather than sintering is the main cause of catalyst deactivation. The rate of carbon formation decreased in the order Pt/y-Al2O3 >> Pt/TiO2 > Pt/ZrO2. Carbon was formed on the ...

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

    International Nuclear Information System (INIS)

    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 104 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.)

  17. 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 The...

  18. Production of negative hydrogen ions on metal grids

    International Nuclear Information System (INIS)

    Negative hydrogen ions are produced on a nickel grid with positive-ion irradiation. In order to investigate the production mechanism, a copper grid without the chemisorption of hydrogen atoms and positive helium ions without negative ionization are used for comparison. Positive hydrogen ions reflected on the metal surface obtain two electrons from the surface and become negatively ionized. It is found that the production yield of negative ions by desorption ionization of chemisorbed hydrogen atoms seems to be small, and the production is a minor mechanism

  19. LETTER TO THE EDITOR: Variation of adatom to substrate charge transfer value along the first-row transition metal series on Mo(110)

    Science.gov (United States)

    Magkoev, T. T.; Christmann, K.; Lecante, P.; Moutinho, A. M. C.

    2002-04-01

    Adsorption of the first-row transition 3d metals (Ti-Cu) on the atomically clean Mo(110) surface in ultra-high-vacuum conditions has been studied by Auger electron spectroscopy and work function measurements (Anderson method). In this letter it is shown that adsorption behaviour of the metals under consideration systematically changes along the 3d series. The observed correlation between the systematic change of the dipole moments and the values of the charge transfer from adatom to substrate along the period leads us to the conclusion that the metal 3d orbitals play an important role in the formation of the chemisorption bond.

  20. Contribution to the study of the hydrogen-deuterium exchange in presence of a catalyst based on nickel oxide

    International Nuclear Information System (INIS)

    This research thesis focuses on the study of the mechanism of the hydrogen-deuterium isotopic exchange reaction upon the contact with a nickel oxide which is either pure or containing other cations like lithium or gallium. The coupling of the reaction system with a chromatographic loop allows the study of the exchange reaction kinetics in a simple and straightforward way. After a presentation of the experimental techniques and materials the author reports the study of hydrogen chemisorption which allowed the identification of different adsorption mechanisms with respect to the temperature. She reports a kinetic study of hydrogen-deuterium exchange at different temperatures (-78 and -196 C)

  1. NOM removal technologies – Norwegian experiences

    Directory of Open Access Journals (Sweden)

    H. Ødegaard

    2009-10-01

    Full Text Available The paper gives an overview of the methods for removal of natural organic matter (NOM, particularly humic substances (HS, in water 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.

  2. 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.

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

    Science.gov (United States)

    Chacko, Melby; Nayak, Jagannath

    2015-06-01

    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.

  4. Purification of ethanol for highly sensitive self-assembly experiments

    Directory of Open Access Journals (Sweden)

    Kathrin Barbe

    2014-08-01

    Full Text Available Ethanol is the preferred solvent for the formation of self-assembled monolayers (SAMs of thiolates on gold. By applying a thin film sensor system, we could demonstrate that even the best commercial qualities of ethanol contain surface-active contaminants, which can compete with the desired thiolates for surface sites. Here we present that gold nanoparticles deposited onto zeolite X can be used to remove these contaminants by chemisorption. This nanoparticle-impregnated zeolite does not only show high capacities for surface-active contaminants, such as thiols, but can be fully regenerated via a simple pyrolysis protocol.

  5. Effects of electric forces on deposit formation in reactor cores with organic coolant

    International Nuclear Information System (INIS)

    Reasons of electric field occurrence in gaps between core conducting surfaces in reactors with organic coolant are considered. It is shown that the main contribution to electric charge accumulation in coolant is made by β particles produced in nuclear fuel fission. Electric field causes electrophoresis of dispersed particle to fuel element surfaces and increases the time of the particle contact with the surface that is the probability of their chemisorption. Examples from the practice of the ARBUS-AST reactor operation supporting the effect of electric forces on intensity of deposit formation are presented. Recommendations on its decrease are given

  6. Kinetic study of CO oxidation over CuO/MO2 (M = Si, Ti and Ce) catalysts

    International Nuclear Information System (INIS)

    A series of supported CuO/MO2 catalysts (M = Si, Ti and Ce) were prepared using a chemisorption-hydrolysis method and tested for CO oxidation. Kinetic study was carried out to investigate reaction pathways on these catalysts. The power-rate law reaction expressions over CuO/SiO2, CuO/TiO2 and CuO/CeO2 were r = 1.78 × 10−7Pco0.85Po20.22, r = 1.62 × 10−7Pco0.65Po20.19 and r = 1.5 × 10−7Pco0.7Po20, respectively. Activation energies were calculated to be 74.8, 53.4 and 46.3 kJ mol−1 for the CuO/SiO2, CuO/TiO2 and CuO/CeO2 catalysts respectively. Elementary steps of CO oxidation were also proposed. For the CuO/SiO2 catalysts, a Langmuir–Hinshelwood (L–H) model involving chemisorption of CO and O2 on surface Cu atoms was proposed; for the CuO/TiO2 catalysts, a L–H model involving chemisorption of CO on Cu atoms and chemisorption of O2 on TiO2 was proposed, which resulted in a interfacial reaction between the two species. For the CuO/CeO2 catalysts, a Mars van–Krevelen model involving chemisorbed CO on Cu atoms reacting with lattice oxygen in CeO2 was proposed. Effect of CuO particle size was also evaluated. It was found that the active site on the periphery of the CuO–TiO2 and CuO–CeO2 interface was more active on large CuO crystallite than that on small one. The enhanced activity could be interpreted by the higher concentration of chemisorbed CO on the active site on the larger CuO crystallite.

  7. New aspects of exoemission of electrons and ions in the surface study in chemistry, physics and mechanics

    International Nuclear Information System (INIS)

    The phenomena have been considered of low temperature emission (exoemission of electrons, negative and positive ions) occurring at relaxation of excited states arising during physico-chemical processes on solid surfaces, at radiation and mechanical actions. The obtained results are discussed with account taken of modern ideas about the phenomena that accompany the formation and relaxation of excited states: electron-stimulated desorption, radiation-induced electrostatic instability, mechanical destruction, chemisorption etc. The chemical and physical aspects of electron and ion exoemission are presented

  8. Effect of porous polymer films (track membranes) on the isothermal evaporation kinetics of water

    Science.gov (United States)

    Novikov, S. N.; Ermolaeva, A. I.; Timoshenkov, S. P.; Korobova, N. E.; Goryunova, E. P.

    2016-06-01

    The kinetics of isothermal evaporation of distilled water that was in remote (10-15-mm) contact with porous polymer films (track membranes (TMs)) was studied by microgravimetry (derivatograph). When the H2O-TM system contained a disperse medium, the supramolecular structure of water changed, and the number of clusters (coherent domains) drastically decreased. The extraction of the light phase from liquid water was correlated with the chemisorption of H2O molecules containing the para-isomer of hydrogen, which predominantly form coherent domains of water.

  9. Production of negative hydrogen ions on metal grids

    Energy Technology Data Exchange (ETDEWEB)

    Oohara, W.; Maetani, Y.; Takeda, Takashi; Takeda, Toshiaki; Yokoyama, H.; Kawata, K. [Department of Electronic Device Engineering, Yamaguchi University, Ube 755-8611 (Japan)

    2015-03-15

    Negative hydrogen ions are produced on a nickel grid with positive-ion irradiation. In order to investigate the production mechanism, a copper grid without the chemisorption of hydrogen atoms and positive helium ions without negative ionization are used for comparison. Positive hydrogen ions reflected on the metal surface obtain two electrons from the surface and become negatively ionized. It is found that the production yield of negative ions by desorption ionization of chemisorbed hydrogen atoms seems to be small, and the production is a minor mechanism.

  10. Enhancement of Nitrite Reduction Kinetics on Electrospun Pd-Carbon Nanomaterial Catalysts for Water Purification.

    Science.gov (United States)

    Ye, Tao; Durkin, David P; Hu, Maocong; Wang, Xianqin; Banek, Nathan A; Wagner, Michael J; Shuai, Danmeng

    2016-07-20

    We report a facile synthesis method for carbon nanofiber (CNF) supported Pd catalysts via one-pot electrospinning and their application for nitrite hydrogenation. A mixture of Pd acetylacetonate (Pd(acac)2), polyacrylonitrile (PAN), and nonfunctionalized multiwalled carbon nanotubes (MWCNTs) was electrospun and thermally treated to produce Pd/CNF-MWCNT catalysts. The addition of MWCNTs with a mass loading of 1.0-2.5 wt % (to PAN) significantly improved nitrite reduction activity compared to the catalyst without MWCNT addition. The results of CO chemisorption confirmed that the addition of MWCNTs increased Pd exposure on CNFs and hence improved catalytic activity. PMID:27387354

  11. Reactions of XeF/sub 2/ with thermally grown SiO/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Joyce, S.; Langan, J.G.; Steinfeld, J.I.

    1988-01-01

    The reactions of XeF/sub 2/ on thermally grown SiO/sub 2/ were studied. XeF/sub 2/ does not readily undergo a dissociative chemisorption on these surfaces. Damaging the oxide with 500-eV argon ions enhances this process significantly through the creation of active sites. XPS analysis of the resulting adlayer, together with molecular-orbital model calculations, reveal the presence of fluorine bound to both silicon and oxygen. The oxyfluoride species can be removed from the surface by annealing the crystal to 200 C.

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

    International Nuclear Information System (INIS)

    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

  13. Preparation and deployment of indigenous 125I- seeds for the treatment of prostate cancer: dawn of prostate brachytherapy in India

    International Nuclear Information System (INIS)

    'Permanent seed implantation' using 125I- seeds represents an effective treatment modality for prostate cancer. An innovative strategy to prepare and deploy 125I- seeds for treatment of prostate cancer has been evolved. Seeds prepared by chemisorptions of 125I on palladium coated silver wires were characterized and encased in titanium tubes by ND:YAG laser. Several batches of critically evaluated seeds exhibiting release of 125I were supplied to P.D. Hinduja Hospital, Mumbai for treatment of prostate cancer patients. Successful deployment of indigenous seeds in prostate brachytherapy has opened a new window for making prostate brachytherapy affordable to needy cancer patients. (author)

  14. VAPOR-PHASE CATALYTIC CONVERSION OF ETHANOL INTO 1,3-BUTADIENE ON Cr-Ba/MCM-41 CATALYSTS

    OpenAIRE

    N. La-Salvia; J. J. Lovón-Quintana; G.P. VALENÇA

    2015-01-01

    AbstractAl-MCM-41, 16%Ba/Al-MCM-41 and 1.4%Cr-16%Ba/Al-MCM-41 were used as catalysts in the vapor-phase catalytic conversion of ethanol. Physical-chemical properties of the catalysts and the effect of barium and chromium on the Al-MCM-41 activity and 1,3-butadiene yield were studied. The catalysts were characterized by X-ray diffraction (XRD), N2 physisorption (BET method), CO2chemisorption and Fourier transform infrared spectroscopy (FT-IR). When ethanol was completely converted on Al-MCM-41...

  15. Electrical conductivity and electrochemical properties of γ-irradiated TiOsub(2)

    International Nuclear Information System (INIS)

    Electrical conductivity and Seebeck voltage developed in γ-irradiated TiOsub(2) was studied as a function of temperature. The conversion of n-type TiOsub(2) into p-type observed after irradiation was explained on the basis of formation of inversion layer of p-type TiOsub(2) due to the chemisorption of oxygen on the oxide surface during irradiation. Sign of the electromotive force (EMF) of the electrochemical concentration cell of Ag/Agsup(+) with the addition of irradiated TiOsub(2) was found to be exactly opposite to that due to the addition of nonirradiated oxide. (author)

  16. Evaluation of the Catalytic Activity and Cytotoxicity of Palladium Nanocubes. The Role of Oxygen

    OpenAIRE

    Dahal, Eshan; Curtiss, Jessica; Subedi, Deepak; Chen, Gen; Houston, Jessica P.; Smirnov, Sergei

    2015-01-01

    Recently it has been reported that palladium nanocubes (PdNC) are capable of generating singlet oxygen without photo-excitation simply via chemisorption of molecular oxygen on its surface. Such a trait would make PdNC a highly versatile catalyst suitable in organic synthesis and a Reactive Oxygen Species (ROS) inducing cancer treatment reagent. Here we thoroughly investigated the catalytic activity of PdNC with respect to their ability to produce singlet oxygen and to oxidize 3,5,3′,5′-tetram...

  17. Chemistry of zirconium related to the behavior of nuclear fuel cladding. Final report

    International Nuclear Information System (INIS)

    Studies of the chemistry of the zirconium-iodine and zirconium-oxygen systems were undertaken to elucidate their thermodynamics and kinetics. It is anticipated that the results obtained will lead to an improved understanding of the chemical processes involved in chemically assisted fuel rod failures. This project not only has classified the thermodynamics of both the gas phase and the solids in the zirconium-iodine system, it has also provided valuable information on the chemisorption of iodine and of oxygen on zirconium surfaces at high temperatures. In addition, the kinetics of reactions on zirconium surfaces were studied. These results have already been helpful in understanding the stress corrosion cracking of Zircaloy

  18. Materials for carbon dioxide separation

    International Nuclear Information System (INIS)

    The CO2 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 CO2 adsorption ability. Another promising class of materials for CO2 capture and separation are CaO derived from the eggshells. Two aspects were studied in present work: a new hybrid materials synthesized by doping the CaTiO3 and the relationship between physisorption and chemisorption properties of CaO-based materials.

  19. A theoretical molecular orbital approach to the adsorption and absorption of atomic hydrogen on Ni(111)

    Energy Technology Data Exchange (ETDEWEB)

    Ferullo, R.M. (Planta Piloto de Ingenieria Quimica (UNS-CONICET), Bahia Blanca (Argentina)); Castellani, N.J. (Planta Piloto de Ingenieria Quimica (UNS-CONICET), Bahia Blanca (Argentina))

    1993-02-19

    A semiempirical molecular orbital approach to the H-Ni interaction for a hydrogen atom adsorbed on the (111) surface or immersed in the bulk of Ni is given. The results show that the chemisorptive surface sites are more stable than the subsurface interstitials and that the bulk octahedral sites are more stable than the tetrahedral sites, in agreement with earlier models. The repulsive influence on hydrogen atom adsorption due to other hydrogen atoms residing in the nearer subsurface interstitials is also considered and discussed in terms of electronic arguments. (orig.)

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

    Science.gov (United States)

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

    2016-03-01

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

  1. Catalytic and photocatalytic activity of lightly doped catalysts M:ZnO (M = Cu, Mn)

    International Nuclear Information System (INIS)

    This work presents a comprehensive investigation on the effect of small amounts of copper or manganese on the catalytic and photocatalytic activities of ZnO powders. The observed effects are interpreted based on the theory of chemisorption, the physics of semiconductors and the chemistry of non-stoichiometric oxides. It turns out that the nature of the investigated processes is determined mainly by both, the influence of admixtures on the electronic band structure parameters and the alteration of the sorption ability of the semiconductor surface.

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

    International Nuclear Information System (INIS)

    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 Sr90 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

  3. Local deposition and patterning of catalytic thin films in microsystems

    International Nuclear Information System (INIS)

    The local deposition of catalysts is desired in a wide range of catalytic microsystems (microreactors and sensors). In this study, we investigate technologies enabling deposition and patterning of catalyst thin films in a manner compatible with standard micromachining processes. We evaluate and compare deposition techniques based on a combination of a self-assembly, soft-lithography and conventional micromachining. Platinum (Pt) and palladium (Pd) were used as model catalysts, both as a sputtered thin film and as nanoparticles supported on γ-alumina. The thin films were characterized and tested in terms of their catalytic activity based on CO chemisorption measurements, stability and reproducibility. (paper)

  4. A NGR study of iron catalysts in CO hydrocondensation reactions

    International Nuclear Information System (INIS)

    Fe/Al2O3, either alone or with K, Mo or Mn additive were studied by absorption NGR spectroscopy in situ. The reduction of the bimetallic systems did not induce alloying. Desorption of hydrogen resulted in oxidizing Fe0 into Fe2+, as an effect of a redox equilibrium involving properties of alumina. The decrease or growth of iron metal, carbides and ionic species during Fischer-Tropsch synthesis are consistent with a mechanism involving a dissociative chemisorption of CO. It is thought that bulk carbide is not an intermediate in the reaction. (orig.)

  5. Catalytic Hydrodeoxygenation of Bio-oils with Supported MoP-Catalysts

    OpenAIRE

    Asphaug, Sindre

    2013-01-01

    The goal of this thesis was to test the MoP catalysts which were made during autumn 2012, in a HDO reaction of phenol to benzene at a HDO rig. The catalysts were supported by Al2O3, SiO2, TiO2 and ZrO2, and they were prepared by impregnation, followed by calcination, reduction and passivation. New samples of the 2 catalysts which showed the highest activity, MoP/Al2O3 and MoP/TiO2, were prepared. They were characterized with N2-adsorption, chemisorption, TPR and XRD, and they were further tes...

  6. MO LCAO approximation in solid state approach for calculations of electronic structure of a crystal surface and chemisorbed molecule

    International Nuclear Information System (INIS)

    A scheme of calculation of the electronic structure of a solid state surface and chemisorbed molecules is discussed. The method of the Green's function and MO LCAO approximation are used which permits to perform calculations, taking into account the whole crystal but not its fragment only, with the accuracy adopted by quantum chemistry. Results of model calculations are presented: chemisorption of hydrogen-like atom on the (100) face of the one-band crystal model and dispersion curves for the density of states of nickel (100) face. (Auth.)

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

    International Nuclear Information System (INIS)

    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 subsea repository. In the event of a failure of the engineered barriers, the mobility of the released radionuclides in the sediment determines the rate and extent of entry into the water of the ocean. In this article, 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

  8. Desulfurization and structural transformation of thiophene on the Pt(111) surface

    International Nuclear Information System (INIS)

    The temperature dependence of near-edge x-ray absorption fine-structure spectra above the C K edge and S L/sub 2,3/ edge for thiophene (C4H4S) on Pt(111) reveals changes in the chemisorption geometry and the cleavage of the carbon-sulfur bond. Our results suggest the formation of a metallocycle intermediate after desulfurization with the S atom replaced by a Pt surface atom. The near-edge x-ray absorption fine-structure results are corroborated by thermal desorption, x-ray photoemission, and electron-energy-loss data

  9. The Role of the Coprecipitation Sequence of Salt Precursors on the Genesis of Cu-ZnO-Al2O3 Catalysts: Synthesis, Characterization and Activity for Low Temperature Shift Reaction

    Directory of Open Access Journals (Sweden)

    R.T. Figueiredo

    1998-06-01

    Full Text Available Cu-ZnO-Al2O3 catalysts for the low-temperature water-gas shift reaction were prepared using methods of direct and reverse coprecipitation. The catalysts obtained were characterized by DRX, TPR, XPS, N2O chemisorption, Hg-Porosimetry and BET surface area. It was observed that the precipitation sequence of the precursors led to significant differences in values of copper dispersion and consequently in the activity of the catalyst for the water-gas shift reaction.

  10. Influence of copper on nickel-based catalysts in the conversion of glycerol

    OpenAIRE

    Miranda Morales, Bárbara C.; Chimentao, Ricardo J; Szanyi, J; Braga, A.H.; Santos, Jeannette B O; Gispert Guirado, Francesc; Llorca Piqué, Jordi; Medina Cabello, Francisco

    2015-01-01

    The catalytic transformation of glycerol to value-added compounds was investigated over bimetallic Ni-Cu/gamma-Al2O3 catalysts with Ni/Cu atomic ratios of 8/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8. XPS analysis revealed that the surface composition of the catalyst exhibited progressive enrichment of Cu as its content in the catalyst increased. H-2-chemisorption indicated that the total number of exposed Ni atoms decreased as the Cu content increased. As a result, deep hydrogenolysis to produce CH...

  11. The role of surface oxides in graphite combustion

    International Nuclear Information System (INIS)

    This research thesis addresses the chemical reaction of oxidation which occurs during graphite combustion, and more particularly addresses the participation of surface oxides to this chemical reaction. The author notably examines whether these oxides are an intermediate step for all oxygen atoms involved in the reaction, or whether they are only incidentally formed during combustion. He also studies to which extent their formation and decomposition rate limits the combustion rate. The first part presents the experimental method: apparatus, installation of graphite samples, types of experiments (combustion, desorption, chemisorption), operating mode for combustion experiments, measurement precision, used products. The second part reports and discusses experimental results obtained for the three types of experiment

  12. Vapor Phase Hydrogenation of Nitrobenzene to Aniline Over Carbon Supported Ruthenium Catalysts.

    Science.gov (United States)

    Srikanth, Chakravartula S; Kumar, Vanama Pavan; Viswanadham, Balaga; Srikanth, Amirineni; Chary, Komandur V R

    2015-07-01

    A series of Ru/Carbon catalysts (0.5-6.0 wt%) were prepared by impregnation method. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), CO-chemisorption, surface area and pore-size distribution measurements. The catalytic activities were evaluated for the vapor phase hydrogenation of nitrobenzene. The dispersion measured by CO-uptake values suggests that a decrease of dispersion is observed with increasing Ru loading on carbon support. These findings are well supported by the crystallite size measured from XRD measurements. XPS study reveals the formation of Ru0 after reduction at 573 K for 3 h. The catalysts exhibit high conversion/selectivity at 4.5 wt% Ru loading during hydrogenation reaction. The particle size measured from CO-chemisorption and TEM analysis are related to the TOF during the hydrogenation reaction. Ru/C catalysts are found to show higher conversion/selectivities during hydrogenation of nitrobenzene to aniline. PMID:26373150

  13. Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

    Energy Technology Data Exchange (ETDEWEB)

    Jennifer Anne Harnisch

    2002-06-27

    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.

  14. Identifying Enclosed Chemical Reaction and Dynamics at the Molecular Level Using Shell-Isolated Miniaturized Plasmonic Liquid Marble.

    Science.gov (United States)

    Han, Xuemei; Lee, Hiang Kwee; Lee, Yih Hong; Hao, Wei; Liu, Yejing; Phang, In Yee; Li, Shuzhou; Ling, Xing Yi

    2016-04-21

    Current microscale tracking of chemical kinetics is limited to destructive ex situ methods. Here we utilize Ag nanocube-based plasmonic liquid marble (PLM) microreactor for in situ molecular-level identification of reaction dynamics. We exploit the ultrasensitive surface-enhanced Raman scattering (SERS) capability imparted by the plasmonic shell to unravel the mechanism and kinetics of aryl-diazonium surface grafting reaction in situ, using just a 2-μL reaction droplet. This reaction is a robust approach to generate covalently functionalized metallic surfaces, yet its kinetics remain unknown to date. Experiments and simulations jointly uncover a two-step sequential grafting process. An initial Langmuir chemisorption of sulfonicbenzene diazonium (dSB) salt onto Ag surfaces forms an intermediate sulfonicbenzene monolayer (Ag-SB), followed by subsequent autocatalytic multilayer growth of Ag-SB3. Kinetic rate constants reveal 19-fold faster chemisorption than multilayer growth. Our ability to precisely decipher molecular-level reaction dynamics creates opportunities to develop more efficient processes in synthetic chemistry and nanotechnology. PMID:27050645

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

    International Nuclear Information System (INIS)

    The modification of pristine Bentonite clay with sulphate and phosphate anions was found to increase its cation-exchange capacity (CEC), adsorption capacity and overall pseudo-second order kinetic rate constant for the adsorption of Cu2+ and Zn2+. Modification with sulphate and phosphate anion decreased the specific surface area of pristine Bentonite clay. Phosphate-modified Bentonite clay was found to give the highest adsorption capacity for both metal ions. The adsorption process was observed to be endothermic and spontaneous in nature for both metal ions with Zn2+ being more adsorbed. Modification with phosphate anion increased the spontaneity of the adsorption process. The effective modification of pristine Bentonite clay with sulphate anion was confirmed from hypochromic shifts in the range of 13-18 cm-1 which is typical of physisorption while modification with phosphate anion was confirmed by its hyperchromic shifts typical of chemisorption in the infrared red region using Fourier transformed infrared spectroscopy (FTIR). Using the model efficiency indicator, kinetic data were found to show very strong fit to the pseudo-second order kinetic model implying that the adsorption of Cu2+ and Zn2+ were basically by chemisorption.

  16. Interaction of hydrogen with palladium clusters deposited on graphene

    International Nuclear Information System (INIS)

    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

  17. Sodium diethyldithiocarbamate as a corrosion inhibitor of cold rolled steel in 0.5 M hydrochloric acid solution

    International Nuclear Information System (INIS)

    Graphical abstract: Relationship between corrosion current density (icorr), inhibition efficiency (ηp) and temperature with and without DDTC. (solid symbols: icorr, open symbols: ηp.) Highlights: ► DDTC can acts as a cathodic type inhibitor for CRS in HCl solution. ► The activation energy, Ea, increases with increasing the concentration of DDTC. ► The driving force for adsorption of DDTC on CRS is the increase in entropy. ► DDTC adsorbs on CRS surface probably by chemisorption and physisorption. ► Variation of DDTC results in different effect for time on inhibition efficiency. - Abstract: Sodium diethyldithiocarbamate (DDTC) as a corrosion inhibitor for cold rolled steel (CRS) in 0.5 M HCl solution was investigated by Tafel polarization and electrochemical impedance spectroscopy (EIS). All the data indicate that DDTC can inhibit the corrosion of CRS in HCl solution. Polarization data show that DDTC mainly acts as a good inhibitor though it can accelerate the anodic reaction somewhat. Adsorption of DDTC is found to follow the Langmuir adsorption isotherm. Thermodynamic analysis indicates that both physisorption and chemisorption probably occur in the adsorption process. SEM and FTIR results further validate that DDTC can adsorb on CRS surface.

  18. Comparison of boranol and silanol reactivities in boron-doped SiO2 chemical vapor deposition from trimethyl borate and tetraethyl orthosilicate

    International Nuclear Information System (INIS)

    For the first time, the relative rates of consumption of surface boranols and silanols reacting with tetraethyl orthosilicate [TEOS, Si(OCH2CH3)4] have been measured. This comparison has direct bearing on understanding the growth of doped SiO2 films from TEOS and trimethyl borate [TMB, B(OCH3)3] sources since surface boranols and silanols are expected to be present during the thermal chemical vapor deposition process. The measurements were accomplished by first derivatizing a porous silica substrate with boranols and silanols via hydrolysis of the products from an initial trimethyl borate (TMB) chemisorption step. TEOS exposures in the mTorr pressure regime were then carried out in a cold-wall reactor. Reaction products on the surface were identified with Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy in analysis chambers adjoining the reactor. Although TEOS does not react with SiOH at 300 K, it does react with BOH at this temperature. Using the deuterated species (SiOD and BOD) to measure the relative rates of hydroxyl consumption without interference from concurrent hydroxyl formation, the reaction rate constant for boranols with TEOS at 1000 K was determined to be twice that of silanols. At 1000 K, subsequent decomposition of the TEOS chemisorption products regenerates both BOH and SiOH

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

    Directory of Open Access Journals (Sweden)

    M. P. Andersson

    2013-01-01

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

  20. The effect of salinity on the sorption of cadmium ions from aqueous medium on Fe(III-sepiolite

    Directory of Open Access Journals (Sweden)

    Habish Amal Juma

    2015-01-01

    Full Text Available In this study, the sorption of cadmium ions onto sepiolite modified with hydrated iron(III oxide, Fe(III-sepiolite, has been investigated in natural seawater, artificial seawater, aqueous solution of NaCl of the same ionic strength as the seawater and distilled water. The sorption experiments were performed as a function of the initial solution pH value, the initial metal concentration and the equilibration time, using the batch method. The equilibrium sorption data were analyzed by the Langmuir, Freundlich and Sips isotherm models and the kinetics of sorption was analyzed using the pseudo-first-order and the pseudo-second-order kinetic models. The maximum sorption capacity and the strength of the sorbate-sorbent bonds at initial pH = 7 were found to decrease in the following order: distilled water > NaCl solution > artificial seawater > natural seawater. The values of parameter nS in the Sips model, which fitted the equilibrium sorption results best, showed that heterogeneity of the sorbent surface was the highest in distilled water and the lowest in natural seawater. The sorption kinetic data fitted well with the pseudo-second-order kinetic model, which suggests that the rate-limiting step in Cd2+ sorption onto Fe(III-sepiolite could be chemisorption. The low desorption percentage in both distilled water and 0.001 M HNO3 indicated that sorption occurred mainly by chemisorption mechanisms. [Projekat Ministarstva nauke republike srbije, br. III 45019

  1. 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.

  2. Adsorptive removal of Congo red from aqueous solutions using crosslinked chitosan and crosslinked chitosan immobilized bentonite.

    Science.gov (United States)

    Huang, Ruihua; Zhang, Lujie; Hu, Pan; Wang, Jing

    2016-05-01

    Batch experiments were executed to investigate the removal of Congo red (CR) from aqueous solutions using the crosslinked chitosan (CCS) and crosslinked chitosan immobilized bentonite (CCS/BT composite). The CCS and CCS/BT composite were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The removal of CR was examined as a function of pH value of CR solution, contact time, and inorganic sodium salt and ionic strength. The equilibrium data of CCS and CCS/BT composite agreed well with the Langmuir model. The adsorption capacities of CCS and CCS/BT composite at 298K and natural pH value were 405 and 500mg/g, respectively. The kinetic data correlated well with the pseudo-second-order model. The adsorption of CR onto the CCS was mainly controlled by chemisorption while the adsorption of CR onto the CCS/BT composite was controlled by chemisorption and the electrostatic attraction. PMID:26820350

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

    Directory of Open Access Journals (Sweden)

    Sun-Hee Kim

    2012-01-01

    Full Text Available 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 4f7/2 and I 3d5/2 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 nanoparicles 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.

  4. A theoretical study of bridged vs atop interactions of Pt2 with CO

    Science.gov (United States)

    Roszak, S.; Balasubramanian, K.

    1995-07-01

    Potential energy curves for the low-lying electronic states of the Pt2CO complex are studied using the Møller-Plesset second-order perturbation theory (MP2) and the complete active space multiconfiguration self-consistent field method (CASSCF). Multireference singles and doubles configuration interaction (MRSDCI) computations that included up to two million configurations were also made. The results for Pt2CO are compared with experimental results for chemisorption of CO on a Pt surface. The atop and bridged bondings of CO on the Pt-surface are modeled using potential energy curves for the ground state linear and bridged Pt2CO structures. It is shown that the atop interaction proceeds without a barrier while the bridge interaction has to surmount a barrier, even though the bridge bonding leads to a more stable equilibrium complex. The calculated vibrational frequencies at the MP2 level for Pt2CO and Pt3CO are compared with the experimentally determined values for different chemisorptive sites. The differences between the atop and bridged chemical bonds are discussed using the Mulliken population analysis. The spin-orbit effect is studied utilizing a relativistic configuration interaction (RCI) approach.

  5. The role of beaded activated carbon's surface oxygen groups on irreversible adsorption of organic vapors.

    Science.gov (United States)

    Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

    2016-11-01

    The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials. PMID:27295065

  6. Spectroscopic Studies on ZrO2 Modified with MoO3 and Activity for Acid Catalysis

    International Nuclear Information System (INIS)

    Zirconia modified with MoO3 was prepared by impregnation of powdered Zr(OH)4 with ammonium heptamolybdate aqueous solution followed by calcining in air at high temperature. Spectroscopic studies on prepared catalysts were performed by using FTIR, Raman, XRD, and DSC and by measuring surface area. Upon the addition of molybdenum oxide to zirconia up to 15 wt%, the specific surface area increased in proportion to the molybdate oxide content, while acidity measured by irreversible chemisorption of ammonia exhibited a maximum value at 3 wt% of MoO3. Since the ZrO2 stabilizes the molybdenum oxide species, for the samples equal to or less than 30 wt%, molybdenum oxide was well dispersed on the surface of zirconia and no phase of crystalline MoO3 was observed at any calcination temperature above 400 .deg. C. The catalytic activities for cumene dealkylation were roughly correlated with the acidity of catalysts measured by ammonia chemisorption method, while the catalytic activities for 2-propanol dehydration were not correlated with the acidity because weak acid sites are necessary for the reaction

  7. Investigation of Tribological Behavior of Lanthanum-Based Thin Films Deposited on Sulfonated Self-Assembled Monolayer

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    3-mercaptopropyl trimethoxysilane (MPTS) was prepared on glass substrate so as to form a two-dimensional self-assembled monolayer (SAM), and the terminal -SH group in the film was in situ oxidized to -SO3H group to confer good chemisorption ability to the film. Thus, lanthanum-based thin films were deposited on oxidized MPTS-SAM, making use of the chemisorption ability of -SO3H group. Atomic force microscopy (AFM) and X-ray photoelectron spectrometry (XPS) and contact angle measurements were used to characterize the thin films. The tribological properties of the as-prepared thin films sliding against a steel ball were evaluated on a friction and wear tester. Tribological experiment shows that the friction coefficient of glass substrate decreases from 0.8 to 0.08 after the rare earth (RE) self-assembled films (SAMs) are formed on its surface. And the RE self-assembled films have longer wear life (500 sliding passes). It is demonstrated that RE self-assembled film exhibits good wear-resistant property. The marked decrease in friction and the longer wear life of RE films are attributed to the excellent adhesion of the film to the substrate and to the special characteristics of the RE elements. The frictional behaviors of RE thin-films-coated silicon surface were sensitive to the applied load and the sliding velocity of the steel ball.

  8. Tungstophosphoric acid supported onto hydrous zirconia: Physicochemical characterization and esterification of 1° and 2° alcohol

    Indian Academy of Sciences (India)

    Pankaj Sharma; Anjali Patel

    2006-10-01

    The Keggin type heteropolyacid, 12-tungstophosphoric acid (PW), was supported onto hydrous zirconia (Z) by impregnation method and designated as ZH3. The ZH3 was calcinated at 300°C and 500°C and designated as ZH33 and ZH35, respectively. The resulting materials were characterized by FTIR, diffuse reflectance spectroscopy (DRS), XRD, surface area measurement (BET method) and particle size distribution. The surface morphology was studied by scanning electron microscopy. The acidity of all materials was evaluated by carrying out chemisorption of ammonia and esterification of 1° alcohol (-butanol) with different acids like formic acid, acetic acid and propionic acid and 2° alcohol (cyclohexanol, iso-butanol) with acetic acid. Above studies show the high dispersion of HPA in a non-crystalline form on the support as well as uniform distribution of particles of ZH3 which contains 30% 12-tungstophosphoric acid. It also shows that when ZH3 was calcinated at 500°C, it possesses highest acidity for both chemisorption of NH3 as well as esterification reactions.

  9. Ethanol steam reforming over Rh/Ce{sub x}Zr{sub 1-x}O{sub 2} catalysts. Impact of the CO-CO{sub 2}-CH{sub 4} interconversion reactions on the H{sub 2} production

    Energy Technology Data Exchange (ETDEWEB)

    Birot, Anne; Epron, Florence; Duprez, Daniel [Laboratoire de Catalyse en Chimie Organique (LACCO), UMR 6503 CNRS and University of Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France); Descorme, Claude [IRCELYON, UMR 5256 CNRS/Universite Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2008-02-21

    Ce{sub x}Zr{sub 1-x}O{sub 2} mixed oxide-supported 1 wt.% Rh catalysts were prepared by wet impregnation using Rh nitrate as a precursor and calcined at 900 C. They were characterized by BET surface area, XRD, CO{sub 2} chemisorption and H{sub 2} chemisorption at -85 C and tested in the ethanol steam reforming at 600 C under atmospheric pressure, with water to ethanol molar ratio equal to 4, without carrier gas. The best performances, i.e. the highest hydrogen yield and the lowest coke deposition, were obtained over Rh/Ce{sub 0.5}Zr{sub 0.5}O{sub 2}, i.e. 3.63 mol H{sub 2}/mol{sub ethanol}. This catalyst was subsequently evaluated under various reaction conditions. Whatever the temperature and the water to ethanol ratio, the ethanol steam reforming yielded a large amount of methane, which tends to reduce the H{sub 2} production. To elucidate the origin of the methane production, CO/CO{sub 2}/CH{sub 4} interconversion reactions were studied. It was shown that such catalyst favours the formation of methane via CO hydrogenation. The direct hydrogenation of CO{sub 2} was not observed. In parallel, the catalyst was active in the reverse water gas shift (RWGS) reaction between CO{sub 2} and H{sub 2}, leading CO and H{sub 2}O. (author)

  10. Phase transition and vapochromism in molecular assemblies of a polymorphic zinc(II) Schiff-base complex.

    Science.gov (United States)

    Oliveri, Ivan Pietro; Malandrino, Graziella; Di Bella, Santo

    2014-09-15

    This paper reports for the first time the irreversible thermally induced phase transition, accompanied by color change, and the vapochromic behavior of an amphiphilic, Lewis acidic Zn(II) Schiff-base complex, through detailed X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry, and optical absorption studies. The unprecedented irreversible phase transition for such kind of complexes is associated with a thermal, lamellar-to-hexagonal columnar structural transition, which involves a different arrangement of each molecular unit within the assembled structure, H- and J-type aggregates, respectively, responsible for the thermochromic behavior. The vapochromism, investigated either in powder samples or in thermally annealed cast films, is related to the formation of 1:1 adducts upon exposure to vapors of strong Lewis bases and implies dramatic optical absorption variations and naked-eye observation of the change in color from red-brown to red. The chemisorption process is fast, completely reversible, reproducible, and selective for amines. The reversible switching of the chemisorption-desorption process in cast films is demonstrated by successive cycles, amine exposure and subsequent heating, by monitoring the substantial optical absorption changes in the visible region. Vapochromism of this material can potentially be used to detect vapors of volatile amines. PMID:25148651

  11. Adsorption of oleic acid at sillimanite/water interface.

    Science.gov (United States)

    Kumar, T V Vijaya; Prabhakar, S; Raju, G Bhaskar

    2002-03-15

    The interaction of oleic acid at sillimanite-water interface was studied by adsorption, FT-IR, and zeta potential measurements. The isoelectric point (IEP) of sillimanite obtained at pH 8.0 was found to shift in the presence of oleic acid. This shift in IEP was attributed to chemisorption of oleic acid on sillimanite. Adsorption experiments were conducted at pH 8.0, where the sillimanite surface is neutral. The adsorption isotherm exhibited a plateau around 5 micromol/m2 that correspond to a monolayer formation. Adsorption of oleic acid on sillimanite, alumina, and aluminum hydroxide was studied by FT-IR. Chemisorption of oleic acid on the above substrates was confirmed by FT-IR studies. Hydroxylation of mineral surface was found to be essential for the adsorption of oleic acid molecules. These surface hydroxyl sites were observed to facilitate deprotonation of oleic acid and its subsequent adsorption. Thus protons from oleic acid react with surface hydroxyl groups and form water molecules. Based on the experimental results, the mechanism of oleic acid adsorption on mineral substrate was proposed. Free energy of adsorption was estimated using the Stern-Graham equation for a sillimanite-oleate system. PMID:16290466

  12. Shape of the hydrogen adsorption regions of MOF-5 and its impact on the hydrogen storage capacity

    Science.gov (United States)

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

    2008-11-01

    The adsorption of molecular hydrogen on a metal-organic framework (MOF) material, MOF-5, has been studied using the density-functional formalism. The calculated potential-energy surface shows that there are two main adsorption regions: both near the OZn4 oxide cores at the vertices of the cubic skeleton of MOF-5. The adsorption energies in those regions are between 100 and 130 meV/molecule. Those adsorption regions have the shape of long, wide, and deep connected trenches and passage of the molecule between regions needs to surpass small barriers of 30-50 meV. The shape of these regions, and not only the presence of metal atoms, explains the large storage capacity measured for MOF-5. The elongated shape explains why some authors have previously identified only one type of adsorption site, associated to the Zn oxide core, and others identified two or three sites. One should consider adsorption regions rather than adsorption sites. A third region of adsorption is near the benzenic rings of the MOF-5. We have also analyzed the possibility of dissociative chemisorption. The chemisorption energy with respect to two separated H atoms is 1.33 eV/H atom; but, since dissociating the free molecule costs 4.75 eV, the physisorbed H2 molecule is more stable than the dissociated chemisorbed state by about 2 eV. Dissociation of the adsorbed molecule costs less energy, but the dissociation barrier is still high.

  13. Diffusion and sorption of 32Si-labelled silica in the boom clay

    International Nuclear Information System (INIS)

    The long term corrosion rate of nuclear waste glass in a repository might be controlled by the steady-state diffusion of dissolved silica and would be enhanced by the sorption of silica onto clay minerals. Irreversible sorption and moderate retardation have been observed for dissolved silica in boom clay. Values of ηR between 10 and 20 have been determined by means of four flow-through migration experiments, while Kd in the range 20 to 100 cm3, g-1 have been measured by batch sorption tests with 32Si on fresh and slightly oxidized boom clay. As non specific interactions cannot explain the sorption of neutral Si(OH)4, or of negative silicate species (Donnan exclusion), onto negatively charged clay minerals other mechanisms must be invoked: i.a., the chemisorption of dissolved silica Si(OH)4 onto specific Lewis acid sites (Al3+, Fe3+) present at the clay surface. The suggested mechanism could be similar to this explaining the irreversible chemisorption of oxy-anions of weak acids (as phosphate, or borate) onto aluminum and iron hydroxides in soils. Ligand exchange of aqueous silica with a hydroxyl group of Al(OH)3 may form a hydroxy-aluminosilicate (HAS) surface complex. Gibbsite layers accessible on the basal plane of kaolinite and on the edges of illite and smectite are possible sorption sites for the dissolved silica in boom clay. Moreover, hydrous ferric oxide produced by pyrite oxidation significantly increases the extent of silica sorption. (orig.)

  14. Tridentate benzylthiols on Au(111): control of self-assembly geometry.

    Science.gov (United States)

    Mezour, Mohamed A; Perepichka, Iryna I; Ivasenko, Oleksandr; Lennox, R Bruce; Perepichka, Dmitrii F

    2015-03-21

    A set of hexasubstituted benzene derivatives with three thiol groups in the 1, 3, 5 positions and varied aliphatic substituents in the 2, 4, 6 positions (Me3-BTMT, Et3-BTMT, ODe3-BTMT) has been synthesized and self-assembled on Au(111). The resulting self-assembled monolayers (SAMs) are characterized by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and electrochemistry. The molecular orientation and long-range order are affected by the “gear effect” of the hexasubstituted benzene ring and van der Waals interactions between the physisorbed alkyl chains drive. Me3-BTMT adopts a standing up orientation which results in the highest molecular surface density but also the lowest degree of chemisorption (1 to 2 Au–S bonds per molecule). In contrast, Et3-BTMT favors a lying down orientation with a greater number of surface-bonded thiol groups (2 to 3) per molecule, associated with the peculiar geometry of this molecule. Finally, ODe3-BTMT adsorbs mainly in a lying down orientation, forming the SAM with the highest degree of chemisorption (all thiol groups are gold-bonded) and the lowest molecular areal density. PMID:25695677

  15. Nano-tribological characteristics of TiO2 films on 3-mercaptopropyl trimethoxysilane sulfonated self-assembled monolayer

    Indian Academy of Sciences (India)

    J Li; X H Sheng

    2009-10-01

    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 oxidized MPTS–SAM to form composite thin films, making use of the chemisorption ability of the –SO3H group. Atomic force microscope (AFM) and contact angle measurements were used to characterize TiO2 films. Adhesive force and friction force of TiO2 thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. Results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. In order to study the effect of capillary force, tests were performed in various relative humidities. Results showed that the adhesive force of silicon substrate increases with relative humidities and the adhesive force of TiO2 thin films only increases slightly with relative humidity. Research showed that surfaces with more hydrophobic property revealed the lower adhesive and friction forces.

  16. Adsorption removal of Congo red from aqueous solution by polyhedral Cu2O nanoparticles: Kinetics, isotherms, thermodynamics and mechanism analysis

    International Nuclear Information System (INIS)

    Highlights: • Polyhedral Cu2O NPs with rough surfaces were prepared by a one-pot sonochemical precipitation method. • The Cu2O NPs show unprecedented adsorption capability toward Congo red. • CR adsorption onto Cu2O is a spontaneous, endothermic and chemisorption process. • The Cu2O adsorbent can be photocatalytically regenerated by visible light irradiation. - Abstract: Polyhedral cuprous oxide nanoparticles (Cu2O NPs) with rough surfaces were prepared by a one-pot sonochemical precipitation method. The products were characterized by SEM, XRD, EDS, XPS, and UV–Vis DRS, respectively. The adsorption behavior of Congo red (CR) from aqueous solution onto the as-prepared Cu2O NPs was systematically investigated. The equilibrium and kinetic studies suggested that the adsorption process followed Freundlich isotherm and pseudo-second order model, respectively. The as-prepared Cu2O NPs exhibited remarkable adsorption properties toward CR. The maximum adsorption capacity at 20 °C was 3904 mg g−1, which was the highest reported value so far in adsorption removal of CR. Together with the evaluation of the thermodynamic parameters such as Gibbs free energy, enthalpy and entropy change, our results show that the adsorption of CR onto Cu2O is a spontaneous, endothermic and chemisorption process. A putative interaction model between CR and Cu2O NPs was proposed. Moreover, the Cu2O adsorbent could be photocatalytically regenerated and reused without significant loss of its adsorption capability

  17. Study of uranium oxide passivation using oxygen

    International Nuclear Information System (INIS)

    Stabilization of the UO2 powders is an important step in the manufacturing process. After the reduction the UO2 powder is made chemically passive by slight oxidation to quite a large extent fixed by specifications that allows to storage powders till the sintering process is performed. In this work the UO2 powders are oxidized with a versatile automated physisorption / chemisorption analyzer as to generate adsorption isotherms with preselected amounts of chemically gases sequentially added to the samples. This process is studied as a O2 chemisorption-diffusion phenomena because the ability of the UO2 powders to get O2 is directly related to the specific surface area available for reaction like chemical adsorption but increases with temperature for equal areas as it occurs in diffusion processes. To check the extent of oxidation of UO2 powders, samples are characterized for O/U ratio analysis. It is found from our experience that the temperature should be less than 80 degree C. Experiences were performed with CO2 instead of O2 as to get the passivated UO2 powder at higher temperatures. The advantage of using CO2 is the possibility of high temperature controlled oxidative step which definitely is very beneficial for fuel manufacturing from an economic point of view. (author)

  18. Interaction of ester functional groups with aluminum oxide surfaces studied using infrared reflection absorption spectroscopy.

    Science.gov (United States)

    van den Brand, J; Blajiev, O; Beentjes, P C J; Terryn, H; de Wit, J H W

    2004-07-20

    The bonding of two types of ester group-containing molecules with a set of different oxide layers on aluminum has been investigated using infrared reflection absorption spectroscopy. The different oxide layers were made by giving typical surface treatments to the aluminum substrate. The purpose of the investigation was to find out what type of ester-oxide bond is formed and whether this is influenced by changes in the composition and chemistry of the oxide. The extent by which these bonded ester molecules resisted disbondment in water or substitution by molecules capable of chemisorption was also investigated. The ester groups were found to show hydrogen bonding with hydroxyls on the oxide surfaces through their carbonyl oxygens. For all oxides, the ester groups showed the same nu(C = O) carbonyl stretching vibration after adsorption, indicating very similar bonding occurs. However, the oxides showed differences in the amount of molecules bonded to the oxide surface, and a clear relation was observed with the hydroxyl concentration present on the oxide surface, which was determined from XPS measurements. The two compounds showed differences in the free to bonded nu(C = O) infrared peak shift, indicating differences in bonding strength with the oxide surface between the two types of molecules. The bonding of the ester groups with the oxide surfaces was found to be not stable in the presence of water and also not in the presence of a compound capable of chemisorption with the aluminum oxide surface. PMID:15248718

  19. Coated kapok fiber for removal of spilled oil

    International Nuclear Information System (INIS)

    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

  20. Self-suspended permanent magnetic FePt ferrofluids.

    Science.gov (United States)

    Dallas, Panagiotis; Kelarakis, Antonios; Sahore, Ritu; DiSalvo, Francis J; Livi, Sebastien; Giannelis, Emmanuel P

    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. PMID:23859815

  1. 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.

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

    Science.gov (United States)

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

    2013-10-01

    Atomic hydrogen modification of the surface energy of GaAs (110) epilayers, grown at high temperatures from molecular beams of Ga and As4, 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/Å2 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 As4 molecules mediated by H on the GaAs (110) surface has been proposed as the most likely explanation for the changes in surface kinetics observed.

  3. Highly Dispersed Gold Nanoparticles Supported on SBA-15 for Vapor Phase Aerobic Oxidation of Benzyl Alcohol.

    Science.gov (United States)

    Kumar, Ashish; Sreedhar, Bojja; Chary, Komandur V R

    2015-02-01

    Gold nanoparticles supported on SBA-15 are prepared by homogenous deposition-precipitation method (HDP) using urea as the precipitating agent. The structural features of the synthesized catalysts were characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption (BET), pore size distribution (PSD), CO chemisorption and X-ray photoelectron spectroscopy (XPS). The catalytic activity and stability of the Au/SBA-15 catalysts are investigated during the vapor phase aerobic oxidation of benzyl alcohol. The BJH pore size distribution results of SBA-15 support and Au/SBA-15 catalysts reveals that the formation of mesoporous structure in all the samples. TEM results suggest that Au nanoparticles are highly dispersed over SBA-15 and long range order of hexagonal mesopores of SBA-15 is well retained even after the deposition of Au metallic nanoparticles. XPS study reveals the formation of Au (0) after chemical reduction by NaBH4. The particle size measured from CO-chemisorption and TEM analysis are well correlated with the TOF values of the reaction. Au/SBA-1 5 catalysts are found to show higher activity compare to Au/TiO2 and Au/MgO catalysts during the vapor phase oxidation of benzyl alcohol. The catalytic functionality are well substantiated with particle size measured from TEM. The crystallite size of Au in both fresh and spent catalysts were measured from X-ray diffraction. PMID:26353720

  4. Structural and electronic properties of Ce overlayers and low-dimensional Pt-Ce alloys on Pt{111}

    International Nuclear Information System (INIS)

    The structural, thermal, chemisorptive, and electronic properties of Ce on Pt{111} are studied by photoemission, Auger spectroscopy, scanning tunnel microscope (STM), and low-energy electron diffraction (LEED). Stranski-Krastanov-like growth of low-density Ce layers is accompanied by substantial valence charge transfer from Ce to Pt: in line with this, the measured dipole moment and polarizability of adsorbed Ce at low coverages are 7.2x10-30Cm and ∼1.3x10-29m3, respectively. Pt-Ce intermixing commences at ∼400K and with increasing temperature a sequence of five different ordered surface alloys evolves. The symmetry, periodicities, and rotational epitaxy observed by LEED are in good accord with the STM data which reveal the true complexity of the system. The various bimetallic surface phases are based on growth of crystalline Pt5Ce, a hexagonal layer structure consisting of alternating layers of Pt2Ce and Kagomacute e nets of Pt atoms. This characteristic ABAB layered arrangement of the surface alloys is clearly imaged, and chemisorption data permit a distinction to be made between the more reactive Pt2Ce layer and the less reactive Pt Kagomacute e net. Either type of layer can appear at the surface as the terminating structure, thicker films exhibiting unit mesh parameters characteristic of the bulk alloy. copyright 1997 The American Physical Society

  5. The role of adsorbed hydrogen species in the dehydrogenation and hydrocracking of saturated hydrocarbons on supported metal catalysts

    Science.gov (United States)

    Babenkova, L. V.; Naidina, I. N.

    1994-07-01

    The role of certain hydrogen absorption complexes in the dehydrogenation and hydrocracking of hydrocarbons on low-percentage one-component, (Pt, Pd/Al2O3) and bimetallic (Pd-Co, Pd-Ce, Pt-Co, Pt-Sn/Al2O3) catalysts is discussed. It is shown that the combination of metals in reduced forms and forms oxidised to different extents on the catalyst surfaces is responsible for their high capacity for the chemisorption of hydrogen, the wide range of its energetic inhomogeneity, and the high activity of the catalysts in the conversion of saturated hydrocarbons. Catalysts containing on the surface mainly sites for the type Hδ- chemisorption are the most active in the dehydrogenation of hydrocarbons, whereas specimens chemisorbing hydrogen mainly in the Hδ+ form are the most active in the hydrockracking of hydrocarbons. It is concluded that the strongly bound atomic hydrogen Hδ+ plays a dual role, since it not only participates directly in the dehydrogenation reaction but also promotes the reduction of the electron-deficient surface centres, which optimises the number of centres for the activation of C-H bonds. The bibliography includes 75 references.

  6. Reaction dynamics of Si(001) oxidation at room temperature induced by supersonic O sub 2 molecular beams

    CERN Document Server

    Teraoka, Y

    2002-01-01

    Potential energy barriers for dissociative chemisorption of O sub 2 molecules on clean and H sub 2 O-preadsorbed Si(001) surfaces were verified using supersonic O sub 2 molecular beams and synchrotron radiation photoemission spectroscopy. The saturated oxygen amount on both kinds of Si(001) surfaces were measured as a function of incident energy of O sub 2 molecules. The saturated oxygen amount was dependent in both cases on the incident energy. Especially, two energy thresholds appeared in the H sub 2 O-preadsorbed Si(001) surface oxidation. An Si-2p photoemission spectrum for the oxygen-saturated Si(001) surface formed by O sub 2 gas possessing incident energy below the first threshold on the clean surface revealed the oxygen insertion into backbond sites of Si dimers. The dimer backbonds, however, were not oxidized by O sub 2 irradiation without incident energy larger than 1.0 eV in the H sub 2 O-preadsorbed surface. These facts indicate that a chemisorption reaction path of the oxygen insertion into dimer...

  7. Reaction dynamics of Si(001) oxidation at room temperature induced by supersonic O2 molecular beams

    International Nuclear Information System (INIS)

    Potential energy barriers for dissociative chemisorption of O2 molecules on clean and H2O-preadsorbed Si(001) surfaces were verified using supersonic O2 molecular beams and synchrotron radiation photoemission spectroscopy. The saturated oxygen amount on both kinds of Si(001) surfaces were measured as a function of incident energy of O2 molecules. The saturated oxygen amount was dependent in both cases on the incident energy. Especially, two energy thresholds appeared in the H2O-preadsorbed Si(001) surface oxidation. An Si-2p photoemission spectrum for the oxygen-saturated Si(001) surface formed by O2 gas possessing incident energy below the first threshold on the clean surface revealed the oxygen insertion into backbond sites of Si dimers. The dimer backbonds, however, were not oxidized by O2 irradiation without incident energy larger than 1.0 eV in the H2O-preadsorbed surface. These facts indicate that a chemisorption reaction path of the oxygen insertion into dimer backbonds through bridge and dangling bond sites is open for the clean surface oxidation, and the path is cut by termination of dangling bonds by H and OH radicals. (author)

  8. Nanocrystalline MgO supported nickel-based bimetallic catalysts for carbon dioxide reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Meshkani, Fereshteh [Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan (Iran); Rezaei, Mehran [Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan (Iran); Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan (Iran)

    2010-10-15

    Nanocrystalline magnesium oxide with high surface area and plate-like shape was employed as catalyst support for preparation of nickel-based bimetallic catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction (XRD), N{sub 2} adsorption (BET), Temperature programmed oxidation and desorption (TPO-TPD), Thermal gravimetric and differential thermal gravimetric (TGA-DTG), H{sub 2} chemisorption and Transmission and electron microscopies (TEM and SEM) analyses. CO{sub 2}-TPD data showed the high CO{sub 2} adsorption capacity of catalysts which improves the resistance of catalysts against the carbon formation. The H{sub 2} chemisorption results also indicated that the addition of Pt to nickel catalyst improved the nickel dispersion. The obtained results revealed that the prepared catalysts showed a high activity and stability during the reaction with a low amount of deposited carbon. Addition of Pt to nickel catalyst improved both the activity and resistivity against carbon formation. (author)

  9. Reduction of NO by CO using Pd-CeTb and Pd-CeZr catalysts supported on SiO2 and La2O3-Al2O3

    Institute of Scientific and Technical Information of China (English)

    Victor Ferrer; Dora Finol; Roger Solano; Alexander Moronta; Miguel Ramos

    2015-01-01

    The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27Ox/SiO2,Ce0.6Zr0.4Ox/SiO2,Ce0.73Tb0.27Ox/La2O3-Al2O3 and Ce0.6Zr0.4Ox/La2O3-Al2O3 was studied using the reduction of NO by CO.The catalysts were characterized by X-ray fluorescence,surface area,X-ray diffraction,temperature-programmed reduction,CO chemisorption and oxygen storage capacity.Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity.CO chemisorption data suggested the presence of large PdO particles due to the low CO/Pd ratio.No significant differences were obtained in light offtemperatures (TLight off) for all Pd catalysts and the most active was 1.5%Pd/Ce0.6Zr0.4Ox/SiO2.

  10. 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.

  11. 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.

  12. 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.

  13. Improved sulfur-resistant ability on CO oxidation of Pd/Ce0.75Zr0.25O2 over Pd/CeO2-TiO2 and Pd/CeO2

    Institute of Scientific and Technical Information of China (English)

    沈美庆; 林放; 魏光曦; 王建强; 朱少春

    2015-01-01

    The influence of sulfation on Pd/Ce0.75Zr0.25O2, Pd/CeO2-TiO2 and Pd/CeO2 was investigated. Physical structure and chemical properties of different catalysts were characterized by N2 adsorption, X-ray diffraction (XRD), CO chemisorption, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and X-ray fluorescence (XRF). After 10 h SO2 sulfation, it was found that the decrement on CO oxidation catalytic activity was limited on Pd/Ce0.75Zr0.25O2 compared to Pd/CeO2-TiO2 and Pd/CeO2. It demonstrated that Pd/Ce0.75Zr0.25O2 was more sulfur resistant compared to the other two catalysts. Af-ter sulfur exposure, catalyst texture was not much influenced as shown by N2 adsorption and XRD, and surface Pd atoms were poi-soned indicated by CO chemisorption results. Pd/Ce0.75Zr0.25O2 and Pd/CeO2-TiO2 exhibited less sulfur accumulation compared to Pd/CeO2 in the sulfation process. Furthermore, XPS results clarified that surface sulfur amount, especially surface sulfates amount on the sulfated catalysts was more crucial for the deactivation in sulfur containing environment.

  14. 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)

    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 + Al2O3, NiAl2O4 and NiO + NiAl2O4) 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+Al2O3 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, O2 and CO2 on the 2NiO+Al2O3 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 (NiAl2O4 and NiO+NiAl2O4) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O2 and CO2 on NiAl2O4, and the kinetic of the oxidation reaction are herein studied

  15. Optical detection of carbon dioxide adsorption on epitaxial CuFe1 -xGaxO2 Delafossite film grown by pulse laser deposition

    Science.gov (United States)

    Rojas, S.; Joshi, T.; Wheatley, R. A.; Sarabia, M.; Borisov, P.; Lederman, D.; Cabrera, A. L.

    2016-06-01

    A highly epitaxial delafossite CuFe1 -xGaxO2 film was made with pulse laser deposition in high vacuum. The sample thickness was around 48 nm and it was terminated with CuFeO2. This delafossite sample was exposed to a CO2 atmosphere under controlled conditions and chemisorption of CO2 on the surface was observed. Transmittance and reflectance spectroscopies were recorded for the sample post surface heat treatment held in a vacuum chamber (0.05 Kpa) and after exposure to CO2. Both spectra were recorded over a wavelength range of 350-1100 nm. Chemisorption of CO2 was correlated with an increase in transmittance and decrease in reflectance in the pressure range 0-60 kPa. These observations were confirmed with X-ray photoelectron spectroscopy and thermal programmed desorption data obtained in an independent experiment. The CO2 is bound to the surface forming a carboxylate structure via coordination of a bent CO2- δ molecule to a Cu center.

  16. Molecular Hydrogen formation on grain surfaces

    International Nuclear Information System (INIS)

    We reconsider H2 formation on grain surfaces. We develop a rate equation model which takes into account the presence of both physisorbed and chemisorbed sites on the surface, including quantum mechanical tunnelling and thermal diffusion. In this study, we take into consideration the uncertainties on the characteristics of graphitic surfaces. We calculate the H2 formation efficiency with the Langmuir Hinshelwood and Eley Rideal mechanisms, and discuss the importance of these mechanisms for a wide range of grain and gas temperatures. We also develop a Monte Carlo simulation to calculate the H2 formation efficiency and compare the results to our rate equation models. Our results are the following: (1) Depending on the barrier againt chemisorption, we predict the efficiency of H2 formation for a wide range of grain and gas temperatures. (2) The Eley-Rideal mechanism has an impact on the H2 formation efficiency at high grain and gas temperatures. (3) The fact that we consider chemisorption in our model makes the rate equation and Monte Carlo approaches equivalent

  17. Molecular hydrogen formation on grain surfaces

    CERN Document Server

    Cazaux, S; Tielens, A G G M; Le Bourlot, J; Walmsley, M C

    2005-01-01

    We reconsider H2 formation on grain surfaces. We develop a rate equation model which takes into account the presence of both physisorbed and chemisorbed sites on the surface, including quantum mechanical tunnelling and thermal diffusion. In this study, we took into consideration the uncertainties on the characteristics of graphitic surfaces. We calculate the H2 formation efficiency with the Langmuir Hinshelwood and Eley Rideal mechanisms, and discuss the importance of these mechanisms for a wide range of grain and gas temperatures. We also develop a Monte Carlo simulation to calculate the H2 formation efficiency and compare the results to our rate equation models. Our results are the following: (1) Depending on the barrier against chemisorption, we predict the efficiency of H2 formation for a wide range of grain and gas temperatures. (2) The Eley-Rideal mechanism has an impact on the H2 formation efficiency at high grain and gas temperatures. (3) The fact that we consider chemisorption in our model makes the ...

  18. Quantum state-resolved CH4 dissociation on Pt(111): coverage dependent barrier heights from experiment and density functional theory.

    Science.gov (United States)

    Ueta, Hirokazu; Chen, Li; Beck, Rainer D; Colón-Dìaz, Inara; Jackson, Bret

    2013-12-21

    The dissociative chemisorption of CH4 on Pt(111) was studied using quantum state-resolved methods at a surface temperature (T(s)) of 150 K where the nascent reaction products CH3(ads) and H(ads) are stable and accumulate on the surface. Most previous experimental studies of methane chemisorption on transition metal surfaces report only the initial sticking coefficients S0 on a clean surface. Reflection absorption infrared spectroscopy (RAIRS), used here for state resolved reactivity measurements, enables us to monitor the CH3(ads) uptake during molecular beam deposition as a function of incident translational energy (E(t)) and vibrational state (ν3 anti-symmetric C-H stretch of CH4) to obtain the initial sticking probability S0, the coverage dependence of the sticking probability S(θ) and the CH3(ads) saturation coverage θ(sat). We observe that both S0 and θ(sat) increase with increasing E(t) as well as upon ν3 excitation of the incident CH4 which indicates a coverage dependent dissociation barrier height for the dissociation of CH4 on Pt(111) at low surface temperature. This interpretation is supported by density functional calculations of barrier heights for dissociation, using large supercells containing one or more H and/or methyl adsorbates. We find a significant increase in the activation energies with coverage. These energies are used to construct simple models that reasonably reproduce the uptake data and the observed saturation coverages. PMID:24177276

  19. A quantum chemistry study on surface reactivity of pristine and carbon-substituted AlN nanotubes

    Science.gov (United States)

    Mahdaviani, Amir; Esrafili, Mehdi D.; Esrafili, Ali; Behzadi, Hadi

    2013-09-01

    A density functional theory investigation was performed to predict the surface reactivity of pristine and carbon-substituted (6,0) single-walled aluminum nitride nanotubes (AlNNTs). The properties determined include the electrostatic potentials VS(r) and average local ionization energies ĪS(r) on the surfaces of the investigated tubes. According to computed VS(r) results, the Al/N atoms in edge or cap regions show a different reactivity pattern than those at the middle portion of the tubes. Due to the carbon-substitution at the either Al or N sites of the tubes, the negative regions associated with nitrogen atoms are stronger than before. The prediction of surface reactivity and regioselectivity using average local ionization energies has been verified by atomic hydrogen chemisorption energies calculated for AlNNTs at the B3LYP/6-31 G* level. There is an acceptable correlation between the minima of ĪS(r) and the atomic hydrogen chemisorption energies, demonstrating that ĪS(r) provides an effective means for rapidly and economically assessing the relative reactivities of finite sized AlNNTs.

  20. Catalytic activity vs. size correlation in platinum catalysts of PEM fuel cells prepared on carbon black by different methods

    Energy Technology Data Exchange (ETDEWEB)

    Nores-Pondal, F.J.; Granada, M.; Corti, H.R. [Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica (CNEA), General Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Vilella, I.M.J.; de Miguel, S.R.; Scelza, O.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE), Facultad de Ingenieria Quimica (Universidad Nacional del Litoral) - CONICET, Santiago del Estero 2654, 3000 Santa Fe (Argentina); Troiani, H. [Departamento de Fisica, Centro Atomico Bariloche, Comision Nacional de Energia Atomica (CNEA), Av. Bustillo 9500, 8400 San Carlos de Bariloche (Argentina)

    2009-10-15

    In this work nanoparticulated platinum catalysts have been prepared on carbon Vulcan XC-72 using three methods starting with chloroplatinic acid as a precursor: (i) formic acid as a reductor agent; (ii) impregnation method followed by reduction in hydrogen atmosphere at moderated temperature; and (iii) microwave-assisted reduction in ethylene glycol. The catalytic and size studies were also performed on a commercial Pt catalyst (E-Tek, De Nora). The characterization of the particle size and distribution was performed by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD). The characterizations of the catalytic and electrocatalytic properties of the catalysts were determined by studying the cyclohexane dehydrogenation reaction (CHD) and the behavior under cyclic voltammetry (CV) in sulfuric acid solutions. The measured electrochemical activity, along with the hydrogen chemisorption of the catalysts allows the estimation of effective particle sizes, which are much larger than those measured by TEM and XRD. The catalysts prepared by reduction with formic acid and ethylene glycol (microwave-assisted) show electrochemical activities very close to those of the commercial catalyst, and are almost insensitive to the Pt dispersion or Pt particle size. The chemical activity in CHD correlates well with the metallic dispersion determined by hydrogen chemisorption, indicating similar accesibility of H{sub 2} and cyclohexane to the catalyst surface. (author)

  1. Chemical Reactions of Silicon Clusters

    CERN Document Server

    Ramakrishna, M V; Ramakrishna, Mushti V.; Pan, Jun

    1994-01-01

    Smalley and co-workers discovered that chemisorption reactivities of silicon clusters vary over three orders of magnitude as a function of cluster size. In particular, they found that \\Si{33}, \\Si{39}, and \\Si{45} clusters are least reactive towards various reagents compared to their immediate neighbors in size. We explain these observations based on our stuffed fullerene model. This structural model consists of bulk-like core of five atoms surrounded by fullerene-like surface. Reconstruction of the ideal fullerene geometry gives rise to four-fold coordinated crown atoms and $\\pi$-bonded dimer pairs. This model yields unique structures for \\Si{33}, \\Si{39}, and \\Si{45} clusters without any dangling bonds and thus explains their lowest reactivity towards chemisorption of closed shell reagents. This model is also consistent with the experimental finding of Jarrold and Constant that silicon clusters undergo a transition from prolate to spherical shapes at \\Si{27}. We justify our model based on an in depth analys...

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

    Directory of Open Access Journals (Sweden)

    M. C. Leuenberger

    2015-08-01

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

  3. Cyclic CO2 chemisorption–desorption behavior of Na2ZrO3: Structural, microstructural and kinetic variations produced as a function of temperature

    International Nuclear Information System (INIS)

    A structural, microstructural and kinetic analysis of the Na2ZrO3–CO2 system was performed over 20 chemisorption–desorption cycles. Different cyclic experiments were performed between 500 and 800 °C. Although the best results were obtained in Na2ZrO3 sample treated at 550 °C, all the samples treated between 500 and 700 °C presented good CO2 chemisorption efficiencies and stabilities. On the contrary, Na2ZrO3 sample treated at 800 °C presented a continuous decrement of the CO2 chemisorption. After 20 cycles all the samples presented a partial Na2ZrO3 decomposition, determined by the ZrO2 formation, which was associated to sodium sublimation. Additionally, the Na2ZrO3 microstructural analysis showed a systematic morphological evolution. It was microscopically observed that Na2ZrO3 particles tend to fracture due to the Na2CO3 formation. Later, after several cycles these tiny fractured particles sinter producing new polyhedral and dense Na2ZrO3–ZrO2 particles. Finally, an exhaustive kinetic analysis showed a high CO2 chemisorption–desorption stability at different temperatures. - Graphical abstract: A CO2 chemisorption–desorption analysis was performed in the Na2ZrO3–CO2 system. Different cyclic experiments were performed between 500 and 800 °C and the results showed high CO2 chemisorption efficiencies. Nevertheless the Na2ZrO3 composition and microstructure evolved during the cycles. Highlights: • Different CO2 chemisorption–desorption cycles were performed in the Na2ZrO3 phase. • Na2ZrO3 presents interesting microstructural changes depending on temperature. • At T≤550 °C, Na2ZrO3 presents the best cyclability due to microstructural factors. • At T≥600 °C, Na2ZrO3 presents a partial decomposition after 20 cycles. • Na2ZrO3 presents excellent CO2 cyclability properties

  4. Coordination modes and bonding of sulfur oxides on transition metal surfaces: combined ab initio and BOC-MP results

    Science.gov (United States)

    Seller, Harrell; Shustorovich, Evgeny

    1996-02-01

    Binding energies for sulfur oxides, SO x, x = 1-3, have been determined for several coordination modes on silver, gold and palladium surfaces employing ab initio quantum chemical methods and the bond order conservation Morse potential (BOC-MP) method. SO 2 coordination was studied in the most detail. In general the agreement between the BOC-MP and ab initio binding energies is good for the (111) surfaces of silver and palladium with both methods predicting that, in the zero coverage limit, di-coordination via S,O and O,O will be more favorable energetically than mono-coordination via S. In the case of chemisorption on the Pd (110) surface the two methods agree well for the cases in which there are formulas for the BOC-MP binding energies. In going from the (111) surfaces to the (110) surfaces of silver and palladium the ab initio calculations predict that the preferred chemisorption site shifts from the bridge site to the hollow site. On the silver surfaces the net charge transferred to the adsorbate as judged from the Mulliken populations correlates roughly with the binding energy. No significant charge transfer was found on the palladium surfaces. Our SO 2 chemisorption calculations indicate that the work functions of the metal surfaces examined should increase upon mono-S adsorption, increase to a lesser extent upon di S,O adsorption and may even decrease upon di O,O adsorption. Ab initio calculations provide evidence of the existence of SO 2 surface dimers. The binding energy predicted by the BOC-MP model for SO 3 in the bridging site agrees well with the ab initio result for SO 3 di-coordinated in the long bridge of the Ag(110) surface. The methods yield similar predictions for the case of SO on silver. Our modeling provides a coherent picture consistent with many aspects of the experimental literature. We present some model predictions, particularly the di O,O coordination mode for SO 2, that require verification experimentally.

  5. Cyclic CO{sub 2} chemisorption–desorption behavior of Na{sub 2}ZrO{sub 3}: Structural, microstructural and kinetic variations produced as a function of temperature

    Energy Technology Data Exchange (ETDEWEB)

    Martínez-dlCruz, Lorena; Pfeiffer, Heriberto, E-mail: pfeiffer@iim.unam.mx

    2013-08-15

    A structural, microstructural and kinetic analysis of the Na{sub 2}ZrO{sub 3}–CO{sub 2} system was performed over 20 chemisorption–desorption cycles. Different cyclic experiments were performed between 500 and 800 °C. Although the best results were obtained in Na{sub 2}ZrO{sub 3} sample treated at 550 °C, all the samples treated between 500 and 700 °C presented good CO{sub 2} chemisorption efficiencies and stabilities. On the contrary, Na{sub 2}ZrO{sub 3} sample treated at 800 °C presented a continuous decrement of the CO{sub 2} chemisorption. After 20 cycles all the samples presented a partial Na{sub 2}ZrO{sub 3} decomposition, determined by the ZrO{sub 2} formation, which was associated to sodium sublimation. Additionally, the Na{sub 2}ZrO{sub 3} microstructural analysis showed a systematic morphological evolution. It was microscopically observed that Na{sub 2}ZrO{sub 3} particles tend to fracture due to the Na{sub 2}CO{sub 3} formation. Later, after several cycles these tiny fractured particles sinter producing new polyhedral and dense Na{sub 2}ZrO{sub 3}–ZrO{sub 2} particles. Finally, an exhaustive kinetic analysis showed a high CO{sub 2} chemisorption–desorption stability at different temperatures. - Graphical abstract: A CO{sub 2} chemisorption–desorption analysis was performed in the Na{sub 2}ZrO{sub 3}–CO{sub 2} system. Different cyclic experiments were performed between 500 and 800 °C and the results showed high CO{sub 2} chemisorption efficiencies. Nevertheless the Na{sub 2}ZrO{sub 3} composition and microstructure evolved during the cycles. Highlights: • Different CO{sub 2} chemisorption–desorption cycles were performed in the Na{sub 2}ZrO{sub 3} phase. • Na{sub 2}ZrO{sub 3} presents interesting microstructural changes depending on temperature. • At T≤550 °C, Na{sub 2}ZrO{sub 3} presents the best cyclability due to microstructural factors. • At T≥600 °C, Na{sub 2}ZrO{sub 3} presents a partial decomposition after 20 cycles

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

    Science.gov (United States)

    Leuenberger, M. C.; Schibig, M. F.; Nyfeler, P.

    2015-12-01

    It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1-10 kJ mol-1, compared to chemisorption which ranges from 100 to 1000 kJ mol-1. Furthermore, chemisorption only forms monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws; however, it can be influenced by hysteresis effects. In the present experiment, we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. Our observations from completely decanting one steel and two aluminium cylinders are in agreement with the pressure dependence of physisorption for CO2, CH4, and H2O. The CO2 results for both cylinder types are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, mole fraction changes due to adsorption on aluminium (< 0.05 and 0 ppm for CO2 and H2O) were significantly lower than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO2 amount adsorbed (5.8 × 1019 CO2 molecules) corresponds to about the fivefold monolayer adsorption, indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH4 and for CO but require further attention since they were only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber, the cylinders were exposed to temperatures between -10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2, ranging from 0.0014 to 0.0184 ppm °C-1 for steel cylinders and -0.0002 to -0

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

    Science.gov (United States)

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

    2015-12-01

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

  8. Use of ultra-thin organic silane films for the improvement of gold adhesion to the silicon dioxide wafers for (bio)sensor applications

    Energy Technology Data Exchange (ETDEWEB)

    Ben Ali, M. [Institut Superieur des Sciences, Appliquees et de Technologies, Cite Taffela-Ebn Kaldoun, 4003-Tunisia (Tunisia); Laboratoire de Physique de Semi-conducteurs et Capteurs, IPEST la Marsa 2070 Tunis (Tunisia)], E-mail: mounirbenali@yahoo.com; Bessueille, F. [LSA, Universite Claude Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex (France); Chovelon, J.M. [IRCELYON, Universite Claude Bernard-Lyon 1.43 Bd du 11 novembre 1918 69622 Villeurbane Cedex (France); Abdelghani, A. [Laboratoire de Physique de Semi-conducteurs et Capteurs, IPEST la Marsa 2070 Tunis (Tunisia); Jaffrezic-Renault, N. [LSA, Universite Claude Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex (France); Maaref, M.A. [Laboratoire de Physique de Semi-conducteurs et Capteurs, IPEST la Marsa 2070 Tunis (Tunisia); Martelet, C. [AMPERE, Ecole Centrale de Lyon, 69134 Ecully Cedex (France)

    2008-07-01

    A mono-functional silane reagent, 3-mercaptopropyltrimethoxysilane (MPS) was used to modify the surface of silicon wafers. The structure of the SAMs formed with the MPS was investigated by contact angle measurements, ellipsometry, AFM, and X-ray photoelectron spectroscopy (XPS). The deposition of a metallic gold layer via ultra-high vacuum (UHV) evaporation reveals good adhesion properties on Au/MPS/SiO{sub 2}/Si structure. The 'chemisorption' between the SAM and the gold evaporated layer is confirmed by adhesion tests and optimum curing treatment is found 1 h at 100 deg. C). This very simple methodology, avoiding the usage of Cr and other metals as undercoating layers and could be proposed further for (bio)sensors applications.

  9. Sorbitol hydrogenolysis to glycols by supported ruthenium catalysts

    Institute of Scientific and Technical Information of China (English)

    Inmaculada Murillo Leo; Manuel Lopez Granados; Jose Luis Garcia Fierro; Rafael Mariscal

    2014-01-01

    Supported Ru catalysts were prepared by wet impregnation to evaluate the role of different oxide supports (Al2O3, SiO2, TiO2, ZrO2) in sorbitol hydrogenolysis to glycols. X-ray diffraction, transmis-sion electron microscopy, hydrogen chemisorption, X-ray photoelectron spectroscopy, and NH3 temperature-programmed desorption were used to characterize the catalysts, which were active in the hydrogenolysis of sorbitol. The support affected both the physicochemical properties and cata-lytic behavior of the supported Ru particles. The characterization results revealed that the Ru/Al2O3 catalyst has a high surface acidity, partially oxidized Ru species on the surface, and a higher surface Ru/Al atomic ratio, which gave it the highest selectivity and yield to glycols.

  10. Low metal loading catalysts used for the selective hydrogenation of styrene

    Directory of Open Access Journals (Sweden)

    Juan Badano

    2010-01-01

    Full Text Available A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98% during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%, but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects.

  11. 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.

  12. Biosorption of Azo dyes by spent Rhizopus arrhizus biomass

    Science.gov (United States)

    Salvi, Neeta A.; Chattopadhyay, S.

    2016-05-01

    In the present study, spent Rhizopus arrhizus biomass was used for the removal of six azo dyes from aqueous solutions. The dye removal capacity of the biomass was evaluated by conducting batch tests as a function of contact time, biomass dosage, pH and initial dye concentrations. The pseudo-second-order kinetic model fitted well with the experimental data with correlation coefficients greater than 0.999, suggesting that chemisorptions might be the rate limiting step. The equilibrium sorption data showed good fit to the Langmuir isotherm model. Among the six dyes tested, the maximum monolayer adsorption capacity for fast red A and metanil yellow was found to be 108.8 and 128.5 mg/g, respectively. These encouraging results suggest that dead Rhizopus arrhizus biomass could be a potential biomaterial for the removal of azo dyes from aqueous dye solution.

  13. Berberine as an Environmental-Friendly Inhibitor for Hot-Dip Coated Steels in Diluted Hydrochloric Acid

    Institute of Scientific and Technical Information of China (English)

    Hong Ju; Yulin Ju; Yan Li

    2012-01-01

    The inhibition effect of an excellent environmental-friendly corrosion inhibitor--berberine on hot-dip coated steels in the diluted HCI has been investigated by using quantum chemistry analysis, mass-loss tests, elec- trochemical measurements and scanning electron microscopy (SEM) observation. Calculation results show that berberine has a nearly planar structure with a number of active centers. The value of Mulliken charge, and the distribution of the highest occupied molecular orbital (HOMO) and the lower unoccupied molecular orbital (LUMO) imply that berberine has a good ability of electron exchange with metal surface. The test results indicate that inhibition efficiency (IE%) increases with the inhibitor concentration and the highest IE can reach 99%. Adsorption of berberine on the coating surface follows Langmuir adsorption isotherm with a single molecular layer by chemisorption.

  14. Ab Initio Studies on Hematite Surface and the Adsorption of Phosphate

    Directory of Open Access Journals (Sweden)

    Swati Chaudhury

    2014-01-01

    Full Text Available This investigation explores the ab initio DFT method for understanding surface structure of hematite and the nature and energetics of phosphate adsorption. Using the full potential linearized plane wave method (FP-LAPW, we derived the structure and energies of various magnetic forms of hematite. The antiferromagnetic (AFM form was observed to be the most stable. Hematite surfaces with Fe-termination, O-termination, or OH-termination were studied. The OH-terminated surface was the most stable. Stability of hematite surfaces follows the order OH-termination > Fe-termination > O-termination. Thus, surface reaction with hematite would occur with the OH at the surface and not with Fe atoms. The structure of phosphate adsorbed on hematite was derived. Bonding is through the H atom of the OH at the surface. An alternative mechanism of phosphate adsorption on hematite has been derived. Adsorption energy is high and suggests chemisorption rather than physisorption of phosphate on hematite.

  15. Use of ultra-thin organic silane films for the improvement of gold adhesion to the silicon dioxide wafers for (bio)sensor applications

    International Nuclear Information System (INIS)

    A mono-functional silane reagent, 3-mercaptopropyltrimethoxysilane (MPS) was used to modify the surface of silicon wafers. The structure of the SAMs formed with the MPS was investigated by contact angle measurements, ellipsometry, AFM, and X-ray photoelectron spectroscopy (XPS). The deposition of a metallic gold layer via ultra-high vacuum (UHV) evaporation reveals good adhesion properties on Au/MPS/SiO2/Si structure. The 'chemisorption' between the SAM and the gold evaporated layer is confirmed by adhesion tests and optimum curing treatment is found 1 h at 100 deg. C). This very simple methodology, avoiding the usage of Cr and other metals as undercoating layers and could be proposed further for (bio)sensors applications

  16. Correlation of acid-base properties of substituted polystyrene-azo-pyrocatechol and characteristics of their chelates with zirconium

    International Nuclear Information System (INIS)

    Acid-base and complexing properties of new synthesized polymeric chelate-forming sorbents (PCS) - substituents of polystyrene-azo-pyrocatechol - are investigated and quantitative correlations between pKOH of functional analytical group (FAG) of sorbent and Hammet constants for para-substituent and ΔpKOH-ΔpK50 correlations of zirconium chelate-forming and pKOH-lgKstb (Kstb - constant of stability of PCS complexes with zirconium) of polychelates to study regularities of effect of peculiarities of structure and acid-base properties of FAG on parameters of zirconium chemical sorption. Established correlations make it possible to predict quantitative physicochemical parameters of sorbents and zirconium chemisorption process with the aim of directed synthesis and application of PCS in concentrating processes

  17. Novel application of a hormone biosynthetic inhibitor for the corrosion resistance enhancement of copper in synthetic seawater

    International Nuclear Information System (INIS)

    Graphical abstract: Highlights: → A novel hormone biosynthetic inhibitor was studied as corrosion inhibitor for copper. → Corrosion inhibition under various conditions were evaluated. → Surface appearances after corrosion were investigated by SEM and EDS. → Uniconazole shows extremely high inhibition efficiency. - Abstract: Effects of a hormone biosynthetic inhibitor on corrosion resistance of copper in synthetic seawater under various conditions were evaluated via quantum chemistry calculations, weight loss, electrochemical techniques, SEM, EDS, and FTIR. Comparable results show that uniconazole acts as a mixed-type inhibitor, suppressing charge transfer process by adsorption on copper surface. Thermodynamic calculation indicates that chemisorption is in accordance with Langmuir isotherm and adsorption amount increases with immersion time. The corrosion resistance with inhibitor under alkaline conditions is better than that under acidic or neutral conditions. Good inhibition performances at different temperatures and during a long time immersion are observed.

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

    Science.gov (United States)

    Deyab, M. A.

    2015-04-01

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

  19. SELECTIVE HYDRODECHLORINATION OF 1,2-DICHLOROETHANE OVER Pd-Sn/SiO2 CATALYSTS

    Directory of Open Access Journals (Sweden)

    F ORELLANA

    2005-03-01

    Full Text Available Pd/SiO2 and Pd-Sn/SiO2 catalysts prepared by sol-gel processing have been characterised and tested in the selective hydrodechlorination of 1,2-dichloroethane. The obtained solids were characterised by N2 adsorption at 77 K, H2 chemisorption, temperature programmed reduction, and X-ray diffraction. It was found that the Pd surface atoms decreases upon the Sn addition, without critical changes on the specific area and reducibility. The turnover frequency increases continuously with the reaction temperature and also as tin loading increases. The selectivity to ethylene is strongly enhanced as temperature increases up to reach almost a constant value of 90 %, in the temperature range 500-600 K. It is proposed that Pd-SnOx are the active sites for the selective hydrodechlorination of 1,2-dichloroethane

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

    Science.gov (United States)

    Monti, Susanna; Carravetta, Vincenzo; Ågren, Hans

    2016-07-14

    The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption. PMID:27305447

  1. ADSORPTION CHARACTERISTICS OF CHLOROPHENOLS FROM AQUATIC SYSTEMS BY HYPERCROSSLINKED RESINS MODIFIED WITH BENZOYL GROUP

    Institute of Scientific and Technical Information of China (English)

    Jing-ping Wang; Zheng-hao Fei

    2006-01-01

    A hypercrosslinked polymeric adsorbent (ZH-03) for adsorbing and removing chlorophenolic compounds from their aqueous solutions was studied, including the static adsorption. The equilibrium adsorption data were fit to Freundlich adsorption isothermic models to evaluate the model parameters. Thermodynamic studies on the adsorption of chlorophenolic compounds on ZH-03 indicated that there were chemisorption transitions for 2,4,6-trichlorophenol and physical adsorption processes for 2-chlorophenol and 2,6-chlorophenol, and ZH-03 showed the homogeneous nature of the adsorbent surface.Column adsorption for chlorophenols wastewater shows the advantages of the ZH-03 adsorbent for adsorbing the following chlorophenolic compounds as 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol. Sodium hydroxide was used for desorpting chlorophenols from ZH-03 and showed excellent performance.

  2. Single-step synthesis of magnetic chitosan composites and application for chromate (Cr(VI)) removal

    Institute of Scientific and Technical Information of China (English)

    杨卫春; 唐琼芝; 董舒宇; 柴立元; 王海鹰

    2016-01-01

    Magnetic chitosan composites (Fe3O4@chitosan) were synthesized in one single-step, characterized and applied in Cr(VI) removal from water. With the increase of loading proportion of chitosan, Cr(VI) adsorption capacity of Fe3O4@chitosan composites increased from 10.771 to 21.040 mg/g. The optimum adsorption capacities of Cr(VI) on Fe3O4@chitosan-3 were found in a pH range of 3.0−5.0. Kinetic study results show that the adsorption process follows pseudo-second-order model, indicating that the rate-limiting step in the adsorption of Cr(VI) involves chemisorptions. Moreover, FT-IR spectra analysis confirms that the amine and hydroxyl groups of chitosan are predominantly responsible for binding. Results from this work demonstrate that the prepared Fe3O4@chitosan composites possess great potential in Cr(VI) removal from contaminated water.

  3. 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.

  4. Reversible CO2 Capture by Conjugated Ionic Liquids through Dynamic Covalent Carbon-Oxygen Bonds.

    Science.gov (United States)

    Pan, Mingguang; Cao, Ningning; Lin, Wenjun; Luo, Xiaoyan; Chen, Kaihong; Che, Siying; Li, Haoran; Wang, Congmin

    2016-09-01

    The strong chemisorption of CO2 is always accompanied by a high absorption enthalpy, and traditional methods to reduce the absorption enthalpy lead to decreased CO2 capacities. Through the introduction of a large π-conjugated structure into the anion, a dual-tuning approach for the improvement of CO2 capture by anion-functionalized ionic liquids (ILs) resulted in a high capacity of up to 0.96 molCO2  mol-1IL and excellent reversibility. The increased capacity and improved desorption were supported by quantum chemical calculations, spectroscopic investigations, and thermogravimetric analysis. The increased capacity may be a result of the strengthened dynamic covalent bonds in these π-electron-conjugated structures through anion aggregation upon the uptake of CO2 , and the improved desorption originates from the charge dispersion of interaction sites through the large π-electron delocalization. These results provide important insights into effective strategies for CO2 capture. PMID:27458723

  5. Transformation of Heavy Metal Compounds during the Remediation of Contaminated Soils

    Directory of Open Access Journals (Sweden)

    Tatiana Minkina

    2011-03-01

    Full Text Available The effect of ameliorants, chalk, glauconite and semidecomposed cattle manure, on ordinary chernozem contaminated with Zn and Pb was studied in a long-term field experiment. The application of ameliorants significantly decreased the mobility of metals. Their effect depended on the ameliorant and was most significant at the simultaneous application of chalk and manure. This effect was presumably due to the strong binding of metals by carbonates through chemisorption and formation of lowsoluble Zn and Pb compounds and to the additional fixation in the form of complexes at the addition of organic material. The share of loosely bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below. The general evolution of the transformation of metal compounds (from less to more firmly bound compounds accelerated by ameliorants remained for both metals.

  6. AMMONIA AND COD REMOVAL FROM SYNTHETIC LEACHATE USING RICE HUSK COMPOSITE ADSORBENT

    Directory of Open Access Journals (Sweden)

    Azhar Abdul Halim

    2011-06-01

    Full Text Available Ammonia and chemical oxygen demand (COD were the most two problematic parameters in the landfill leachate. In this study, a new composite adsorbent derived from rice husk ash waste is evaluated with respect to its ability to remove these contaminants from synthetic leachate. Results indicate that the new composite adsorbent is able to adsorb both ammonia and COD. It has a higher adsorption capacity for ammonia (Q = 2.2578 mg/g and an almost equal adsorption capacity for COD (Q = 2.8893 when compared with commercially activated carbon. The adsorption kinetics of this new product for ammonia and COD were primarily represented by the pseudo second-order mechanism. The overall adsorption rate of the ammonia and COD adsorption processes appears to be determined by chemisorption process. The regenerated composite adsorbent indicated higher adsorption capacities of ammonia and COD, i.e. 12.9366 mg/g and 3.1162 mg/g, respectively.

  7. Eletrodos quimicamente modificados aplicados à eletroanálise: uma breve abordagem Chemically modified electrodes applyes to electroanalysis: a brief presentation

    Directory of Open Access Journals (Sweden)

    Maria de Fátima Brito Souza

    1997-04-01

    Full Text Available Chemically modified electrodes (CMEs have been subject of considerable attention since its inception about 23 years ago. CMEs result of a deliberate immobilization of a modifier agent onto the electrode surface obtained through chemical reactions, chemisorption, composite formation or polymer coating. This immobilization seeks transfer the physicochemical properties of the modifier to the electrode surface and thus to dictate and control the behavior of the electrode/solution interface. In recent years the interest in CMEs has increased particularly to enhance the sensitivity and/or the selectivity of electroanalytical techniques. In general higher sensitivity and/or selectivity may be achieved by exploiting one or more of the following phenomena: electrocatalysis, preconcentration and interferents exclusion. This paper deals with the application of CMEs in electroanalysis, including a brief presentation of the more general procedures that have been employed for the modification of electrode surfaces.

  8. Electronic and energetic properties of FeCl{sub 3} and CrO{sub 3} interacting with single wall BN nanotube

    Energy Technology Data Exchange (ETDEWEB)

    Serejo, J.A.S.; Guerini, S., E-mail: silvete.guerini@ufma.br

    2015-09-15

    Highlights: • The interaction between the BNNT and molecules occurs through chemical process. • The FeCl{sub 3} and CrO{sub 3} molecules are predicted to behave as an electron acceptor. • The binding energy is high, suggesting that the interaction is quite stable. - Abstract: Structural, electronic and energetic properties of FeCl{sub 3} and CrO{sub 3} interacting with (10,0) BN nanotube were obtained using ab initio calculation based on the density functional theory. It was found that the FeCl{sub 3} and CrO{sub 3} molecules behave as an electron acceptor in the presence of the BNNT in all the configurations studied. In a more stable configuration, the binding energy is much stronger, suggesting that the interaction is through a chemisorption regime.

  9. 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.

  10. Consolidation of tin sulfide chalcogels and xerogels with and without adsorbed iodine

    Energy Technology Data Exchange (ETDEWEB)

    Riley, Brian J.; Pierce, David A.; Lepry, William C.; Kroll, Jared O.; Chun, Jaehun; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.; Alblouwy, Fares K.; Bulbule, Aneeruddha; Sabolsky, Edward

    2015-11-18

    Tin sulfide (Sn2S3) chalcogels are one of the most effective non-oxide aerogels evaluated to date for iodine gas capture. This is attributed to the fact that the Sn within the gel network has a strong affinity for chemisorption of iodine to form SnI4. This study demonstrates an approach for consolidating the raw and iodine-sorbed Sn2S3 chalcogels into a chalcogenide glass using GeS2 as a glass forming additive. The system with both iodine-sorbed and iodine-free Sn2S3 chalcogels provides better glass-forming characteristics than Sn-S or Sn-S-I alone, and the quantity of iodine measured in the bulk glass of the consolidated iodine-sorbed Sn2S3 chalcogel was at ~45 mass%. Additional experiments were also conducted using microwave sintering and hot isostatic pressing with Sn2S3 xerogels.

  11. Ultrasonic Extraction and TLC Determination of Glyphosate in the Spiked Red Soils

    Directory of Open Access Journals (Sweden)

    Sandra Babić

    2005-09-01

    Full Text Available Pesticides that get into soil bind mostly to its solid phase by physical or chemical processes. In the valley of the Neretva River the use of herbicides, especially of glyphosate is widespread and sometimes uncontrolled. In this work ultrasonic solvent extraction (USE followed by thin-layer chromatography (TLC was applied for determining glyphosate presence in soil. The experiments were conducted with two characterised soil types. The impact of soil composition on extraction efficiency is discussed. Chemical analysis showed that soil 1 contained much more iron and aluminium oxides than soil 2, which was richer in humic substances. Low glyphosate efficiency (ca 44 % in both soils could be attributed either to its binding to iron and aluminium oxides (soil 1, or to chemisorption on humic macromolecules (soil 2.

  12. Field-Assisted and Thermionic Contributions to Conductance in SnO Thick-Films

    Directory of Open Access Journals (Sweden)

    C. Malagù

    2009-01-01

    Full Text Available A deep analysis of conductance in nanostructured SnO2 thick films has been performed. A model for field-assisted thermionic barrier crossing is being proposed to explain the film conductivity. The model has been applied to explain the behavior of resistance in vacuum of two sets of nanostructured thick-films with grains having two well-distinct characteristic radii (=25 nm and =125 nm. In the first case the grain radius is shorter than the depletion region width, a limit at which overlapping of barriers takes place, and in the second case it is longer. The behavior of resistance in the presence of dry air has been explained through the mechanism of barrier modulation through gas chemisorption.

  13. Preparation of Palladium-Supported Periodic Mesoporous Organosilicas and their Use as Catalysts in the Suzuki Cross-Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Francisco J. Romero-Salguero

    2013-04-01

    Full Text Available Three periodic mesoporous materials, i.e., two organosilicas with either ethylene or phenylene bridges and one silica, have been used as supports for Pd nanoparticles. All Pd-supported samples (1.0 wt% were prepared by the incipient wetness method and subsequently reduced in an H2 stream at 200 °C. Both hydrogen chemisorption and temperature programmed reduction experiments revealed significant differences depending on the support. Pd2+ species were more reducible on the mesoporous organosilicas than on their silica counterpart. Also, remarkable differences on the particle morphology were observed by transmission electron microscopy. All Pd-supported samples were active in the Suzuki cross-coupling reaction between bromobenzene and phenylboronic acid.

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

    Directory of Open Access Journals (Sweden)

    Francisco José Sánchez Castellanos

    2010-04-01

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

  15. A study of sulfonamides (used as corrosion inhibitor for the possibility to adsorption on steel

    Directory of Open Access Journals (Sweden)

    Andrei Sikachina

    2016-05-01

    Full Text Available The published work presents modeled using quantum chemistry package HyperChem version 8.0.7 using semiempirical method ZINDO/1 the adsorption process of organic compounds of the class of sulfonamides, such as iron (available in steel St3S in the amount of 97%. This approach, as will be shown, with high accuracy reflects the process of corrosion protection, with bacterial content by means of chemisorption of organic compounds on the metal surface with the formation of complex compounds. In the research process were obtained and analyzed: the composition of the complexes, a graph showing the dependence of the charge density per atom of iron, from corrosion rates.

  16. 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

  17. Synthesis of supported bimetallic nanoparticles with controlled size and composition distributions for active site elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Hakim, Sikander H.; Sener, Canan; Alba Rubio, Ana C.; Gostanian, Thomas M.; O' neill, Brandon J; Ribeiro, Fabio H.; Miller, Jeffrey T.; Dumesic, James A

    2015-08-01

    Elucidation of active sites in supported bimetallic catalysts is complicated by the high level of dispersity in the nanoparticle size and composition that is inherent in conventional methods of catalyst preparation. We present a synthesis strategy that leads to highly dispersed, bimetallic nanoparticles with uniform particle size and composition by means of controlled surface reactions. We demonstrate the synthesis of three systems, RhMo, PtMo, and RhRe, consisting of a highly reducible metal with an oxophilic promoter. These catalysts are characterized by FTIR, CO chemisorption, STEM/EDS, TPR, and XAS analysis. The catalytic properties of these bimetallic nanoparticles were probed for the selective CO hydrogenolysis of (hydroxymethyl)tetrahydropyran to produce 1,6 hexanediol. Based on the characterization results and reactivity trends, the active sites in the hydrogenolysis reaction are identified to be small ensembles of the more noble metal (Rh, Pt) adjacent to highly reduced moieties of the more oxophilic metal (Mo, Re).

  18. 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.

  19. Thin film nanophase and nanocomposite fluorine-containing wear inhibitors

    Directory of Open Access Journals (Sweden)

    Yauheni Auchynnikau

    2015-12-01

    Full Text Available The paper examines features of the morphology and structure of thin films based on fluorine-containing oligomers modified by nanoparticles of different composition and obtaining technology. A classification of nanophase and nanocomposite thin film coatings is proposed. The oligomeric fluorine-containing components by using mortar technology develop thin-film coatings, comprising a quasi-crystalline nanophases in oligomeric matrix with high chemisorption activity to a metal substrate. Modifying of the oligomeric matrix by active components with uncompensated charge leads to the formation of ordered areas at the interface “low-dimensional filler-matrix”. In composites, containing synthetic polytetrafluoroethylene thermogas dynamic products, synergistic effect is realized due to thermodynamic compatibility of oligomeric polar and nonpolar components and high-molecular particles with uncompensated charge. This ensures the formation of coating with improved adhesion, deformation strength and tribological characteristics parameters.

  20. Experimental and quantum chemical characterization of the adsorption of some Schiff base compounds of phthaloyl thiocarbohydrazide on the mild steel in acid solutions

    International Nuclear Information System (INIS)

    Three derivatives of 2-[2-(hydrazinecarbonothioyl)hydrazinecarbonyl]benzoic acid (IL1) have been evaluated as new corrosion inhibitors for the corrosion of mild steel in 1 M HCl solutions using weight loss, polarization and electrochemical impedance spectroscopy (EIS) techniques. The adsorption of these compounds has been tested thermodynamically which was found to be of neither a typical physisorption nor a typical chemisorption mode. The thermodynamic functions (such as Ea, ΔHoads, ΔSoads and ΔGoads) of dissolution and adsorption processes have been evaluated. The polarization measurements indicated that the inhibitors are of mixed type. The adsorption of the compounds was found to obey Langmuir's adsorption isotherm. In addition, quantum chemical calculations have been made to correlate inhibition efficiencies determined experimentally.

  1. Effect of Cobalt Particle Size on Acetone Steam Reforming

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Junming; Zhang, He; Yu, Ning; Davidson, Stephen D.; Wang, Yong

    2015-06-11

    Carbon-supported cobalt nanoparticles with different particle sizes were synthesized and characterized by complementary characterization techniques such as X-ray diffraction, N-2 sorption, acetone temperature-programmed desorption, transmission electron microscopy, and CO chemisorption. Using acetone steam reforming reaction as a probe reaction, we revealed a volcano-shape curve of the intrinsic activity (turnover frequency of acetone) and the CO2 selectivity as a function of the cobalt particle size with the highest activity and selectivity observed at a particle size of approximately 12.8nm. Our results indicate that the overall performance of acetone steam reforming is related to a combination of particle-size-dependent acetone decomposition, water dissociation, and the oxidation state of the cobalt nanoparticles.

  2. 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. PMID:26295765

  3. 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.

  4. Adsorption and mobility of metals in build-up on road surfaces.

    Science.gov (United States)

    Gunawardana, Chandima; Egodawatta, Prasanna; Goonetilleke, Ashantha

    2015-01-01

    The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal. PMID:24630452

  5. Required catalytic properties for alkane production from carboxylic acids: Hydrodeoxygenation of acetic acid

    Institute of Scientific and Technical Information of China (English)

    Zhong; He; Xianqin; Wang

    2013-01-01

    The supported Pt catalysts(1 wt%)were prepared by the incipient impregnation method and analyzed using synchrotron-based X-ray diffraction,BET surface area,oxygen adsorption,CO pulse chemisorption,temperature-programmed desorption(TPD)of acetic acid,H2-TPD,NH3-TPD,O2-TPD,and H2-TPR.The reactivity of Pt-based catalysts was studied using a fixed bed reactor at 300 C and 4 MPa for hydrodeoxygenation of acetic acid,where Pt/TiO2 was very selective for ethane production.TPD experiments revealed that several conditions must be satisfied to achieve this high selectivity to ethane from acetic acid,such as Pt sites,moderate acidity,and medium metal-oxygen bond strength in the oxide support.This work provides insights in developing novel catalytic materials for hydrocarbon productions from various organics including bio-fuels.

  6. Catalytic synthesis of 2-methylpyrazine over Cr-promoted copper based catalyst via a cyclo-dehydrogenation reaction route

    Indian Academy of Sciences (India)

    Fangli Jing; Yuanyuan Zhang; Shizhong Luo; Wei Chu; Hui Zhang; Xinyu Shi

    2010-07-01

    The cyclo-dehydrogenation of ethylene diamine and propylene glycol to 2-methylpyrazine was performed under the atmospheric conditions at 380°C. The Cr-promoted Cu-Zn/Al2O3 catalysts were prepared by impregnation method and characterized by ICP-AES, N2 adsorption/desorption, XRD, XPS, N2O chemisorption, TPR and NH3-TPD techniques. The amorphous chromium species existing in Cu-Zn-Cr/Al2O3 catalyst enhanced the dispersion of active component Cu, promoted the reduction of catalyst. Furthermore, the catalytic performance was significantly improved. The acidity of the catalyst played an important role in increasing the 2-MP selectivity. To optimize the reaction parameters, influences of different chromium content, reaction temperature, liquid hourly space velocity (LHSV), reactants molar ratio and time on stream on the product pattern were studied. The results demonstrated that addition of chromium promoter revealed satisfying catalytic activity, stability and selectivity of 2-methylpyrazine.

  7. Indirect coupling of an organic semiconductor to a d -orbital surface state

    Science.gov (United States)

    Wang, Jingying; Dougherty, Daniel B.

    2015-10-01

    Adsorption of the organic semiconductor perylene tetracarboxylic dianhydride onto Cr (001 ) decreases the metal d -derived surface-state lifetime without causing a shift in its energy. This suggests an indirect electronic interaction that contrasts sharply with expectations of p-d electronic coupling based on direct chemisorption. Lifetime changes are measured with scanning tunneling spectroscopy as a function of temperature and quantified as arising from a molecule-induced increase in electron-electron scattering rate into bulk bands within Fermi-liquid theory. Adsorbate-induced effects extend far beyond the adsorption site of the molecule, decaying exponentially away with a characteristic length scale of ˜2.4 nm , similar to the carrier mean free path in Cr.

  8. Environmental friendly lubricants through selective hydrogenation of rapeseed oil over supported copper catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ravasio, Nicoletta; Zaccheria, Federica; Fusi, Achille; Poli, Nicola; Psaro, Rinaldo [Centro CNR CSSCMTBSO e Dip. Chimica Inorganica Metallorganica e Analitica, Universita degli Studi di Milano, Via Venezian 21, 20133 Milan (Italy); Gargano, Michele [Dipartimento di Chimica, Universita di Bari, Via Orabona 4, 70126 Bari (Italy); Recchia, Sandro [Dipartimento Scienze CCFFMM, Universita dell' Insubria, Via Lucini 3, 22100 Como (Italy)

    2002-07-10

    Different supported copper catalysts are compared in the selective hydrogenation of vegetable oils and their methylesters. The influence of parameters such as the catalysts preparation method, the support used and the activation treatment are critically evaluated in terms of catalytic activity and selectivity. All ex situ reduced catalysts prepared by the chemisorption-hydrolysis (CH) method show better performances than the ones prepared by incipient wetness technique. These data are directly matched up to the different morphology of the supported copper particles obtained with these two methods. By using a 8% Cu/SiO{sub 2} catalyst the trienic component C18:3 can be eliminated and the dienic one lowered from 22 to 3-5% without increasing the stearic C18:0 content and limiting the cis/trans-isomerisation process. These oils, with a C18:1 content up to 88% show remarkable oxidation stability and keep fluid down to -15C.

  9. Kinetics and Mechanism of Adsorption of Phosphate on Fluorine-containing Calcium Silicate

    Institute of Scientific and Technical Information of China (English)

    ZHU Xinhua; ZHANG Zhao; SHEN Jun

    2016-01-01

    The nanowires-reticulated calcium silicate with a speciifc surface area more than 100 m2/g was prepared by a hydrothermal process using hydrated lime (Ca(OH)2, HL) and silica containing soluble lfuoride, which was a by-product of lfuorine industry, and the soluble lfuoride in raw silica was ifxed as CaSiF6 at the same time. The kinetic characteristics and mechanism of adsorbing phosphate by lfuorine-containing calcium silicate were investigated in the experiments of phosphorus (P) removal from aqueous solution. The results show that the prepared lfuorine-containing calcium silicate has excellent performance for adsorbing phosphate, the adsorption process appears to follow pseudo-second-order reaction kinetics and the process is mainly controlled by chemisorption. The product resulted from P adsorption is mainly composed of hydroxyapatite (HAP) and lfuorapatite (FAP), which are further used as adsorbents of heavy metal ion Cd2+ in aqueous solution and display excellent performance.

  10. Transition metal contacts to graphene

    Energy Technology Data Exchange (ETDEWEB)

    Politou, Maria, E-mail: Maria.Politou@imec.be; De Gendt, Stefan; Heyns, Marc [KU Leuven, 3001 Leuven (Belgium); imec, Kapeldreef 75, 3001 Leuven (Belgium); Asselberghs, Inge; Radu, Iuliana; Conard, Thierry; Richard, Olivier; Martens, Koen; Huyghebaert, Cedric; Tokei, Zsolt [imec, Kapeldreef 75, 3001 Leuven (Belgium); Lee, Chang Seung [SAIT, Samsung Electronics Co., Suwon 443-803 (Korea, Republic of); Sayan, Safak [imec, Kapeldreef 75, 3001 Leuven (Belgium); Intel Corporation, 2200 Mission College Blvd, Santa Clara, California 95054 (United States)

    2015-10-12

    Achieving low resistance contacts to graphene is a common concern for graphene device performance and hybrid graphene/metal interconnects. In this work, we have used the circular Transfer Length Method (cTLM) to electrically characterize Ag, Au, Ni, Ti, and Pd as contact metals to graphene. The consistency of the obtained results was verified with the characterization of up to 72 cTLM structures per metal. Within our study, the noble metals Au, Ag and Pd, which form a weaker bond with graphene, are shown to result in lower contact resistance (Rc) values compared to the more reactive Ni and Ti. X-ray Photo Electron Spectroscopy and Transmission Electron Microscopy characterization for the latter have shown the formation of Ti and Ni carbides. Graphene/Pd contacts show a distinct intermediate behavior. The weak carbide formation signature and the low Rc values measured agree with theoretical predictions of an intermediate state of weak chemisorption of Pd on graphene.

  11. Improved properties of the catalytic model system Ni/Ru(0001)

    DEFF Research Database (Denmark)

    Egeberg, Rasmus; Chorkendorff, Ib

    2001-01-01

    ) illustrating the unique properties of metal-on-metal systems. The effect of enhanced reactivity is primarily ascribed to electronic effects induced by a straining of the Ni overlayer. The enhanced reactivity towards CH4 is accompanied by new features in the thermal desorption spectra of CO. The reactivity of......The dissociative chemisorption of CH4 on Ni overlayers on Ru(0001) has been investigated. It is found that the initial sticking probability at T = 530 K is approximately a factor of 20-30 higher on a pseudomorphic overlayer of Ni than on Ni(111) and a factor of two higher than on Ru(0001...... the, system depends strongly on the annealing temperature. Molecular beam experiments at high translational energy are qualitatively different from thermal data showing a monotonic decrease of the CH4 sticking probability as Ni is added....

  12. 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.

  13. Hydrogen Storage in Iron/Carbon Nano powder Composite Materials: Effect of Varying Spiked Iron Content on Hydrogen Adsorption

    International Nuclear Information System (INIS)

    This study investigates the effects of varying the spiked iron content of iron/carbon nano powder (Fe/CNP) composite materials on hydrogen storage capacity. Among four such samples, a maximum hydrogen uptake of approximately 0.48 wt % was obtained with 14 wt % of spiked iron under 37 atm and 300 K. This higher hydrogen uptake capacity was believed to be closely related to the physisorption mechanism rather than chemisorption. In this case, the formation of maghemite catalyzed the attraction of hydrogen molecules and the CNP skeleton was the principal absorbent material for hydrogen storage. However, as the iron content exceeded 14 wt %, the formation of larger and poorly dispersed maghemite grains reduced the available surface areas of CNP for the storage of hydrogen molecules, leading to decreased uptake. Our study shows that hydrogen uptake capacities can be improved by appropriately adjusting the surface polarities of the CNP with well dispersed iron oxides crystals.

  14. Toward an Enhancement of the Photoactivity of Multiphotochromic Dimers Using Plasmon Resonance: A Theoretical Study.

    Science.gov (United States)

    Fihey, Arnaud; Le Guennic, Boris; Jacquemin, Denis

    2015-08-01

    Building dimers of organic photochromic compounds paves the way to multifunctional switches, but such architectures often undergo partial photoreactivity only. Combining photochromism of molecules and plasmon resonance of gold nanoparticles (NPs) is known to affect the photochromism of monomers, yet the impact on multimers remains unknown. Here we propose a theoretical study of dimers of dithienylethenes by the mean of a hybrid calculation scheme (discrete-interaction model/quantum mechanics). We aim to assess how the optical properties of multiphotochromes are tuned by the influence of the plasmon resonances. We show that, for a typical chemisorption orientation on the NP, the absorption bands responsible for the photochromism are significantly enhanced for both the doubly open and mixed closed-open isomers of the dyad, hinting that plasmon resonance could be used to boost the generally poor photoactivity of dithienylethene dyads. PMID:26267018

  15. Corrosion Inhibitive Evaluation of an Environmentally Friendly Water-Base Acrylic Terpolymer on Mild Steel in Hydrochloric Acid Media

    Science.gov (United States)

    Azghandi, Mojtaba Vakili; Davoodi, Ali; Farzi, Gholam Ali; Kosari, Ali

    2013-12-01

    The corrosion inhibitive performance of an environmentally friendly water-base acrylic terpolymer [methyl methacrylate/Butyl Acrylate/Acrylic acid (ATP)] on mild steel in 1 M HCl was investigated by alternating current and direct current electrochemical techniques and the quantum chemical method. An efficiency of more than 97 pct was obtained with 0.8 mmol/L ATP. The increase in inhibitor concentration and immersion time has a positive effect, while the temperature influence is negligible on the inhibitor efficiency. The present terpolymer obeys the Langmuir isotherm, and thermodynamic calculation reveals a chemisorption type on the surface. Density functional calculations showed that the lone pairs of electrons of oxygen in the structure of three monomers are suitable sites to adsorb onto the metal surface. Finally, in the presence of ATP, a decrease in surface roughness and corrosion attacks was demonstrated by atomic force microscopy and optical microscopy examinations, respectively.

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

    Science.gov (United States)

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

    2015-12-01

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

  17. Self-assembled mesoporous carbon films for platinum metal catalyst loading

    International Nuclear Information System (INIS)

    This work demonstrates the use of self-assembled carbon films in designing fuel cell electrode. Well-dispersed mesoporous carbon particles were prepared based on the spontaneous and strong chemisorption of polyoxometalate (POM) solution on carbon surface. Electrostatically self-assembled films of the POM stabilized carbon interlaced with cationic polyelectrolyte binding layer were useful for confining electrodeposition of platinum (Pt) catalyst. The structure and morphology of the resulting films were characterized by X-ray diffraction and scanning electron microscopy respectively. The electrocatalytic activities of Pt deposited on the self-assembled carbon films toward the degradation of small organic molecules are largely dependent on the quantity of Pt and carbon. This work represents a simply controlled test-bed for fundamental studies on loading metal catalysts on ordered mesoporous carbon films for catalysis.

  18. 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

    2015-02-11

    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. PMID:25414147

  19. Luminescence of photoactivated pristine and Cr-doped MgAl2O4 spinel

    Science.gov (United States)

    Artemyeva, E. S.; Barinov, D. S.; Atitar, F. M.; Murashkina, A. A.; Emeline, A. V.; Serpone, N.

    2015-04-01

    This Letter reports a comparative study of the luminescence from pristine and Cr-doped MgAl2O4 spinel induced by different excitation mechanisms: photoluminescence (PhL), thermoluminescence (ThL) and Photo-Induced Chemisorption Luminescence (the PhICL phenomenon) to understand the mechanism of PhICL emission. Cr-doping alters the major pathway of physical relaxation through a luminescence pathway: quenching of the luminescence associated with intrinsic defects and appearance of the luminescence from Cr3+-states. The similarity between ThL and PhICL spectra suggest the mechanism of the PhICL phenomenon is due to electron transfer from the surface to the emission centers of luminescence; an energy transfer pathway is not precluded.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sirwardane, Ranjani V.

    2005-06-21

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