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Sample records for bimetallic dispersed catalysts

  1. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan, Song; Kirby, S.; Schmidt, E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  2. Bimetallic Catalysts.

    Science.gov (United States)

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  3. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan Song; Schobert, H.H.; Parfitt, D.P. [and others

    1997-11-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

  4. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, July--September 1993

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, E.; Song, C.; Schobert, H.H.

    1994-01-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts can be superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. The primary objective of this research is to explore novel bimetallic dispersed catalysts from heterometallic molecular precursors, that can be used in low concentrations but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. This quarterly report describes the preparation of two precursors. The first is a heterometallic complex consisting of two transition metals, Mo and Ni, and sulfur in a single molecule synthesized. The second is a thiocubane type cluster consisting of iron and sulfur.

  5. Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh32Ru-SnX3 (X = Cl or Br

    Directory of Open Access Journals (Sweden)

    Ana Cláudia Bernardes Silva

    2003-06-01

    Full Text Available In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh32Ru-SnX3 (X = Cl or Br complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR (Temperature Programmed Reduction experiments carried out with these RuSn catalysts suggested a strong interaction between Ruthenium and Tin. Mössbauer measurements showed that these materials when exposed to air are immediately oxidized to form Sn (IV. It was shown that upon controlled reduction conditions with H2 it is possible to reduce selectively Sn to different oxidation states and different phases. The Sn oxidation state showed significant effect on the catalytic hydrogenation of 1,5-cyclooctadiene. The use of these single source precursors with a controlled decomposition/reduction procedure allows the preparation of unique catalysts with an intimate interaction between the components ruthenium and tin and the possibility of varying the Sn oxidation state around the Ru metal.

  6. Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh3)2Ru-SnX3 (X = Cl or Br)

    OpenAIRE

    Ana Cláudia Bernardes Silva; Ana Paula Guimarães de Sousa; José Domingos Ardisson; Helmuth Guido Luna Siebald; Edmilson Moura; Eduardo Nicolau dos Santos; Nelcy Della Santina Mohallem; Rochel Montero Lago

    2003-01-01

    In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh3)2Ru-SnX3 (X = Cl or Br) complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR...

  7. Theoretical predictions of platinum-rhodium bimetallic catalysts

    International Nuclear Information System (INIS)

    After a general introduction to supported bimetallic catalysts and automobile catalytic converters (supports, base metal promoters, noble metals, deterioration of 3-way catalysts, current/future technology), a paper is presented for surface segregation in bimetallic catalysts: The catalytic properties are influenced by the structure of the cluster surface. Two methods are described to treat this problem, from the demanding corrected effective medium (CEM) theory (a non-self-consistent density functional based method) and the simple method of surface modified pair potentials. Predictions are compared with experiment for the heat of formation in RhxPt1-x alloys and for surface segregation in Rh0.9Pt0.1(111). Results on shape, site composition, surface micromixing are shown for 201 atom clusters (dispersion of 0.6) and RhxPt1-x(111). The CEM calculated cohesive energy of Rh is slightly smaller than for Pt, but the surface energy of Rh is larger: the driving force for surface segregation is the relative surface energies, not the relative cohesive energies. One can predict surface energy differences by accounting for the variation of the bond energy with coordination. Recommendations for the development of improved automobile exhaust catalysts are given. The Monte Carlo bimetallic simulation program is described

  8. Fundamental investigations of supported monometallic and bimetallic catalysts by proton magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xi.

    1990-09-21

    Proton magnetic resonance spectroscopy, or nuclear magnetic resonance (NMR) of hydrogen, has been applied to investigate silica-supported Group VIII monometallic and Group VIII-Group IB bimetallic catalysts and alumina- and silica-supported platinum-rhenium bimetallic catalysts. Two adsorbed states of hydrogen, i.e., irreversible and reversible hydrogen, on the surfaces of monometallic Ru, Pt, and Cu particles and bimetallic Ru-Group Ib, Pt-Group Ib, and Pt-Re particles were observed directly via proton NMR. The same amounts of the irreversible hydrogen adsorbed on pure Ru catalysts were measured by both proton NMR and the volumetric technique. The electronic environments on surfaces of monometallic catalysts are sensitive to changes in metal dispersion, state of adsorbed hydrogen, and residual chlorine. Surface compositions for the Ru--Cu and Pt--Cu bimetallic catalysts were determined by NMR of adsorbed hydrogen. 297 refs., 96 figs., 19 tabs.

  9. Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

    Science.gov (United States)

    Marks, Tobin J.; Rodriguez, Brandon A.; Delferro, Massimiliano

    2012-08-07

    A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

  10. Platinum-Bismuth Bimetallic Catalysts: Synthesis, Characterization and Applications

    OpenAIRE

    Saucedo, Jose A, Jr; Xiao, Yang; Varma, Arvind

    2015-01-01

    Bimetallic catalysts have been explored and shown to exhibit unique characteristics which are not present in monometallic catalysts. Platinum is well known as an effective catalyst for oxidation and reduction reactions, and it can be made more effective when bismuth is introduced as a promotor. Thus, the effectiveness of the Pt-Bi catalyst was demonstrated in prior work. What is not clear, however, is the mechanism behind the catalyst function; why addition of bismuth to platinum decreases de...

  11. Direct decomposition of methane over SBA-15 supported Ni, Co and Fe based bimetallic catalysts

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Synthesis and characterization of Ni, Co and Fe based bimetallic catalysts supported over SBA-15. • Thermocatalytic decomposition of methane over the SBA-15 supported bimetallic catalysts. • Enhanced catalytic efficiency of the bimetallic catalysts for the production of COx free hydrogen and nanocarbon. • Production of value added open tip hollow multi-walled carbon nanotubes. • Crystalline characterization of carbon nanotubes by XRD, Raman and thermogravimetric analysis. - Abstract: Thermocatalytic decomposition of methane is an alternative route for the production of COx-free hydrogen and carbon nanomaterials. In this work, a set of novel Ni, Co and Fe based bimetallic catalysts supported over mesoporous SBA-15 was synthesized by a facile wet impregnation route, characterized for their structural, textural and reduction properties and were successfully used for the methane decomposition. The fine dispersion of metal oxide particles on the surface of SBA-15, without affecting its mesoporous texture was clearly shown in the low angle X-ray diffraction patterns and the transmission electron microscopy (TEM) images. The nitrogen sorption analysis showed the reduced specific surface area and pore volume of SBA-15, after metal loading due to the partial filling of hexagonal mesopores by metal species. The results of methane decomposition experiments indicated that all of the bimetallic catalysts were highly active and stable for the reaction at 700 °C even after 300 min of time on stream (TOS). However, a maximum hydrogen yield of ∼56% was observed for the NiCo/SBA-15 catalyst within 30 min of TOS. A high catalytic stability was shown by the CoFe/SBA-15 catalyst with 51% of hydrogen yield during the course of reaction. The catalytic stability of the bimetallic catalysts was attributed to the formation of bimetallic alloys. Moreover, the deposited carbons were found to be in the form of a new set of hollow multi

  12. Direct decomposition of methane over SBA-15 supported Ni, Co and Fe based bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pudukudy, Manoj, E-mail: manojpudukudy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia); Yaakob, Zahira, E-mail: zahirayaakob65@gmail.com [Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia); Akmal, Zubair Shamsul [Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia)

    2015-03-01

    Graphical abstract: - Highlights: • Synthesis and characterization of Ni, Co and Fe based bimetallic catalysts supported over SBA-15. • Thermocatalytic decomposition of methane over the SBA-15 supported bimetallic catalysts. • Enhanced catalytic efficiency of the bimetallic catalysts for the production of CO{sub x} free hydrogen and nanocarbon. • Production of value added open tip hollow multi-walled carbon nanotubes. • Crystalline characterization of carbon nanotubes by XRD, Raman and thermogravimetric analysis. - Abstract: Thermocatalytic decomposition of methane is an alternative route for the production of CO{sub x}-free hydrogen and carbon nanomaterials. In this work, a set of novel Ni, Co and Fe based bimetallic catalysts supported over mesoporous SBA-15 was synthesized by a facile wet impregnation route, characterized for their structural, textural and reduction properties and were successfully used for the methane decomposition. The fine dispersion of metal oxide particles on the surface of SBA-15, without affecting its mesoporous texture was clearly shown in the low angle X-ray diffraction patterns and the transmission electron microscopy (TEM) images. The nitrogen sorption analysis showed the reduced specific surface area and pore volume of SBA-15, after metal loading due to the partial filling of hexagonal mesopores by metal species. The results of methane decomposition experiments indicated that all of the bimetallic catalysts were highly active and stable for the reaction at 700 °C even after 300 min of time on stream (TOS). However, a maximum hydrogen yield of ∼56% was observed for the NiCo/SBA-15 catalyst within 30 min of TOS. A high catalytic stability was shown by the CoFe/SBA-15 catalyst with 51% of hydrogen yield during the course of reaction. The catalytic stability of the bimetallic catalysts was attributed to the formation of bimetallic alloys. Moreover, the deposited carbons were found to be in the form of a new set of hollow

  13. CO methanation over supported bimetallic Ni-Fe catalysts: From computational studies towards catalyst optimization

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Frey, Anne Mette; Larsen, Kasper Emil;

    2007-01-01

    DFT calculations combined with a computational screening method have previously shown that bimetallic Ni-Fe alloys should be more active than the traditional Ni-based catalyst for CO methanation. That was confirmed experimentally for a number of bimetallic Ni-Fe catalysts supported on MgAl2O4. He...

  14. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  15. Controlled Surface Segregation Leads to Efficient Coke-Resistant Nickel/Platinum Bimetallic Catalysts for the Dry Reforming of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lidong [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Zhou, Lu [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Ould-Chikh, Samy [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Anjum, Dalaver H. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Kanoun, Mohammed B. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Scaranto, Jessica [SABIC Corporate Research and Innovation Center, Thuwal (Saudi Arabia); Hedhili, Mohamed N. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Khalid, Syed [Brookhaven National Lab. (BNL), Upton, NY (United States); Laveille, Paco V. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); D' Souza, Lawrence [SABIC Corporate Research and Innovation Center, Thuwal (Saudi Arabia); Clo, Alain [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Basset, Jean-Marie [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)

    2015-02-03

    The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  16. Improvements in NOx reduction by carbon using bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Illan-Gomez, M.J.; Brandan, S.; Salinas-Martinez de Lecea, C.; Linares-Solano, A. [Universidad de Alicante, Alicante (Spain). Departamento de Quimica Inorganica

    2001-11-30

    A catalysis of the C-NOx reaction has been studied to optimize the composition of the catalysts in order to decrease the carbon consumption by oxygen. Both the metal content and the composition of the catalysts have been investigated. The activity of bimetallic (KNi, NiCo and NiCu) catalysts for NOx reduction by carbon has been studied using both isothermal reactions at 300{sup o}C and temperature programmed reaction up to 500{sup o}C. It has been found that the experimental variables (i.e. amount of catalysts and nature of the bimetallic catalysts) determine the selectivity against carbon combustion by oxygen. Thus, it has been observed that the amount of catalyst greatly affects the C-O{sub 2} reaction but only lightly the C-NOx reaction and, consequently, modifies the selectivity of the catalyst for NOx reduction. Among the bimetallic catalysts tested, NiCu catalyst presents the best performance, at a temperature as low as 250{sup o}C, a high de-NOx activity and a high NOx selectivity due to a low carbon burn-off, with the additional advantage of the absence of N{sub 2}O and CO in the reaction products. Thus, the results obtained in this study show, in comparison with our previous results, that better selectivities are achieved. 20 refs., 3 figs., 2 tabs.

  17. High pressure CO hydrogenation over bimetallic Pt-Co catalysts

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt; Medford, Andrew James; Studt, Felix;

    2014-01-01

    The potential of bimetallic Pt-Co catalysts for production of higher alcohols in high pressure CO hydrogenation has been assessed. Two catalysts (Pt3Co/SiO2 and PtCo/SiO2) were tested, and the existing literature on CO hydrogenation over Pt-Co catalysts was reviewed. It is found that the catalysts...... produce mainly methanol in the Pt-rich composition range andmainly hydrocarbons (and to a modest extent higher alcohols) in the Co-rich composition range. The transition between the two types of behavior occurs in a narrow composition range around a molar Pt:Co ratio of 1:1....

  18. Bimetallic catalysts for upgrading of biomass to fuels and chemicals.

    Science.gov (United States)

    Alonso, David Martin; Wettstein, Stephanie G; Dumesic, James A

    2012-12-21

    Research interest in biomass conversion to fuels and chemicals has increased significantly in the last decade as the necessity for a renewable source of carbon has become more evident. Accordingly, many different reactions and processes to convert biomass into high-value products and fuels have been proposed in the literature. Special attention has been given to the conversion of lignocellulosic biomass, which does not compete with food sources and is widely available as a low cost feedstock. In this review, we start with a brief introduction on lignocellulose and the different chemical structures of its components: cellulose, hemicellulose, and lignin. These three components allow for the production of different chemicals after fractionation. After a brief overview of the main reactions involved in biomass conversion, we focus on those where bimetallic catalysts are playing an important role. Although the reactions are similar for cellulose and hemicellulose, which contain C(6) and C(5) sugars, respectively, different products are obtained, and therefore, they have been reviewed separately. The third major fraction of lignocellulose that we address is lignin, which has significant challenges to overcome, as its structure makes catalytic processing more challenging. Bimetallic catalysts offer the possibility of enabling lignocellulosic processing to become a larger part of the biofuels and renewable chemical industry. This review summarizes recent results published in the literature for biomass upgrading reactions using bimetallic catalysts. PMID:22872312

  19. Bimetallic Catalysts Containing Gold and Palladium for Environmentally Important Reactions

    Directory of Open Access Journals (Sweden)

    Ahmad Alshammari

    2016-07-01

    Full Text Available Supported bimetallic nanoparticles (SBN are extensively used as efficient redox catalysts. This kind of catalysis particularly using SBN has attracted immense research interest compared to their parent metals due to their unique physico-chemical properties. The primary objective of this contribution is to provide comprehensive overview about SBN and their application as promising catalysts. The present review contains four sections in total. Section 1 starts with a general introduction, recent progress, and brief summary of the application of SBN as promising catalysts for different applications. Section 2 reviews the preparation and characterization methods of SBN for a wide range of catalytic reactions. Section 3 concentrates on our own results related to the application of SBN in heterogeneous catalysis. In this section, the oxidation of cyclohexane to adipic acid (an eco-friendly and novel approach will be discussed. In addition, the application of bimetallic Pd catalysts for vapor phase toluene acetoxylation in a fixed bed reactor will also be highlighted. Acetoxylation of toluene to benzyl acetate is another green route to synthesize benzyl acetate in one step. Finally, Section 4 describes the summary of the main points and also presents an outlook on the application of SBN as promising catalysts for the production of valuable products.

  20. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Chao [The Key Laboratory of Fuel Cell Technology of Guangdong Province and The Key Laboratory for New Energy of Guangdong Universities, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou (China); Yang, Xu [Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China); Yang, Hui; Huang, Peiyan; Song, Huiyu [The Key Laboratory of Fuel Cell Technology of Guangdong Province and The Key Laboratory for New Energy of Guangdong Universities, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou (China); Liao, Shijun, E-mail: chsjliao@scut.edu.cn [The Key Laboratory of Fuel Cell Technology of Guangdong Province and The Key Laboratory for New Energy of Guangdong Universities, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou (China)

    2014-10-01

    Graphical abstract: The addition of Ru could significantly improve the performance of the mesoporous silica nanoparticles supported PdRu/MSN catalyst, which showed over 5 times higher mass activity than the mono-Pd/MSN towards the liquid-phase hydrogenation of phenol. The improved dispersion and the electronic interaction contributed to the enhanced catalytic activity for the catalyst towards phenol hydrogenation. - Highlights: • PdRu bimetal catalyst supported on mesoporous silica nanoparticles was prepared. • The average sizeof PdRu alloy is smaller than that of mono-Pd. • The addition of Ru to Pd modulates the electronic properties between Pd and Ru. • PdRu/MSN catalyst shows superior activity on phenol hydrogenation than Pd/MSN. • PdRu/MSN catalyst shows good selectivity for cyclohexanol to some extent. - Abstract: A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation–hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity.

  1. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    International Nuclear Information System (INIS)

    Graphical abstract: The addition of Ru could significantly improve the performance of the mesoporous silica nanoparticles supported PdRu/MSN catalyst, which showed over 5 times higher mass activity than the mono-Pd/MSN towards the liquid-phase hydrogenation of phenol. The improved dispersion and the electronic interaction contributed to the enhanced catalytic activity for the catalyst towards phenol hydrogenation. - Highlights: • PdRu bimetal catalyst supported on mesoporous silica nanoparticles was prepared. • The average sizeof PdRu alloy is smaller than that of mono-Pd. • The addition of Ru to Pd modulates the electronic properties between Pd and Ru. • PdRu/MSN catalyst shows superior activity on phenol hydrogenation than Pd/MSN. • PdRu/MSN catalyst shows good selectivity for cyclohexanol to some extent. - Abstract: A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation–hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity

  2. 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)

  3. thesis of high-purity carbon nanotubes over alumina and silica supported bimetallic catalysts

    Directory of Open Access Journals (Sweden)

    Sanja Ratković

    2009-10-01

    Full Text Available Carbon nanotubes (CNTs were synthesized by a catalytic chemical vapor deposition method (CCVD of ethylene over alumina and silica supported bimetallic catalysts based on Fe, Co and Ni. The catalysts were prepared by a precipitation method, calcined at 600 °C and in situ reduced in hydrogen flow at 700 °C. The CNTs growth was carried out by a flow the mixture of C2H4 and nitrogen over the catalyst powder in a horizontal oven. The structure and morphology of as-synthesized CNTs were characterized using SEM. The as-synthesized nanotubes were purified by acid and basic treatments in order to remove impurities such as amorphous carbon, graphite nanoparticles and metal catalysts. XRD and DTA/TG analyses showed that the amounts of by-products in the purified CNTs samples were reduced significantly. According to the observed results, ethylene is an active carbon source for growing high-density CNTs with high yield but more on alumina-supported catalysts than on their silica- supported counterparts. The last might be explained by SMSI formed in the case of alumina-supported catalysts, resulting in higher active phase dispersion.

  4. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.

    2010-11-24

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  5. Performance enhancement of bimetallic Co-Ru/CNTs nano catalysts using microemulsion technique

    Institute of Scientific and Technical Information of China (English)

    Ahmad; Tavasoli; Somayeh; Taghavi

    2013-01-01

    Bimetallic cobalt-ruthenium nano catalysts supported on carbon nanotubes(CNTs)are prepared using microemultion technique with water-to-surfactant ratios of 0.5—1.5.The nano catalysts were extensively characterized by different methods and their activity and selectivity in Fischer-Tropsch synthesis(FTS)have been assessed in a fixed-bed microreactor.The physicochemical properties and performance of the nanocatalysts were compared with the catalyst prepared by impregnation method.Very narrow particle size distribution has been produced by the microemulsion technique at relatively high loadings of active metals(15 wt%Co and 1 wt%Ru).According to TEM images,small Co particles(2—7 nm)were mostly confined inside the CNTs.Comparing with the catalyst prepared by impregnation,the use of microemulsion technique with water to surfactant ratio of 0.5 decreased the average cobalt oxide particle size to 4.8 nm,the dispersion was almost doubled and the reduction increased by 28%.Activity and selectivity were found to be dependent on the catalyst preparation method and water-to-surfactant ratio(as well as cobalt particle sizes).CO conversion increased from 59.1%to 75.1%and the FTS rate increased from 0.291 to0.372 gHC/(gcath).C5+liquid hydrocarbons selectivity decreased from 92.4%to 87.6%.

  6. Enhancement of bimetallic Fe-Mn/CNTs nano catalyst activity and product selectivity using microemulsion technique

    Institute of Scientific and Technical Information of China (English)

    Zahra; Zolfaghari; Ahmad; Tavasoli; Saber; Tabyar; Ali; Nakhaei; Pour

    2014-01-01

    Bimetallic Fe-Mn nano catalysts supported on carbon nanotubes(CNTs) were prepared using microemulsion technique with water-to-surfactant ratios of 0.4-1.6. The nano catalysts were extensively characterized by different methods and their activity and selectivity in Fischer-Tropsch synthesis(FTS) have been assessed in a fixed-bed microreactor. The physicochemical properties and performance of the nanocatalysts were compared with the catalyst prepared by impregnation method. Very narrow particle size distribution has been produced by the microemulsion technique at relatively high loading of active metal. TEM images showed that small metal nano particles in the range of 3–7 nm were not only confined inside the CNTs but also located on the outer surface of the CNTs. Using microemulsion technique with water to surfactant ratio of0.4 decreased the average iron particle sizes to 5.1 nm. The reduction percentage and dispersion percentage were almost doubled. Activity and selectivity were found to be dependent on the catalyst preparation method and average iron particle size. CO conversion and FTS rate increased from 49.1% to 71.0% and 0.144 to 0.289 gHC/(gcat h), respectively. While the WGS rate decreased from 0.097 to 0.056 gCO2/(gcat h). C5+liquid hydrocarbons selectivity decreased slightly and olefins selectivity almost doubled.

  7. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    KAUST Repository

    Shaikh Ali, Anaam

    2015-07-06

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  8. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  9. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  10. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

    KAUST Repository

    Biausque, Gregory

    2015-04-28

    Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

  11. Synergistic Effects in Bimetallic Palladium-Copper Catalysts Improve Selectivity in Oxygenate Coupling Reactions.

    Science.gov (United States)

    Goulas, Konstantinos A; Sreekumar, Sanil; Song, Yuying; Kharidehal, Purnima; Gunbas, Gorkem; Dietrich, Paul J; Johnson, Gregory R; Wang, Y C; Grippo, Adam M; Grabow, Lars C; Gokhale, Amit A; Toste, F Dean

    2016-06-01

    Condensation reactions such as Guerbet and aldol are important since they allow for C-C bond formation and give higher molecular weight oxygenates. An initial study identified Pd-supported on hydrotalcite as an active catalyst for the transformation, although this catalyst showed extensive undesirable decarbonylation. A catalyst containing Pd and Cu in a 3:1 ratio dramatically decreased decarbonylation, while preserving the high catalytic rates seen with Pd-based catalysts. A combination of XRD, EXAFS, TEM, and CO chemisorption and TPD revealed the formation of CuPd bimetallic nanoparticles with a Cu-enriched surface. Finally, density functional theory studies suggest that the surface segregation of Cu atoms in the bimetallic alloy catalyst produces Cu sites with increased reactivity, while the Pd sites responsible for unselective decarbonylation pathways are selectively poisoned by CO. PMID:27195582

  12. Levulinic acid hydrogenolysis on Al2O3-based Ni-Cu bimetallic catalysts

    Institute of Scientific and Technical Information of China (English)

    Iker Obregón; Eriz Corro; Urko Izquierdo; Jesus Requies; Pedro L. Arias

    2014-01-01

    Inexpensive γ-alumina-based nickel-copper bimetallic catalysts were studied for the hydrogenolysis of levulinic acid, a key platform molecule for biomass conversion to biofuels and other valued chemicals, into γ-valerolactone as a first step towards the production of 2-methyltetrahydrofurane. The activities of both monometallic and bimetallic catalysts were tested. Their textural and chemical characteristics were determined by nitrogen physisorption, elemental analysis, temperature-pro-grammed ammonia desorption, and temperature-programmed reduction. The monometallic nickel catalyst showed high activity but the highest by-product production and significant amounts of carbon deposited on the catalyst surface. The copper monometallic catalyst showed the lowest activity but the lowest carbon deposition. The incorporation of the two metals generated a bimetal-lic catalyst that displayed a similar activity to that of the Ni monometallic catalyst and significantly low by-product and carbon contents, indicating the occurrence of important synergetic effects. The influence of the preparation method was also examined by studying impregnated- and sol-gel-derived bimetallic catalysts. A strong dependency on the preparation procedure and calcina-tion temperature was observed. The highest activity per metal atom was achieved using the sol-gel-derived catalyst that was calcined at 450 °C. High reaction rates were achieved;the total levulinic acid conversion was obtained in less than 2 h of reaction time, yielding up to 96%γ-valerolactone, at operating temperature and pressure of 250 °C and 6.5 MPa hydrogen, respec-tively.

  13. Synergy between metals in bimetallic zeolite supported catalyst for NO-promoted N2O decomposition

    NARCIS (Netherlands)

    Pieterse, J.A.Z.; Mul, G.; Melian-Cabrera, I.; van den Brink, R.W.

    2005-01-01

    The detrimental effect of NO on N2O decomposition over zeolite supported noble metal catalysts can be (partly) eliminated by combining noble metal with iron or cobalt. In the presence of NO, the total conversion of N2O over these bimetallic-zeolites exceeds the sum of conversions over the monometall

  14. Comparison of Bimetallic and Trimetallic Catalyst in Reductive Dechlorination; Influence of Copper Addition

    Czech Academy of Sciences Publication Activity Database

    Kaštánek, František; Kaštánek, Petr; Maléterová, Ywetta; Kallistová, A.; Šolcová, Olga

    2015-01-01

    Roč. 2, č. 7 (2015), s. 1954-1958. E-ISSN 3159-0040 R&D Projects: GA TA ČR TA04020700 Institutional support: RVO:67985858 ; RVO:67985831 Keywords : PCB * reductive dechlorination * bimetallic and trimetallic catalysts Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.jmest.org/wp-content/uploads/JMESTN42350950.pdf

  15. Nanosegregated bimetallic oxide anode catalyst for proton exchange membrane electrolyzer

    Energy Technology Data Exchange (ETDEWEB)

    Danilovic, Nemanja; Kang, Yijin; Markovic, Nenad; Stamenkovic, Vojislav; Myers, Deborah J.; Subbaraman, Ram

    2016-08-23

    A surface segregated bimetallic composition of the formula Ru.sub.1-xIr.sub.x wherein 0.1.ltoreq.x.ltoreq.0.75, wherein a surface of the material has an Ir concentration that is greater than an Ir concentration of the material as a whole is provided. The surface segregated material may be produced by a method including heating a bimetallic composition of the formula Ru.sub.1-xIr.sub.x, wherein 0.1.ltoreq.x.ltoreq.0.75, at a first temperature in a reducing environment, and heating the composition at a second temperature in an oxidizing environment. The surface segregated material may be utilized in electrochemical devices.

  16. SULFUR-RESISTANT BIMETALLIC NOBLE METAL CATALYSTS FOR AROMATIC HYDROGENATION OF DIESEL FUEL

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Y zeolite supporting noble metal catalysts, as the important industrial catalysts for aromatics hydrogenation, have received increasing attention in recent years. Pd-M/Y bimetallic catalysts, where M is non-noble metal element, were prepared to investigate the effects of the addition of a second metal. Pd-M/Y catalysts were evaluated under the following conditions: H2 pressure 4.2 MPa, MHSV 4.0 h-1, sulfur content in feed 3000 μg/g. The microreactor results indicated that the second metal remarkably affects the hydrogenation activity of Pd/Y catalysts. Among them, Cr and W improve the sulfur resistance of Pd/Y, but La, Mn, Mo and Ag make the sulfur resistance worse and the second metals have no evident influence on product selectivity and acidic properties of the catalysts.

  17. Selective hydrogenation of citral over Au-based bimetallic catalysts in supercritical carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Selective hydrogenation of citral was investigated over Au-based bimetallic catalysts in the environmentally benign supercritical carbon dioxide (scCO2) medium.The catalytic performances were different in citral hydrogenation when Pd or Ru was mixed (physically and chemically) with Au.Compared with the corresponding monometallic catalyst,the total conversion and the selectivity to citronellal (CAL) were significantly enhanced over TiO2 supported Pd and Au bimetallic catalysts (physically and chemically mixed);however,the conversion and selectivity did not change when Ru was physically mixed with Au catalyst compared to the monometallic Ru/TiO2,and the chemically mixed Ru-Au/TiO2 catalyst did not show any activity.The effect of CO2 pressure on the conversion of citral and product selectivity was significantly different over the Au/TiO2,Pd-Au/TiO2,and Pd/TiO2 catalysts.It was assumed to be ascribed to the difference in the interactions between Au,Pd nanoparticles and CO2 under different CO2 pressures.

  18. Bimetallic Palladium Catalysts for Methane Combustion in Gas Turbines

    OpenAIRE

    Persson, Katarina

    2006-01-01

    Catalytic combustion is a promising combustion technology for gas turbines, which results in ultra low emission levels of nitrogen oxides (NOx), carbon monoxide (CO) and unburned hydrocarbons (UHC). Due to the low temperature achieved in catalytic combustion almost no thermal NOx is formed. This thesis is concentrated on the first stage in a catalytic combustion chamber, i.e. the ignition catalyst. The catalyst used for this application is often a supported palladium based catalyst due to its...

  19. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    Science.gov (United States)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  20. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  1. Controllable synthesis of carbon nanotubes by changing the Mo content in bimetallic Fe-Mo/MgO catalyst

    International Nuclear Information System (INIS)

    Research highlights: → Increasing the Mo content in the Fe-Mo/MgO catalysts resulted in an increase in wall number, diameter and growth yield of carbon nanotubes. → The Fe interacts with MgO to form complex (MgO)x(FeO)1-x (0 4 and relative large metal Mo particles can be generated after reduction. → The avalanche-like reduction of MgMoO4 makes the catalyst particles to be small thus enhances the utilize efficiency of Fe nanoparticles. - Abstract: A series of Fe-Mo/MgO catalysts with different Mo content were prepared by combustion method and used as catalysts for carbon nanotube (CNT) growth. Transmission electron microscopy studies of the nanotubes show that the number of the CNT walls and the CNT diameters increase with the increasing of Mo content in the bimetallic catalyst. The growth yield determined by thermogravimetric analysis also follows the trend: the higher the Mo content, the higher the yield of the CNTs. However, the increase of Mo content leads to the lower degree of graphitization of CNTs. A comparative study on the morphology and catalytic functions of Fe/MgO, Mo/MgO and Fe-Mo/MgO catalysts was carried out by scanning electron microscopy and X-ray diffraction. It is found that the Fe interacts with MgO to form complexes and is then dispersed into the MgO support uniformly, resulting in very small Fe nanoparticles after reduction. The Mo interacts with MgO to form stoichiometry compound MgMoO4 and relative large metal Mo particles can be generated after reduction. High yield CNTs with small diameter can be generated from Fe-Mo/MgO because the avalanche-like reduction of MgMoO4 makes the catalyst particles to be small thus enhances the utilize efficiency of Fe nanoparticles.

  2. Effects of bimetallic catalysts on synthesis of nitrogen-doped carbon nanotubes as nanoscale energetic materials

    Institute of Scientific and Technical Information of China (English)

    Hao Liu; Yong Zhang; Ruying Li; Xueliang Sun; Hakima Abou-Rachid

    2011-01-01

    Well aligned nitrogen-doped carbon nanotubes (CNx-NTs),as energetic materials,are synthesized on a silicon substrate by aerosol-assisted chemical vapor deposition.Tungsten (W) and molybdenum (Mo) metals are respectively introduced to combine with iron (Fe) to act as a bimetallic co-catalyst layer.Correlations between the composition and shape of the co-catalyst and morphology,size,growth rate and nitrogen doping amount of the synthesized CNx-NTs are investigated by secondary and backscattered electron imaging in a field emission scanning electron microscope (FESEM) and X-ray photoelectron spectrometer (XPS).Compared to pure iron catalyst.W-Fe co-catalyst can result in lower growth rate,larger diameter and wider size distribution of the CNx-NTs; while incorporation of molybdenum into the iron catalyst layer can reduce the diameter and size distribution of the nanotubes.Compared to the sole iron catalyst,Fe-W catalyst impedes nitrogen doping while Fe-Mo catalyst promotes the incorporation of nitrogen into the nanotubes.The present work indicates that CNx-NTs with modulated size,growth rate and nitrogen doping concentration are expected to be synthesized by tuning the size and composition of co-catalysts,which may find great potential in producing CNx-NTs with controlled structure and properties.

  3. Understanding and controlling nanoporosity formation for improving the stability of bimetallic fuel cell catalysts.

    Science.gov (United States)

    Gan, Lin; Heggen, Marc; O'Malley, Rachel; Theobald, Brian; Strasser, Peter

    2013-03-13

    Nanoporosity is a frequently reported phenomenon in bimetallic particle ensembles used as electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. It is generally considered a favorable characteristic, because it increases the catalytically active surface area. However, the effect of nanoporosity on the intrinsic activity and stability of a nanoparticle electrocatalyst has remained unclear. Here, we present a facile atmosphere-controlled acid leaching technique to control the formation of nanoporosity in Pt-Ni bimetallic nanoparticles. By statistical analysis of particle size, composition, nanoporosity, and atomic-scale core-shell fine structures before and after electrochemical stability test, we uncover that nanoporosity formation in particles larger than ca. 10 nm is intrinsically tied to a drastic dissolution of Ni and, as a result of this, a rapid drop in intrinsic catalytic activity during ORR testing, translating into severe catalyst performance degradation. In contrast, O2-free acid leaching enabled the suppression of nanoporosity resulting in more solid core-shell particle architectures with thin Pt-enriched shells; surprisingly, such particles maintained high intrinsic activity and improved catalytic durability under otherwise identical ORR tests. On the basis of these findings, we suggest that catalytic stability could further improve by controlling the particle size below ca. 10 nm to avoid nanoporosity. Our findings provide an explanation for the degradation of bimetallic particle ensembles and show an easy to implement pathway toward more durable fuel cell cathode catalysts. PMID:23360425

  4. Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

    Energy Technology Data Exchange (ETDEWEB)

    B Cheney; J Lauterbach; J Chen

    2011-12-31

    Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structure (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.

  5. Strategies for designing supported gold-palladium bimetallic catalysts for the direct synthesis of hydrogen peroxide.

    Science.gov (United States)

    Edwards, Jennifer K; Freakley, Simon J; Carley, Albert F; Kiely, Christopher J; Hutchings, Graham J

    2014-03-18

    Hydrogen peroxide is a widely used chemical but is not very efficient to make in smaller than industrial scale. It is an important commodity chemical used for bleaching, disinfection, and chemical manufacture. At present, manufacturers use an indirect process in which anthraquinones are sequentially hydrogenated and oxidized in a manner that hydrogen and oxygen are never mixed. However, this process is only economic at a very large scale producing a concentrated product. For many years, the identification of a direct process has been a research goal because it could operate at the point of need, producing hydrogen peroxide at the required concentration for its applications. Research on this topic has been ongoing for about 100 years. Until the last 10 years, catalyst design was solely directed at using supported palladium nanoparticles. These catalysts require the use of bromide and acid to arrest peroxide decomposition, since palladium is a very active catalyst for hydrogen peroxide hydrogenation. Recently, chemists have shown that supported gold nanoparticles are active when gold is alloyed with palladium because this leads to a significant synergistic enhancement in activity and importantly selectivity. Crucially, bimetallic gold-based catalysts do not require the addition of bromide and acids, but with carbon dioxide as a diluent its solubility in the reaction media acts as an in situ acid promoter, which represents a greener approach for peroxide synthesis. The gold catalysts can operate under intrinsically safe conditions using dilute hydrogen and oxygen, yet these catalysts are so active that they can generate peroxide at commercially significant rates. The major problem associated with the direct synthesis of hydrogen peroxide concerns the selectivity of hydrogen usage, since in the indirect process this factor has been finely tuned over decades of operation. In this Account, we discuss how the gold-palladium bimetallic catalysts have active sites for the

  6. Using supported Au nanoparticles as starting material for preparing uniform Au/Pd bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Villa, Alberto [Universita di Milano, Italy; Prati, Laura [Universita di Milano, Italy; Su, Dangshen [Fritz Haber Institute of the Max Planck Society, Berlin, Germany; Wang, Di [Fritz Haber Institute of the Max Planck Society, Berlin, Germany; Veith, Gabriel M [ORNL

    2010-01-01

    One of the best methods for producing bulk homogeneous (composition) supported bimetallic AuPd clusters involves the immobilization of a protected Au seed followed by the addition of Pd. This paper investigates the importance of this gold seed in controlling the resulting bimetallic AuPd clusters structures, sizes and catalytic activities by investigating three different gold seeds. Uniform Au-Pd alloy were obtained when a steric/electrostatic protecting group, poly(vinyl alcohol) (PVA), was used to form the gold clusters on activated carbon (AC). In contrast Au/AC precursors prepared using Au nanoparticles with only electrostatic stabilization (tetrakis(hydroxypropyl)phosphonium chloride (THPC)), or no stabilization (magnetron sputtering) produced inhomogeneous alloys and segregation of the gold and palladium. The uniform alloyed catalyst (Pd{at}Au{sub PVA}/AC) is the most active and selective catalyst, while the inhomogenous catalysts are less active and selective. Further study of the PVA protected Au clusters revealed that the amount of PVA used is also critical for the preparation of uniform alloyed catalyst, their stability, and their catalytic activity.

  7. Ethanol oxidation on carbon supported platinum-rhodium bimetallic catalysts

    International Nuclear Information System (INIS)

    Platinum is the most investigated catalyst for the electrochemical oxidation of small organic molecules. This metal presents high overpotentials for the oxidation of organic compounds and the poisoning of active sites by strongly adsorbed intermediates, mainly CO, which decrease the efficiency of a direct alcohol fuel cell (DAFC). Ethanol is an ideal fuel for these DAFC systems due to its high energy density, but one of the problems with the electro-oxidation of this fuel is the low yield for the total oxidation to CO2. The purpose of the work reported here was to study the influence of the composition of Pt-Rh/C catalysts on the CO2 yields. In addition, using the differential electrochemical mass spectrometry (DEMS) technique, it is shown that Pt-Rh/C catalysts enhance the total ethanol oxidation with respect to pure Pt/C by driving the reaction via the CO2 route. The faradaic current efficiency for the oxidation of ethanol to CO2 increased from 0.08 on pure Pt/C to 0.5 on the Pt47Rh53/C catalyst at 0.7 V vs. RHE. It was concluded that electronic effects play a key role in the mechanism of ethanol oxidation on Pt-Rh/C electrodes

  8. Final technical report. Bimetallic complexes as methanol oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    McElwee-White, Lisa

    2002-01-21

    Our work on the electrocatalyzed oxidation of methanol was initially motivated by the interest in methanol as an anodic reactant in fuel cells. The literature on electrochemical oxidation of alcohols can be roughly grouped into two sets: fuel cell studies and inorganic chemistry studies. Work on fuel cells primarily focuses on surface-catalyzed oxidation at bulk metal anodes, usually Pt or Pt/Ru alloys. In the surface science/electrochemistry approach to these studies, single molecule catalysts are generally not considered. In contrast, the inorganic community investigates the electrooxidation of alcohols in homogeneous systems. Ruthenium complexes have been the most common catalysts in these studies. The alcohol substrates are typically either secondary alcohols (e.g., isopropanol) such that the reaction stops after 2 e{sup -} oxidation to the aldehyde and 4 e{sup -} oxidation to the carboxylic acid can be observed. Methanol, which can also undergo 6 e{sup -} oxidation to CO{sub 2}, rarely appears in the homogeneous catalysis studies. Surface studies have shown that two types of metal centers with different functions result in more effective catalysts than a single metal; however, application of this concept to homogeneous systems has not been demonstrated. The major thrust of the work is to apply this insight from the surface studies to homogeneous catalysis. Even though homogeneous systems would not be appropriate models for active sites on Pt/Ru anodes, it is possible that heterobimetallic catalysts could also utilize two metal centers for different roles. Starting from that perspective, this work involves the preparation and investigation of heterobinuclear catalysts for the electrochemical oxidation of methanol.

  9. Catalytic performance of dealuminated H-Y zeolite supported bimetallic nano catalysts in Hydroizomerization of n-hexane and n-heptane

    International Nuclear Information System (INIS)

    A series of dealuminated Y-zeolites impregnated by 0.5 wt % Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt %) were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydro conversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 degree C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption-desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2-4 nm and 7-8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5 Pt-0.3 Cr)/D18 H-Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5 Pt-0.6 Ni)/D18 H-Y catalyst can be designed as most suitable as a cracking catalyst

  10. CuAu–ZnO–graphene nanocomposite: A novel graphene-based bimetallic alloy-semiconductor catalyst with its enhanced photocatalytic degradation performance

    International Nuclear Information System (INIS)

    Graphical abstract: In this work, we have successfully synthesized a novel graphene-based bimetallic alloy-semiconductor catalyst: CuAu–ZnO–Gr nanocomposite, and which behaved an enhanced photocatalytic activity. - Highlights: • A bimetallic alloy-based catalyst: CuAu–ZnO–Gr is synthesized. • CuAu–ZnO–Gr behaves an enhanced photocatalytic activity. • The detailed explanation of photocatalytic mechanism of CuAu–ZnO–Gr. - Abstract: The bimetallic alloy CuAu nanoparticles (NPs) can produce more photogenerated electrons when compared with single metal Au NPs. Moreover, graphene (Gr) sheets can help the charge separation and slow down the recombination of the electron hole pairs of ZnO. Hence, a novel graphene-based bimetallic alloy-semiconductor catalyst: CuAu–ZnO–Gr nanocomposite is synthesized. Due to the synergistic effect among CuAu NPs, ZnO nanopyramids, and Gr sheets, CuAu–ZnO–Gr behaves an enhanced photocatalytic activity for the photocatalytic degradation of synthetic colorants methyl orange (MO), methylene blue (MB), indigotin (IN), sunset yellow (SY), and tartrazine (TT) under the simulated sunlight irradiation. Furthermore, the apparent rate constants (kapp) of MO, MB, IN, SY, and TT degradation are estimated respectively. In addition, the as-prepared CuAu–ZnO–Gr nanocomposite is characterized by X-ray diffraction, UV–vis spectrum, transmission electron microscopy, energy dispersive X-ray analysis (EDX), and EDX mapping. As a result of the facile synthesis route and the enhanced photocatalytic activity, this new material CuAu–ZnO–Gr can be a promising photocatalyst for the degradation of dyes

  11. CuAu–ZnO–graphene nanocomposite: A novel graphene-based bimetallic alloy-semiconductor catalyst with its enhanced photocatalytic degradation performance

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Hong [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Ye, Xiaoliang [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Duan, Kaiyue; Xue, Muyin; Du, Yongling; Ye, Weichun [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Wang, Chunming, E-mail: wangcm@lzu.edu.cn [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2015-07-05

    Graphical abstract: In this work, we have successfully synthesized a novel graphene-based bimetallic alloy-semiconductor catalyst: CuAu–ZnO–Gr nanocomposite, and which behaved an enhanced photocatalytic activity. - Highlights: • A bimetallic alloy-based catalyst: CuAu–ZnO–Gr is synthesized. • CuAu–ZnO–Gr behaves an enhanced photocatalytic activity. • The detailed explanation of photocatalytic mechanism of CuAu–ZnO–Gr. - Abstract: The bimetallic alloy CuAu nanoparticles (NPs) can produce more photogenerated electrons when compared with single metal Au NPs. Moreover, graphene (Gr) sheets can help the charge separation and slow down the recombination of the electron hole pairs of ZnO. Hence, a novel graphene-based bimetallic alloy-semiconductor catalyst: CuAu–ZnO–Gr nanocomposite is synthesized. Due to the synergistic effect among CuAu NPs, ZnO nanopyramids, and Gr sheets, CuAu–ZnO–Gr behaves an enhanced photocatalytic activity for the photocatalytic degradation of synthetic colorants methyl orange (MO), methylene blue (MB), indigotin (IN), sunset yellow (SY), and tartrazine (TT) under the simulated sunlight irradiation. Furthermore, the apparent rate constants (k{sub app}) of MO, MB, IN, SY, and TT degradation are estimated respectively. In addition, the as-prepared CuAu–ZnO–Gr nanocomposite is characterized by X-ray diffraction, UV–vis spectrum, transmission electron microscopy, energy dispersive X-ray analysis (EDX), and EDX mapping. As a result of the facile synthesis route and the enhanced photocatalytic activity, this new material CuAu–ZnO–Gr can be a promising photocatalyst for the degradation of dyes.

  12. Synthesis and Characterization of Cluster-Derived Supported Bimetallic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Adams, Richard D; Amiridis, Michael D

    2008-10-10

    New procedures have been developed for synthesizing di- and tri-metallic cluster complexes. The chemical properties of the new complexes have been investigated, particularly toward the activation of molecular hydrogen. These complexes were then converted into bi- and tri-metallic nanoparticles on silica and alumina supports. These nanoparticles were characterized by electron microscopy and were then tested for their ability to produce catalytic hydrogenation of unsaturated hydrocarbons and for the preferential oxidation of CO in the presence of hydrogen. The bi- and tri-metallic nanoparticles exhibited far superior activity and selectivity as hydrogenation catalysts when compared to the individual metallic components. It was found that the addition of tin greatly improved the selectivity of the catalysts for the hydrogenation of polyolefins. The addition of iron improves the catalysts for the selective oxidation of CO by platinum in the presence of hydrogen. The observations should lead to the development of lower cost routes to molecules that can be used to produce polymers and plastics for use by the general public and for procedures to purify hydrogen for use as an alternative energy in the hydrogen economy of the future.

  13. Synergetic effects leading to coke-resistant NiCo bimetallic catalysts for dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-01-08

    A new dry reforming of methane catalyst comprised of NiCo bimetallic nanoparticles and a Mgx(Al)O support that exhibits high coke resistance and long-term on-stream stability is reported. The structural characterization by XRD, TEM, temperature-programmed reduction, and BET analysis demonstrates that the excellent performance of this catalyst is ascribed to the synergy of various parameters, including metal-nanoparticle size, metal-support interaction, catalyst structure, ensemble size, and alloy effects.

  14. Synthesis and Electrochemical Evaluation of Carbon Supported Pt-Co Bimetallic Catalysts Prepared by Electroless Deposition and Modified Charge Enhanced Dry Impregnation

    Directory of Open Access Journals (Sweden)

    John Meynard M. Tengco

    2016-06-01

    Full Text Available Carbon-supported bimetallic Pt-Co cathode catalysts have been previously identified as higher activity alternatives to conventional Pt/C catalysts for fuel cells. In this work, a series of Pt-Co/C catalysts were synthesized using electroless deposition (ED of Pt on a Co/C catalyst prepared by modified charge enhanced dry impregnation. X-ray diffraction (XRD and scanning transmission electron microscopy (STEM characterization of the base catalyst showed highly dispersed particles. A basic ED bath containing PtCl62− as the Pt precursor, dimethylamine borane as reducing agent, and ethylenediamine as stabilizing agent successfully targeted deposition of Pt on Co particles. Simultaneous action of galvanic displacement and ED resulted in Pt-Co alloy formation observed in XRD and energy dispersive X-ray spectroscopy (XEDS mapping. In addition, fast deposition kinetics resulted in hollow shell Pt-Co alloy particles while particles with Pt-rich shell and Co-rich cores formed with controlled Pt deposition. Electrochemical evaluation of the Pt-Co/C catalysts showed lower active surface but much higher mass and surface activities for oxygen reduction reaction compared to a commercial Pt/C fuel cell catalyst.

  15. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.

    2011-07-26

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  16. CATALYSIS SCIENCE INITIATIVE: From First Principles Design to Realization of Bimetallic Catalysts for Enhanced Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    MAVRIKAKIS, MANOS

    2007-05-03

    In this project, we have integrated state-of-the-art Density Functional Theory (DFT) models of heterogeneous catalytic processes with high-throughput screening of bimetallic catalytic candidates for important industrial problems. We have studied a new class of alloys characterized by a surface composition different from the bulk composition, and investigated their stability and activity for the water-gas shift reaction and the oxygen reduction reaction. The former reaction is an essential part of hydrogen production; the latter is the rate-limiting step in low temperature H2 fuel cells. We have identified alloys that have remarkable stability and activity, while having a much lower material cost for both of these reactions. Using this knowledge of bimetallic interactions, we have also made progress in the industrially relevant areas of carbohydrate reforming and conversion of biomass to liquid alkanes. One aspect of this work is the conversion of glycerol (a byproduct of biodiesel production) to synthesis gas. We have developed a bifunctional supported Pt catalyst that can cleave the carbon-carbon bond while also performing the water-gas shift reaction, which allows us to better control the H2:CO ratio. Knowledge gained from the theoretical metal-metal interactions was used to develop bimetallic catalysts that perform this reaction at low temperature, allowing for an efficient coupling of this endothermic reaction with other reactions, such as Fischer-Tropsch or methanol synthesis. In our work on liquid alkane production from biomass, we have studied deactivation and selectivity in these areas as a function of metal-support interactions and reaction conditions, with an emphasis on the bifunctionality of the catalysts studied. We have identified a stable, active catalyst for this process, where the selectivity and yield can be controlled by the reaction conditions. While complete rational design of catalysts is still elusive, this work demonstrates the power of

  17. Low-temperature aqueous-phase reforming of ethanol on bimetallic PdZn catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Haifeng; DelaRiva, Andrew; Wang, Yong; Dayte, Abhaya

    2015-01-01

    Bimetallic PdZn catalysts supported on carbon black (CB) and carbon nanotubes (CNTs) were found to be selective for CO-free H-2 production from ethanol at low temperature (250 degrees C). On Pd, the H-2 yield was low (similar to 0.3 mol H-2/mol ethanol reacted) and the CH4/CO2 ratio was high (similar to 1.7). Addition of Zn to Pd formed the intermetallic PdZn beta phase (atomic ratio of Zn to Pd is 1) with increased H-2 yield (similar to 1.9 mol H-2/mol ethanol reacted) and CH4/CO2 ratio of <1. The higher H-2 yield and low CH4 formation was related to the improved dehydrogenation activity of the L1(0) PdZn beta phase. The TOF increased with particle size and the CNTs provided the most active and selective catalysts, which may be ascribed to pore-confinement effects. Furthermore, no significant changes in either the supports or the PdZn beta particles was found after aqueous-phase reforming (APR) indicating that the metal nanoparticles and the carbon support are hydrothermally stable in the aqueous phase at elevated temperatures and pressures (>200 degrees C, 65 bar). No CO was detected for all the catalysts performed in aqueous-phase reaction, indicating that both monometallic Pd and bimetallic PdZn catalysts have high water-gas shift activity during APR. However, the yield of H-2 is considerably lower than the theoretical value of 6 H-2 per mole ethanol which is due to the presence of oxygenated products and methane on the PdZn catalysts.

  18. Synthesis of nanostructured lean-NOx catalysts by direct laser deposition of monometallic Pt-, Rh- and bimetallic PtRh-nanoparticles on SiO2 support

    International Nuclear Information System (INIS)

    Monometallic Pt and Rh and bimetallic PtRh catalysts with a highly dispersed noble metal weight loading of ca. 1 wt% were produced via the direct deposition of nanoparticles on different SiO2 supports by means of pulsed ultra-violet (248 nm) excimer laser ablation of Pt, Rh bulk metal and PtRh alloy targets. Backscattered electron microscopy (BSE), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) were employed to characterize the deposited nanoparticles, which were found to exhibit narrow size distribution centred around 2.5 nm. The catalytic activities for lean NOx reduction of the monometallic and bimetallic catalyst samples were investigated in a flow reactor setup in the temperature range 100-400 deg. C using a test gas mixture representative of oxygen rich diesel engine exhaust gas. For comparison a Rh/SiO2 reference catalyst prepared by a conventional impregnation method was also tested. Further experiments were performed in which PtRh nanoparticles were deposited on a Rh/SiO2 reference catalyst sample to study the possibility for controlled modification of its activity. The catalytic activity measurements revealed that among the samples solely prepared by laser deposition the PtRh-SiO2 nanoparticle catalyst showed the highest activity for NOx reduction at low temperatures 100-300 deg. C. In addition, it could be demonstrated that the initially low NOx reduction activity and the N2 selectivity of the Rh/SiO2 reference catalyst sample for temperatures below 250 deg. C can be enhanced by post laser deposition of PtRh nanoparticles

  19. Surface-Bound Ligands Modulate Chemoselectivity and Activity of a Bimetallic Nanoparticle Catalyst

    KAUST Repository

    Vu, Khanh B.

    2015-04-03

    "Naked" metal nanoparticles (NPs) are thermodynamically and kinetically unstable in solution. Ligands, surfactants, or polymers, which adsorb at a particle\\'s surface, can be used to stabilize NPs; however, such a mode of stabilization is undesirable for catalytic applications because the adsorbates block the surface active sites. The catalytic activity and the stability of NPs are usually inversely correlated. Here, we describe an example of a bimetallic (PtFe) NP catalyst stabilized by carboxylate surface ligands that bind preferentially to one of the metals (Fe). NPs stabilized by fluorous ligands were found to be remarkably competent in catalyzing the hydrogenation of cinnamaldehyde; NPs stabilized by hydrocarbon ligands were significantly less active. The chain length of the fluorous ligands played a key role in determining the chemoselectivity of the FePt NP catalysts. (Chemical Presented). © 2015 American Chemical Society.

  20. Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Felix-Navarro, R. M., E-mail: moi6salazar@hotmail.com; Beltran-Gastelum, M.; Salazar-Gastelum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Perez-Sicairos, S.; Lin, S. W. [Centro de Graduados e Investigacion, Instituto Tecnologico de Tijuana (Mexico); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados (Mexico); Alonso-Nunez, G. [Centro de Nanociencias y Nanotecnologia (Mexico)

    2013-08-15

    Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O{sub 2} to H{sub 2}O{sub 2}. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H{sub 2}SO{sub 4} electrolyte using dissolved O{sub 2}. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H{sub 2}O{sub 2} electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H{sub 2}O{sub 2} alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

  1. Highly selective bimetallic Pt-Cu/Mg(Al)O catalysts for the aqueous-phase reforming of glycerol

    NARCIS (Netherlands)

    Boga, D.A.; Oord, R.; Beale, A.M.; Chung, Y.M.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2013-01-01

    Monometallic Pt and bimetallic Pt-Cu catalysts supported on Mg(Al)O mixed oxides, obtained by calcination of the corresponding layered double hydroxides (LDHs), were prepared and tested in the aqueous-phase reforming (APR) of glycerol. The effect of the Mg/Al ratio and calcination temperature of the

  2. Sn surface-enriched Pt-Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation

    KAUST Repository

    Zhu, Haibo

    2014-12-01

    A new one pot, surfactant-free, synthetic route based on the surface organometallic chemistry (SOMC) concept has been developed for the synthesis of Sn surface-enriched Pt-Sn nanoparticles. Bu3SnH selectively reacts with [Pt]-H formed in situ at the surface of Pt nanoparticles, Pt NPs, obtained by reduction of K2PtCl4 by LiB(C2H5)3H. Chemical analysis, 1H MAS and 13C CP/MAS solid-state NMR as well as two-dimensional double-quantum (DQ) and triple-quantum (TQ) experiments show that organo-tin moieties Sn(n-C4H9) are chemically linked to the surface of Pt NPs to produce, in fine, after removal of most of the n-butyl fragment, bimetallic Pt-Sn nanoparticles. The Sn(n-CH2CH2CH2CH3) groups remaining at the surface are believed to stabilize the as-synthesized Pt-Sn NPs, enabling the bimetallic NPs to be well dispersed in THF. Additionally, the Pt-Sn nanoparticles can be supported on MgAl2O4 during the synthesis of the nanoparticles. Some of the Pt-Sn/MgAl2O4 catalyst thus prepared exhibits high activity in PROX of CO and an extremely high selectivity and stability in propane dehydrogenation to propylene. The enhanced activity in propane dehydrogenation is associated with the high concentration of inactive Sn at the surface of Pt nanoparticles which ”isolates” the active Pt atoms. This conclusion is confirmed by XRD, NMR, TEM, and XPS analysis.

  3. Selective Liquid-Phase Semihydrogenation of Functionalized Acetylenes and Propargylic Alcohols with Silica-Supported Bimetallic Palladium—Copper Catalysts

    NARCIS (Netherlands)

    Koten, G. van; Spee, M.P.R.; Meijer, M.D.; Slagt, M.Q.; Geus, John W.

    2001-01-01

    Silica-supported, bimetallic palladium-copper catalysts were prepared in solution under mild conditions by reacting lithium di(4-tolyl)cuprate with palladium acetate in the presence of silica particles. Small bimetallic palladium-copper particles were deposited on the silica surface as confirmed wit

  4. Ag-Cu Bimetallic Nanoparticles Prepared by Microemulsion Method as Catalyst for Epoxidation of Styrene

    Directory of Open Access Journals (Sweden)

    Hong-Kui Wang

    2012-01-01

    Full Text Available Ag/Cu bimetallic nanocatalysts supported on reticulate-like γ-alumina were prepared by a microemulsion method using N2H4·H2O as the reducing agent. The catalysts were activated by calcination followed with hydrogen reduction at 873K, and the properties were confirmed using various characterization techniques. Compared with metal oxides particles, Ag-Cu particles exhibited smaller sizes (<5 nm after calcination in H2 at 873K. XPS results indicated that the binding energies changed with the Ag/Cu ratios, suggesting that increasing the copper content gave both metals a greater tendency to lose electrons. Furthermore, Ag-Cu bimetallic nanoparticles supported on γ-alumina showed better catalytic activity on the epoxidation of styrene as compared with the corresponding monometallic silver or copper. The styrene oxide selectivity could reach 76.6% at Ag/Cu molar ratio of 3/1, while the maximum conversion (up to 94.6% appeared at Ag/Cu molar ratio of 1/1 because of the maximum interaction between silver and copper.

  5. Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

    Directory of Open Access Journals (Sweden)

    Gloria Lourdes Dimas-Rivera

    2014-01-01

    Full Text Available In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA. The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al2O3 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al2O3 support helped to stabilize the furfural molecule on the surface.

  6. Design of Pd-Based Bimetallic Catalysts for ORR: A DFT Calculation Study

    Directory of Open Access Journals (Sweden)

    Lihui Ou

    2015-01-01

    Full Text Available Developing Pd-lean catalysts for oxygen reduction reaction (ORR is the key for large-scale application of proton exchange membrane fuel cells (PEMFCs. In the present paper, we have proposed a multiple-descriptor strategy for designing efficient and durable ORR Pd-based alloy catalysts. We demonstrated that an ideal Pd-based bimetallic alloy catalyst for ORR should possess simultaneously negative alloy formation energy, negative surface segregation energy of Pd, and a lower oxygen binding ability than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pd-M alloys, Pd-V, Pd-Fe, Pd-Zn, Pd-Nb, and Pd-Ta, are identified theoretically to have stable Pd segregated surface and improved ORR activity. Factors affecting these properties are analyzed. The alloy formation energy of Pd with transition metals M can be mainly determined by their electron interaction. This may be the origin of the negative alloy formation energy for Pd-M alloys. The surface segregation energy of Pd is primarily determined by the surface energy and the atomic radius of M. The metals M which have smaller atomic radius and higher surface energy would tend to favor the surface segregation of Pd in corresponding Pd-M alloys.

  7. Preparation and characterization of bi-metallic nanoparticle catalyst having better anti-coking properties using reverse micelle technique

    Science.gov (United States)

    Zacharia, Thomas

    Energy needs are rising on an exponential basis. The mammoth energy sources like coal, natural gas and petroleum are the cause of pollution. The large outcry for an alternate energy source which is environmentally friendly and energy efficient is heard during the past few years. This is where “Clean-Fuel” like hydrogen gained its ground. Hydrogen is mainly produced by steam methane reforming (SMR). An alternate sustainable process which can reduce the cost as well as eliminate the waste products is Tri-reforming. In both these reforming processes nickel is used as catalyst. However as the process goes on the catalyst gets deactivated due to coking on the catalytic surface. This goal of this thesis work was to develop a bi-metallic catalyst which has better anti-coking properties compared to the conventional nickel catalyst. Tin was used to dope nickel. It was found that Ni3Sn complex around a core of Ni is coking resistant compared to pure nickel catalyst. Reverse micelle synthesis of catalyst preparation was used to control the size and shape of catalytic particles. These studies will benefit researches on hydrogen production and catalyst manufactures who work on different bi-metallic combinations.

  8. Monolayer dispersion thresholds and threshold effect displayed by supported catalysts

    Institute of Scientific and Technical Information of China (English)

    Cun DENG

    2008-01-01

    The principle of spontaneous monolayer dis-persion holds that active components of many supported catalysts will disperse spontaneously onto the surface of the carrier. The monolayer dispersion threshold of the active component on the surface of the carrier can be measured by X-ray diffraction phase-quantitative extra-polation method, etc. By measuring the monolayer disper-sion threshold, beneficial information on the surface structure and dispersion of supported catalysts can be obtained, and the optimal preparative processing condi-tions of the catalysts can be chosen. The proportion of the active component of many supported catalysts can be optimized while its monolayer dispersion threshold is observed. Mutation values of many physicochemical properties of supported catalysts are related to monolayer dispersion thresholds; the threshold effect on catalysts is apparent, and the proposal regarding the threshold effect provides instruction for the research on catalysts.

  9. Facile Synthesis of Porous Dendritic Bimetallic Platinum-Nickel Nanocrystals as Efficient Catalysts for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Eid, Kamel; Wang, Hongjing; Malgras, Victor; Alothman, Zeid Abdullah; Yamauchi, Yusuke; Wang, Liang

    2016-05-01

    Certain bimetallic nanocrystals (NCs) possess promising catalytic properties for electrochemical energy conversion. Herein, we report a facile method for the one-step synthesis of porous dendritic PtNi NCs in aqueous solution at room temperature that contrasts with the traditional multistep thermal decomposition approach. The dendritic PtNi NCs assembled by interconnected arms are efficient catalysts for the oxygen reduction reaction. This direct and efficient method is favorable for the up-scaled synthesis of active catalysts used in electrochemical applications. PMID:26879517

  10. Carbon nanotubes supported Cu-Ni bimetallic catalysts and their properties for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide

    International Nuclear Information System (INIS)

    Multi-walled carbon nanotubes (MWCNTs) supported Cu-Ni bimetallic catalysts for the direct synthesis of dimethyl carbonate (DMC) from CH3OH and CO2 were synthesized and investigated. The supporting materials and the synthesized catalysts were fully characterized using FTIR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction (XRD) and X-ray photoelectron spectrum (XPS) techniques. The catalytic activities were investigated by performing micro-reactions. The experimental results showed that the metal phase and Cu-Ni alloy phase in the catalyst were partially formed during the calcination and activation step. Active metal particles were dispersed homogeneously on the surface of the MWCNTs. Cu-Ni/MWCNTs catalysts were efficient for the direct synthesis of DMC. The highest conversion of CH3OH was higher than 4.3% and the selectivity of DMC was higher than 85.0% under the optimal catalytic conditions of 120 deg. C and around 1.2 MPa. The high catalytic activity of Cu-Ni/MWCNTs in DMC synthesis can be attributed to the synergetic effects of metal Cu, Ni and Cu-Ni alloy in the activation of CH3OH and CO2, the unique structure of MWCNTs and the interaction between the metal particles and the supports.

  11. Designing supported palladium-on-gold bimetallic nano-catalysts for controlled hydrogenation of acetylene in large excess of ethylene

    Science.gov (United States)

    Malla, Pavani

    Ethylene is used as a starting point for many chemical intermediates in the petrochemical industry. It is predominantly produced through steam cracking of higher hydrocarbons (ethane, propane, butane, naphtha, and gas oil). During the cracking process, a small amount of acetylene is produced as a side product. However, acetylene must be removed since it acts as a poison for ethylene polymerization catalysts at even ppm concentrations (>5 ppm). Thus, the selective hydrogenation of acetylene to ethylene is an important process for the purification of ethylene. Conventional, low weight loading Pd catalysts are used for this selective reaction in high concentration ethylene streams. Gold was initially considered to be catalytically inactive for a long time. This changed when gold was seen in the context of the nanometric scale, which has indeed shown it to have excellent catalytic activity as a homogeneous or a heterogeneous catalyst. Gold is proved to have high selectivity to ethylene but poor at conversion. Bimetallic Au and Pd catalysts have exhibited superior activity as compared to Pd particles in semi-hydrogenation. Hydrogenation of acetylene was tested using this bimetallic combination. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. TiO 2 as a support material and 0.05%Pd loading on 1%Au on titania support and used different treatment methods like washing plasma and reduction between the two metal loadings and was observed under 2:1 ratio. In my study there were two set of catalysts which were prepared by a modified incipient wetness impregnation technique. Out of all the reaction condition the catalyst which was reduced after impregnating gold and then impregnating palladium which was further treated in non-thermal hydrogen plasma and then pretreated in hydrogen till 250°C for 1 hour produced the best activity of 76% yield at 225°C. Stability tests were conducted

  12. Combination of supported bimetallic rhodium–molybdenum catalyst and cerium oxide for hydrogenation of amide

    International Nuclear Information System (INIS)

    Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6–7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh–MoOx/SiO2, and the addition of CeO2 much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2–8 MPa and 393–433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh–MoOx/SiO2 + CeO2 was 63%. The effect of CeO2 addition was highest when CeO2 was not calcined, and CeO2 calcined at >773 K showed a smaller effect. The use of CeO2 as a support rather decreased the activity in comparison with Rh–MoOx/SiO2. The weakly-basic nature of CeO2 additive can affect the surface structure of Rh–MoOx/SiO2, i.e. reducing the ratio of Mo–OH/Mo–O− sites. (focus issue paper)

  13. Combination of supported bimetallic rhodium-molybdenum catalyst and cerium oxide for hydrogenation of amide

    Science.gov (United States)

    Nakagawa, Yoshinao; Tamura, Riku; Tamura, Masazumi; Tomishige, Keiichi

    2015-02-01

    Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6-7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh-MoOx/SiO2, and the addition of CeO2 much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2-8 MPa and 393-433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh-MoOx/SiO2 + CeO2 was 63%. The effect of CeO2 addition was highest when CeO2 was not calcined, and CeO2 calcined at >773 K showed a smaller effect. The use of CeO2 as a support rather decreased the activity in comparison with Rh-MoOx/SiO2. The weakly-basic nature of CeO2 additive can affect the surface structure of Rh-MoOx/SiO2, i.e. reducing the ratio of Mo-OH/Mo-O- sites.

  14. Catalytic thermal decomposition of methane to COx-free hydrogen and carbon nanotubes over MgO supported bimetallic group VIII catalysts

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Bimetallic of group VIII/MgO catalysts were tested for methane decomposition reaction. • Fe–Co/MgO catalyst showed superior activity and stability toward H2 production. • Both Ni–Fe and Ni–Co catalysts exhibited lower catalytic activities. • The formation of MgxNi(1−x)O leads to the inhibition of catalytic activity. • High quality MWCNTs were obtained over all binary catalysts. - Abstract: Bimetallic Ni–Fe, Ni–Co and Fe–Co supported on MgO catalysts with a total metals content of 50 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nanomaterials. The catalytic runs were carried out at 700 °C under atmospheric pressure using fixed bed horizontal flow reactor. The materials were characterized by XRD, TEM, Raman spectroscopy, surface analysis and TGA–DTG. The data showed that the bimetallic 25% Fe–25%Co/MgO catalyst exhibited remarkable higher activity and stability up to ∼10 h time-on-stream with respect to H2 production. However, the catalytic activity and durability was greatly declined after incorporating 25%Ni to either 25%Fe or 25%Co/MgO catalysts at all time on stream. The main reason for the catalytic inhibition of Ni containing catalysts is consuming NiO during the formation of rock-salt MgxNi(1−x)O solid solution. However, the almost complete segregation of Fe2O3 and Co3O4 oxides played an important role for the high activity of the Fe–Co based catalyst. TEM images illustrate that the accumulated carbon over all catalysts are multi-walled carbon nanotubes in nature. The TG data showed that a higher yield of MWCNTs was achieved over bimetallic Fe–Co catalyst compared to the Ni–Fe or Ni–Co containing catalysts

  15. Model bimetallic Pd-Ni automotive exhaust catalysts. Influence of thermal aging and hydrocarbon self-poisoning

    Energy Technology Data Exchange (ETDEWEB)

    Hungria, A.B.; Martinez-Arias, A. [Instituto de Catalisis y Petroleoquimica, CSIC, C/Marie Curie 2, Campus Cantoblanco, 28049 Madrid (Spain); Calvino, J.J. [Dpto. de Ciencia de los Materiales e Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, 11510 Puerto Real, Cadiz (Spain); Anderson, J.A. [Surface Chemistry and Catalysis Group, Department of Chemistry, University of Aberdeen, AB24 3UE Scotland (United Kingdom)

    2006-02-22

    Bimetallic Pd-Ni catalysts supported on Al{sub 2}O{sub 3} and (Ce,Zr)O{sub x}/Al{sub 2}O{sub 3} were examined with respect to their catalytic performance for the elimination of CO, NO and C{sub 3}H{sub 6} under stoichiometric conditions. The effects of a thermal aging treatment at 1273K, reactant competition in the presence of the hydrocarbon and the influence of the presence of nickel in the catalyst have been analysed by XRD, HREM, catalytic activity measurements and in situ DRIFTS spectroscopy. Self-poisoning effects, induced by the presence of the hydrocarbon in the reactant mixture, were identified as the main factor affecting the light-off activity. While a Ni-induced preferential interaction between Pd and the Ce-Zr mixed oxide component appears, in general terms, to be beneficial for the catalytic performance of the fresh (Ce,Zr)O{sub x}/Al{sub 2}O{sub 3}-supported bimetallic catalyst, it is shown to be detrimental for the aged system as a consequence of a facilitated degradation of the (Ce,Zr)O{sub x} component and encapsulation of the active palladium particles. (author)

  16. Low-temperature 1 3-butadiene Hydrogenation over Supported Pt/3d/gamma-Al2O3 Bimetallic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    W Lonergan; X Xing; R Zheng; S Qi; B Huang; J Chen

    2011-12-31

    Low-temperature 1,3-butadiene hydrogenation is used as a probe reaction to investigate the hydrogenation activity over several {gamma}-Al{sub 2}O{sub 3} supported Pt/3d (3d = Co, Ni, Cu) bimetallic catalysts. Batch and flow reactor studies are employed to quantify the kinetic activity and steady-state conversion, respectively, of each catalyst. Transmission electron microscopy (TEM) is utilized to characterize particle sizes and extended X-ray absorption fine structure (EXAFS) measurements are performed to verify the Pt-3d bimetallic bond formation. Pulse carbon monoxide chemisorption measurements are also performed to characterize the number of active sites. Additionally, density functional theory (DFT) calculations are included to determine the binding energies of 1,3-butadiene and atomic hydrogen on the corresponding model surfaces. The binding energies of the adsorbates are found to correlate with the hydrogenation activity, allowing for use of such correlation to potentially predict hydrogenation catalysts with enhanced activity based on the binding energies of the adsorbates of interest.

  17. Hydrotreatment of wood-based pyrolysis oil using zirconia-supported mono- and bimetallic (Pt, Pd, Rh) catalysts

    OpenAIRE

    Ardiyanti, A. R.; GUTIERREZ, A.; Honkela, M. L.; Krause, A.O.I.; Heeres, H. J.

    2011-01-01

    Fast pyrolysis oil (PO), the liquid product of fast pyrolysis of lignocellulosic biomass, requires upgrading to extent its application range and for instance to allow for co-feeding in an existing oil-refinery. Catalytic hydrotreatment reactions (350 degrees C, 20 MPa total pressure, and 4h reaction time) with mono- and bimetallic metal catalysts based on Rh, Pt, Pd on a zirconia support were performed in a batch set-up. Pd/ZrO(2) showed the highest activity, followed by Rh/ZrO(2). Upgraded o...

  18. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale

    Science.gov (United States)

    Shan, Shiyao; Petkov, Valeri; Prasai, Binay; Wu, Jinfang; Joseph, Pharrah; Skeete, Zakiya; Kim, Eunjoo; Mott, Derrick; Malis, Oana; Luo, Jin; Zhong, Chuan-Jian

    2015-11-01

    The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo phase

  19. Synergy between Two Metal Catalysts: A Highly Active Silica Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane

    KAUST Repository

    Samantaray, Manoja K

    2016-06-01

    A well-defined, silica supported, bimetallic precatalyst [≡Si-O-W(Me)5 ≡Si-O-Zr(Np)3](4) has been synthesized for the first time via successively grafting two organometallic complexes [W(CH3)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of Zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON: 1436) than the monometallic W hydride (TON: 650) in metathesis of n-decane at 150 0C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation which occurs on Zr. The produced olefin resulting from a ß–H elimination undergoes easy metathesis on W.

  20. Enhanced performance of the catalytic conversion of allyl alcohol to 3-hydroxypropionic acid using bimetallic gold catalysts.

    Science.gov (United States)

    Falletta, Ermelinda; Della Pina, Cristina; Rossi, Michele; He, Qian; Kiely, Christopher J; Hutchings, Graham J

    2011-01-01

    One of the strategic building blocks in organic synthesis is 3-hydroxypropionic acid, which is particularly important for the manufacture of high performance polymers. However, to date, despite many attempts using both biological and chemical routes, no large scale effective process for manufacturing 3-hydroxypropionic acid has been developed. One potentially useful starting point is from allyl alcohol, as this can be obtained in principle from the dehydration of glycerol, thereby presenting a bio-renewable green pathway to this important building block. The catalytic transformation of allyl alcohol to 3-hydroxypropionic acid presents interesting challenges in catalyst design, particularly with respect to the control of selectivity among the products that can be expected, as acrylic acid, acrolein and glyceric acid can also be formed. In this paper, we present a novel eco-sustainable catalytic pathway leading to 3-hydroxypropionic acid, which highlights the outstanding potential of gold-based and bimetallic catalysts in the aerobic oxidation of allyl alcohol. PMID:22455056

  1. Enhanced Hydrodeoxygenation of m -Cresol over Bimetallic Pt–Mo Catalysts through an Oxophilic Metal-Induced Tautomerization Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Allison; Ferguson, Glen Allen; Gallagher, James R.; Cheah, Singfoong; Beckham, Gregg T.; Schaidle, Joshua A.; Hensley, Jesse E.; Medlin, J. Will

    2016-07-01

    Supported bimetallic catalysts consisting of a noble metal (e.g., Pt) and an oxophilic metal (e.g., Mo) have received considerable attention for the hydrodeoxygenation of oxygenated aromatic compounds produced from biomass fast pyrolysis. Here, we report that PtMo can catalyze m-cresol deoxygenation via a pathway involving an initial tautomerization step. In contrast, the dominant mechanism on monometallic Pt/Al2O3 was found to be sequential Pt-catalyzed ring hydrogenation followed by dehydration on the support. Bimetallic Pt10Mo1 and Pt1Mo1 catalysts were found to produce the completely hydrogenated and deoxygenated product, methylcyclohexane (MCH), with much higher yields than monometallic Pt catalysts with comparable metal loadings and surface areas. Over an inert carbon support, MCH formation was found to be slow over monometallic Pt catalysts, while deoxygenation was significant for PtMo catalysts even in the absence of an acidic support material. Experimental studies of m-cresol deoxygenation together with density functional theory calculations indicated that Mo sites on the PtMo bimetallic surface dramatically lower the barrier for m-cresol tautomerization and subsequent deoxygenation. The accessibility of this pathway arises from the increased interaction between the oxygen of m-cresol and the Mo sites in the Pt surface. This interaction significantly alters the configuration of the precursor and transition states for tautomerization. A suite of catalyst characterization techniques including X-ray absorption spectroscopy (XAS) and temperature-programmed reduction (TPR) indicate that Mo was present in a reduced state on the bimetallic surface under conditions relevant for reaction. Overall, these results suggest that the use of bifunctional metal catalysts can result in new reaction pathways that are unfavorable on monometallic noble metal catalysts.

  2. Aqueous Phase Glycerol Reforming by PtMo Bimetallic Nano-Particle Catalyst: Product Selectivity and Structural Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Stach E. A.; Dietrich, P.J.; Lobo-Lapidus, R.J.; Wu, T.; Sumer, A.; Akatay, M.C.; Fingland, B.R.; Guo, N.; Dumesic, J.A.; Marshall, C.L.; Jellinek, J.; Delgass, W.N.; Ribeiro, F.H.; Miller, J.T.

    2012-03-01

    A carbon supported PtMo aqueous phase reforming catalyst for producing hydrogen from glycerol was characterized by analysis of the reaction products and pathway, TEM, XPS and XAS spectroscopy. Operando X-ray absorption spectroscopy (XAS) indicates the catalyst consists of bimetallic nano-particles with a Pt rich core and a Mo rich surface. XAS of adsorbed CO indicates that approximately 25% of the surface atoms are Pt. X-ray photoelectron spectroscopy indicates that there is unreduced and partially reduced Mo oxide (MoO{sub 3} and MoO{sub 2}), and Pt-rich PtMo bimetallic nano-particles. The average size measured by transmission electron microscopy of the fresh PtMo nano-particles is about 2 nm, which increases in size to 5 nm after 30 days of glycerol reforming at 31 bar and 503 K. The catalyst structure differs from the most energetically stable structure predicted by density functional theory (DFT) calculations for metallic Pt and Mo atoms. However, DFT indicates that for nano-particles composed of metallic Pt and Mo oxide, the Mo oxide is at the particle surface. Subsequent reduction would lead to the experimentally observed structure. The aqueous phase reforming reaction products and intermediates are consistent with both C-C and C-OH bond cleavage to generate H{sub 2}/CO{sub 2} or the side product CH{sub 4}. While the H{sub 2} selectivity at low conversion is about 75%, cleavage of C-OH bonds leads to liquid products with saturated carbon atoms. At high conversions (to gas), these will produced additional CH{sub 4} reducing the H{sub 2} yield and selectivity.

  3. Greatly improved electrochemical performance of lithium-oxygen batteries with a bimetallic platinum-copper alloy catalyst

    Science.gov (United States)

    Lee, Minwook; Hwang, Yubin; Yun, Kyung-Han; Chung, Yong-Chae

    2015-08-01

    Research on the cathode catalysts of lithium-oxygen (Li-O2) batteries is one of the most important branches to commercialize these batteries to overcome the sluggish kinetics during both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). In this study, a high performance catalyst based on a bimetallic Pt-Cu alloy is investigated for Li-O2 batteries using first-principles calculation. The theoretical prediction shows that the Pt-Cu alloy is much more effective than the pure Pt according to the electrochemical performance. In particular, the effectiveness of the catalytic property is maximized in the case of the PtCu (111) surface which greatly reduces the large overpotentials of the original Li-O2 batteries during the OER/ORR. It is identified for the first time that the charge overpotentials are affected mainly by the inherent surface charge character of the alloy catalyst. It is observed that the more negatively charged PtCu (111) surface can act as a weakly positively charged surface for the adsorption of Li-O intermediates and thus result in weak ionic bonding of the intermediates on the surface. As a result, the dominant factor improving the catalytic performance is clearly demonstrated, providing insight into the design of an efficient catalyst for Li-O2 battery technologies.

  4. Efficiently cubic platinum-cobalt bimetallic nano-catalysts for use in low-cost dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Graphical abstract: Low-platinum (Pt) alloy can be expected to substitute for the conventional Pt catalyst due to its modified Pt electronic structure with highly electrocatalytic activity and Pt-skin nano-structure with high durability. Pt3Co bimetallic nano-catalysts show high catalytic activity for the reduction of triiodide to iodide and low charge transfer resistance at the electrolyte/counter electrode interface as well as those of pure cubic Pt nano-catalysts. DSSC based on Pt3Co CE achieves an enhanced efficiency of 8.16% compared to that of thermal decomposition Pt CE (7.26%). - Highlights: • Cubic Co, Pt, PtCo, and Pt3Co nano-catalysts were synthesized in the oleylamine. • Pt-metal alloy with modified Pt electronic structure shows highly electrocatalytic activity. • Pt-metal alloy with Pt-skin nano-structure shows high durability. • The efficiency of DSSC with Pt3Co bimetallic counter electrode reaches 8.16%. - Abstract: Low-platinum (Pt) alloy can be expected to substitute for the conventional Pt catalyst due to its modified Pt electronic structure with highly electrocatalytic activity and Pt-skin nano-structure with high durability. Here we synthesize the pure cobalt (Co), pure Pt, PtCo, and Pt3Co nano-catalysts in the oleylamine and use their as the counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). Cyclic voltammetry and electrochemical impedance spectroscopy measurements indicate that the cubic Pt3Co CE has a high catalytic activity for the reduction of triiodide to iodide and a low charge transfer resistance at the electrolyte/CE interface, which are close to those of the pure cubic Pt CE but superior than those of the thermal decomposition platinum (TDPt) CE due to its modified Pt electronic structure and its catalytic surfaces are composed of Pt-rich and Pt-skin nano-structure. DSSC based on Pt3Co CE achieves a photovoltaic conversion efficiency of 8.16% under full sunlight illumination (100 mW cm−2, AM1.5 G), which

  5. Dispersed catalysts for co-processing and coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Bockrath, B.; Parfitt, D.; Miller, R. [Pittsburgh Energy Technology Center, PA (United States)

    1995-12-31

    The basic goal is to improve dispersed catalysts employed in the production of clean fuels from low value hydrocarbons. The immediate objective is to determine how the properties of the catalysts may be altered to match the demands placed on them by the properties of the feedstock, the qualities of the desired end products, and the economic constraints put upon the process. Several interrelated areas of the application of dispersed catalysts to co-processing and coal conversion are under investigation. The first involves control of the selectivity of MoS{sub 2} catalysts for HDN, HDS, and hydrogenation of aromatics. A second area of research is the development and use of methods to evaluate dispersed catalysts by means of activity and selectivity tests. A micro-flow reactor has been developed for determining intrinsic reactivities using model compounds, and will be used to compare catalysts prepared in different ways. Micro-autoclaves will also be used to develop data in batch experiments at higher partial pressures of hydrogen. The third area under investigation concerns hydrogen spillover reactions between MoS{sub 2} catalysts and carbonaceous supports. Preliminary results obtained by monitoring H{sub 2}/D{sub 2} exchange reactions with a pulse-flow microreactor indicate the presence of spillover between MoS{sub 2} and a graphitic carbon. A more complete study will be made at a later stage of the project. Accomplishments and conclusions are discussed.

  6. Stability of bimetallic Pd-Zn catalysts for the steam reforming of methanol

    OpenAIRE

    Conant, T.; Karim, A.; Lebarbier, V.; Wang, Y.; F. Girgsdies; Schlögl, R.; Datye, A.

    2008-01-01

    ZnO-supported palladium-based catalysts have been shown in recent years to be both active and selective towards the steam reforming of methanol, although they are still considered to be less active than traditional copper-based catalysts. The activity of PdZn catalysts can be significantly improved by supporting them on alumina. Here we show that the Pd/ZnO/Al2O3 catalysts have better long-term stability when compared with commercial Cu/ZnO/Al2O3 catalysts, and that they are also stable under...

  7. Electrochemical oxidation of sodium borohydride on carbon supported Pt-Zn nanoparticle bimetallic catalyst and its implications to direct borohydride-hydrogen peroxide fuel cell

    International Nuclear Information System (INIS)

    Highlights: • The Pt-Zn/C catalyst as anode catalyst for DBHFC were facilely synthesized. • The average particle size of Pt-Zn bimetallic nanoparticles is approximately 2.5 nm. • The Zn-doping can apparently improve the catalytic activity for BH4− electrochemical oxidation. • The maximum power density of DBHFC employing Pt-Zn/C as anode catalyst is as high as 79.9 mW cm−2 at 79.5 mA cm−2 and 25 °C. - Abstract: Carbon supported Pt-Zn bimetallic nanoparticle electrocatalysts (Pt-Zn/C) are facilely prepared by a modified NaBH4 reduction method in aqueous solution at room temperature and investigated as alternative anode catalysts for direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the as-prepared nanospherical electrocatalysts are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), chronoamperometry (CA) and fuel cell test. Based on results of TEM and XRD, the Pt-Zn nanoparticles show average particle size of approximately 2.5 nm on the carbon surface. The fundamental electrochemical results show that the Pt-Zn/C catalysts exhibit much higher catalytic activity and stability for the direct oxidation of BH4− than Pt/C catalyst since Pt atoms are partly substituted by Zn atoms in Pt-Zn catalyst. Among various Pt-Zn catalysts with different compositions, the Pt67Zn33/C catalyst presents the highest catalytic activity for BH4− electrooxidation. The DBHFC using Pt67Zn33/C as anode catalyst and Pt/C as cathode catalyst obtains the maximum power density as high as 79.9 mW cm−2 at 79.5 mA cm−2 and 25 °C

  8. Hydrogenation Conversion of Phenanthrene over Dispersed Mo-based Catalysts

    Institute of Scientific and Technical Information of China (English)

    Hu Yiwen; Da Zhijian; Wang Zijun

    2015-01-01

    With oil-soluble molybdenum compound and sublimed sulfur serving as raw materials, two dispersed Mo-based catalysts were prepared, characterized and then applied to the hydrogenation conversion of phenanthrene. The test results showed that under the conditions speciifed by this study, the catalyst prepared in a higher sulifding atmosphere was more catalytically active due to its higher content of MoS2 and stronger intrinsic catalytic activity of MoS2 unit, which demon-strated that the sulifding atmosphere for the preparation of catalysts not only could inlfuence the yield of MoS2 but also the structure of MoS2. The analysis on the selectivity of octahydrophenanthrene isomers revealed that the catalyst prepared in a lower sulifding atmosphere had a relatively higher catalytic selectivity to the hydrogenation of outer aromatic ring and the structure of catalysts could be modiifed under the speciifc reaction conditions. Moreover, the selectivity between the isomers of as-octahydrophenanthrene at different reaction time and temperature was analyzed and, based on the results, a hydroge-nation mechanism over dispersed Mo-based catalysts was suggested, with monatomic hydrogen transfer and catalytic sur-face desorption of the half-addition intermediates functioning as the key points. In addition, it is concluded that the catalyst prepared in a lower sulifding atmosphere was more capable of adsorption than the other one.

  9. Homogeneously dispersed multimetal oxygen-evolving catalysts.

    Science.gov (United States)

    Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; Comin, Riccardo; Bajdich, Michal; García-Melchor, Max; Han, Lili; Xu, Jixian; Liu, Min; Zheng, Lirong; García de Arquer, F Pelayo; Dinh, Cao Thang; Fan, Fengjia; Yuan, Mingjian; Yassitepe, Emre; Chen, Ning; Regier, Tom; Liu, Pengfei; Li, Yuhang; De Luna, Phil; Janmohamed, Alyf; Xin, Huolin L; Yang, Huagui; Vojvodic, Aleksandra; Sargent, Edward H

    2016-04-15

    Earth-abundant first-row (3d) transition metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials substantially above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxyhydroxides materials with an atomically homogeneous metal distribution. These gelled FeCoW oxyhydroxides exhibit the lowest overpotential (191 millivolts) reported at 10 milliamperes per square centimeter in alkaline electrolyte. The catalyst shows no evidence of degradation after more than 500 hours of operation. X-ray absorption and computational studies reveal a synergistic interplay between tungsten, iron, and cobalt in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER. PMID:27013427

  10. A Novelγ-Alumina Supported Fe-Mo Bimetallic Catalyst for Reverse Water Gas Shift Reaction

    Institute of Scientific and Technical Information of China (English)

    Abolfazl Gharibi Kharaji; Ahmad Shariati; Mohammad Ali Takassi

    2013-01-01

    In reverse water gas shift (RWGS) reaction CO2 is converted to CO which in turn can be used to pro-duce beneficial chemicals such as methanol. In the present study, Mo/Al2O3, Fe/Al2O3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H2-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch re-actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/Al2O3 catalyst enhances its activity as compared to Fe/Al2O3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/Al2O3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fe2(MoO4)3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fe2(MoO4)3 phase has low reducibility, therefore the Fe2(MoO4)3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.

  11. Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

    Directory of Open Access Journals (Sweden)

    Anna M. Venezia

    2013-06-01

    Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

  12. Highly Dispersed Alloy Catalyst for Durability

    Energy Technology Data Exchange (ETDEWEB)

    Murthi, Vivek S.; Izzo, Elise; Bi, Wu; Guerrero, Sandra; Protsailo, Lesia

    2013-01-08

    Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them with existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.

  13. Correlating ethylene glycol reforming activity with in-situ EXAFS detection of Ni segregation in supported NiPt bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Trupy, Sarah A.; Karim, Ayman M.; Bagia, Christtina; Deng, Weihua; Huang, Yulin; Vlachos, Dionisios G.; Chen, Jingguang

    2012-10-31

    The structural changes in supported NiPt/C and NiPt/γ-Al2O3 catalysts were investigated using in-situ extended X-ray absorption fine structure (EXAFS) under aqueous phase reforming (APR) of ethylene glycol conditions. Reverse Monte Carlo is introduced to analyze the EXAFS data. Parallel reactor studies of APR of ethylene glycol showed that NiPt catalysts were initially more active than monometallic Pt catalysts. The enhanced activity was correlated to changes in the catalyst structure. Under APR conditions, Ni segregated to the surface of the catalysts, resembling Ni-terminated bimetallic surfaces that were predicted to be more active than Pt from theoretical and experimental studies on model surfaces.

  14. 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).

  15. Bimetallic catalysts for CO.sub.2 hydrogenation and H.sub.2 generation from formic acid and/or salts thereof

    Energy Technology Data Exchange (ETDEWEB)

    Hull, Jonathan F.; Himeda, Yuichiro; Fujita, Etsuko; Muckeman, James T.

    2015-08-04

    The invention relates to a ligand that may be used to create a catalyst including a coordination complex is formed by the addition of two metals; Cp, Cp* or an unsubstituted or substituted .pi.-arene; and two coordinating solvent species or solvent molecules. The bimetallic catalyst may be used in the hydrogenation of CO.sub.2 to form formic acid and/or salts thereof, and in the dehydrogenation of formic acid and/or salts thereof to form H.sub.2 and CO.sub.2.

  16. Purification of Carbon Nanotubes Synthesized by Catalytic Decomposition of Methane using Bimetallic Fe-Co Catalysts Supported on MgO

    Energy Technology Data Exchange (ETDEWEB)

    Guan, Beh Hoe; Ramli, Irmawati [Advanced Materials and Nanotechnology Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia 43400 UPM Serdang, Selangor (Malaysia); Yahya, Noorhana [Fundamental and Applied Science Department Universiti Teknologi Petronas, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Pah, Lim Kean, E-mail: irmawati@science.upm.edu.my [Physics department, Faculty of Science, Universiti Putra Malaysia 43400 UPM Serdang, Selangor (Malaysia)

    2011-02-15

    This work reports the synthesis of carbon nanotubes by catalytic decomposition of methane using bimetallic Fe-Co catalysts supported on MgO. Transmission electron microscopy (TEM) results show the as-prepared carbon nanotubes are multi-walled carbon nanotubes (MWCNTs) with diameter in the range of 15nm to 45nm. Purification of as-prepared MWCNTs was carried out by acid and heat treatment method. EDX results show the Fe, Co and MgO catalysts were successfully removed by refluxing the as-prepared MWCNTs in 3M H{sub 2}SO{sub 4}.

  17. Molecular Level Control Through Dual Site Participation Using Bimetallic Catalysts - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    d' Itri, Julie, L.; Kovalchuk, Vladimir, I.

    2010-02-08

    The overall goal of this research program was to explore the hypothesis that it is possible to design a bimetallic surface such that each metal catalyzes different elementary reaction steps in an overall reaction pathway. A corollary to this hypothesis is that the different ensemble size requirements for an elementary reaction step can be used to force an elementary reaction step to occur on only one of the metals. The research program involved a combination of materials synthesis, chemical kinetics experiments, spectroscopic studies and computational investigations. The major outcome of this research program was the development and dissemination of the Dual Site Model, for which chlorocarbon reactions in the presence of hydrogen were used as model systems.

  18. Cu-Sn Bimetallic Catalyst for Selective Aqueous Electroreduction of CO2 to CO

    KAUST Repository

    Sarfraz, Saad

    2016-03-23

    We report a selective and stable electrocatalyst utilizing non-noble metals consisting of Cu and Sn for the efficient and selective reduction of CO2 to CO over a wide potential range. The bimetallic electrode was prepared through the electrodeposition of Sn species on the surface of oxide-derived copper (OD-Cu). The Cu surface, when decorated with an optimal amount of Sn, resulted in a Faradaic efficiency (FE) for CO greater than 90% and a current density of −1.0 mA cm−2 at −0.6 V vs. RHE, compared to the CO FE of 63% and −2.1 mA cm−2 for OD-Cu. Excess Sn on the surface caused H2 evolution with a decreased current density. X-ray diffraction (XRD) suggests the formation of Cu-Sn alloy. Auger electron spectroscopy of the sample surface exhibits zero-valent Cu and Sn after the electrodeposition step. Density functional theory (DFT) calculations show that replacing a single Cu atom with a Sn atom leaves the d-band orbitals mostly unperturbed, signifying no dramatic shifts in the bulk electronic structure. However, the Sn atom discomposes the multi-fold sites on pure Cu, disfavoring the adsorption of H and leaving the adsorption of CO relatively unperturbed. Our catalytic results along with DFT calculations indicate that the presence of Sn on reduced OD-Cu diminishes the hydrogenation capability—i.e., the selectivity towards H2 and HCOOH—while hardly affecting the CO productivity. While the pristine monometallic surfaces (both Cu and Sn) fail to selectively reduce CO2, the Cu-Sn bimetallic electrocatalyst generates a surface that inhibits adsorbed H*, resulting in improved CO FE. This study presents a strategy to provide a low-cost non-noble metals that can be utilized as a highly selective electrocatalyst for the efficient aqueous reduction of CO2.

  19. Catalyst dispersion and activity under conditions of temperature- staged liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  20. Driving the Oxygen Evolution Reaction by Nonlinear Cooperativity in Bimetallic Coordination Catalysts.

    Science.gov (United States)

    Wurster, Benjamin; Grumelli, Doris; Hötger, Diana; Gutzler, Rico; Kern, Klaus

    2016-03-23

    Developing efficient catalysts for electrolysis, in particular for the oxygen evolution in the anodic half cell reaction, is an important challenge in energy conversion technologies. By taking inspiration from the catalytic properties of single-atom catalysts and metallo-proteins, we exploit the potential of metal-organic networks as electrocatalysts in the oxygen evolution reaction (OER). A dramatic enhancement of the catalytic activity toward the production of oxygen by nearly 2 orders of magnitude is demonstrated for novel heterobimetallic organic catalysts compared to metallo-porphyrins. Using a supramolecular approach we deliberately place single iron and cobalt atoms in either of two different coordination environments and observe a highly nonlinear increase in the catalytic activity depending on the coordination spheres of Fe and Co. Catalysis sets in at about 300 mV overpotential with high turnover frequencies that outperform other metal-organic catalysts like the prototypical hangman porphyrins. PMID:26937997

  1. An anodic alumina supported Ni-Pt bimetallic plate-type catalysts for multi-reforming of methane, kerosene and ethanol

    KAUST Repository

    Zhou, Lu

    2014-05-01

    An anodic alumina supported Ni-Pt bimetallic plate-type catalyst was prepared by a two-step impregnation method. The trace amount 0.08 wt% of Pt doping efficiently suppressed the nickel particle sintering and improved the nickel oxides reducibility. The prepared Ni-Pt catalyst showed excellent performance during steam reforming of methane, kerosene and ethanol under both 3000 h stationary and 500-time daily start-up and shut-down operation modes. Self-activation ability of this catalyst was evidenced, which was considered to be resulted from the hydrogen spillover effect over Ni-Pt alloy. In addition, an integrated combustion-reforming reactor was proposed in this study. However, the sintering of the alumina support is still a critical issue for the industrialization of Ni-Pt catalyst. Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  2. Carbon-Supported bimetallic Pd-Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Junming; Karim, Ayman M.; Zhang, He; Kovarik, Libor; Li, Xiaohong S.; Hensley, Alyssa; McEwen, Jean-Sabin; Wang, Yong

    2013-10-01

    Abstract Carbon supported metal catalysts (Cu/C, Fe/C, Pd/C, Pt/C, PdFe/C and Ru/C) have been prepared, characterized and tested for vapor-phase hydrodeoxygenation (HDO) of guaiacol (GUA) at atmospheric pressure. Phenol was the major intermediate on all catalysts. Over the noble metal catalysts saturation of the aromatic ring was the major pathway observed at low temperature (250 °C), forming predominantly cyclohexanone and cyclohexanol. Substantial ring opening reaction was observed on Pt/C and Ru/C at higher reaction temperatures (e.g., 350 °C). Base metal catalysts, especially Fe/C, were found to exhibit high HDO activity without ring-saturation or ring-opening with the main products being benzene, phenol along with small amounts of cresol, toluene and trimethylbenzene (TMB). A substantial enhancement in HDO activity was observed on the PdFe/C catalysts. Compared with Fe/C, the yield to oxygen-free aromatic products (i.e., benzene/toluene/TMB) on PdFe/C increased by a factor of four at 350 °C, and by approximately a factor of two (83.2% versus 43.3%) at 450 °C. The enhanced activity of PdFe/C is attributed to the formation of PdFe alloy as evidenced by STEM, EDS and TPR.

  3. Selectivity, activity and metal-support interactions of Group VIII bimetallic catalysts. Progress report, 15 August 1983-15 August 1984

    International Nuclear Information System (INIS)

    Progress on supported bimetallic catalysts and the development of techniques for the characterization of supported catalysts is reported. Three bimetallic systems were studied: Rh-Pt, Ru-Cu and Rh-Ag. Goal has been the determination of the effect of the support on the kind and degree of metal-metal interaction. Small particles of Rh-Pt are found to be enriched in Rh on all supports, the degree of enrichment increasing in the order SiO22O32. The kind of SiO2 used to support Ru-Cu is found to have a large influence on the change in the H/Ru ratio when Ru and Ru-Cu/SiO2 catalysts are compared although the effect on ethane hydrogenolysis is comparable. For pure Rh supported on TiO2 and reduced at high temperature, EXAFS analysis suggests direct Rh-Ti bonding following a high temperature reduction. EXAFS also indicates that there is a stronger interaction between Ag and TiO2 than Ag and SiO2 and clearly demonstrates that there is greater metal-metal interaction for Rh-Ag supported on TiO2 than for Rh-Ag supported on SiO2. A fourth system, NiMoP/Al2O3, is not a bimetallic but was chosen as an interesting and convenient catalyst on which to initiate magic angle spinning NMR research. 27Al NMR proves that formation of the surface compound Al2(MoO4)3 on Mo/Al2O3 is induced by calcination but on NiMoP/Al2O3 this compound formation is inhibited and AlPO4 is formed instead

  4. How to Determine the Core-Shell Nature in Bimetallic Catalyst Particles?

    Directory of Open Access Journals (Sweden)

    Emma Westsson

    2014-11-01

    Full Text Available Nanometer-sized materials have significantly different chemical and physical properties compared to bulk material. However, these properties do not only depend on the elemental composition but also on the structure, shape, size and arrangement. Hence, it is not only of great importance to develop synthesis routes that enable control over the final structure but also characterization strategies that verify the exact nature of the nanoparticles obtained. Here, we consider the verification of contemporary synthesis strategies for the preparation of bimetallic core-shell particles in particular in relation to potential particle structures, such as partial absence of core, alloying and raspberry-like surface. It is discussed what properties must be investigated in order to fully confirm a covering, pin-hole free shell and which characterization techniques can provide such information. Not uncommonly, characterization strategies of core-shell particles rely heavily on visual imaging like transmission electron microscopy. The strengths and weaknesses of various techniques based on scattering, diffraction, transmission and absorption for investigating core-shell particles are discussed and, in particular, cases where structural ambiguities still remain will be highlighted. Our main conclusion is that for particles with extremely thin or mono-layered shells—i.e., structures outside the limitation of most imaging techniques—other strategies, not involving spectroscopy or imaging, are to be employed. We will provide a specific example of Fe-Pt core-shell particles prepared in bicontinuous microemulsion and point out the difficulties that arise in the characterization process of such particles.

  5. Catalyst dispersion and activity under conditions of temperature- staged liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1991-09-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation. Liquefaction experiments of solvent-treated and untreated Blind Canyon (DECS-6) and Texas lignite (DECS-1) have been performed using ammonium tetrathiomolybdate (ATTM) and bis (dicarbonylcyclopentadienyl) iron (CPI) as catalyst precursors using temperature-staged conditions (275{degrees}C, 30 min; 425{degrees}C, 30 min). Solid state {sup 13}C NMR analysis was carried out for each coal and for selected residues. 12 refs., 14 figs., 9 tabs.

  6. Low-Temperature 1,3-Butadiene Hydrogenation over Supported Pt/3d/gamma-Al2O3 Bimetallic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lonergan, William W; Xing, X; Zheng, Renyang; Qi, Suitao; Huang, B; Chen, Jingguang

    2011-02-02

    Low-temperature 1,3-butadiene hydrogenation is used as a probe reaction to investigate the hydrogenation activity over several γ-Al{sub 2}O{sub 3} supported Pt/3d (3d = Co, Ni, Cu) bimetallic catalysts. Batch and flow reactor studies are employed to quantify the kinetic activity and steady-state conversion, respectively, of each catalyst. Transmission electron microscopy (TEM) is utilized to characterize particle sizes and extended X-ray absorption fine structure (EXAFS) measurements are performed to verify the Pt–3d bimetallic bond formation. Pulse carbon monoxide chemisorption measurements are also performed to characterize the number of active sites. Additionally, density functional theory (DFT) calculations are included to determine the binding energies of 1,3-butadiene and atomic hydrogen on the corresponding model surfaces. The binding energies of the adsorbates are found to correlate with the hydrogenation activity, allowing for use of such correlation to potentially predict hydrogenation catalysts with enhanced activity based on the binding energies of the adsorbates of interest.

  7. From First Principles Design to Realization of Bimetallic Catalysts for Enhanced Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Lobo, Raul F.; Crooks, Richard M.; Mavrikakis, Manos

    2014-04-08

    “Catalysis by design” has been a dream for decades. To specify the composition and structure of matter to effect a desired catalytic transformation with desired and predicted rate and selectivity remains a monumental challenge, especially in heterogeneous catalysis. Our research thrusts have been chosen not only for their practical and scientific relevance, e.g. for more efficient and sustainable chemicals and fuels production, but also because they provide a foundation for developing and exploring broadly applicable principles and strategies for catalyst design.

  8. Preparation of Pt–Ru bimetallic catalyst supported on carbon nanotubes

    Indian Academy of Sciences (India)

    B Rajesh; K Ravindranathan Thampi; J -M Bonard; B Viswanathan

    2000-10-01

    The template carbonization of polyphenyl acetylene yields hollow, uniform cylindrical carbon nanotubes with outer diameter almost equal to pore diameter of the template used. High resolution transmission electron microscopic investigation reveals that Pt–Ru nanoparticles are highly dispersed inside the tube with an average particle size of 1.7 nm.

  9. SURFACE-MODIFIED COALS FOR ENHANCED CATALYST DISPERSION AND LIQUEFACTION

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Yaw D. Yeboah

    1999-09-01

    This is the final report of the Department of Energy Sponsored project DE-FGF22-95PC95229 entitled, surface modified coals for enhanced catalyst dispersion and liquefaction. The aims of the study were to enhance catalyst loading and dispersion in coal for improved liquefaction by preadsorption of surfactants and catalysts on the coal and to train and educate minority scientists in catalysts and separation science. Illinois No. 6 Coal (DEC-24) was selected for the study. The surfactants investigated included dodecyl dimethyl ethyl ammonium bromide (DDAB), a cationic surfactant, sodium dodecyl sulfate, an anionic surfactant, and Triton x-100, a neutral surfactant. Ammonium molybdate tetrahydrate was used as the molybdenum catalyst precursor. Zeta potential, BET, FTIR, AFM, UV-Vis and luminescence intensity measurements were undertaken to assess the surface properties and the liquefaction activities of the coal. The parent coal had a net negative surface charge over the pH range 2-12. However, in the presence of DDAB the negativity of the surface charge decreased. At higher concentrations of DDAB, a positive surface charge resulted. In contrast to the effect of DDAB, the zeta potential of the coal became more negative than the parent coal in the presence of SDS. Adsorption of Triton reduced the net negative charge density of the coal samples. The measured surface area of the coal surface was about 30 m{sup 2}/g compared to 77m{sup 2}/g after being washed with deionized water. Addition of the surfactants decreased the surface area of the samples. Adsorption of the molybdenum catalyst increased the surface area of the coal sample. The adsorption of molybdenum on the coal was significantly promoted by preadsorption of DDAB and SDS. Molybdenum adsorption showed that, over a wide range of concentrations and pH values, the DDAB treated coal adsorbed a higher amount of molybdenum than the samples treated with SDS. The infrared spectroscopy (FTIR) and the atomic force

  10. Effects of the ratio of Fe to Co over Fe-Co/SiO2 bimetallic catalysts on their catalytic performance for Fischer-Tropsch synthesis

    Institute of Scientific and Technical Information of China (English)

    Xiangdong Ma; Qiwen Sun; Weiyong Ying; Dingye Fang

    2009-01-01

    The Fe-Co/SiO2 bimetallic catalysts with different ratios of Fe to Co were prepared by aqueous incipient wetness impregnation. The catalysts of 10%Fe:0%Co/SiO2, 10%Fe:6%Co/SiO2, 10%Fe:2%Co/SiO2, 10%Fe: 10%Co/SiO2, 6%Fe: 10%Co/SiO2, 2%Fe: 10%Co/SiO2 and 0%Fe: 10%Co/SiO2 by mass were tested in a fixed reactor by the Fischer-Tropsch synthesis. Activity and hydrocarbon distribution were found to be determined by the ratio of iron to cobalt of the catalysts. Higher iron content inhibited the activity, whereas higher cobalt content enhanced the activity of the Fe-Co/SiO2 catalysts. On the other hand, for the catalysts of 10%Fe:6%Co/SiO2, 10%Fe: 10%Co/SiO2, 6%Fe: 10%Co/SiO2, and 2%Fe: 10%Co/SiO2, the total C2-C4 fraction increased (from 10.65% to 26.78%) and C5+ fraction decreased (from 75.75% to 57.63%) at 523 K. Temperature programmed reduction revealed that the addition of cobalt enhanced the reducibility of the Fe-Co/SiO2 catalyst. Metal oxides were present in those catalysts as shown by XRD. The Fe-Co alloy phase was found in the 2%Fe: 10%Co/SiO2, 6%Fe: 10%Co/SiO2, 10%Fe:10%Co/SiO2, 10%Fe:6%Co/SiO2 catalysts and their crystals were perfect.

  11. A structure investigation of Pt-Co bimetallic catalysts fabricated by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Lucariello, Marialaura; Penazzi, Nerino [Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, C.so Duca Abruzzi n. 24, I-10129 Torino (Italy); Arca, Elisabetta; Mulas, Gabriele [Dipartimento di Chimica, Universita di Sassari, Via Vienna n. 2, I-07100 Sassari (Italy); Enzo, Stefano [Dipartimento di Chimica, Universita di Sassari, Via Vienna n. 2, I-07100 Sassari (Italy)], E-mail: enzo@uniss.it

    2009-03-15

    Three Pt-Co mixtures of composition Pt{sub 25}Co{sub 75}, Pt{sub 50}Co{sub 50} and Pt{sub 75}Co{sub 25} respectively, were synthesized using the high-energy ball milling technique of the elemental powders with a view to prepare catalysts for fuel cells. The kinetics of phase evolution, their structure and average microstructure properties were quantitatively investigated by X-ray powder diffraction with the Rietveld method. The results show that the ball milling technique is able to produce Pt-Co solid solutions soon after few minutes of mechanical treatment. Of the two polymorphs of cobalt the fcc allotrope appears to be involved preferentially in the early stage of alloying reaction with fcc platinum. For the three compositions, a sigmoidal equation based on an interdiffusion-controlled mechanism satisfactorily accounts for the evolution of the solid solution as a function of mechanical treatment time. A characteristic reaction time of 3-6 h is observed for the solid state transformation reaction with the milling conditions adopted in our reactor. In the case of the Pt{sub 25}Co{sub 75} composition, a competitive-consecutive reaction is observed. Lattice parameters of the solid solutions after extended times of milling and related atomic volumes turn out to be slightly above the values ideally predicted on the basis of the Vegard's law. For the Pt{sub 75}Co{sub 25} composition the average crystallite size is reduced down to ca. 150 A after 12 h when the lattice microstrain is also at a maximum, but further mechanical treatment increases the average crystal size value and to decrease the strain. Similar results are found for equiatomic and Co-rich compositions. Annealing of the alloyed equiatomic powders promotes a cubic-to-tetragonal transformation which is already operative at 600 deg. C. In fact, after this treatment two tetragonal phases are observed. Further thermal treatment and annealing at 700 deg. C induces peak sharpening of the diffraction patterns

  12. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst

    Science.gov (United States)

    Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang; Cho, Sung June; Yun, Seongho; Kim, Hee-Tak; Mayrhofer, Karl J. J.; Kim, Hyungjun; Choi, Minkee

    2016-01-01

    Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H2O, but selectively produces H2O2 even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H2O2, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts. PMID:26952517

  13. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst

    Science.gov (United States)

    Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang; Cho, Sung June; Yun, Seongho; Kim, Hee-Tak; Mayrhofer, Karl J. J.; Kim, Hyungjun; Choi, Minkee

    2016-03-01

    Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H2O, but selectively produces H2O2 even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H2O2, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts.

  14. Synthesis of coal-derived single-walled carbon nanotube from coal by varying the ratio of Zr/Ni as bimetallic catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Rajesh, E-mail: rajeshbhu1@gmail.com [Banaras Hindu University, Nanoscience and Nanotechnology Unit, Department of Physics (India); Singh, Rajesh Kumar, E-mail: rksbhu@gmail.com [Indian Institute of Technology (Banaras Hindu University), Department of Applied Physics (India); Ghosh, A. K.; Sen, Raja; Srivastava, S. K. [Central Institute of Mining and Fuel Research (India); Tiwari, R. S.; Srivastava, O. N. [Banaras Hindu University, Nanoscience and Nanotechnology Unit, Department of Physics (India)

    2013-01-15

    In this paper coal, source has been used in place of graphite for synthesis of single-walled carbon nanotubes (SWCNTs) with new Zr/Ni bimetallic catalyst. Using coal as starting material to produce the high-value-added SWCNTs is an economically competent route. SWCNTs have been synthesized by the electric arc discharge method using the so-called heterogeneous annealed coal anode filled with Zr and Ni catalyst. SWCNTs have been synthesized using annealed coal rod. The SWCNTs bundles synthesized generally have diameters of 4-10 nm. Most of those produced with Zr/Ni as the catalyst has a diameter ranging from 2.0 to 1.0 nm. The as-synthesized SWCNTs have been characterized employing XRD, HRTEM, EDX, Raman spectroscopy, and FTIR. It has been found that the change of the ratio of Zr and Ni concentration (wt%) in the catalyst affects the yield of SWCNTs. However, the purity of SWCNTs is very sensitive to the concentration of Zr. An optimal range of Zr/Ni compositions for synthesis of SWCNTs with relatively high purity and yield is obtained at specific concentration of 3:1.

  15. Role of Pt(0) in bimetallic (Pt,Fe)-FER catalysts in the N2O decomposition

    Czech Academy of Sciences Publication Activity Database

    Tabor, Edyta; Jíša, Kamil; Nováková, Jana; Bastl, Zdeněk; Vondrová, Alena; Závěta, K.; Sobalík, Zdeněk

    2013-01-01

    Roč. 165, JAN 2013 (2013), s. 40-47. ISSN 1387-1811 R&D Projects: GA ČR GA203/09/1627 Institutional support: RVO:61388955 Keywords : bimetallic Pt,Fe- FER * Pt- FER * Pt(0) clusters Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.209, year: 2013

  16. Advanced liquefaction using coal swelling and catalyst dispersion techniques

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. (Auburn Univ., AL (United States)); Gutterman, C. (Foster Wheeler Development Corp., Livingston, NJ (United States)); Chander, S. (Pennsylvania State Univ., University Park, PA (United States))

    1992-08-26

    Research in this project centers upon developing a new approach to the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates all aspects of the coal liquefaction process including coal selection, pretreatment, coal swelling with catalyst impregnation, coal liquefaction experimentation, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. On May 28, 1992, the Department of Energy authorized starting the experimental aspects of this projects; therefore, experimentation at Amoco started late in this quarterly report period. Research contracts with Auburn University, Pennsylvania State University, and Foster Wheeler Development Corporation were signed during June, 1992, so their work was just getting underway. Their work will be summarized in future quarterly reports. A set of coal samples were sent to Hazen Research for beneficiation. The samples were received and have been analyzed. The literature search covering coal swelling has been up-dated, and preliminary coal swelling experiments were carried out. Further swelling experimentation is underway. An up-date of the literature on the liquefaction of coal using dispersed catalysts is nearing completion; it will be included in the next quarterly report.

  17. Heterogenized Bimetallic Pd-Pt-Fe3O4 Nanoflakes as Extremely Robust, Magnetically Recyclable Catalysts for Chemoselective Nitroarene Reduction.

    Science.gov (United States)

    Byun, Sangmoon; Song, Yeami; Kim, B Moon

    2016-06-15

    A very simple synthesis of bimetallic Pd-Pt-Fe3O4 nanoflake-shaped alloy nanoparticles (NPs) for cascade catalytic reactions such as dehydrogenation of ammonia-borane (AB) followed by the reduction of nitro compounds (R-NO2) to anilines or alkylamines (R-NH2) in methanol at ambient temperature is described. The Pd-Pt-Fe3O4 NPs were easily prepared via a solution phase hydrothermal method involving the simple one-pot coreduction of potassium tetrachloroplatinate (II) and palladium chloride (II) in polyvinylpyrrolidone with subsequent deposition on commercially available Fe3O4 NPs. The bimetallic Pd-Pt alloy NPs decorated on Fe3O4 NPs provide a unique synergistic effect for the catalysis of cascade dehydrogenation/reduction. Various nitroarene derivatives were reduced to anilines with very specific chemoselectivity in the presence of other reducible functional groups. The bimetallic Pd-Pt-Fe3O4 NPs provide a unique synergistic effect for the catalysis of cascade dehydrogenation/reduction. The nitro reduction proceeded in 5 min with nearly quantitative conversions and yields. Furthermore, the magnetically recyclable nanocatalysts were readily separated using an external magnet and reused up to 250 times without any loss of catalytic activity. A larger scale (10 mmol) reaction was also successfully performed with >99% yield. This efficient, recyclable Pd-Pt-Fe3O4 NPs system can therefore be repetitively utilized for the reduction of various nitro-containing compounds. PMID:27191706

  18. Dendritic Pt-Cu bimetallic nanocrystals with a high electrocatalytic activity toward methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Jintao; Ma Jizhen [Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576 (Singapore); Wan Yong [Institute of Multifunctional Materials (IMM), Laboratory of New Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071 (China); Jiang Jianwen [Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576 (Singapore); Zhao, X.S., E-mail: george.zhao@uq.edu.au [Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576 (Singapore); Institute of Multifunctional Materials (IMM), Laboratory of New Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071 (China)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer Dendritic Pt-Cu bimetallic nanocrystals were synthesized by one-step aqueous-phase reduction. Black-Right-Pointing-Pointer The formation process of dendritic Pt-Cu bimetallic nanocrystals can be carried out under mild conditions. Black-Right-Pointing-Pointer The dendritic Pt-Cu bimetallic nanocrystals exhibited a higher catalytic activity toward the electro-oxidation of methanol than commercial Pt/C catalysts. Black-Right-Pointing-Pointer The new findings are of fundamental importance to the development of high-performance electrocatalysts for direct methanol fuel cell. - Abstract: Dendritic Pt-Cu bimetallic nanocrystals were synthesized by one-step aqueous-phase reduction of H{sub 2}PtCl{sub 6} and CuCl{sub 2} at a mild temperature (60 Degree-Sign C). The morphology and composition of the dendritic Pt-Cu nanocrystals were characterized by means of high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectrometer. The electrochemical properties were characterized by the cyclic voltammetry technique. It was found that the dendritic Pt-Cu bimetallic nanocrystals exhibited a higher catalytic activity toward the electro-oxidation of methanol than commercial Pt/C catalyst The enhanced catalytic activity would be contributed to the unique dendritic structure and the formation of Pt-Cu alloy nanocrystals.

  19. Surface structure and reaction property of CuCl2-PdCl2 bimetallic catalyst in methanol oxycarbonylation: A DFT approach

    International Nuclear Information System (INIS)

    Surface structure of CuCl2-PdCl2 bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl2-PdCl2 surfaces was also investigated. On the CuCl2-PdCl2 surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl2 surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH3 on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH3 species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl2-PdCl2 surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl2-CuCl2 catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.

  20. Electrochemical and structural characterization of carbon-supported Pt-Pd bimetallic electrocatalysts prepared by electroless deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Masato; Beard, Kevin D.; Ma Shuguo; Blom, Douglas A.; St-Pierre, Jean; Van Zee, John W. [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Monnier, John R., E-mail: monnier@cec.sc.ed [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States)

    2010-10-01

    Electrochemical and structural characteristics of various Pt-Pd/C bimetallic catalysts prepared by electroless deposition (ED) methods have been investigated. Structural analysis was conducted by X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy (EDS). Monometallic Pt or Pd particles were not detected by EDS, indicating the ED methodology formed only bimetallic particles. The size of the Pt-Pd bimetallic particles was smaller than those of a commercially available Pt/C catalyst. The morphology of the Pt on Pd/C catalysts was identified and corresponded to Pd particles partially encapsulated by Pt. The electrochemical characteristics of the lowest Pd loading catalyst (7.0% Pt on 0.5% Pd/C) for the oxygen reduction reaction (ORR) have been investigated by the rotating ring disk electrode technique. The electrochemical activity was equal or lower than the commercially available Pt/C catalyst; however, the amount of hydrogen peroxide observed at the ring was reduced by the Pd, suggesting that such a catalyst has the potential to decrease ionomer degradation in applications. The Pt on Pd/C catalysts also show a higher tolerance to ripening induced by potential cycling. Therefore, catalyst suitability cannot be judged solely by its initial performance; information related to specific degradation mechanisms is also needed for a more complete assessment.

  1. Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ying; Gao, Guang; Zhang, Xin; Li, Fuwei [ChinaU - Petroleum; (Chinese Aca. Sci.)

    2016-02-04

    Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (RuxNi1–x–OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophase before pyrolysis and silica removal. The resulting RuxNi1–x–OMC materials are in-depth characterized with X-ray diffraction, N2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru0.9Ni0.1–OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h–1) was obtained, and the Ru0.9Ni0.1–OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.

  2. One step electrochemical synthesis of bimetallic PdAu supported on nafion–graphene ribbon film for ethanol electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Shendage, Suresh S., E-mail: sureshsshendage@gmail.com; Singh, Abilash S.; Nagarkar, Jayashree M., E-mail: jm.nagarkar@ictmumbai.edu.in

    2015-10-15

    Highlights: • Electrochemical deposition of bimetallic PdAu NPs. • Highly loaded PdAu NPs are obtained. • Nafion–graphene supported PdAu NPs shows good activity for ethanol electrooxidation. - Abstract: A nafion–graphene ribbon (Nf–GR) supported bimetallic PdAu nanoparticles (PdAu/Nf–GR) catalyst was prepared by electrochemical codeposition of Pd and Au at constant potential. The prepared catalyst was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM) and X-ray diffraction analysis (XRD). The average particle size of PdAu nanoparticles (NPs) determined from XRD was 3.5 nm. The electrocatalytic activity of the PdAu/Nf–GR catalyst was examined by cyclic voltametry. It was observed that the as prepared catalyst showed efficient activity and good stability for ethanol electrooxidation in alkaline medium.

  3. Different dispersions of group II catalysts over SBA 15 and MCM-41: Effects on transesterification reactivity

    OpenAIRE

    Sullivan, James A; Sherry, Linda

    2015-01-01

    Activities of CaO catalysts on SBA-15 and MCM-41 have been compared in transesterification and SBA-15 supported samples invariably more active than those on MCM-41. Increased activity is not due to diffusional effects (as measured using substrates of differing size) but rather to increased dispersion of CaO on SBA-15 (as measured using NOx TPD). The effect, i.e. increased reactivity of SBA-15 supported catalysts being related to increased dispersion, is also noted in supported BaO catalysts w...

  4. Energy dispersive EXAFS studies on homogeneous metal catalysts

    International Nuclear Information System (INIS)

    Extended X-ray Absorption Fine Structure (EXAFS), Quick EXAFS (QuEXAFS) and Energy Dispersive EXAFS (EDE) data have been analysed for the nickel β-diketonate catalysts, Ni(dpm)2 and Ni(dpm)2(PPh3)2, and palladium diimine catalysts, Pd(phen)Cl2, Pd(bipy)Cl2 and Pd(tmeda)Cl2, using curved wave theory with ab initio phaseshifts. The derived parameters for metal compounds were in good agreement between all methods, within experimental error of 0.02-0.05 A for the bond distances. QuEXAFS studies on Ni(dpm)2/AlEt2(OEt)/1-hexene of different ratios (1:1:20 and 1:2:20) were acquired using Si(220) monochromator at sub-ambient temperature (-20 deg. C and 0 deg. C) monitored the formation of Ni(dpm)C2H5(R), R=alkyl, and Ni(dpm)(C2H5)(PPh3) on the addition of PPh3. The derived structural parameters from QuEXAFS gave averaged distances of Ni-O 1.86 A, Ni-C 2.00 A and Ni-P 2.20 A. A stopped flow system was used for in situ time-resolved EDE and UV-visible kinetic studies on the nickel systems at room temperature. EDE measurements using a new rectangular Si(111) monochromator and Hamamatsu S4874 photodiode array at Station 9.3, Daresbury Laboratory has yielded consecutive spectra taken at 1-1000 accumulations with 2-30 ms integration time to follow the changes during initiation of the catalytic reaction. The Ni(dpm)2:AlEt2(OEt):1-hexene of ratio of 1:6:20 were acquired within 16 s, and Ni(dpm)2:PPh3:AlEt2(OEt):1-hexene of 1:2:4:20 were acquired within 0.24 s for each spectrum. The growth of a pre-edge feature and change at the top of the edge can be clearly seen to show the reaction reached completion in less than 6 s indicates averaged distances of 3 Ni-O/C 2.00 A and 1 Ni-P 2.11 A. Using the stronger reagent of AlEt3, EDE was able to follow the reaction within 31 ms (15 ms dead-time). The bond lengths in the palladium complexes in solid state were refined at 2 Pd-N 2.12 A and 2 Pd-Cl 2.33 A. Addition of AgBF4 to one of the palladium complexes gives the cationic complex, Pd

  5. Fabrication of PdCo Bimetallic Nanoparticles Anchored on Three-Dimensional Ordered N-Doped Porous Carbon as an Efficient Catalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Xue, Hairong; Tang, Jing; Gong, Hao; Guo, Hu; Fan, Xiaoli; Wang, Tao; He, Jianping; Yamauchi, Yusuke

    2016-08-17

    PdCo bimetallic nanoparticles (NPs) anchored on three-dimensional (3D) ordered N-doped porous carbon (PdCo/NPC) were fabricated by an in situ synthesis. Within this composite, N-doped porous carbon (NPC) with an ordered mesoporous structure possesses a high surface area (659.6 m(2) g(-1)), which can facilitate electrolyte infiltration. NPC also acts as a perfect 3D conductive network, guaranteeing fast electron transport. In addition, homogeneously distributed PdCo alloy NPs (∼15 nm) combined with the doping of the N element can significantly improve the electrocatalytic activity for the oxygen reduction reaction (ORR). Due to the structural and material superiority, although the weight percentage of PdCo NPs (∼8 wt%) is much smaller than that of commercial Pt/C (20 wt%), the PdCo/NPC catalyst exhibits similar excellent electrocatalytic activity; however, its superior durability and methanol-tolerance ability of the ORR are as great as those of commercial Pt/C in alkaline media. PMID:27441490

  6. Uninterrupted galvanic reaction for scalable and rapid synthesis of metallic and bimetallic sponges/dendrites as efficient catalysts for 4-nitrophenol reduction.

    Science.gov (United States)

    Barman, Barun Kumar; Nanda, Karuna Kar

    2015-03-01

    Here, we demonstrate an uninterrupted galvanic replacement reaction (GRR) for the synthesis of metallic (Ag, Cu and Sn) and bimetallic (Cu-M, M=Ag, Au, Pt and Pd) sponges/dendrites by sacrificing the low reduction potential metals (Mg in our case) in acidic medium. The acidic medium prevents the oxide formation on Mg surface and facilitates the uninterrupted reaction. The morphology of dendritic/spongy structures is controlled by the volume of acid used for this reaction. The growth mechanism of the spongy/dendritic microstructures is explained by diffusion-limited aggregate model (DLA), which is also largely affected by the volume of acid. The significance of this method is that the yield can be easily predicted, which is a major challenge for the commercialization of the products. Furthermore, the synthesis is complete in 1-2 minutes at room temperature. We show that the sponges/dendrites efficiently act as catalysts to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4-a widely studied conversion process. PMID:25628256

  7. Sulfided heterogeneous, bimetallic RuMo catalysts derived from mixtures of Ru{sub 3}(CO){sub 12} (or RuCl{sub 3}) and a molybdenum heteropolyanion. The reactions of ethanol with tetrahydroquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Koo, Sang-Man; Ryan, D.; Laine, R.M.

    1992-09-01

    Efforts have been made to develop Ru/Mo bimetallic catalyst systems for hydrodenitrogenation (HDN) of tetrahydroquinoline (THQ)- In the course of these studies, it was discovered that in ethanol, under H{sub 2} and in the presence Of CS2, Precatalyst solutions containing Ru [as Ru{sub 3} (CO){sub 12} or RuCl{sub 3}] and Mo [as the H{sub 3}PMO{sub 12}0{sub 40} heteropolyanion (HPA)] decompose to form bimetallic, sulfided particles. Particle diameters run from 0.1 to 5 {mu}m depending on the rate of stirring. Catalyst particles with sizes ranging from 0.1--1 {mu}m can be prepared reproducibly. BET measured surface areas for these size particles ranged from 2 to 20 m2/g. These sulfided particles were found to catalyze, at temperatures of 200--250{degrees}C and hydrogen pressures of 200--1000 psig H{sub 2}, the N-ethylation of THQ to form NEt-THQ; rather than the formation of propylcyclohexane or propylbenzene, reaction products expected for HDN of THQ. Monometallic heterogeneous catalysts prepared from the individual precatalyst complexes, under identical conditions, show minimal activity for N-ethylation by comparison with the bimetallic catalyst. In the absence of H{sub 2}, the reaction proceeds such that THQ is converted to Q, N-EtTHQ, N-C{sub 6}H{sub 9}-THQ, and N-C{sub 6}H{sub 13}-THQ. The latter products appear to arise via acetaldehyde, formed as an intermediate by dehydrogenation of ethanol. Acetaldehyde either condenses with THQ to form N-Et-THQ, or self condenses (aldol condensation) prior to reaction with THQ thereby giving higher homolog alkylation products.

  8. Sulfided heterogeneous, bimetallic RuMo catalysts derived from mixtures of Ru sub 3 (CO) sub 12 (or RuCl sub 3 ) and a molybdenum heteropolyanion. The reactions of ethanol with tetrahydroquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Koo, Sang-Man; Ryan, D.; Laine, R.M.

    1992-01-01

    Efforts have been made to develop Ru/Mo bimetallic catalyst systems for hydrodenitrogenation (HDN) of tetrahydroquinoline (THQ)- In the course of these studies, it was discovered that in ethanol, under H{sub 2} and in the presence Of CS2, Precatalyst solutions containing Ru (as Ru{sub 3} (CO){sub 12} or RuCl{sub 3}) and Mo (as the H{sub 3}PMO{sub 12}0{sub 40} heteropolyanion (HPA)) decompose to form bimetallic, sulfided particles. Particle diameters run from 0.1 to 5 {mu}m depending on the rate of stirring. Catalyst particles with sizes ranging from 0.1--1 {mu}m can be prepared reproducibly. BET measured surface areas for these size particles ranged from 2 to 20 m2/g. These sulfided particles were found to catalyze, at temperatures of 200--250{degrees}C and hydrogen pressures of 200--1000 psig H{sub 2}, the N-ethylation of THQ to form NEt-THQ; rather than the formation of propylcyclohexane or propylbenzene, reaction products expected for HDN of THQ. Monometallic heterogeneous catalysts prepared from the individual precatalyst complexes, under identical conditions, show minimal activity for N-ethylation by comparison with the bimetallic catalyst. In the absence of H{sub 2}, the reaction proceeds such that THQ is converted to Q, N-EtTHQ, N-C{sub 6}H{sub 9}-THQ, and N-C{sub 6}H{sub 13}-THQ. The latter products appear to arise via acetaldehyde, formed as an intermediate by dehydrogenation of ethanol. Acetaldehyde either condenses with THQ to form N-Et-THQ, or self condenses (aldol condensation) prior to reaction with THQ thereby giving higher homolog alkylation products.

  9. Characterization of Metal Dispersion of Some Naphtha Reforming Catalysts by Methylcyclohexane Dehydrogenation Reaction

    Directory of Open Access Journals (Sweden)

    Ameel Mohammed Rahman

    2009-01-01

    Full Text Available The dispersion of supported Pt and Pt–Ir reforming catalysts have been studied, after treatment with oxidative and reducing atmosphere. Methylcyclohexane dehydrogenation reaction in the absence of hydrogen was used as a test reaction. An attempt was made to relate the behavior of the catalysts upon subject to reaction, to the dispersion of the same type of catalysts upon treatment with similar atmosphere and temperatures which appeared in literature. The total conversion of reaction can be explained by a change in metal dispersion. Thus, methylcyclohexane dehydrogenation reaction appears to be a really “structure sensitive” reaction. The toluene yield increases as the oxidation temperature increases over the studied catalyst RG-402, RG-412, RG-422 and RG-432 respectively and reached a maximum value at 550°C. Above 550 the conversion decreases due to the effect of catalyst sintering. No significant change were observed for reduction temperature range 400-600°C for the above studied catalysts.The selectivity order for the studied catalysts and for reduction treatment experiments arranged as follows:RG-422> RG-432> RG-412> RG-402

  10. Chirality specific and spatially uniform synthesis of single-walled carbon nanotubes from a sputtered Co-W bimetallic catalyst

    Science.gov (United States)

    An, Hua; Kumamoto, Akihito; Takezaki, Hiroki; Ohyama, Shinnosuke; Qian, Yang; Inoue, Taiki; Ikuhara, Yuichi; Chiashi, Shohei; Xiang, Rong; Maruyama, Shigeo

    2016-07-01

    Synthesis of single-walled carbon nanotubes (SWNTs) with well-defined atomic arrangements has been widely recognized in the past few decades as the biggest challenge in the SWNT community, and has become a bottleneck for the application of SWNTs in nano-electronics. Here, we report a selective synthesis of (12, 6) SWNTs with an enrichment of 50%-70% by chemical vapor deposition (CVD) using sputtered Co-W as a catalyst. This is achieved under much milder reduction and growth conditions than those in the previous report using transition-metal molecule clusters as catalyst precursors (Nature, 2014, 510, 522). Meanwhile, in-plane transmission electron microscopy unambiguously identified an intermediate structure of Co6W6C, which is strongly associated with selective growth. However, most of the W atoms disappear after a 5 min CVD growth, which implies that anchoring W may be important in this puzzling Co-W system.Synthesis of single-walled carbon nanotubes (SWNTs) with well-defined atomic arrangements has been widely recognized in the past few decades as the biggest challenge in the SWNT community, and has become a bottleneck for the application of SWNTs in nano-electronics. Here, we report a selective synthesis of (12, 6) SWNTs with an enrichment of 50%-70% by chemical vapor deposition (CVD) using sputtered Co-W as a catalyst. This is achieved under much milder reduction and growth conditions than those in the previous report using transition-metal molecule clusters as catalyst precursors (Nature, 2014, 510, 522). Meanwhile, in-plane transmission electron microscopy unambiguously identified an intermediate structure of Co6W6C, which is strongly associated with selective growth. However, most of the W atoms disappear after a 5 min CVD growth, which implies that anchoring W may be important in this puzzling Co-W system. Electronic supplementary information (ESI) available: Raman spectroscopy (G-band) of SWNTs grown from Co and Co-W catalyst; Kataura plot for chirality

  11. Nano structural Formation of Pd-Co Bimetallic Complex on HOPG Surfaces: XPS and AFM Studies

    International Nuclear Information System (INIS)

    A new single source approach was developed to synthesize Pd-Co nanoparticles using a bimetallic compound, [Et3NH]2[CoPd2(μ-4-I-3,5-Me2pz)4Cl4](CoPd2), as a molecular precursor to obtain dispersed catalyst on highly ordered pyrolytic graphite (HOPG) surface, in view of preparing oxygen reduction catalysts for low temperature fuel cells. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques were employed to characterize the nano structure formations and to determine the composition and morphology of the complex on the HOPG. Results of high resolution XPS analysis (HR-XPS) revealed the binding energies corresponding to the atomic constituents of the precursor. When the precursor solution was placed on the surface of the HOPG, the bimetallic complex assumes a tubular structure and it appears that the surface of the HOPG offers a ground for the self-organization of nano structural formations.

  12. PROPERTIES OF HIGHLY DISPERSED PALLADIUM CATALYSTS ON POLY N—VINYL—2—PYRROLIDONE

    Institute of Scientific and Technical Information of China (English)

    SUNJuntan; CHENChunfu; 等

    1992-01-01

    Four kinds of palladium catalysts dispersed on poly-N-vinyl-2-pyrrolidone were prepared by using CH3OH-NaOH,NaBH4,H2O or CH3OH-H2O as the reducing agent in the process of catalyst preparation. The catalysts were characterized by XPS,TEM,XRD and used for the hydrogenation of methyl acrylate.It was found that the valence state of palladium and distribution of palladium particles as well as the hydrogenation rate were greatly affected by the reducing agent.The best evenly dispersed palladium catalyst showing high hydrogenation activity was prepared using CH3OH-NaOH as the reducing agent.

  13. Chirality specific and spatially uniform synthesis of single-walled carbon nanotubes from a sputtered Co-W bimetallic catalyst.

    Science.gov (United States)

    An, Hua; Kumamoto, Akihito; Takezaki, Hiroki; Ohyama, Shinnosuke; Qian, Yang; Inoue, Taiki; Ikuhara, Yuichi; Chiashi, Shohei; Xiang, Rong; Maruyama, Shigeo

    2016-08-14

    Synthesis of single-walled carbon nanotubes (SWNTs) with well-defined atomic arrangements has been widely recognized in the past few decades as the biggest challenge in the SWNT community, and has become a bottleneck for the application of SWNTs in nano-electronics. Here, we report a selective synthesis of (12, 6) SWNTs with an enrichment of 50%-70% by chemical vapor deposition (CVD) using sputtered Co-W as a catalyst. This is achieved under much milder reduction and growth conditions than those in the previous report using transition-metal molecule clusters as catalyst precursors (Nature, 2014, 510, 522). Meanwhile, in-plane transmission electron microscopy unambiguously identified an intermediate structure of Co6W6C, which is strongly associated with selective growth. However, most of the W atoms disappear after a 5 min CVD growth, which implies that anchoring W may be important in this puzzling Co-W system. PMID:27412697

  14. Development of a PtSn bimetallic catalyst for direct fuel cells using bio-butanol fuel

    OpenAIRE

    Puthiyapura, V.K.; Brett, D. J. L.; Russell, A E; Lin, W.F.; Hardacre, C.

    2015-01-01

    Pt and PtSn catalysts were studied for n-butanol electro-oxidation at various temperatures. PtSn showed a higher activity towards butanol electro-oxidation compared to Pt in acidic media. The onset potential for n-butanol oxidation on PtSn is similar to 520 mV lower than that found on Pt, and significantly lower activation energy was found for PtSn compared with that for Pt.

  15. Development of a PtSn bimetallic catalyst for direct fuel cells using bio-butanol fuel.

    Science.gov (United States)

    Puthiyapura, V K; Brett, D J L; Russell, A E; Lin, W F; Hardacre, C

    2015-09-01

    Pt and PtSn catalysts were studied for n-butanol electro-oxidation at various temperatures. PtSn showed a higher activity towards butanol electro-oxidation compared to Pt in acidic media. The onset potential for n-butanol oxidation on PtSn is ∼520 mV lower than that found on Pt, and significantly lower activation energy was found for PtSn compared with that for Pt. PMID:26214283

  16. Dispersed catalysts for transforming extra heavy crude oil into transportable upgraded crude: phase identification

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, S.; Canizales, E.; Machin, I. [Gerencia Depttal de Investigacion Estrategica en Refinacion PDVSA Intevep (Venezuela); Segovia, X.; Rivas, A.; Lopez, E.; Pena, J.P.; Rojas, J.D.; Sardella, R. [Gerencia Depttal de Infraestructura y Mejoramiento en Faja Petrolifera PDVSA Intevep (Venezuela)

    2011-07-01

    A new technology to convert extra heavy crude oil into transportable upgraded crude has been developed. A water/oil emulsion composed of steam and catalyst precursors is introduced in the feed which then generates unsupported dispersed catalyst in situ under thermal decomposition. The aim of this paper is to characterize the particles. The study was conducted in a laboratory and on a pilot scale on three different vacuum residues using high resolution transmission electron microscopy and a transmission electron microscope. Results showed that the particles were formed by oxides and inorganic sulphur based in transition metals and their sizes ranged between 5 and 120 nm; in addition, good dispersion was observed. This study demonstrated that the process involved in the generation of dispersed catalyst is extremely complex and showed that further work with heavy crude oils and its residua is required to understand the mechanisms involved.

  17. Science Letters: Structure relationship of nitrochlorobenzene catalytic degradation process in water over palladium-iron bimetallic catalyst

    Institute of Scientific and Technical Information of China (English)

    NIU Shao-feng; ZHOU Hong-yi; AO Xu-ping; XU Xin-hua; LOU Zhang-hua

    2006-01-01

    Two isomers of nitrochlorobenzene (o-, and p-NCB) were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines (CAN) first through an amination process, and then rapidly dechlorinated to become aniline (AN) and Cl-, without the involvement of any other intermediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene (o-, and p-NCB) in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy (correlation with the activation energy) of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.

  18. Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1993-02-01

    This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275{degrees}C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

  19. Catalyst dispersion and activity under conditions of temperature-staged liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1993-02-01

    This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275[degrees]C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

  20. Investigation on Dispersed Catalyst for Slurry Bed Hydroprocessing of Heavy Oil

    Institute of Scientific and Technical Information of China (English)

    Liu Dong; Guo Aijun; Ma Kuiju; Que Guohe

    2006-01-01

    The slurry-bed hydrocracking of Karamay VGO with water-soluble dispersed catalyst was studied and the catalyst after being separated from the reaction products was analyzed by using LRS, XRD and XPS to identify the crystal structure of the catalyst. In this paper, the catalytic functions of molybdenum, nickel and iron were studied respectively during the slurry-phase hydrocracking while using diphenylmethane as the model compound and VGO from Karamay crude as the feedstock. The test results showed that, during the slurry-phase hydrocracking of heavy oil, the metal sulfides entered into chemical reactions with the free radical intermediate H· formed on the catalyst surface. The free-radical intermediate H· formed on the catalyst surface could react with the free-radicals of big molecules and could suppress coke deposition.

  1. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  2. The Simple, Effective Synthesis of Highly Dispersed Pd/C and CoPd/C Heterogeneous Catalysts via Charge-Enhanced Dry Impregnation

    Directory of Open Access Journals (Sweden)

    Lawrence D’Souza

    2016-05-01

    Full Text Available Pd/C and CoPd/C heterogeneous catalysts have been synthesized by adopting Charge Enhanced Dry Impregnation (CEDI. The particles size distribution, their high metal surface-to-bulk ratios, and synthesis feasibility are unmatchable to any known noble metal bimetallic heterogeneous catalyst preparation techniques. Next generation Fuel Cells and Fischer-Tropsch catalytic processes economy will be benefited from the proposed methodology.

  3. Synthesis of highly dispersed and active palladium/carbon nanofiber catalyst for formic acid electrooxidation

    Science.gov (United States)

    Qin, Yuan-Hang; Yue-Jiang; Yang, Hou-Hua; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2011-05-01

    Highly dispersed and active palladium/carbon nanofiber (Pd/CNF) catalyst is synthesized by NaBH4 reduction with trisodium citrate as the stabilizing agent. The obtained Pd/CNF catalyst is characterized by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The results show that the Pd nanoparticles with an average particle size of ca. 3.8 nm are highly dispersed on the CNF support even with a small ratio of citrate to Pd precursor, which is believed to be due to the pH adjustment of citrate stabilized colloidal Pd nanoparticles. The cyclic voltammetry and chronoamperometry techniques show that the obtained Pd/CNF catalyst exhibits good catalytic activity and stability for the electrooxidation of formic acid.

  4. Catalyst dispersion and activity under conditions of temperature-staged liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  5. The role of the catalysts with highly dispersed and isolated active sites in the selective oxidation of light hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    WANG Hongxuan; ZHAO Zhen

    2005-01-01

    This review summarizes the role of catalysts with highly dispersed and isolated active sites (active sites: supported atoms f≤0.5 % ) in the selective oxidation of light hydrocarbons, such as methane, ethane and propane, into oxygenatesand the epoxidation of olefins. The plausible structures of the highly dispersed and isolated active species, as well as their effects on the catalytic performances are discussed. The special physico-chemical properties and the functional mechanism of the catalysts with highly dispersed and isolated active sites, as well as the preparation, characterization of the catalysts with highly dispersed and isolated active sites and their applications in other types of reactions of lower hydrocarbons are summarized.

  6. Catalytic selectivity and H-transfer in the hydroconversion of a petroleum residue using dispersed catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cebolla, V.L.; Membrado, L.; Vela, J.; Bacaud, R.; Rouleau, L. [Instituto de Carboquimica, Zaragoza (Spain). Dept. de Procesos Quimicos

    1995-09-01

    Hydroconversion of a deasphalted vacuum residue of a crude oil has been performed in the presence of various disposable, dispersed catalysts at low concentration (450 ppm of metal) under identical conditions: a plasma-prepared nickel-carbon catalyst, an oil-soluble molybdenum naphthenate, and a commercial nickel-molybdenum supported on alumina, in order to obtain some insight into their influence upon their mechanisms of hydrogen transfer, and to evaluate their selectivities toward the production of various hydrocarbon groups. For this last purpose, a quantitative, rapid and accurate method for hydrocarbon group type analysis has been used, based on an improved system of thin-layer chromatography with flame ionization detection. The catalysts significantly affect the quantitative distribution of hydrocarbon groups without producing new chemical families. The total hydrogen consumption is only slightly increased in the presence of these kind of catalysts. However, a different distribution of the hydrogen is achieved depending on the catalyst. Molybdenum naphthenate exhibits the higher hydrogen incorporation to its derived distillates, which in turn present significantly higher number-average molecular weight and percentage of saturates than those obtained with the other catalysts. For every catalyst studied, the more the incorporation of hydrogen in distillates, the less the production of coke and gas. Throughout this paper, the agreement between the data obtained from TLC-FID and hydrogen balance is evidenced and explained. 18 refs., 5 figs., 2 tabs.

  7. Improvements of Pd/C Catalyst Support Characteristics by Various Physical Dispersion Methods.

    Science.gov (United States)

    Baek, Jae Ho; Kim, Ji Sun; Moon, Myung-Jun; Lee, Man Sig

    2015-07-01

    Pd/C catalysts were prepared by ion exchange in aqueous solution. Physical dispersion methods including sonication, high share mixer and stirrer were used for though high dispersion of carbon. The physical properties of the prepared Pd/C particles were investigated by BET, XRD, and FE-TEM. The dispersion of Pd nanoparticles on carbon was measured on the basis of CO adsorption capacity using a pulse technique. FE-TEM micrographs showed that Pd nano particles possessed a spherical morphology with a narrow size distribution, with particles sizes ranging from 2-25 nm. The Pd particles prepared using sonication and high share mixer are well dispersed compared to the stirrer method. In addition, metal dispersions as calculated by CO uptake were 11.3, 20.4, and 25.0% for the stirrer, sonication and high share mixer methods, respectively. PMID:26373131

  8. Microwave-assisted synthesis of high-loading, highly dispersed Pt/carbon aerogel catalyst for direct methanol fuel cell

    Indian Academy of Sciences (India)

    Zhijun Guo; Hong Zhu; Xinwei Zhang; Fanghui Wang; Yubao Guo; Yongsheng Wei

    2011-06-01

    A Pt supported on carbon aerogel catalyst has been synthesized by the microwave-assisted polyol process. The Pt supported on carbon aerogel catalyst was characterized by high resolution transmission electron microscopy and X-ray diffraction. The results show a uniform dispersion of spherical Pt nanoparticles 2.5–3.0 nm in diameter. Cyclic voltammetry and chronoamperometry were used to evaluate the electrocatalytic activity of the Pt/carbon aerogel catalyst for methanol oxidation at room temperature. The Pt/carbon aerogel catalyst shows higher electrochemical catalytic activity and stability for methanol oxidation than a commercial Pt/C catalyst of the same Pt loading.

  9. Deoxyribonucleic acid-directed growth of well dispersed nickel-palladium-platinum nanoclusters on graphene as an efficient catalyst for ethanol electrooxidation

    Science.gov (United States)

    Ma, Jingwen; Wang, Jun; Zhang, Guanghui; Fan, Xiaobin; Zhang, Guoliang; Zhang, Fengbao; Li, Yang

    2015-03-01

    Trimetallic NiPdPt alloy nanoclusters with diameter of about 10 nm are successfully dispersed on the deoxyribonucleic acid-modified reduced graphene oxide (DNA-rGO) by using NaBH4 as reductant. The prepared NiPdPt nanoclusters grown on DNA-rGO (NiPdPt/DNA-rGO) composite are used as electrocatalysts for ethanol electrooxidation in alkaline solution. Cyclic voltammetry and chronoamperometry are used to investigate the electrochemical activities and stabilities of the catalysts. The Ni1Pd1Pt1/DNA-rGO (molar ratio of Ni, Pd, Pt is 1:1:1) has extraordinary electrocataltic activity, with their mass current density reaching 3.4 A mg-1metal and better stability. As compared with the bimetallic counterparts and NiPdPt grown on multi-wall carbon nanotubes, Ni1Pd1Pt1/DNA-rGO retains the highest mass current density after a 2000 s current-time test at 0 V.

  10. Synthesis, characterization, and growth simulations of Cu–Pt bimetallic nanoclusters

    Directory of Open Access Journals (Sweden)

    Subarna Khanal

    2014-08-01

    Full Text Available Highly monodispersed Cu–Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM and spherical aberration (Cs-corrected scanning transmission electron microscopy (STEM images shows that the average diameter of the Cu–Pt nanoclusters is 3.0 ± 1.0 nm. The high angle annular dark field (HAADF-STEM images, intensity profiles, and energy dispersive X-ray spectroscopy (EDX line scans, allowed us to study the distribution of Cu and Pt with atomistic resolution, finding that Pt is embedded randomly in the Cu lattice. A novel simulation method is applied to study the growth mechanism, which shows the formation of alloy structures in good agreement with the experimental evidence. The findings give insight into the formation mechanism of the nanosized Cu–Pt bimetallic catalysts.

  11. CuO role in {gamma}-Fe{sub 2}O{sub 3}-supported Pt-Cu bimetallic nanoparticles synthesized by radiation-induced reduction as catalysts for preferential CO oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Moriya, Toshiharu, E-mail: t-moriya@mit.eng.osaka-u.ac.jp; Kugai, Junichiro; Seino, Satoshi; Ohkubo, Yuji; Nakagawa, Takashi [Osaka University, Graduate School of Engineering (Japan); Nitani, Hiroaki [High Energy Accelerator Research Organization (KEK), Institute of Materials Structure Science (Japan); Yamamoto, Takao A. [Osaka University, Graduate School of Engineering (Japan)

    2013-02-15

    Modification of supported Pt catalyst by transition metal is effective for improving catalytic performance in fuel processing and electrochemical processes. In order to identify the role of CuO in Pt-Cu bimetallic nanoparticle catalyst in CO preferential oxidation in H{sub 2}-rich gas, three {gamma}-Fe{sub 2}O{sub 3}-supported Pt-Cu catalyst samples consisting of Pt-Cu alloy with different CuO content were synthesized by a radiolytic process. By managing the concentrations of the copper source and oxygen dissolved in the precursor solution, the CuO content was successfully varied by an order of magnitude without changing the structure and composition of the Pt-Cu alloy. In the catalytic tests, CuO-promoted CO oxidation significantly at around 100 Degree-Sign C. The catalyst with the highest CuO content showed the highest CO and O{sub 2} conversions. It was considered that the CuO phase promotes oxygen supply to CO chemisorbed on the Pt-Cu alloy surface. The alloy-CuO contact was suggested to be critical for the promoting effect.

  12. CuO role in γ-Fe2O3-supported Pt–Cu bimetallic nanoparticles synthesized by radiation-induced reduction as catalysts for preferential CO oxidation

    International Nuclear Information System (INIS)

    Modification of supported Pt catalyst by transition metal is effective for improving catalytic performance in fuel processing and electrochemical processes. In order to identify the role of CuO in Pt–Cu bimetallic nanoparticle catalyst in CO preferential oxidation in H2-rich gas, three γ-Fe2O3-supported Pt–Cu catalyst samples consisting of Pt–Cu alloy with different CuO content were synthesized by a radiolytic process. By managing the concentrations of the copper source and oxygen dissolved in the precursor solution, the CuO content was successfully varied by an order of magnitude without changing the structure and composition of the Pt–Cu alloy. In the catalytic tests, CuO-promoted CO oxidation significantly at around 100 °C. The catalyst with the highest CuO content showed the highest CO and O2 conversions. It was considered that the CuO phase promotes oxygen supply to CO chemisorbed on the Pt–Cu alloy surface. The alloy-CuO contact was suggested to be critical for the promoting effect.

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

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

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

  14. Synthesis, Characterization, and Catalytic Function of Novel Highly Dispersed Tungsten Oxide Catalysts on Mesoporous Silica

    Energy Technology Data Exchange (ETDEWEB)

    Herrera, Jose E.; Kwak, Ja Hun; Hu, Jian Zhi; Wang, Yong; Peden, Charles HF; Macht, Josef; Iglesia, Enrique

    2006-04-01

    The physical and chemical properties of tungsten oxide supported on SBA-15 mesoporous silica prepared by a controlled grafting process through atomic layer deposition (ALD) were studied using complementary characterization methods. X-ray diffraction, optical absorption and transmission electron microscopy showed that tungsten oxide species are highly dispersed on SBA-15 surfaces, even at 30 wt.% WOx contents (surface density: 1.33 WOx/nm2). ALD methods led to samples with much better thermal stability than those prepared via impregnation. Dehydration reactions of 2-butanol and methanol dehydration were used as probe reactions. Differences in reaction rates between the samples prepared by ALD and conventional impregnation reflect the sintering resistance of catalysts prepared by ALD. Notably, temperature programmed oxidation of spent catalysts showed that carbon formation was not responsible for the different dehydration rates in samples prepared by ALD and impregnation..

  15. Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

    OpenAIRE

    Anna M. Venezia; Fabrizio Puleo; Valeria La Parola; Giuseppe Pantaleo; Hongjing Wu; Leonarda F. Liotta

    2013-01-01

    Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside...

  16. The study on preparation of high dispersion and pure cerium dioxide for producing automotive exhaust catalysts

    International Nuclear Information System (INIS)

    The multi-stage counter-current solvent extraction process using TBP as the solvent has been carried out for purifying cerium and the ammonium carbonate precipitation method has been used to produce the cerium oxide of high dispersion and pure. The flow sheet of extraction system includes 3 extraction stages with O/A = 0.7,2 stripping stages and 4 scrubbing stages with O/A = 5. The condition for ammonium carbonate precipitation, drying and calcination have been investigated and a procedure that seem to be practically suitable to prepare cerium dioxide powder with great specific surface area for producing automotive exhaust catalyst has been proposed. (LMT)

  17. Nanocrystal and surface alloy properties of bimetallic Gold-Platinum nanoparticles

    Directory of Open Access Journals (Sweden)

    Mott Derrick

    2006-01-01

    Full Text Available AbstractWe report on the correlation between the nanocrystal and surface alloy properties with the bimetallic composition of gold-platinum(AuPt nanoparticles. The fundamental understanding of whether the AuPt nanocrystal core is alloyed or phase-segregated and how the surface binding properties are correlated with the nanoscale bimetallic properties is important not only for the exploitation of catalytic activity of the nanoscale bimetallic catalysts, but also to the general exploration of the surface or interfacial reactivities of bimetallic or multimetallic nanoparticles. The AuPt nanoparticles are shown to exhibit not only single-phase alloy character in the nanocrystal, but also bimetallic alloy property on the surface. The nanocrystal and surface alloy properties are directly correlated with the bimetallic composition. The FTIR probing of CO adsorption on the bimetallic nanoparticles supported on silica reveals that the surface binding sites are dependent on the bimetallic composition. The analysis of this dependence further led to the conclusion that the relative Au-atop and Pt-atop sites for the linear CO adsorption on the nanoparticle surface are not only correlated with the bimetallic composition, but also with the electronic effect as a result of the d-band shift of Pt in the bimetallic nanocrystals, which is the first demonstration of the nanoscale core-surface property correlation for the bimetallic nanoparticles over a wide range of bimetallic composition.

  18. Catalyst dispersion and activity under conditions of temperature- staged liquefaction. [Catalyst precursors for molybdenum-based catalyst and iron-based catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-07-01

    Two coals, a Texas subbituminous C and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling and catalyst impregnation on liquefaction conversion behavior in temperature staged reactions for 30 minutes each at 275{degree} and 425{degree}C in H{sub 2} and 95:5 H{sub 2}:H{sub 2}S atmospheres. Methanol, pyridine, tetrahydrofuran, and tetrabutylammonium hydroxide were used as swelling agents. Molybdenum-based catalyst precursors were ammonium tetrathiomolybdate, molybdenum trisulfide, molybdenum hexacarbonyl, and bis(tricarbonylcyclopentadienyl-molybdenum). Ferrous sulfate and bis(dicarbonylcyclo-pentadienyliron) served as iron-based catalyst precursors. In addition, ion exchange was used for loading iron onto the subbituminous coal. For most experiments, liquefaction in H{sub 2}:H{sub 2}S was superior to that in H{sub 2}, regardless of the catalyst precursor. The benefit of the H{sub 2}S was greater for the subbituminous, presumably because of its higher iron content relative to the hvab coal. Tetrabutylammonium hydroxide was the only swelling agent to enhance conversion of the hvab coal significantly; it also caused a remarkable increase in conversion of the subbituminous coal. The combined application of solvent swelling and catalyst impregnation also improves liquefaction, mainly through increased oil yields from the hvab coal and increased asphaltenes from the subbituminous. A remarkable effect from use of ammonium tetrathiomolybdate as a catalyst precursor is substantial increase in pristane and phytane yields. Our findings suggest that these compounds are, at least in part, bound to the coal matrix.

  19. Cobalt Fischer-Tropsch catalysts: influence of cobalt dispersion and titanium oxides promotion

    Energy Technology Data Exchange (ETDEWEB)

    Azib, H.

    1996-04-10

    The aim of this work is to study the effect of Sol-Gel preparation parameters which occur in silica supported cobalt catalysts synthesis. These catalysts are particularly used for the waxes production in natural gas processing. The solids have been characterized by several techniques: transmission electron microscopy (TEM), X-ray absorption near edge spectroscopy (XANES), programmed temperature reduction (TPR), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), Magnetism, thermodesorption of H{sub 2} (TPD). The results indicate that the control of the cobalt dispersion and oxide phases nature is possible by modifying Sol-Gel parameters. The catalytic tests in Fischer-Tropsch synthesis were conducted on a pilot unit under pressure (20 atm) and suggested that turnover rates were independent of Co crystallite size, Co phases in the solids (Co deg., cobalt silicate) and titanium oxide promotion. On the other methane, the C{sub 3}{sup +} hydrocarbon selectivity is increased with increasing crystallite size. Inversely, the methane production is favoured by very small crystallites, cobalt silicate increase and titanium addition. However, the latter, used as a cobalt promoter, has a benefic effect on the active phase stability during the synthesis. (author). 149 refs., 102 figs., 71 tabs.

  20. Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Technical progress report, October--December 1991

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  1. Catalyst dispersion and activity under conditions of temperature- staged liquefaction. Technical progress report, July--September 1991

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  2. Effect of the Dispersibility of Nano-CuO Catalyst on Heat Releasing of AP/HTPB Propellant

    OpenAIRE

    Yi Yang; Xinjie Yu; Jun Wang; Yaxue Wang

    2011-01-01

    Kneading time is adjusted to change the dispersibility of nano-CuO in AP/HTPB (Ammonia Perchlorate/Hydroxyl-Terminated Polybutadiene) composite propellants. Nano-CuO/AP is prepared to serve as the other dispersing method of nano-CuO, named predispersing procedure. Several kinds of heat releasing, thermal decomposition by DSC, combustion heat in oxygen environment, and explosion heat in nitrogen environment, are characterized to learn the effect of dispersibility of nano-CuO catalyst on heat r...

  3. Highly Dispersed Pseudo-Homogeneous and Heterogeneous Catalysts Synthesized via Inverse Micelle Solutions for the Liquefaction of Coal

    Energy Technology Data Exchange (ETDEWEB)

    Hampden-Smith, M.; Kawola, J.S.; Martino, A.; Sault, A.G.; Yamanaka, S.A.

    1999-01-05

    The mission of this project was to use inverse micelle solutions to synthesize nanometer sized metal particles and test the particles as catalysts in the liquefaction of coal and other related reactions. The initial focus of the project was the synthesis of iron based materials in pseudo-homogeneous form. The frost three chapters discuss the synthesis, characterization, and catalyst testing in coal liquefaction and model coal liquefaction reactions of iron based pseudo-homogeneous materials. Later, we became interested in highly dispersed catalysts for coprocessing of coal and plastic waste. Bifunctional catalysts . to hydrogenate the coal and depolymerize the plastic waste are ideal. We began studying, based on our previously devised synthesis strategies, the synthesis of heterogeneous catalysts with a bifunctional nature. In chapter 4, we discuss the fundamental principles in heterogeneous catalysis synthesis with inverse micelle solutions. In chapter 5, we extend the synthesis of chapter 4 to practical systems and use the materials in catalyst testing. Finally in chapter 6, we return to iron and coal liquefaction now studied with the heterogeneous catalysts.

  4. Bimetallic Wiregauze Supported Pt-Ru Nanocatalysts for Hydrogen Mitigation.

    Science.gov (United States)

    Sanap, Kiran K; Varma, S; Waghmode, S B; Sharma, P; Manoj, N; Vatsa, R K; Bharadwaj, S R

    2015-05-01

    Passive autocatalytic recombiner (PAR) is one of the most suitable devices for mitigation of hydrogen, generated in nuclear power plant under accidental conditions. For this purpose we report development of stainless steel wire gauze supported Pt-Ru nanoparticles as catalysts. Simultaneous electroless deposition has been employed for the synthesis of the catalysts. Pt-Ru based bimetallic catalysts were characterized for their rate of coating kinetics, noble metal loading, phase purity by XRD and surface morphology by SEM, TEM and elemental analysis by SIMS. Developed catalysts were found to be active for efficient recombination of hydrogen and oxygen in air as well as in presence of various prospective poisons like CO2, CH4, CO and relative humidity. Pt-Ru based bimetallic catalyst with 0.9% loading was found to be active for CO poisoning up to 400 ppm of CO. PMID:26504972

  5. Catalytic Combustion of Voc in Air Stream Over Bimetallic Chromium-Copper Supported On Sicl4-Modified H-Zsm-5 Catalyst

    Directory of Open Access Journals (Sweden)

    A.Z. Abdullah

    2010-09-01

    Full Text Available The performance of chromium (Cr and copper (Cu on silicon tetrachloride modified H-ZSM-5 (SiCl4-Z catalyst in VOC combustion is reported. H-ZSM-5, modified with SiCl4 at 500?C for 3 h was impregnated with 1.0 wt. % of Cr and 0.5 wt. % of Cu. Performance studies were carried out at GHSV of 3,800 to 32,000 h-1 with 2,000 to 35,000 ppm of VOC. Changes in the activity of Cr-Cu/ SiCl4-Z were ascribed to extra framework deposits, surface acidity and pore characteristics. Cr-Cu/SiCl4-Z catalyst was more stable to coking, humidity and HCl than Cr-Cu/Z. In the combustion of chlorinated VOC, the chlorination of metal species deactivated the catalyst by rendering lower redox ability.

  6. Study of the re-dispersion of platinum containing bimetallic phases supported on chlorinated or neutralized alumina; Etude de la redispersion de phases bimetalliques a base de platine supportees sur alumine chloree ou neutralisee

    Energy Technology Data Exchange (ETDEWEB)

    Cholley, T.

    1997-01-31

    The re-dispersion by oxy-chlorination of platinum-tin catalysts supported on alumina constitute the matter of this work. Influence of parameters like the nature of the platinum-tin phases and particles size has been examined. The use of organometallic precursors has allowed an optimum control of the preparation and of the particles growth of the catalysts. Characterization by programmed temperature reduction (TPR), X-ray photoelectron spectroscopy (XPS), Moessbauer spectroscopy, near-edge absorption spectra (XANES) and X-ray absorption fine structure (EXAFS) has led to a better understanding of the phenomena ruling the tin reducibility. Sintering has been studied, showing that only platinum-tin alloy can sinter, while tin oxides are strongly stabilized by the support. It is shown similarly that oxy-chlorination of these catalysts causes the re-dispersion of the platinum and the platinum-tin alloy only. A re-dispersion mechanism through platinum-tin oxychloride species has been proposed. Furthermore, the main parameters influencing the re-dispersion have been highlighted. (author) 175 refs.

  7. Synthesis of higher alcohols over highly dispersed Cu-Fe based catalysts derived from layered double hydroxides.

    Science.gov (United States)

    Han, Xinyou; Fang, Kegong; Zhou, Juan; Zhao, Lu; Sun, Yuhan

    2016-05-15

    Highly dispersed Cu-Fe based catalysts with Fe/Cu molar ratios ranging from 0.2 to 1 were prepared via thermal decomposition of layered double hydroxides (LDHs) precursors and tested for higher alcohol synthesis (HAS) via CO hydrogenation. The catalysts were characterized using different techniques such as XRD, TEM, XPS, and H2-TPR. It was demonstrated that the Cu and Fe ions were highly dispersed in the brucite-like layers of the LDHs. With increased Fe/Cu atomic ratio, the tetrahedrally coordinated Cu ion content, Cu reduction temperatures, and the spacing of layers initially increase until the Fe/Cu ratio reaches 0.5 and then decrease. In addition to the catalytic evaluation for CO hydrogenation and catalyst characterization, the relationships between the physical-chemical properties of the catalysts and their catalytic performances were also investigated. It was also found that the alcohols/hydrocarbons ratios correlate linearly with the tetrahedrally coordinated Cu ion content. Moreover, higher reduction temperatures of Cu species as well as larger spacing between the layers in the catalyst are favorable for the synthesis of alcohols. The incorporation of a suitable amount of Fe is beneficial for the production of higher alcohols, with the best catalytic performance (alcohol selectivity of 20.77% and C2+ alcohol selectivity of 48.06%) obtained from a Fe/Cu atomic ratio of 0.5. PMID:26943001

  8. Structure-Property Relationship in Metal Carbides and Bimetallic Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jingguan [University of Delaware

    2014-03-04

    The primary objective of our DOE/BES sponsored research is to use carbide and bimetallic catalysts as model systems to demonstrate the feasibility of tuning the catalytic activity, selectivity and stability. Our efforts involve three parallel approaches, with the aim at studying single crystal model surfaces and bridging the “materials gap” and “pressure gap” between fundamental surface science studies and real world catalysis. The utilization of the three parallel approaches has led to the discovery of many intriguing catalytic properties of carbide and bimetallic surfaces and catalysts. During the past funding period we have utilized these combined research approaches to explore the possibility of predicting and verifying bimetallic and carbide combinations with enhanced catalytic activity, selectivity and stability.

  9. 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.

  10. Promotion of the electrocatalytic activity of a bimetallic platinum-ruthenium catalyst by repetitive redox treatments for direct methanol fuel cell

    Science.gov (United States)

    Huang, Sheng-Yang; Yeh, Chuin-Tih

    Pt-Ru/C catalyst (12 wt%) was prepared by the incipient wetness impregnation method followed by a redox heat-treatment. Transmission electron microscopy (TEM) results revealed uniformly distributed metallic crystallites of Pt-Ru alloy nanoparticles (d PtRu = 2.1 ± 1.0 nm). The effect of redox treatments of the impregnated catalysts on methanol oxidation reaction (MOR) was examined by cyclic voltammetry (CV). The MOR activity of the PtRu/C was significantly improved after each oxidation step of the redox treatment cycles. The enhanced catalytic activity was found to be quite stable in chronoamperometry (CA) measurements. CV, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results strongly suggested that the improved catalytic activity was due to the formation of a stable c-RuO x (x = 2-3) domain during the oxidation treatments. A bifunctional based mechanism was proposed for the MOR on the oxidized PtRu/C catalysts. Formation of Ru-OH species on the surface of c-RuO x domains was suggested as stale sites for the oxidation of carbon monoxide adsorbed on the Pt catalytic sites.

  11. Formation of Catalyst Model Dispersed of Pd on a thin MgO(100)

    Science.gov (United States)

    Baara, F.; Chemam, A.

    2016-04-01

    The nucleation kinetics or the formation of a catalyst model dispersed for the system Pd/thin MgO (100) are calculated by developing many programs using Fortran software. This simulation is based upon parameters studied in situ by transmission electron microscopy (TEM), related to the first quantitative study on the nucleation and the growth. Palladium nanoparticles deposited on thin MgO are tested in the temperature range 573-1073 K and deposition time of 1000 s. The nucleation kinetics are interpreted according to the theory of random nucleation. The general scheme is consisting of three stages namely, nucleation, growth and coalescence. The saturation density of clusters decreases when the substrate temperature increases following Arrhenius law. This behavior is in agreement with a recent AFM study for Ag/MgO and Au/MgO. The phenomenon of coalescence is explained via island migration process. It is shown that the coalescence occurs more rapidly when the substrate temperature is high.

  12. A facile reflux procedure to increase active surface sites form highly active and durable supported palladium@platinum bimetallic nanodendrites

    Science.gov (United States)

    Wang, Qin; Li, Yingjun; Liu, Baocang; Xu, Guangran; Zhang, Geng; Zhao, Qi; Zhang, Jun

    2015-11-01

    A series of well-dispersed bimetallic Pd@Pt nanodendrites uniformly supported on XC-72 carbon black are fabricated by using different capping agents. These capping agents are essential for the branched morphology control. However, the surfactant adsorbed on the nanodendrites surface blocks the access of reactant molecules to the active surface sites, and the catalytic activities of these bimetallic nanodendrites are significantly restricted. Herein, a facile reflux procedure to effectively remove the capping agent molecules without significantly affecting their sizes is reported for activating supported nanocatalysts. More significantly, the structure and morphology of the nanodendrites can also be retained, enhancing the numbers of active surface sites, catalytic activity and stability toward methanol and ethanol electro-oxidation reactions. The as-obtained hot water reflux-treated Pd@Pt/C catalyst manifests superior catalytic activity and stability both in terms of surface and mass specific activities, as compared to the untreated catalysts and the commercial Pt/C and Pd/C catalysts. We anticipate that this effective and facile removal method has more general applicability to highly active nanocatalysts prepared with various surfactants, and should lead to improvements in environmental protection and energy production.

  13. Synthesis of Supported NiPt Bimetallic Nanoparticles, Methods for Controlling the Surface Coverage of Ni Nanoparticles With Pt, Methods Of Making NiPt Multilayer Core-Shell Structures and Application of the Supported Catalysts for CO2 Reforming

    KAUST Repository

    Li, Lidong

    2015-06-25

    Embodiments of the present disclosure provide for supported Ni/Pt bimetallic nanoparticles, compositions including supported NiPt nanoparticles, methods of making supported NiPt nanoparticles, methods of using supported NiPt nanoparticles, and the like.

  14. Biosensors Incorporating Bimetallic Nanoparticles

    Directory of Open Access Journals (Sweden)

    John Rick

    2015-12-01

    Full Text Available This article presents a review of electrochemical bio-sensing for target analytes based on the use of electrocatalytic bimetallic nanoparticles (NPs, which can improve both the sensitivity and selectivity of biosensors. The review moves quickly from an introduction to the field of bio-sensing, to the importance of biosensors in today’s society, the nature of the electrochemical methods employed and the attendant problems encountered. The role of electrocatalysts is introduced with reference to the three generations of biosensors. The contributions made by previous workers using bimetallic constructs, grouped by target analyte, are then examined in detail; following which, the synthesis and characterization of the catalytic particles is examined prior to a summary of the current state of endeavor. Finally, some perspectives for the future of bimetallic NPs in biosensors are given.

  15. Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

    Science.gov (United States)

    Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

    2016-01-01

    Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology. PMID:27340940

  16. Catalytic Combustion of Voc in Air Stream Over Bimetallic Chromium-Copper Supported On Sicl4-Modified H-Zsm-5 Catalyst

    OpenAIRE

    Abdullah, A.Z.; M.Z. Abu Bakar; Bhatia, S

    2010-01-01

    The performance of chromium (Cr) and copper (Cu) on silicon tetrachloride modified H-ZSM-5 (SiCl4-Z) catalyst in VOC combustion is reported. H-ZSM-5, modified with SiCl4 at 500?C for 3 h was impregnated with 1.0 wt. % of Cr and 0.5 wt. % of Cu. Performance studies were carried out at GHSV of 3,800 to 32,000 h-1 with 2,000 to 35,000 ppm of VOC. Changes in the activity of Cr-Cu/ SiCl4-Z were ascribed to extra framework deposits, surface acidity and pore characteristics. Cr-Cu/SiCl4-Z cat...

  17. Synthesis and characterization of highly dispersed Pt–TiO2|WC/BC as anode catalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Highlights: • WC could enhance the electron transfer between the catalyst and support and accelerate the oxidation of residual carbon species. • TiO2 could absorb methanol and accelerate the breakage of O–H bond. • An enduring, versatile and renewable materials, bamboo charcoals, which have tremendous mesoporous structure were used as the support. - Abstract: To search the active anode electrocatalyst in direct methanol fuel cells, bamboo charcoals (BC)—supported titanium oxide|tungsten carbide system (TiO2|WC/BC) was constructed with a well defined structure in a designed process. Platinum was homogeneously dispersed on TiO2|WC/BC with an average particle size of 3.75 nm by microwave-assisted ethylene glycol process. The electro-catalytic performance of the catalyst Pt–TiO2|WC/BC toward methanol oxidation reaction (MOR) was studied by cyclic voltammetry (CV), chronoamperometry and CO stripping experiments. Results showed that the new electro-catalyst had a higher activity towards MOR compared with that of Pt–WC/BC and commercial Pt/C. The components in the complex were proved to play different roles in MOR where BC offered the larger surface areas and higher conductivity, the TiO2 could absorb methanol and accelerate the breakage of O–H bond, meanwhile WC may enhance the electron transfer between the catalyst and support and accelerate the oxidation of residual carbon species

  18. XPS analysis of dispersed catalysts prepared via w/o microemulsion

    International Nuclear Information System (INIS)

    Rh/AI2O3 catalysts prepared by water in oil w/o microemulsion were studied by X-ray photoelectron spectroscopy. The effect of water content (Rw) on rhodium particle size formed in microemulsion was investigated. Interest is focused on core level binding energy shifting for Rh 3d5/2 peak and its relationship with rhodium particle size. The Rh 3d5/2 peak was found to undergo changes in terms of shifting in binding energy, and the amount of such changes depends on the size of rhodium particle. TEM (transmission electron spectroscopy) studied showed that rhodium particle size on Rh/AI2O3 catalysts increase as water content in microemulsion increases (Average diameter for catalysts with Rw = 4, 5.7 and 11.5 are 4 nm, 8 nm and form aggregate like). These results were correlated with XPS results where Rh 3d5/2 binding energy increases for catalysts with lower water content or smaller particle size (binding energy for catalysts with Rw = 4, 5.7 and 11.5 are 311.3 eV, 311.0 eV and 310.0 eV). The rhodium catalysts with smaller particle size were found to exhibit a higher catalytic activity for the methane oxidation in rich oxygen than those catalysts with bigger particle size. For catalysts with smaller particle size, surface to volume ratio of rhodium metal increases which will increase the active sites of Rh/AI2O3 catalysts and led to higher catalytic activity performance. (Author)

  19. Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cullen, David A [ORNL

    2016-01-01

    Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions, can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on

  20. Effect of the Dispersibility of Nano-CuO Catalyst on Heat Releasing of AP/HTPB Propellant

    International Nuclear Information System (INIS)

    Kneading time is adjusted to change the dispersibility of nano-CuO in AP/HTPB (Ammonia Perchlorate/Hydroxyl-Terminated Polybutadiene) composite propellants. Nano-CuO/AP is prepared to serve as the other dispersing method of nano-CuO, named pre dispersing procedure. Several kinds of heat releasing, thermal decomposition by DSC, combustion heat in oxygen environment, and explosion heat in nitrogen environment, are characterized to learn the effect of dispersibility of nano-CuO catalyst on heat releasing of propellants. With pre-dispersing procedures, thermal decomposition temperature of nano-CuO/AP and its propellant are about 25 degree C and 8.6 degree C lower than that of AP simple mixed with nano-CuO and its propellant, respectively. Comparing propellant with simple mixed nano-CuO kneading 3 hours, combustion heat and explosion heat of propellant with nano-CuO/AP increase about 1.4% and 1.7%, respectively. However, because of the breaking of nano-CuO/AP structure during kneading procedure, combustion heat and explosion heat of all the samples are decreased with the increase of kneading time after 3 hours.

  1. The chemical properties of bimetallic surfaces: Importance of ensemble and electronic effects in the adsorption of sulfur and SO 2

    Science.gov (United States)

    Rodriguez, José A.

    The understanding of the interaction of sulfur with bimetallic surfaces is a critical issue for preventing the deactivation of hydrocarbon reforming catalysts and for the design of better hydrodesulfurization catalysts. The alloying or combination of two metals can lead to materials with special chemical properties due to an interplay of “ensemble” and “electronic” effects. In recent years, several new interesting phenomena have been discovered when studying the interaction of sulfur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulfur are able to induce dramatic changes in the morphology of bimetallic surfaces that combine noble metals (Cu, Ag, Au) and transition metals. This phenomenon can lead to big modifications in the activity and selectivity of bimetallic catalysts used for hydrocarbon reforming. In many cases, bimetallic bonding produces a significant redistribution of charge around the bonded metals. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond can affect the reactivity of the bonded metals toward sulfur. This can be a very important issue to consider when trying to minimize the negative effects of sulfur poisoning (Sn/Pt versus Ag/Pt and Cu/Pt catalysts) or when trying to improve the performance of desulfurization catalysts (Co/Mo and Ni/Mo systems). Clearly much more work is necessary in this area, but new concepts are emerging that can be useful for designing more efficient bimetallic catalysts.

  2. Chlorination of Carbon Nanotubes Obtained on the Different Metal Catalysts

    Directory of Open Access Journals (Sweden)

    Iwona Pełech

    2013-01-01

    Full Text Available In this paper, a chlorination method is proposed for simultaneous purification and functionalization of carbon nanotubes, thus increasing their ability to use. Carbon nanotubes were obtained by CVD method through ethylene decomposition on the nanocrystalline iron or cobalt or bimetallic iron-cobalt catalysts. The effects of temperature (50, 250, and 450°C in the case of carbon nanotubes obtained on the Fe-Co catalyst and type of catalyst (Fe, Co, Fe/Co on the effectiveness of the treatment and functionalization were tested. The phase composition of the samples was determined using the X-ray diffraction method. The quantitative analysis of metal impurity content was validated by means of the thermogravimetric analysis. Using X-ray Photoelectron Spectroscopy (XPS, Energy Dispersive Spectroscopy (EDS analysis, and also Mohr titration method, the presence of chlorine species on the surface of chlorinated samples was confirmed.

  3. Characterization and electrocatalytic properties of PtRu/C catalysts prepared by impregnation-reduction method using Nd2O3 as dispersing reagent

    International Nuclear Information System (INIS)

    A simple impregnation-reduction method introducing Nd2O3 as dispersing reagent has been used to synthesize PtRu/C catalysts with uniform Pt-Ru spherical nanoparticles. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis have been used to characterize the composition, particle size and crystallinity of the catalysts. Well-dispersed catalysts with average particle size about 2 nm are achieved. The electrochemically active surface area of the different PtRu/C catalysts is determined by the COad-stripping voltammetry experiment. The electrocatalytic activities of these catalysts towards methanol electrooxidation are investigated by cyclic voltammetry measurements and ac impedance spectroscopy. The in-house prepared PtRu/C catalyst (PtRu/C-03) in 0.5 M H2SO4 + 1.0 M CH3OH at 30 deg. C display a higher catalytic activity and lower charge-transfer resistance (R t) than that of the standard PtRu/C catalyst (PtRu/C-C). It is mainly due to enhanced electrochemically active specific surface, higher alloying extent of Ru and the abundant Pt and Ru oxides on the surface of the PtRu/C catalyst

  4. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, July--September 1992

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States); Gutterman, C. [Foster Wheeler Development Corp., Livingston, NJ (United States); Chander, S. [Pennsylvania State Univ., University Park, PA (United States)

    1992-12-31

    The experimental study of coal swelling ratios have been determined with a wide variety of solvents. Only marginal levels of coal swelling were observed for the hydrocarbon solvents, but high levels were found with solvents having heteroatom functionality. Blends were superior to pure solvents. The activity of various catalyst precursors for pyrene hydrogenation and coal conversion was measured. Higher coal conversions were observed for the S0{sub 2}-treated coal than the raw coal, regardless of catalyst type. Coal conversions were highest for Molyvan-L, molybdenum naphthenate, and nickel octoate, respectively. Bottoms processing consists of a combination of the ASCOT process coupling solvent deasphalting with delayed coking. Initial results indicate that a blend of butane and pentane used near the critical temperature of butane is the best solvent blend for producing a yield/temperature relationship of proper sensitivity and yet retaining an asphalt phase of reasonable viscosity. The literature concerning coal swelling, both alone and in combination with coal liquefaction, and the use of dispersed or unsupported catalysts in coal liquefaction has been updated.

  5. Effect of the Dispersibility of Nano-CuO Catalyst on Heat Releasing of AP/HTPB Propellant

    Directory of Open Access Journals (Sweden)

    Yi Yang

    2011-01-01

    Full Text Available Kneading time is adjusted to change the dispersibility of nano-CuO in AP/HTPB (Ammonia Perchlorate/Hydroxyl-Terminated Polybutadiene composite propellants. Nano-CuO/AP is prepared to serve as the other dispersing method of nano-CuO, named predispersing procedure. Several kinds of heat releasing, thermal decomposition by DSC, combustion heat in oxygen environment, and explosion heat in nitrogen environment, are characterized to learn the effect of dispersibility of nano-CuO catalyst on heat releasing of propellants. With pre-dispersing procedures, thermal decomposition temperature of nano-CuO/AP and its propellant are about 25∘C and 8.6∘C lower than that of AP simple mixed with nano-CuO and its propellant, respectively. Comparing propellant with simple mixed nano-CuO kneading 3 hours, combustion heat and explosion heat of propellant with nano-CuO/AP increase about 1.4% and 1.7%, respectively. However, because of the breaking of nano-CuO/AP structure during kneading procedure, combustion heat and explosion heat of all the samples are decreased with the increase of kneading time after 3 hours.

  6. Ni-Co/Mg-Al catalyst derived from hydrotalcite-like compound prepared by plasma for dry reforming of methane

    Institute of Scientific and Technical Information of China (English)

    Huali; Long; Yan; Xu; Xiaoqing; Zhang; Shijing; Hu; Shuyong; Shang; Yongxiang; Yin; Xiaoyan; Dai

    2013-01-01

    Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was investigated with dry reforming of methane.Experimental results showed that the hydrotalcite-like precursors could be completely decomposed and partly reduced by cold plasma jet,and the Nicontained catalysts exhibited much higher activity than the catalyst without Ni.Especially,the catalyst with Ni/Co ratio of 8/2 achieved not only the highest conversions of 80.3%and 69.3%for CH4 and CO2,respectively,but also the best stability in 100 h testing.The catalysts were characterized by XRD,XPS,TEM and N2 adsorption techniques,and the results showed that the better performance of the 8Ni2Co bimetallic catalyst was attributed to its higher metal dispersion,smaller metal particle size,as well as the interaction effect between Ni and Co,which were brought by the special catalyst preparation method.

  7. A theoretical and experimental XAS study of monolayer dispersive supported CuO/γ-Al2O3 catalysts

    International Nuclear Information System (INIS)

    The local structures of supported CuO/γ-Al2O3 monolayer dispersive catalysts with different CuO loadings have been investigated by EXAFS and multiple scattering XANES simulations. The EXAFS results show that the first nearest neighbors around the Cu atoms in the CuO/γ-Al2O3 catalysts are similar to that of the polycrystalline CuO powder, which is independent of the CuO loadings. Moreover, the Cu K-XANES FEFF8 calculations for CuO reveal that the monolayer-dispersed CuO species are of small distorted (CuO4) mn+ clusters, which is mainly composed of a distorted CuO6 octahedron incorporated in the surface octahedral vacant sites of the γ-Al2O3 support. We consider that the CuO species for the CuO/γ-Al2O3 catalysts with loadings of 0.4 and 0.8 mmol/100 m2 are distorted (CuO4) mn+ clusters composed mainly of a distorted CuO6 octahedron incorporated in the surface octahedral vacant sites of the γ-Al2O3 support after calcinations at high temperature in air for a few hours. On the contrary, for the CuO/γ-Al2O3 with loading of 1.2 mmol/100 m2, the local structure of Cu atoms in CuO/γ-Al2O3 is similar to that of polycrystalline CuO powder

  8. Effect of ball-milling duration and dehydrogenation on the morphology, microstructure and catalyst dispersion in Ni-catalyzed MgH2 hydrogen storage materials

    International Nuclear Information System (INIS)

    The effects of high-energy ball-milling on catalyst morphology and dispersion as a function of milling duration and on hydrogen desorption were investigated. Samples of MgH2 doped with 0.05 Ni catalyst were examined after 1, 5 and 10 h of milling. Longer milling durations produced finer catalyst particle sizes and more uniform dispersions, but yielded higher hydrogen desorption temperatures. This behavior is attributed to the formation of Mg2NiH4 with increased milling times. Electron tomography was used to show that the Ni particles reside both inside and outside the MgH2 particles. On dehydrogenation there was a redistribution of catalyst and continued formation of Mg2Ni. The formation of this phase is proposed to explain the reported degradation of hydrogen capacity and the change in kinetics of this system with cycling

  9. Nanophase Systems Dispersed in Mesoporous MCM-41 as Catalysts for Hydrodesupfurization

    Czech Academy of Sciences Publication Activity Database

    Kraleva, E.; Spojakina, A.A.; Avdeev, G.; Jirátová, Květa; Petrov, L.

    2006-01-01

    Roč. 6, č. 7 (2006), s. 160-165. ISBN 978-954-580-228-7. ISSN N Institutional research plan: CEZ:AV0Z40720504 Keywords : mechanochemical treatment * heteropolycompounds * hds catalysts Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  10. Highly-dispersed Ta-oxide catalysts prepared by electrodeposition in a non-aqueous plating bath for polymer electrolyte fuel cell cathodes

    KAUST Repository

    Seo, Jeongsuk

    2012-01-01

    The Ta-oxide cathode catalysts were prepared by electrodeposition in a non-aqueous solution. These catalysts showed excellent catalytic activity and have an onset potential of 0.92 V RHE for the oxygen reduction reaction (ORR). The highly-dispersed Ta species at the nanometer scale on the carbon black was an important contributor to the high activity. © 2012 The Royal Society of Chemistry.

  11. Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

    2015-09-30

    To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

  12. New catalysts for exhaust gas cleaning

    Energy Technology Data Exchange (ETDEWEB)

    Haerkoenen, M. [Kemira Metalkat Oy, Oulu (Finland)

    1996-12-31

    Major challenge for future catalyst systems was to develop thermally more stable washcoats for close coupled operating conditions and for engines operating under high speed and load conditions. To design these future emission systems extensive research and development was undertaken to develop methods to disperse and stabilize the key catalytic materials for operation at much higher temperatures. Second priority was to design catalysts that are more effective under low temperature exhaust conditions and have improved oxygen storage properties in the washcoats. Incorporating new materials and modified preparation technology a new generation of metallic catalyst formulations emerged, those being trimetallic K6 (Pt:Pd:Rh and bimetallic K7) (Pd+Pd:Rh). The target was to combine the best property of Pt:Rh (good NO{sub x} reduction) with that of the good HC oxidation activity of Pd and to ensure that precious metal/support interactions were positively maintained. Both K6 and K7 concepts contain special catalyst structures with optimized washcoat performance which can be brick converter configuration. Improvement in light-off, thermal stability and transient performance with these new catalyst formulations have clearly been shown in both laboratory and vehicle testing. (author) (20 refs.)

  13. Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James

    2016-01-04

    microcopy (STEM) to measure size and structure, energy dispersive X-ray spectroscopy (EDS) to measure atomic composition, X-ray absorption spectroscopy (XAS) to measure oxidation state and metal coordination, Fourier transform infrared spectroscopy (FTIR) to study adsorbed species, laser Raman spectroscopy to probe metal oxide promoters, and temperature programmed reaction/desorption to study the energetics of adsorption and desorption processes. We have studied our bimetallic catalysts for the selective cleavage of carbon-oxygen bonds, and we have studied the effects of adding metal oxide promoters to supported platinum and gold catalysts for water-gas shift (i.e., the production of hydrogen by reaction of carbon monoxide with water). We anticipate that the knowledge obtained from our studies will allow us to identify promising directions for new catalysts that show high activity, selectivity, and stability for important reactions, such as the conversion of biomass-derived oxygenated hydrocarbons to fuels and chemicals.

  14. CVD synthesis of carbon nanotubes using a finely dispersed cobalt catalyst and their use in double layer electrochemical capacitors

    International Nuclear Information System (INIS)

    Carbon nanotubes (CNT) were obtained by chemical vapour deposition (CVD), decomposing turpentine oil over finely dispersed Co metal as a catalyst at 675 deg. C. Scanning electron microscope (SEM) and transmission electron microscope (TEM) images reveal that the nanotubes are densely packed and of 10-50 nm in diameter. The XRD pattern of purified CNT shows that they are graphitic in nature. Resistivity measurements of these CNT indicate that they are highly conducting. Hall measurements of CNT reveal that electrons are the majority carriers with a carrier concentration of 1.35x1020 cm-3. Cyclic voltammetry (CV) and constant current charging/discharging was used to characterise the behaviour of electrochemical double layer capacitors of purified CNT with H2SO4. For CNT/2 M H2SO4/CNT, a capacitance of 12 F g-1 (based on the weight of the active material) was obtained

  15. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, April--June 1992

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States); Gutterman, C. [Foster Wheeler Development Corp., Livingston, NJ (United States); Chander, S. [Pennsylvania State Univ., University Park, PA (United States)

    1992-08-26

    Research in this project centers upon developing a new approach to the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates all aspects of the coal liquefaction process including coal selection, pretreatment, coal swelling with catalyst impregnation, coal liquefaction experimentation, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. On May 28, 1992, the Department of Energy authorized starting the experimental aspects of this projects; therefore, experimentation at Amoco started late in this quarterly report period. Research contracts with Auburn University, Pennsylvania State University, and Foster Wheeler Development Corporation were signed during June, 1992, so their work was just getting underway. Their work will be summarized in future quarterly reports. A set of coal samples were sent to Hazen Research for beneficiation. The samples were received and have been analyzed. The literature search covering coal swelling has been up-dated, and preliminary coal swelling experiments were carried out. Further swelling experimentation is underway. An up-date of the literature on the liquefaction of coal using dispersed catalysts is nearing completion; it will be included in the next quarterly report.

  16. Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation

    Science.gov (United States)

    Zhang, Zhuo-Qun; Huang, Jianliu; Zhang, Lan; Sun, Mei; Wang, You-Cheng; Lin, Yue; Zeng, Jie

    2014-10-01

    The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2.

  17. Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation

    International Nuclear Information System (INIS)

    The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2. (paper)

  18. Well-dispersed Pt cubes on porous Cu foam: high-performance catalysts for the electrochemical oxidation of glucose in neutral media.

    Science.gov (United States)

    Niu, Xiangheng; Lan, Minbo; Zhao, Hongli; Chen, Chen

    2013-07-15

    The investigation of highly efficient catalysts for the electrochemical oxidation of glucose is the most critical challenge to commercialize nonenzymatic glucose sensors, which display a few attractive superiorities including the sufficient stability of their properties and the desired reproducibility of results over enzyme electrodes. Herein we propose a new and very promising catalyst: Pt cubes well-dispersed on the porous Cu foam, for the the electrochemical oxidation reaction of glucose in neutral media. The catalyst is fabricated in situ on a homemade screen-printed carbon electrode (SPCE) substrate through initially synthesizing the three-dimensional (3D) porous Cu foam using a hydrogen evolution assisted electrodeposition strategy, followed by electrochemically reducing the platinic precursor simply and conveniently. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) proofs demonstrate that Pt cubes, with an average size (the distance of opposite faces) of 185.1 nm, highly dispersed on the macro/nanopore integrated Cu foam support can be reproducibly obtained. The results of electrochemical tests indicate that the cubic Pt-based catalyst exhibits significant enhancement on the catalytic activity towards the electrooxidation of glucose in the presence of chloride ions, providing a specific activity 6.7 times and a mass activity 5.3 times those of commercial Pt/C catalysts at -0.4 V (vs. Ag/AgCl). In addition, the proposed catalyst shows excellent stability of performance, with only a 2.8% loss of electrocatalytic activity after 100 repetitive measurements. PMID:23744705

  19. Sonochemically synthesized mono and bimetallic Au-Ag reduced graphene oxide based nanocomposites with enhanced catalytic activity.

    Science.gov (United States)

    Neppolian, Bernaurdshaw; Wang, Chang; Ashokkumar, Muthupandian

    2014-11-01

    Graphene oxide (GO) supported Ag and Au mono-metallic and Au-Ag bimetallic catalysts were synthesized using a sonochemical method. Bimetallic catalysts containing different weight ratios of Au and Ag were loaded onto GO utilizing a low frequency horn-type ultrasonicator. High frequency ultrasonication was used to efficiently reduce Ag(I) and Au(III) ions in the presence of polyethylene glycol and 2-propanol. Transmission electron microscopy (TEM-EDX) and X-ray photoelectron spectroscopy were used to analyze the morphology, size, shape and chemical oxidation states of the prepared metallic catalysts on GO. The catalytic efficiency of the prepared catalysts were compared using 4-nitrophenol (4-NP) reduction reaction and the subsequent formation of 4-aminophenol (4-AP) that was also monitored using UV-vis spectrophotometry. The results revealed that Au-Ag-GO bimetallic catalysts showed high activity for the conversion of 4-NP to 4-AP than their monometallic counterparts. Amongst different weight ratios (1:1, 1:2 and 2:1) between Au and Ag, the 1:2 (Au:Ag) catalyst exhibited very good catalytic performance for the conversion of 4-NP to 4-AP. A total reduction of 4-NP took place within a short period of time if Au-GO was reduced first followed by Ag reduction, whereas a lower reduction rate was observed if Ag-GO was reduced first. The same trend was observed for all the ratios of bimetallic catalysts prepared by this method. The initial unfavorable reduction potential of Ag(I) is likely to be responsible for the above order. It was found that applying dual frequency ultrasonication was a highly effective way of preparing bimetallic catalysts requiring relatively low levels of added chemicals and producing bimetallic catalysts with GO with improved catalytic efficiency. PMID:24582660

  20. Fractal Dimension Calculation of a Manganese-Chromium Bimetallic Nanocomposite Using Image Processing

    OpenAIRE

    Amir Lashgari; Shahriar Ghamami; Saeedeh Shahbazkhany; Guillermo Salgado-Morán; Daniel Glossman-Mitnik

    2015-01-01

    Bimetallic materials, which have the ability to convert heat change into mechanical movement, normally consist of two bonded strips of dissimilar metals that expand at different rates. We describe how we made a manganese-chromium (Mn-Cr) bimetallic nanocomposite using the centrifuge method and a low-to-high approach. We conducted scanning electron microscope (SEM) imaging, energy-dispersive X-ray spectroscopy (EDX) analysis, and X-ray diffraction spectra of the nanocomposite to prove its iden...

  1. Transmission electron microscopy and energy dispersive x-ray spectroscopy studies of Pt-Re/[gamma]-Al[sub 2]O[sub 3] catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Z.; Fryer, J.R.; Park, C.; Stirling, D.; Webb, G. (Univ. of Glasgow (United Kingdom))

    1994-08-01

    A series of Pt/[gamma]-Al[sub 2]O[sub 3], Re/[gamma]-Al[sub 2]O[sub 3], and Pt-Re/[gamma]-Al-O[sub 3] catalysts have been studied by transmission electron microscopy and energy dispersive X-ray spectroscopy. It has been shown that rhenium was not alloyed with platinum, but widely dispersed on the surface of alumina. Two types of platinum were found: (i) three-dimensional metallic particles, and (ii) small particles consisting of a few platinum atoms. Some aggregation of the platinum particles occurred during use of the catalysts in the reforming of octane. It is suggested that the interaction of rhenium with the alumina support and therefore the modification to the platinum play an essential role in promoting the enhanced stability and selectivity of these catalysts to cycloalkanes and aromatics in reforming reactions. 40 refs., 13 figs., 2 tabs.

  2. Effect of Copper Nanoparticles Dispersion on Catalytic Performance of Cu/SiO2 Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

    International Nuclear Information System (INIS)

    Cu/SiO2 catalysts, for the synthesis of ethylene glycol (EG) from hydrogenation of dimethyl oxalate (DMO), were prepared by ammonia-evaporation and sol-gel methods, respectively. The structure, size of copper nanoparticles, copper dispersion, and the surface chemical states were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) and N2 adsorption. It is found the structures and catalytic performances of the catalysts were highly affected by the preparation method. The catalyst prepared by sol-gel method had smaller average size of copper nanoparticles (about 3-4 nm), better copper dispersion, higher Cu+/C0 ratio and larger BET surface area, and higher DMO conversion and EG selectivity under the optimized reaction conditions.

  3. Effect of Copper Nanoparticles Dispersion on Catalytic Performance of Cu/SiO2 Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

    Directory of Open Access Journals (Sweden)

    Yajing Zhang

    2013-01-01

    Full Text Available Cu/SiO2 catalysts, for the synthesis of ethylene glycol (EG from hydrogenation of dimethyl oxalate (DMO, were prepared by ammonia-evaporation and sol-gel methods, respectively. The structure, size of copper nanoparticles, copper dispersion, and the surface chemical states were investigated by X-ray diffraction (XRD, transmission electron microscopy (TEM, temperature-programmed reduction (TPR, and X-ray photoelectron spectroscopy (XPS and N2 adsorption. It is found the structures and catalytic performances of the catalysts were highly affected by the preparation method. The catalyst prepared by sol-gel method had smaller average size of copper nanoparticles (about 3-4 nm, better copper dispersion, higher Cu+/C0 ratio and larger BET surface area, and higher DMO conversion and EG selectivity under the optimized reaction conditions.

  4. Study of Pd-Sn/Al{sub 2}O{sub 3} catalysts prepared by an oxide colloidal route; Etude de catalyseurs Pd-Sn/Al{sub 2}O{sub 3} prepares par voie colloidale oxyde

    Energy Technology Data Exchange (ETDEWEB)

    Verdier, St.

    2001-09-01

    The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the oxide particles. To synthesize oxide bimetallic sols, three strategies were defined. Copolymerization (formation of a mixed oxide nano-sol by cross condensation of both metals) does not lead to a mixed oxide Pd-Sn phase. Surface precipitation (neutralization of the second metal in the presence of the first oxide sol) yields nano-particles of both oxides in close interaction. Adsorption (adsorption of the second metal onto the first oxide sol) significantly occurs when contacting tin with a basic PdO sol (hydrolytic adsorption). The characterization and the assessment of the catalytic properties (selective hydrogenation of buta-1,3-diene) of the catalysts prepared by deposition of oxide bimetallic sols showed that the oxide colloidal route allows the control of the properties of the supported bimetallic phase. Moreover, our results display that both Pd-Sn alloy formation and,aggregation of the metallic particles contribute to increase the selectivity for this reaction. (author)

  5. Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst.

    Science.gov (United States)

    Manthiram, Karthish; Beberwyck, Brandon J; Alivisatos, A Paul

    2014-09-24

    Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO2. The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic conditions and the resulting Faradaic efficiency for methane. The improved activity and Faradaic efficiency for methanation involves a mechanism that is distinct from what is generally thought to occur on copper foils. Electrochemical data indicate that the early steps of methanation on n-Cu/C involve a pre-equilibrium one-electron transfer to CO2 to form an adsorbed radical, followed by a rate-limiting non-electrochemical step in which the adsorbed CO2 radical reacts with a second CO2 molecule from solution. These nanoscale copper electrocatalysts represent a first step toward the preparation of practical methanation catalysts that can be incorporated into membrane-electrode assemblies in electrolyzers. PMID:25137433

  6. Evaluation of Pt-Ru-Ni and Pt-Sn-Ni catalysts as anodes in direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Ribadeneira, Esteban; Hoyos, Bibian A. [Escuela de Procesos y Energia, Facultad de Minas, Universidad Nacional de Colombia, Medellin (Colombia)

    2008-05-15

    In this study, the electrooxidation of ethanol on carbon supported Pt-Ru-Ni and Pt-Sn-Ni catalysts is electrochemically studied through cyclic voltammetry at 50 C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt{sub 75}Ru{sub 15}Ni{sub 10}/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials. (author)

  7. Atomic layer deposition-Sequential self-limiting surface reactions for advanced catalyst "bottom-up" synthesis

    Science.gov (United States)

    Lu, Junling; Elam, Jeffrey W.; Stair, Peter C.

    2016-06-01

    Catalyst synthesis with precise control over the structure of catalytic active sites at the atomic level is of essential importance for the scientific understanding of reaction mechanisms and for rational design of advanced catalysts with high performance. Such precise control is achievable using atomic layer deposition (ALD). ALD is similar to chemical vapor deposition (CVD), except that the deposition is split into a sequence of two self-limiting surface reactions between gaseous precursor molecules and a substrate. The unique self-limiting feature of ALD allows conformal deposition of catalytic materials on a high surface area catalyst support at the atomic level. The deposited catalytic materials can be precisely constructed on the support by varying the number and type of ALD cycles. As an alternative to the wet-chemistry based conventional methods, ALD provides a cycle-by-cycle "bottom-up" approach for nanostructuring supported catalysts with near atomic precision. In this review, we summarize recent attempts to synthesize supported catalysts with ALD. Nucleation and growth of metals by ALD on oxides and carbon materials for precise synthesis of supported monometallic catalyst are reviewed. The capability of achieving precise control over the particle size of monometallic nanoparticles by ALD is emphasized. The resulting metal catalysts with high dispersions and uniformity often show comparable or remarkably higher activity than those prepared by conventional methods. For supported bimetallic catalyst synthesis, we summarize the strategies for controlling the deposition of the secondary metal selectively on the primary metal nanoparticle but not on the support to exclude monometallic formation. As a review of the surface chemistry and growth behavior of metal ALD on metal surfaces, we demonstrate the ways to precisely tune size, composition and structure of bimetallic metal nanoparticles. The cycle-by-cycle "bottom up" construction of bimetallic (or multiple

  8. Synthesis of highly stable, water-dispersible copper nanoparticles as catalysts for nitrobenzene reduction.

    Science.gov (United States)

    Kaur, Ravneet; Giordano, Cristina; Gradzielski, Michael; Mehta, Surinder K

    2014-01-01

    We report an aqueous-phase synthetic route to copper nanoparticles (CuNPs) using a copper-surfactant complex and tests of their catalytic efficiency for a simple nitrophenol reduction reaction under atmospheric conditions. Highly stable, water-dispersed CuNPs were obtained with the aid of polyacrylic acid (PAA), but not with other dispersants like surfactants or polymethacrylic acid (PMAA). The diameter of the CuNPs could be controlled in the range of approximately 30-85 nm by modifying the ratio of the metal precursor to PAA. The catalytic reduction of p-nitrophenol to p-aminophenol takes place at the surface of CuNPs at room temperature and was accurately monitored by UV/Vis spectroscopy. The catalytic efficiency was found to be remarkably high for these PAA-capped CuNPs, given the fact that at the same time PAA is efficiently preventing their oxidation as well. The activity was found to increase as the size of the CuNPs decreased. It can therefore be concluded that the synthesized CuNPs are catalytically highly efficient in spite of the presence of a protective PAA coating, which provides them with a long shelf life and thereby enhances the application potential of these CuNPs. PMID:24124135

  9. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, fla...... active sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....... and stepped, which includes platinum-based alloys with ruthenium, tin, and copper, as well as nonprecious alloys, overlayer structures, and modified edges. A common lower bound on the overpotential is estimated (ca. 0.3 V). A model for bifunctional alloys is employed to investigate the nature of the...

  10. Gold/Iron Carbonyl Clusters for Tailored Au/FeOx Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Stefania Albonetti

    2011-12-01

    Full Text Available A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO16] and [NEt4][AuFe4(CO16] as precursors of highly dispersed nanoparticles over different supports. A series of catalysts with different metal loadings were prepared and tested in the complete oxidation of dichlorobenzene, toluene, methanol and in the preferential oxidation of CO in the presence of H2 (PROX as model reactions. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS point out the way the nature of the precursors and the thermal treatment conditions affected the dispersion of the active phase and their catalytic activity in the studied reactions.

  11. Production of biodiesel from sunflower oil using highly catalytic bimetallic gold–silver core–shell nanoparticle

    International Nuclear Information System (INIS)

    Bimetallic Gold–silver core–shell nanoparticles (Au@Ag NPs) were synthesized at room temperature, where gold nanoparticles (AuNPs) served as seeds for continuous deposition of silver atoms on its surface. The core–shell structure was examined by UV–vis spectroscopy, transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis. The catalytic activity of these nanoparticles toward biodiesel production from Sunflower oil through transesterification was studied. The confirmation for biofuel synthesis was performed using Fourier Transform Infra-Red (FTIR) spectroscopy. Fuel properties are determined by standard ASTM (American society for Testing and Materials) protocols. Our observations show that at certain catalyst concentration, temperature and reaction time, highest yield of biodiesel (86.9%) is attained. The fuel properties of the synthesized biofuel are at par with standard biofuel. Further, the catalyst showed sustained activity for 3 cycles of transesterification. - Highlights: • Gold–silver core–shell NPs were used for biofuel synthesis from sunflower oil. • At the optimized condition, biodiesel yield of 86.9% was achieved. • Fuel properties of the biofuel synthesized are at par with standard biofuel. • The catalyst showed sustained activity for 3 cycles of transesterification

  12. In Situ Structure-Function Studies of Oxide Supported Rhodium Catalysts by Combined Energy Dispersive XAFS and DRIFTS Spectroscopies

    International Nuclear Information System (INIS)

    The techniques of energy dispersive EXAFS (EDE), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and mass spectrometry (MS) have been combined to study the structure and function of an oxide supported metal catalyst, namely 5 wt% Rh/Al2O3. Using a FreLoN camera as the EDE detector and a rapid-scanning IR spectrometer, experiments could be performed with a repetition rate of 50 ms. The results show that the nature of the rhodium centers is a function of the partial pressures of the reacting gases (CO and NO) and also temperature. This combination of gases oxidizes metallic rhodium particles to Rh(CO)2 at room temperature. The proportion of the rhodium adopting this site increases as the temperature is raised (up to 450 K). Above that temperature the dicarbonyl decomposes and the metal reclusters. Once this condition is met, catalysis ensues. Gas switching techniques show that at 573 K with NO in excess, the clusters can be oxidized rapidly to afford a linear nitrosyl complex; re-exposure to CO also promotes reclustering and the CO adopts terminal (atop) and bridging (2-fold) sites

  13. Synthesis of subnanometer-diameter vertically aligned single-walled carbon nanotubes with copper-anchored cobalt catalysts

    Science.gov (United States)

    Cui, Kehang; Kumamoto, Akihito; Xiang, Rong; An, Hua; Wang, Benjamin; Inoue, Taiki; Chiashi, Shohei; Ikuhara, Yuichi; Maruyama, Shigeo

    2016-01-01

    We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high-quality SWNTs are expected to pave the way to replace silicon for next-generation optoelectronic and photovoltaic devices.We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high

  14. Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural

    Science.gov (United States)

    Wang, Guang-Hui; Hilgert, Jakob; Richter, Felix Herrmann; Wang, Feng; Bongard, Hans-Josef; Spliethoff, Bernd; Weidenthaler, Claudia; Schüth, Ferdi

    2014-03-01

    The synthesis of 2,5-dimethylfuran (DMF) from 5-hydroxymethylfurfural (HMF) is a highly attractive route to a renewable fuel. However, achieving high yields in this reaction is a substantial challenge. Here it is described how PtCo bimetallic nanoparticles with diameters of 3.6 ± 0.7 nm can solve this problem. Over PtCo catalysts the conversion of HMF was 100% within 10 min and the yield to DMF reached 98% after 2 h, which substantially exceeds the best results reported in the literature. Moreover, the synthetic method can be generalized to other bimetallic nanoparticles encapsulated in hollow carbon spheres.

  15. Preparation of promoted platinum catalysts of designed geometry and the role of promoters in the liquid-phase oxidation of 1-methoxy-2-propanol

    Energy Technology Data Exchange (ETDEWEB)

    Mallat, T.; Bodnar, Z.; Baiker, A. (Swiss Federal Institute of Technology, Zuerich (Switzerland)); Greis, O.; Struebig, H. (Technical Univ., Hamburg (Germany)); Reller, A. (Univ. of Hamburg (Germany))

    1993-07-01

    Alumina-supported or unsupported M/Pt-type catalysts were prepared by consecutive reduction of Bi, Pb, Sn, Ru, Au, or Ag modifiers (M) onto Pt particles. Structural and chemical properties of the bimetallics were studied by electron microscopy combined with energy dispersive X-ray analysis and an electrochemical (cyclic voltammetric) polarization method. Preferential deposition of promoter metal submonolayers on Pt was observed at moderate surface coverages ([theta][sub M]<0.5-0.8). Some bulk metal crystallite formation as [open quotes]bridges[close quotes] between small Pt particles covered partially with promoter was also observed on alumina-supported Bi/Pt and Pb/Pt catalysts. Measurement of the electrochemical potential of the catalyst slurry during the oxidation of 1-methoxy-2-propanol to methoxyacetone and the cyclic voltammetric polarization of the bimetallic catalysts revealed that the catalysts are in an oxidized state during reaction. The following order of promoting influence was observed: Bi > Pb [approximately] Sn > Au [approximately] Ru. Two major effects of promoters are suggested: (i) they suppress the initial irreversible adsorption of the reactant alcohol on Pt which results in self-poisoning, and (ii) they form new active centers that adsorb the oxidizing species (OH) better than Pt. A formal rate equation is suggested (r = f [center dot] [theta][sub org] [center dot] [theta][sub OH]) which explains the optimum in promoter/platinum ratio. The different influences of the promoters are explained by their hydrogen and oxygen sorption characteristics and by the surface geometry of the bimetallic catalysts. 51 refs., 12 figs., 1 tab.

  16. Controllable Catalysis with Nanoparticles: Bimetallic Alloy Systems and Surface Adsorbates

    KAUST Repository

    Chen, Tianyou

    2016-05-16

    Transition metal nanoparticles are privileged materials in catalysis due to their high specific surface areas and abundance of active catalytic sites. While many of these catalysts are quite useful, we are only beginning to understand the underlying catalytic mechanisms. Opening the “black box” of nanoparticle catalysis is essential to achieve the ultimate goal of catalysis by design. In this Perspective we highlight recent work addressing the topic of controlled catalysis with bimetallic alloy and “designer” adsorbate-stabilized metal nanoparticles.

  17. Adhesive forces at bimetallic interfaces

    International Nuclear Information System (INIS)

    Force concepts in condensed systems have progressed significantly in recent years. In the context of bimetallic interfaces we consider the Pauli-Hellman-Feynman theorem, use it to check the variational calculations of interfacial energies and estimate the force constants. (author). 13 refs, 2 figs, 2 tabs

  18. X-ray characterization of platinum group metal catalysts

    Science.gov (United States)

    Peterson, Eric J.

    complements information obtained from both XRD and XAS. With aberration-corrected HAADF, particles ranging from sub-nm-size down to clusters of a few atoms and isolated single-atoms can be routinely imaged. A challenge to the interpretation of these images is the characterization of mixed atomic species, in this case, palladium and lanthanum. In this work we show for the first time that quantitative chemical identification of atomically-dispersed mixtures of palladium and lanthanum in an industrially relevant catalyst (palladium on lanthanum-stabilized gamma-alumina) can be obtained through image intensity analysis. Using these techniques we have characterized the state of bimetallic fuel cell catalysts, ex situ, and have examined the state of Pd catalysts under operando CO oxidation conditions.

  19. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds

    Directory of Open Access Journals (Sweden)

    Huishan Shang

    2016-06-01

    Full Text Available To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni and nickel-platinum (NiPt nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD, high-resolution transmission electron microscopy (HRTEM, energy dispersive X-ray spectroscopy (EDS mapping, and X-ray photoelectron spectroscopy (XPS techniques. The Ni2+ was reduced to metallic Ni0 via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka of 18.82 × 10−3 s−1, 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes.

  20. Kinetics of Oxidation of L-Leucine by Mono-and Bimetallic Gold and Silver Nanoparticles in Hydrogen Peroxide Solution

    Institute of Scientific and Technical Information of China (English)

    P.VENKATESAN; J.SANTHANALAKSHMI

    2012-01-01

    The catalytic activity of surfactant stabilized mono- and bimetallic Au and Ag nanoparticles for the oxidation of an amino acid,L-leucine,was studied using hydrogen peroxide as the oxidant.The Au and Ag nanoparticle catalysts exhibited very good catalytic activity and the kinetics of the reaction were found to be pseudo-first order with respect to the amino acid.The effects of several factors,such as oxidant concentration,ionic strength,pH,and catalyst concentration on the reaction,were also investigated.In particular,optimal oxidant and catalyst concentrations were determined.Very high concentrations of the metal nano-catalysts or the oxidant led to a dramatic increase in reaction rate.Moreover,bimetallic Au-Ag catalysts provided higher selectivity than pure Au or Ag.

  1. Monometallic Pd and Pt and Bimetallic Pd-Pt/Al2O3-TiO2 for the HDS of DBT: Effect of the Pd and Pt Incorporation Method

    Directory of Open Access Journals (Sweden)

    Reynaldo Martínez Guerrero

    2014-01-01

    Full Text Available The effect of the preparation method of monometallic Pd and Pt and bimetallic Pd-Pt/Al2O3-TiO2 catalysts on the hydrodesulfurization (HDS of dibenzothiophene (DBT was investigated in this study. The synthesis was accomplished using three methods: (A impregnation, (B metal organic chemical vapor deposition (MOCVD, and (C impregnation-MOCVD. The bimetallic Pd-Pt catalyst prepared by the impregnation-MOCVD method was most active for the HDS of DBT compared to those prepared by the single impregnation or MOCVD method due to the synergetic effect between both noble metals. The greater selectivity toward biphenyl indicated that this bimetallic Pd-Pt catalyst preferentially removes sulfur via the direct desulfurization mechanism. However, the bimetallic Pd-Pt catalyst prepared using the single MOCVD method did not produce any cyclohexylbenzene, which is most likely associated with the hydrogenation/dehydrogenation sites.

  2. 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.

  3. Surface composition changes of redox stabilized bimetallic CoCu nanoparticles supported on silica under H-2 and O-2 atmospheres and during reaction between CO2 and H-2 : in situ X-ray spectroscopic characterization.

    OpenAIRE

    Alayoglu, S.; Beaumont, Simon K.; Melaet, G.; Lindeman, A.E.; Musselwhite, N.; Brooks, C J; Marcus, M. A.; Guo, J. G.; Liu, Z.; Kruse, N; Somorjai, G.A.

    2013-01-01

    In this paper, we report the colloidal synthesis and detailed characterization of 11 nm bimetallic CoCu nanoparticle catalysts. Presently Co and Cu is an attractive combination because of their respective properties for industrially important Fischer–Tropsch and methanol synthesis reactions of CO (and CO2) with H2. We report the preparation of catalysts by deposition of bimetallic metal nanoparticles, both within mesoporous silica (MCF-17) and on the native oxide surface of a silicon wafer. S...

  4. Preparation and Characterization of Polymer-Stabilized Ruthenium-Platinum and Ruthenium-Palladium Bimetallic Colloids and Their Catalytic Properties for Hydrogenation of o-Chloronitrobenzene.

    Science.gov (United States)

    Liu; Yu; Liu; Zheng

    1999-06-15

    Colloidal dispersions of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium-platinum and ruthenium-palladium bimetallic colloids were prepared by NaBH4 reduction of the corresponding mixed-metal salts at room temperature and characterized by TEM, XPS, and XRD. The resulting bimetallic colloids were used as catalysts for the selective hydrogenation of o-chloronitrobenzene (o-CNB) in methanol at 303 K under 0.1 MPa of hydrogen. It was observed that the catalytic performance of PVP-stabilized ruthenium-platinum colloids (PVP-Ru/Pt) and ruthenium-palladium colloids (PVP-Ru/Pd) was dependent on their compositions and could be remarkably affected by some added metal cations. In the presence of cobalt ion, nearly 100% selectivity to o-chloroaniline (o-CAN) was achieved over PVP-Ru/Pt colloids at 100% conversion of o-CNB, with an activity two orders of magnitude higher than that of monometallic PVP-Ru colloid. Copyright 1999 Academic Press. PMID:10339363

  5. Enhanced Activity of CuCeO Catalysts for CO Oxidation: Influence of Cu2O and the Dispersion of Cu2O, CuO, and CeO2.

    Science.gov (United States)

    Wang, Zhenhua; Li, Ren; Chen, Qianwang

    2015-08-01

    CuCeO catalysts prepared by a hydrothermal method with subsequent calcination are tested for the catalytic oxidation of CO. This synthesis method leads to a homogeneous dispersion of Cu2 O, CuO, and CeO2 in the catalysts. The composition of the catalysts is determined by the molar ratio of the metals, the hydrothermal process, and calcination temperature and influences the catalytic performance. The catalyst containing Cu2 O exhibits high catalytic activity with almost 100 % CO conversion at 105 °C and shows excellent stability with the conversion ratio not decreasing after four months of storage. PMID:26017784

  6. Characterization and Preparation of Bimetallic Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Bing; Joe; Hwang; Ching; Hsiang; Chen; Loka; Subramanyam; Sarma; Din-gao; Liu; Jyh; Fu; Lee

    2007-01-01

    1 Results Bimetallic particles in the nanometer size range are of substantial interest due to their vast applications in catalysis[1].The synthesis of bimetallic nanoparticles with definite size with a well-control over their nanostructure remains a challenging problem.Thus there exists a great demand for both synthesis and atomic level characterization of nanostructure of bimetallic nanoparticles (NPs).With the recent advent of high-intensity tunable sources of X-rays,now available at synchrotron radia...

  7. Electrocatalytical study of carbon supported Pt, Ru and bimetallic Pt–Ru nanoparticles for oxygen reduction reaction in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Hosseini, M.G., E-mail: mg-hosseini@tabrizu.ac.ir; Zardari, P.

    2015-08-01

    Highlights: • Binary catalyst Pt.Ru/C is evaluated towards ORR. • Pt.Ru/C nanoparticles revealed best ORR catalytical activity. • The 120 mV/dec Tafel slope indicated that the first electron transfer is the rds. • The active number sites of Pt.Ru/C catalyst were 3 times higher than Pt/C. - Abstract: Carbon supported Pt, Ru and bimetallic Pt–Ru nanoparticles (Pt/C, Ru/C and Pt.Ru/C) have been prepared by the chemical reduction method. Particle morphology, composition and structure of nanoparticles have been investigated by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. SEM results showed a uniform dispersion of nanoparticles with rough and porous structure into carbon supports with the average particle size of 30–64 nm. EDX analysis demonstrated the presence of both Pt and Ru nanoparticles in each gas diffusion electrode. The Pt/C, Ru/C and Pt.Ru/C composites were used as electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. The ORR activities of cathodes were characterized using cyclic voltammetry (CV), polarization technique, AC impedance spectroscopy (EIS) and chronoamperometry. CV and polarization curves showed significantly higher activity on Pt.Ru/C electrocatalyst than observed on Pt/C and Ru/C catalysts, which can be related to synergistic effect, which is playing a critical role in ORR activity. The Tafel slope values of 120 mV/dec showed that the first electron transfer is the rate determining step. The EIS results of cathodes under different polarization potentials indicated two different behaviours which depend on the applied dc potentials and reveal different electrochemical processes occurring on the electrodes.

  8. Electrocatalytical study of carbon supported Pt, Ru and bimetallic Pt–Ru nanoparticles for oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Highlights: • Binary catalyst Pt.Ru/C is evaluated towards ORR. • Pt.Ru/C nanoparticles revealed best ORR catalytical activity. • The 120 mV/dec Tafel slope indicated that the first electron transfer is the rds. • The active number sites of Pt.Ru/C catalyst were 3 times higher than Pt/C. - Abstract: Carbon supported Pt, Ru and bimetallic Pt–Ru nanoparticles (Pt/C, Ru/C and Pt.Ru/C) have been prepared by the chemical reduction method. Particle morphology, composition and structure of nanoparticles have been investigated by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. SEM results showed a uniform dispersion of nanoparticles with rough and porous structure into carbon supports with the average particle size of 30–64 nm. EDX analysis demonstrated the presence of both Pt and Ru nanoparticles in each gas diffusion electrode. The Pt/C, Ru/C and Pt.Ru/C composites were used as electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. The ORR activities of cathodes were characterized using cyclic voltammetry (CV), polarization technique, AC impedance spectroscopy (EIS) and chronoamperometry. CV and polarization curves showed significantly higher activity on Pt.Ru/C electrocatalyst than observed on Pt/C and Ru/C catalysts, which can be related to synergistic effect, which is playing a critical role in ORR activity. The Tafel slope values of 120 mV/dec showed that the first electron transfer is the rate determining step. The EIS results of cathodes under different polarization potentials indicated two different behaviours which depend on the applied dc potentials and reveal different electrochemical processes occurring on the electrodes

  9. The effect of lanthanum addition on the catalytic activity of ?-alumina supported bimetallic Co–Mo carbides for dry methane reforming

    OpenAIRE

    France, Liam J; Du, Xian; Almuqati, Naif; Vladimir L. Kuznetsov; Zhao, Yongxiang; Jiang, Zheng; Xiao, Tiancun; Bagabas, Abdulaziz; Almegren, Hamid; Edwards, Peter P.

    2014-01-01

    The effect of lanthanum addition to ?-alumina supported bimetallic carbides has been studied for the reaction of dry methane reforming using four different lanthanum loading levels of 1, 5, 10 and 15 wt% of lanthanum. It has been demonstrated that the addition of lanthanum to supported bimetallic carbides at low loading levels (1 wt%) results in smaller carbide crystallite sizes compared to catalysts containing either no lanthanum or higher lanthanum loading levels (5–15 wt%). Increased lanth...

  10. Antibacterial activity of graphene supported FeAg bimetallic nanocomposites.

    Science.gov (United States)

    Ahmad, Ayyaz; Qureshi, Abdul Sattar; Li, Li; Bao, Jie; Jia, Xin; Xu, Yisheng; Guo, Xuhong

    2016-07-01

    We report the simple one pot synthesis of iron-silver (FeAg) bimetallic nanoparticles with different compositions on graphene support. The nanoparticles are well dispersed on the graphene sheet as revealed by the TEM, XRD, and Raman spectra. The antibacterial activity of graphene-FeAg nanocomposite (NC) towards Bacillus subtilis, Escherichia coli, and Staphylococcus aureus was investigated by colony counting method. Graphene-FeAg NC demonstrates excellent antibacterial activity as compared to FeAg bimetallic without graphene. To understand the antibacterial mechanism of the NC, oxidative stress caused by reactive oxygen species (ROS) and the glutathione (GSH) oxidation were investigated in the system. It has been observed that ROS production and GSH oxidation are concentration dependent while the increase in silver content up to 50% generally enhances the ROS production while ROS decreases on further increase in silver content. Graphene loaded FeAg NC demonstrates higher GSH oxidation capacity than bare FeAg bimetallic nanocomposite. The mechanism study suggests that the antibacterial activity is probably due to membrane and oxidative stress produced by the nanocomposites. The possible antibacterial pathway mainly includes the non-ROS oxidative stress (GSH oxidation) while ROS play minor role. PMID:27038914

  11. An EXAFS Study of Platinum-Oxygen Bonds in the Metal-Support Interface of a Highly Dispersed Platinum/Aluminum Oxide Catalyst

    OpenAIRE

    Koningsberger, D.C.; Sayers, D.E.

    1985-01-01

    EXAFS measurements have been performed on the Pt LIII-edge of a highly dispersed (H/M~1.14) Pt/@c-Al{2}O{3} catalyst, reduced at 673 K after calcination at the same temperature. After reduction an oxidic platinum oxygen bond (2.05@9) is present with a very low average oxygen coordination number. This bond arises from a few not reduced platinum-oxide crystallites. Platinum oxygen bonds with a coordination distance of 2.65 @9 could be detected significantly due to the high quality of the EXAFS ...

  12. Synthesis and characterization of bimetallic nanocatalysts and their application in selective hydrogenation of citral to unsaturated alcohols

    Indian Academy of Sciences (India)

    S A Ananthan; R Suresh; K Giribabu; V Narayanan

    2013-11-01

    TiO2-supported bimetallic nanocatalysts were prepared and reduced at two different temperatures, 375°C and 575°C for selective hydrogenation of citral to corresponding unsaturated alcohols (geraniol (GOL) and nerol (NOL)). The nanocatalysts were characterized by difference techniques of Fourier transform infrared spectroscopy (FT-IR), Brunauer, Emmett and Teller (BET) surface area measurement, scanning electron microscopy (SEM), Energy Dispersive X-ray Analysis (EDAX), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The prepared nanocatalysts are uniformly dispersed with an average particle size of 50-100 nm and zero valence metallic state. Catalysts reduced at higher temperature lead to an increase in selectivity toward unsaturated alcohols (GOL and NOL). The Pt-Ru/TiO2 shows higher activity compared to Pt-Pd/TiO2 and Pt-Au/TiO2 nanocatalysts. In addition, a second metal (Ru) also leads to an increase in GOL and NOL selectivity during citral hydrogenation. Partially generated oxidized second metal species due to the difference in electronegativity, strongly binds the C=O group and also paves the way for selective activation of C=O bond.

  13. Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

    KAUST Repository

    Song, HyonMin

    2012-01-01

    The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

  14. Catalyst dispersion and activity under conditions of temperature- staged liquefaction. Technical progress report, January--March 1992

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-07-01

    Two coals, a Texas subbituminous C and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling and catalyst impregnation on liquefaction conversion behavior in temperature staged reactions for 30 minutes each at 275{degree} and 425{degree}C in H{sub 2} and 95:5 H{sub 2}:H{sub 2}S atmospheres. Methanol, pyridine, tetrahydrofuran, and tetrabutylammonium hydroxide were used as swelling agents. Molybdenum-based catalyst precursors were ammonium tetrathiomolybdate, molybdenum trisulfide, molybdenum hexacarbonyl, and bis(tricarbonylcyclopentadienyl-molybdenum). Ferrous sulfate and bis(dicarbonylcyclo-pentadienyliron) served as iron-based catalyst precursors. In addition, ion exchange was used for loading iron onto the subbituminous coal. For most experiments, liquefaction in H{sub 2}:H{sub 2}S was superior to that in H{sub 2}, regardless of the catalyst precursor. The benefit of the H{sub 2}S was greater for the subbituminous, presumably because of its higher iron content relative to the hvab coal. Tetrabutylammonium hydroxide was the only swelling agent to enhance conversion of the hvab coal significantly; it also caused a remarkable increase in conversion of the subbituminous coal. The combined application of solvent swelling and catalyst impregnation also improves liquefaction, mainly through increased oil yields from the hvab coal and increased asphaltenes from the subbituminous. A remarkable effect from use of ammonium tetrathiomolybdate as a catalyst precursor is substantial increase in pristane and phytane yields. Our findings suggest that these compounds are, at least in part, bound to the coal matrix.

  15. Porous Diatomite-Immobilized Cu–Ni Bimetallic Nanocatalysts for Direct Synthesis of Dimethyl Carbonate

    Directory of Open Access Journals (Sweden)

    Yong Chen

    2012-01-01

    Full Text Available A series of diatomite-immobilized Cu–Ni bimetallic nanocatalysts was prepared under ultrasonication and evaluated for the direct synthesis of dimethyl carbonate under various conditions. Upon being fully characterized by TPR, TPD, BET, SEM, XRD, and XPS methodologies, it is found that the bimetallic composite is effectively alloyed and well immobilized inside or outside the pore of diatomite. Under the optimal conditions of 1.2 MPa and 120∘C, the prepared catalyst with loading of 15% exhibited the highest methanol conversion of 6.50% with DMC selectivity of 91.2% as well as more than 10-hour lifetime. The possible reaction mechanism was proposed and discussed in detail. To our knowledge, this is the first report to use diatomite as a catalyst support for direct DMC synthesis from methanol and CO2.

  16. Dispersion state and catalytic properties of vanadia species on the surface of V2O5/TiO2 catalysts

    Institute of Scientific and Technical Information of China (English)

    许波连; 范以宁; 刘浏; 林明; 陈懿

    2002-01-01

    The dispersion state and catalytic properties of anatase-supported vanadia species are studied by means of X-ray diffraction (XRD), laser Raman spectroscopy (LRS), H2 temperature-programmed reduction (TPR) and the selective oxidation of o-xylene to phthalic anhydride. The almost identical values of the experimental dispersion capacity of V2O5 on anatase and the surface vacant sites available on the preferentially exposed (001) plane of anatase suggest that the highly dispersed vanadium cations are bonded to the vacant sites on the surface of anatase as derived by the incorporation model. When the loading amount of V2O5 is far below its dispersion capacity, the dispersed vanadia species might mainly consist of isolated VOx species bridging to the surface through V-O-Ti bonds. With the increase of V2O5 loading the isolated vanadia species interact with their nearest neighbors (either isolated or polymerized vanadia) through bridging V-O-V at the expenses of V-O-Ti bonds, resulting in the increase of the ratio of polymerized to isolated vanadia species and the decrease of the reactivity of the associated surface oxygen anions and, consequently, although the activity increases with loading to reach a maximum value, the turn over number (TON) of the V2O5/TiO2 catalyst decreases linearly. When the loading amount of V2O5 is higher than its dispersion capacity, the turn over number decreases more rapidly with the increase of V2O5 loading due to the formation of V2O5 crystallites in which the oxygen anions associated with V-O-V bonds are less reactive and only partially exposed on the surface.

  17. Facile synthesis of PtAu nanoparticles supported on polydopamine reduced and modified graphene oxide as a highly active catalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Graphical abstract: A facile and clean method for the synthesis of PtAu nanoparticles with different Pt/Au ratios supported on polydopamine reduced and modified graphene oxide (PtAu/PDA-RGO) is reported, which exhibit higher electro-catalytic performance and stability towards methanol oxidation in alkaline medium. - Highlights: • GO could be reduced and modified simultaneously by PDA without using reducing agents. • PDA plays an important role in enhancing the dispersion and stability of the catalyst. • The bimetallic PtAu/PDA-RGO catalysts exhibits higher catalytic activity than the monometallic Pt/PDA-RGO toward MOR. • The PtAu(3:1)/PDA-RGO catalyst also shows better catalytic activity for MOR than PtAu(3:1)/RGO and PtAu(3:1)/C catalysts. - Abstract: In this paper, a facile strategy for the synthesis of PtAu nanoparticles (NPs) with different Pt/Au ratios supported on polydopamine reduced and modified graphene oxide (PtAu/PDA-RGO) is reported. The as-prepared PtAu/PDA-RGO composites were extensively analyzed by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. It is found that PDA plays an important role in enhancing the dispersion and stability of the catalyst. Moreover, the bimetallic PtAu/PDA-RGO catalysts exhibits higher catalytic activity than the monometallic Pt/PDA-RGO toward methanol oxidation reaction (MOR), with the best performance found for the Pt/Au molar ratio of 3/1. The PtAu(3:1)/PDA-RGO catalyst also shows better catalytic activity for MOR than PtAu(3:1)/RGO and PtAu(3:1)/C catalysts, suggesting that PDA-RGO can be a promising catalyst support for fuel cells. These findings also indicate that the molar ratios of Pt/Au and the catalyst support are the two critical factors to affect the overall performance of the catalyst

  18. Rhodium-technetium catalysts in dehydrogenation of cyclohexane

    International Nuclear Information System (INIS)

    Catalytic properties of Rh-Tc/support (γ-Al2O3, SiO2 or MgO) system in dehydrogenation of cyclohexane were studied. A nonadditive increase in catalytic activity of bimetallic catalysts in comparison with monometallic catalysts has been established. Diffuse reflectance spectra have shown the presence of ionic forms of the metals in bimetallic catalysts. From the comparison of catalytic and optical properties a conclusion was drawn about the nature of synergism observed, which was accounted for by the formation of RhxTcy clusters. 6 refs.; 5 figs.; 1 tab

  19. 4,6-Dimethyl-dibenzothiophene conversion over Al2O3-TiO2-supported noble metal catalysts

    International Nuclear Information System (INIS)

    Research highlights: → Al2O3 and Al2O3-TiO2 (molar ratio Al/Ti = 2, AT2) mixed oxides were pore-filling impregnated to obtain Pd, Pt and Pd-Pt catalysts with ∼1 wt% nominal metal loading. → Reduced catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS). → In Pd-containing materials, TiO2 incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts. → Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide. → Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion. - Abstract: Al2O3 and Al2O3-TiO2 (molar ratio Al/Ti = 2, AT2) mixed oxides were synthesized using a low-temperature sol-gel method and were further pore-filling impregnated to obtain Pd and Pt catalysts with ∼1 wt% nominal metal loading. Simultaneous impregnation was used to prepare bimetallic materials at Pd:Pt = 80:20. Solids characterization was carried out by N2-physisorption, high-resolution transmission electron microscopy (HR-TEM and E-FTEM), X-ray diffraction, temperature-programmed reduction and CO-chemisorption. Reduced (350 deg. C, H2 flow) catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS) (in n-dodecane, at 300 deg. C and 5.5 MPa, batch reactor). In Pd-containing materials, TiO2 incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts, where bimetallic Pd-Pt with AT2 carrier had the highest organo-S compound conversion. Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide (as compared to alumina-supported ones). Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion.

  20. Catalyst in alternate energy resources for producing environment friendly clean energy

    International Nuclear Information System (INIS)

    Carbon monoxide, a by-product of the Chemical Process Industries, is a deadly poisonous gas; if released into the atmosphere causes irreparable damage to the environment. A bimetallic catalyst system Ru: Mn doped with different concentrations of 'K' (Potassium) and supported on high surface area alumina support was prepared by co impregnation method, dispersed and reduced at 450 deg. C under hydrogen flow using a closed reactor system at atmospheric pressure for the utilization of poisonous CO gas to produce environmental friendly clean energy. Fischer Tropsch catalyst, when subjected to CO/hydrogenation, gives methane and other hydrocarbon products. The main purpose of this research work was two fold: 1. The powder catalyst when dispersed/reduced on a high surface area oxide support spreads on the surface of the system in a different orientations and shapes. The particle size of the prepared catalysts ranges from 5.0-25.0 nm. The whole system forms a complicated mixture of numerous particles and hence becomes very complicated to study. The characterisation of these randomly oriented particles having different sizes and shapes is a difficult job. This required sensitive UHV spectroscopic techniques like SSIMS, XPS, EEls, XRD and TEM. Their operations needs strong skills. Hence the first aim was to utilize these techniques for the characterization of the prepared catalysts and to establish the usefulness of these techniques in studying such complicated systems. 2. Since Ru is a very good Fischer Tropsch catalyst for the production of aliphatic hydrocarbons product. Our other aim was to find out whether if by surface modification through additives or by surface reconstructing through chemical treatment, we could alter the path of this CO/hydrogenation reaction to produce potentially important unsaturated/aromatic hydrocarbon products. This would serve our dual purpose in which we could use poisonous CO for useful purpose. Hence 'K' potassium as surface modifier is

  1. Bimetallic nanoparticles for arsenic detection.

    Science.gov (United States)

    Moghimi, Nafiseh; Mohapatra, Mamata; Leung, Kam Tong

    2015-06-01

    Effective and sensitive monitoring of heavy metal ions, particularly arsenic, in drinking water is very important to risk management of public health. Arsenic is one of the most serious natural pollutants in soil and water in more than 70 countries in the world. The need for very sensitive sensors to detect ultralow amounts of arsenic has attracted great research interest. Here, bimetallic FePt, FeAu, FePd, and AuPt nanoparticles (NPs) are electrochemically deposited on the Si(100) substrate, and their electrochemical properties are studied for As(III) detection. We show that trace amounts of As(III) in neutral pH could be determined by using anodic stripping voltammetry. The synergistic effect of alloying with Fe leads to better performance for Fe-noble metal NPs (Au, Pt, and Pd) than pristine noble metal NPs (without Fe alloying). Limit of detection and linear range are obtained for FePt, FeAu, and FePd NPs. The best performance is found for FePt NPs with a limit of detection of 0.8 ppb and a sensitivity of 0.42 μA ppb(-1). The selectivity of the sensor has also been tested in the presence of a large amount of Cu(II), as the most detrimental interferer ion for As detection. The bimetallic NPs therefore promise to be an effective, high-performance electrochemical sensor for the detection of ultratrace quantities of arsenic. PMID:25938763

  2. Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

    Science.gov (United States)

    Quinn, Jacqueline W. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor); Aitken, Brian S. (Inventor)

    2012-01-01

    A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

  3. P–C-Activated Bimetallic Rhodium Xantphos Complexes: Formation and Catalytic Dehydrocoupling of Amine–Boranes**

    Science.gov (United States)

    Johnson, Heather C; Weller, Andrew S

    2015-01-01

    {Rh(xantphos)}-based phosphido dimers form by P–C activation of xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) in the presence of amine–boranes. These dimers are active dehydrocoupling catalysts, forming polymeric [H2BNMeH]n from H3B⋅NMeH2 and dimeric [H2BNMe2]2 from H3B⋅NMe2H at low catalyst loadings (0.1 mol %). Mechanistic investigations support a dimeric active species, suggesting that bimetallic catalysis may be possible in amine–borane dehydropolymerization. PMID:26140498

  4. Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Kuila, Debasish; Ilias, Shamsuddin

    2013-02-13

    In steam reforming reactions (SRRs) of alkanes and alcohols to produce H2, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N2 adsorption, and Transmission electron microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m2/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean

  5. Partial oxidation of methane over bimetallic copper- and nickel-actinide oxides (Th, U)

    International Nuclear Information System (INIS)

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi2 (An = Th, U) and ThCu2 were used as precursors and the products (2NiO.UO3, 2NiO.ThO2 and 2CuO.ThO2) characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and temperature-programmed reduction. The catalysts were active and selective for the conversion of methane to H2 and CO and stable for a period of time of ∼18 h on stream. The nickel catalysts were more active and selective than the copper catalyst and, under the same conditions, show a catalytic behaviour comparable to that of a platinum commercial catalyst, 5 wt% Pt/Al2O3. The catalytic activity increases when uranium replaces thorium and the selectivity of this type of materials is clearly different from that of single metal oxides and/or mechanical mixtures. The good catalytic behaviour of the bimetallic copper- and nickel-actinide oxides was attributed to an unusual interaction between copper or nickel oxide and the actinide oxide phase as showed by H2-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  6. Bimetallic materials for large diameter pipelines

    International Nuclear Information System (INIS)

    The results are presented of the investigation of bimetallic pipes made of Ni-Mn-Mo-V + Cb08Kh19N10G2B steel and of 19MN5 (type 22K) + SB 08Kh19N10G2B steels, manufactured in Japan for piping nuclear power stations for service under corrosion attack by coolants at high both pressure and temperature and under heavy cyclic loads. The procedures are described for manufacturing elements of piping from bimetallic seamless large-diameter pipes. A study has been made of the variation in bimetallic microstructure of the short-time mechanical properties, of the impact strength, of the critical brittleness point in initial and aged states of the cyclic strength and of the strength of the bimetallic joint

  7. Bimetallic nanoalloys in heterogeneous catalysis of industrially important reactions: synergistic effects and structural organization of active components

    International Nuclear Information System (INIS)

    The review is concerned with correlations between the synergistic effects and structural organization of the surface of bimetallic alloys that are used as active components of catalysts for selective hydrogenation of organic compounds and for CO oxidation in hydrogen-rich mixtures. Studies on the preparation of novel highly efficient catalysts using modern theoretical approaches, computer-assisted molecular design and original synthetic procedures are considered. It is shown that introduction of the second metal into the monometallic catalyst and subsequent formation of alloy particles with modified structure of the surface and near-surface layers leads to nonadditive enhancement of catalytic activity and/or selectivity. The bibliography includes 203 references

  8. Catalysts and process for liquid hydrocarbon fuel production

    Energy Technology Data Exchange (ETDEWEB)

    White, Mark G.; Ranaweera, Samantha A.; Henry, William P.

    2016-08-02

    The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality distillates, gasoline components, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel supported bimetallic ion complex catalyst for conversion, and provides methods of preparing such novel catalysts and use of the novel catalysts in the process and system of the invention.

  9. Improved catalytic activity of laser generated bimetallic and trimetallic nanoparticles.

    Science.gov (United States)

    Singh, Rina; Soni, R K

    2014-09-01

    We report synthesis of silver nanoparticles, bimetallic (Al2O3@Ag) nanoparticles and trimetallic (Al2O3@AgAu) nanoparticles by nanosecond pulse laser ablation (PLA) in deionized water. Two-step laser ablation methodologies were adopted for the synthesis of bi- and tri-metallic nanoparticles. In this method a silver or gold target was ablated in colloidal solution of γ-alumina nanoparticles prepared by PLA. The TEM image analysis of bimetallic and trimetallic particles reveals deposition of fine silver particles and Ag-Au alloy particles, respectively, on large alumina particles. The laser generated nanoparticles were tested for catalytic reduction of 4-nitrophenol to 4-aminophenol and showed excellent catalytic behaviour. The catalytic rate was greatly improved by incorporation of additional metal in silver nanoparticles. The catalytic efficiency of trimetallic Al2O3@AgAu for reduction of 4-nitrophenol to 4-aminophenol was remarkably enhanced and the catalytic reaction was completed in just 5 sec. Even at very low concentration, both Al2O3@Ag nanoparticles and Al2O3@AgAu nanoparticles showed improved rate of catalytic reduction than monometallic silver nanoparticles. Our results demonstrate that alumina particles in the solution not only provide the active sites for particle dispersion but also improve the catalytic activity. PMID:25924343

  10. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

    Directory of Open Access Journals (Sweden)

    Subbarao Duvvuri

    2011-11-01

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

  11. Hydrogen purification for fuel cell by copper promoted gold catalysts; Purificacao de hidrogenio para pilha a combustivel utilizando catalisadores de ouro promovidos com cobre

    Energy Technology Data Exchange (ETDEWEB)

    Mozer, Thiago S.; Vieira, Carlos T.P.; Passos, Fabio B. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil); Dziuba, Dominika A. [Hochschule Mannheim (Germany)

    2008-07-01

    Copper promoted gold catalysts were studied for hydrogen purification through selective CO oxidation. The Cu acted as a selectivity promoter favoring the CO conversion and decreasing the H{sub 2} consumption. The deposition-precipitation method, used to prepare the samples generated small and well dispersed gold particles, as the UV-vis DRS spectra did not show the 'plasmon' band, which indicates that the samples are active for SELOX. The activity tests showed high CO conversion, the bimetallic 2,5%Au-0,5%Cu/Al{sub 2}O{sub 3} catalyst showed the best behavior in the tested condition, 95% of CO conversion and 75% of selectivity at 50 deg C. Increasing the O{sub 2} content in the feedstream the CO conversion also increased, although the selectivity decreased. (author)

  12. Catalytic Activity of Mono- and Bi-Metallic Nanoparticles Synthesized via Microemulsions

    Directory of Open Access Journals (Sweden)

    Ramona Y.G. König

    2014-07-01

    Full Text Available Water-in-oil (w/o microemulsions were used as a template for the synthesis of mono- and bi-metallic nanoparticles. For that purpose, w/o-microemulsions containing H2PtCl6, H2PtCl6 + Pb(NO32 and H2PtCl6 + Bi(NO3, respectively, were mixed with a w/o-microemulsion containing the reducing agent, NaBH4. The results revealed that it is possible to synthesize Pt, PtPb and PtBi nanoparticles of ~3–8 nm in diameter at temperatures of about 30°C. The catalytic properties of the bimetallic PtBi and PtPb nanoparticles were studied and compared with monometallic platinum nanoparticles. Firstly, the electrochemical oxidation of formic acid to carbon monoxide was investigated, and it was found that the resistance of the PtBi and PtPb nanoparticles against the catalyst-poisoning carbon monoxide was significantly higher compared to the Pt nanoparticles. Secondly, investigating the reduction of 4-nitrophenol to 4-aminophenol,we found that the bimetallic NPs are most active at 23 °C, while the order of the activity changes at higher temperatures, i.e., that the Pt nanoparticles are the most active ones at 36 and 49 °C. Furthermore, we observed a strong influence of the support, which was either a polymer or Al2O3. Thirdly, for the hydrogenation of allylbenzene to propylbenzene, the monometallic Pt NPs turned out to be the most active catalysts, followed by the PtPb and PtBi NPs. Comparing the two bimetallic nanoparticles, one sees that the PtPb NPs are significantly more active than the respective PtBi NPs.

  13. Nature, density, and catalytic role of exposed species on dispersed VOx/CrOx/Al2O3 catalysts.

    Science.gov (United States)

    Yang, Shuwu; Iglesia, Enrique; Bell, Alexis T

    2006-02-16

    The structure and surface composition of binary oxides consisting of CrO(x) and VO(x) dispersed on alumina and their effects on the rate and selectivity of oxidative dehydrogenation (ODH) of propane were examined and compared with those for CrO(x) and VO(x) dispersed on alumina. VO(x) deposition on an equivalent CrO(x) monolayer on alumina and deposition of CrO(x) on an equivalent monolayer of VO(x) deposited on alumina led to CrVO(4) species during thermal treatment with concomitant reduction of Cr(6+) to Cr(3+). Autoreduction of Cr(6+) to Cr(3+) is also detected for CrO(x), even without the presence of VO(x). Infrared spectroscopy of NO adsorbed at 153 K probes the relative abundance of alumina and of V(5+), Cr(3+), and Cr(6+) at surfaces. This technique detects differences in the surface composition of VO(x)/CrO(x)()/Al(2)O(3) and CrO(x)/VO(x)/Al(2)O(3). The first of these samples is enriched in VO(x) relative to CrO(x) compared with the second sample. Consistent with this finding, VO(x)/CrO(x)/Al(2)O(3) and CrO(x)/VO(x)/Al(2)O(3) are distinguishable in their ODH activities and propene selectivities. The highest ODH activity and propene selectivity is observed for VO(x)/CrO(x)/Al(2)O(3), which exhibits a surface enriched in VO(x) and having a low surface concentration of Cr(6+). PMID:16471878

  14. Effect of titania on the characteristics of a Tin-Platinum catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Gil, P., E-mail: moralesp@imp.mx; Nava, N. [Instituto Mexicano del Petróleo (Mexico); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Físicas (Brazil)

    2015-06-15

    Pt-Sn bimetallic catalysts dispersed on alumina are commonly used for reforming and dehydrogenation reactions. In this research work, Pt and Sn were supported on titania. The resulting interactions between the components in the prepared samples, before and after treatment with hydrogen, were studied by Mössbauer spectroscopy, X-ray diffraction and Rietveld refinement. The results show the presence of Pt and SnO{sub 2} after calcinations. After the reduction process, metallic Pt, PtSn, and Pt{sub 3}Sn alloys were identified. The Rietveld refinement analysis shows that some Ti{sup 4+} atoms were replaced by Sn{sup 4+} atoms in the titania structure. Finally, the Mössbauer spectroscopy and X-ray diffraction results indicate that metallic platinum and SnO{sub 2} are encapsulated by a TiOx layer.

  15. Effect of titania on the characteristics of a Tin-Platinum catalyst

    International Nuclear Information System (INIS)

    Pt-Sn bimetallic catalysts dispersed on alumina are commonly used for reforming and dehydrogenation reactions. In this research work, Pt and Sn were supported on titania. The resulting interactions between the components in the prepared samples, before and after treatment with hydrogen, were studied by Mössbauer spectroscopy, X-ray diffraction and Rietveld refinement. The results show the presence of Pt and SnO2 after calcinations. After the reduction process, metallic Pt, PtSn, and Pt3Sn alloys were identified. The Rietveld refinement analysis shows that some Ti4+ atoms were replaced by Sn4+ atoms in the titania structure. Finally, the Mössbauer spectroscopy and X-ray diffraction results indicate that metallic platinum and SnO2 are encapsulated by a TiOx layer

  16. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

    Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

  17. Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Pingping; Siddiqi, Georges; Vining, William C.; Chi, Miaofang; Bell, Alexis T. (UCB); (ORNL)

    2011-10-28

    Catalysts for the dehydrogenation of light alkanes were prepared by dispersing Pt on the surface of a calcined hydrotalcite-like support containing indium, Mg(In)(Al)O. Upon reduction in H{sub 2} at temperatures above 673 K, bimetallic particles of PtIn are observed by TEM, which have an average diameter of 1 nm. Analysis of Pt LIII-edge extended X-ray absorption fine structure (EXAFS) data shows that the In content of the bimetallic particles increases with increasing bulk In/Pt ratio and reduction temperature. Pt LIII-edge X-ray absorption near edge structure (XANES) indicates that an increasing donation of electronic charge from In to Pt occurs with increasing In content in the PtIn particles. The activity and selectivity of the Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation reactions are strongly dependent on the bulk In/Pt ratio. For both reactants, maximum activity was achieved for a bulk In/Pt ratio of 0.48, and at this In/Pt ratio, the selectivity to alkene was nearly 100%. Coke deposition was observed after catalyst use for either ethane or propane dehydrogenation, and it was observed that the alloying of Pt with In greatly reduced the amount of coke deposited. Characterization of the deposit by Raman spectroscopy indicates that the coke is present as highly disordered graphite particles <30 nm in diameter. While the amount of coke deposited during ethane and propane dehydrogenation are comparable, the effects on activity are dependent on reactant composition. Coke deposition had no effect on ethane dehydrogenation activity, but caused a loss in propane dehydrogenation activity. This difference is attributed to the greater ease with which coke produced on the surface of PtIn nanoparticles migrates to the support during ethane dehydrogenation versus propane dehydrogenation.

  18. Hierarchical paramecium-like hollow and solid Au/Pt bimetallic nanostructures constructed using goethite as template

    Energy Technology Data Exchange (ETDEWEB)

    Liu Wei; Repo, Eveliina; Sillanpaeae, Mika [Laboratory of Applied Environmental Chemistry, University of Eastern Finland, Patteristonkatu 1, FI-50100 Mikkeli (Finland); Heikkilae, Mikko; Leskelae, Markku, E-mail: weiliuzk@yahoo.cn, E-mail: mika.sillanpaa@uef.fi [Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, PO Box 55 (A.I. Virtasen aukio 1), FI-00014, Helsinki (Finland)

    2010-10-01

    Novel hollow and solid paramecium-like hierarchical Au/Pt bimetallic nanostructures were constructed using goethite as template via a seed-mediated growth method. Transmission electron microscopy (TEM), {xi}-potential measurement, UV-vis spectroscopy, energy dispersive x-ray spectroscopy (EDS), ICP-AES measurement, x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) were utilized to systematically characterize the bimetallic nanostructures. It is found that the core structure of the paramecium-like bimetallic nanomaterial is closely related to reducing agent. When ascorbic acid is used as reducing agent, goethite serves as in situ sacrificed template and hollow paramecium-like bimetallic structure is obtained. When NH{sub 2}OH{center_dot}HCl is used, solid nanostructure with preserved goethite core is produced. Heating the reaction solution is necessary to obtain the paramecium-like morphology with rough interconnected Pt cilia shell. The thickness of Pt cilia layer can be controlled by adjusting the molar ratio of H{sub 2}PtCl{sub 6} to Au nanoseeds. The overgrowth of the rough Pt cilia is proposed to be via an autocatalytic and three-dimensional heterogeneous nucleation process first through flower-like morphology. Both the hollow and solid hierarchical paramecium-like Au/Pt bimetallic nanostructures show good catalytic activities.

  19. Simulating cyclic voltammograms of bimetallic model surfaces

    International Nuclear Information System (INIS)

    Cyclic voltammograms recorded at bimetallic surfaces reflect the superposition of current contributions from adsorption, desorption, and reaction processes at surface regions with laterally varying chemical properties. As will be demonstrated for some selected well-defined single crystalline model systems including Pt films on Ru(0001) and PtAu/Pt(111) surface alloys, voltammetric features at bimetallic surfaces can be simulated using the corresponding features for the monometallic surfaces in combination with information on the adsorption properties and abundance of the dominating sites at the bimetallic surfaces. Trends in the local adsorption properties can be predicted based on density functional theory calculations, whereas the necessary information about the local vertical and lateral metal distribution is obtained from scanning tunnelling microscopy imaging.

  20. The remarkable activity and stability of a highly dispersive beta-brass Cu-Zn catalyst for the production of ethylene glycol

    Science.gov (United States)

    Li, Molly Meng-Jung; Zheng, Jianwei; Qu, Jin; Liao, Fenglin; Raine, Elizabeth; Kuo, Winson C. H.; Su, Shei Sia; Po, Pang; Yuan, Youzhu; Tsang, Shik Chi Edman

    2016-02-01

    Incorporation of Zn atoms into a nanosize Cu lattice is known to alter the electronic properties of Cu, improving catalytic performance in a number of industrially important reactions. However the structural influence of Zn on the Cu phase is not well studied. Here, we show that Cu nano-clusters modified with increasing concentration of Zn, derived from ZnO support doped with Ga3+, can dramatically enhance their stability against metal sintering. As a result, the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol, an important reaction well known for deactivation from copper nanoparticle sintering, can show greatly enhanced activity and stability with the CuZn alloy catalysts due to no noticeable sintering. HRTEM, nano-diffraction and EXAFS characterization reveal the presence of a small beta-brass CuZn alloy phase (body-centred cubic, bcc) which appears to greatly stabilise Cu atoms from aggregation in accelerated deactivation tests. DFT calculations also indicate that the small bcc CuZn phase is more stable against Cu adatom migration than the fcc CuZn phase with the ability to maintain a higher Cu dispersion on its surface.

  1. The remarkable activity and stability of a highly dispersive beta-brass Cu-Zn catalyst for the production of ethylene glycol

    Science.gov (United States)

    Li, Molly Meng-Jung; Zheng, Jianwei; Qu, Jin; Liao, Fenglin; Raine, Elizabeth; Kuo, Winson C. H.; Su, Shei Sia; Po, Pang; Yuan, Youzhu; Tsang, Shik Chi Edman

    2016-01-01

    Incorporation of Zn atoms into a nanosize Cu lattice is known to alter the electronic properties of Cu, improving catalytic performance in a number of industrially important reactions. However the structural influence of Zn on the Cu phase is not well studied. Here, we show that Cu nano-clusters modified with increasing concentration of Zn, derived from ZnO support doped with Ga3+, can dramatically enhance their stability against metal sintering. As a result, the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol, an important reaction well known for deactivation from copper nanoparticle sintering, can show greatly enhanced activity and stability with the CuZn alloy catalysts due to no noticeable sintering. HRTEM, nano-diffraction and EXAFS characterization reveal the presence of a small beta-brass CuZn alloy phase (body-centred cubic, bcc) which appears to greatly stabilise Cu atoms from aggregation in accelerated deactivation tests. DFT calculations also indicate that the small bcc CuZn phase is more stable against Cu adatom migration than the fcc CuZn phase with the ability to maintain a higher Cu dispersion on its surface. PMID:26856760

  2. Magneto-optical response in bimetallic metamaterials

    CERN Document Server

    Atmatzakis, Evangelos; Fedotov, Vassili; Vienne, Guillaume; Zheludev, Nikolay I

    2016-01-01

    We demonstrate resonant Faraday polarization rotation in plasmonic arrays of bimetallic nano-ring resonators consisting of Au and Ni sections. This metamaterial design allows to optimize the trade-off between the enhancement of magneto-optical effects and plasmonic dissipation. Although Ni sections correspond to as little as ~6% of the total surface of the metamaterial, the resulting magneto-optically induced polarization rotation is equal to that of a continuous film. Such bimetallic metamaterials can be used in compact magnetic sensors, active plasmonic components and integrated photonic circuits.

  3. Highly branched PtCu bimetallic alloy nanodendrites with superior electrocatalytic activities for oxygen reduction reactions

    Science.gov (United States)

    Fu, Shaofang; Zhu, Chengzhou; Shi, Qiurong; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-02-01

    Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst.Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07682j

  4. Temperature-programmed oxidation of coked noble metal catalysts after autothermal reforming of n-hexadecane

    Energy Technology Data Exchange (ETDEWEB)

    Kauppi, E.I.; Linnekoski, J.A.; Krause, A.O.I.; Veringa Niemelae, M.K. [Aalto University, School of Science and Technology, Department of Biotechnology and Chemical Technology, Research Group Industrial Chemistry, P.O. Box 16100, FI-00076 Aalto (Finland); Kaila, R.K. [VTT Technical Research Centre of Finland, Biologinkuja 7, Espoo, P.O. Box 1001, FI-02044 VTT (Finland)

    2010-08-15

    Autothermal reforming (ATR) of n-hexadecane was carried out on zirconia-supported mono- and bimetallic noble metal (Rh, Pt) catalysts at 600, 700, and 800 C. After ATR, the reactivity of coke deposits (2.8-9.9 wt%) on the catalysts was investigated by temperature-programmed oxidation (TPO). Analysis of the results obtained from ATR and TPO experiments at various temperatures and on the different catalysts gave information on the reaction conditions where the detrimental coke can be minimized and allows estimating the nature of carbon deposits. H{sub 2} production increased with temperature on the tested Rh-containing catalysts and the ZrO{sub 2} support, but decreased as a function of temperature on the Pt catalyst. The formation of coke was least at 800 C, evidently due to the intensifying reaction of carbon and steam with increasing temperature, as well as to the better activity of the catalysts. The amount of coke formed was highest at 700 C. Comparison of the TPO profiles obtained for the monometallic Rh and Pt catalysts with the bimetallic RhPt revealed differences in the nature of carbon deposits on their surface. At 600 C, the coke formed on the monometallic Rh and Pt catalysts was located mostly on the support, whereas on the bimetallic RhPt catalyst the formation of this type of coke was suppressed. The bimetallic RhPt catalyst also exhibited better tolerance toward coking at 700 C. Therefore, although the selectivity toward hydrogen was not related to the amount of coke formed, the deactivation patterns differed on the mono- and bimetallic catalysts. (author)

  5. Cation exchange resin immobilized bimetallic nickel-iron nanoparticles to facilitate their application in pollutants degradation.

    Science.gov (United States)

    Ni, Shou-Qing; Yang, Ning

    2014-04-15

    Nanoscale zerovalent iron (nZVI) usually suffers from reduction of reactivity by aggregation, difficulty of assembling, environmental release and health concerns. Furthermore, data are lacking on the effect of cheap nickel on debromination of decabromodiphenyl ether (DBDE) by immobilized nZVI in aqueous system. In this study, strong acid polystyrene cation-exchange resins with particle diameter from 0.4 to 0.6 mm were utilized as matrices to immobilize bimetallic nickel-iron nanoparticles in order to minimize aggregation and environmental leakage risks of nZVI and to enhance their reactivity. Elemental distribution mapping showed that iron particles distributed uniformly on the surface of the resin and nickel particles were dispersed homogeneously into Fe phase. The reaction rate of resin-bound nZVI is about 55% higher than that of dispersed nZVI. The immobilized bimetallic nanoparticles with 9.69% Ni had the highest debromination percent (96%) and reaction rate (0.493 1/h). The existence of Ni significantly improved the debromination rate, due to the surface coverage of catalytic metal on the reductive metal and the formation of a galvanic cell. The environmental dominant congeners, such as BDE 154, 153, 100, 99 and 47, were produced during the process. Outstanding reactive performance, along with magnetic separation assured that resin-bound bimetallic nickel-iron nanoparticles are promising material that can be utilized to remediate a wide variety of pollutants contaminated sites including polybrominated diphenyl ethers. PMID:24559714

  6. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    Science.gov (United States)

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-03-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system.

  7. Influence of silver on the glycerol electro-oxidation over AuAg/C catalysts in alkaline medium: a cyclic voltammetry and in situ FTIR spectroscopy study

    International Nuclear Information System (INIS)

    In the present work, we investigated the influence of silver on the glycerol electro-oxidation over carbon-supported AuAg catalysts by cyclic voltammetry and in situ FTIR spectroscopy. We observed that the presence of Ag in the bimetallic materials provided a more efficient catalyst in terms of the ability to electro-oxidize glycerol at relatively low potentials. On the other hand, the bimetallic catalysts were found to be less promising than the Au/C catalyst with respect to the reaction rate. Ag addition influenced the mechanism of glycerol electro-oxidation, favoring the C-C-C bond breaking, as evidenced by the selective formation of formic acid on the bimetallic catalysts. The impact of Ag on the glycerol electro-oxidation over AuAg/C may be driven by electronic modifications and Ag segregation on the catalysts surface

  8. Final Technical Report: First Principles Investigations for the Ensemble Effects of PdAu and PtAu Bimetallic Nanocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ruqian Wu

    2012-05-18

    Bimetallic surfaces with tunable chemical properties have attracted broad attention in recent years due to their ample potential for heterogeneous catalysis applications. The local chemical properties of constituents are strongly altered from their parent metals by 'ligand effect', a term encompassing the influences of charge transfer, orbital rehybridization and lattice strain. In comparison to the aforementioned, the 'ensemble effect' associated with particular arrangements of the active constituents have received much less attention, despite their notable importance towards the determination of reactivity and selectivity of bimetallic catalysts. We performed theoretical studies for understanding the ensemble effects on bimetallic catalysis: (i) simulations for the formation of different ensembles on PdAu and PtAu nanoclusters; (ii) studies of the size, shape, and substrate dependence of their electronic properties; and (iii) simulations for model reactions such as CO oxidation, methanol, ethylene and water dehydrogenation on PdAu and PtAu nanoclusters. In close collaboration with leading experimental groups, our theoretical research elucidated the fundamentals of Au based bimetallic nanocatalysts.

  9. Etat actuel des recherches fondamentales sur les catalyseurs bimétalliques à base de platine, sur support alumine, comparables à ceux utilisés dans l'industrie pétrolière. Current State of Fundamental Research on Platinum-Base Bimetallic Catalysts on an Alumina Support, Comparable to the Ones Used in the Petroleum Industry

    Directory of Open Access Journals (Sweden)

    Charcosset H.

    2006-11-01

    és promoteurs diminuant l'hydrogénolyse ou (et inhibiteurs par encrassement ; 6 le fait que dans les 158 références de l'article la moitié date de 1976 et après, souligne l'intérêt croissant porté aux recherches fondamentales dans ce domaine. This article mainly concerns the pairs (Pt, Re, (Pt, Ir and (Pt,Ru dealt with in the following order - catalyst preparation (impregnation of the support, reduction by hydrogen ; - characterization of reduced catalysts ; - catalytic activities ; - scale-up tests ta industriel catalysts , - conclusions. Special emphasis is placed on I the difficulty of obtaining data on the degree of reduction which are meaningful concerning the state of the catalyst under normal working conditions, hence the need ta combine several techniques such as DTA, TGA, volumetry, catharometry, ESCA, in-frared spectroscopy, HL thermodesorption and the measuring of catalytic activities ; 21 the dference between the phase diagrams of divided and massed systems ; 3 the usefulness of the hydrogen titration of the unsorbed oxygen ta give evidence for the presence of small pure Mell particles in (Pt, Mell/AI20a catalysts; 4 the dependence of the final state of the catalyst on the activation mode. The pair (Pt, Re con be stabilized in a state of alloy particles having similar superficial and mean composition or in a state of particle mixture of (Pt, Re with an Re content of less than the rated composition and of pure and well dispersed Re. The pairs (Pt, Ir and especially (Pt, Ru are characterized by the difficulty in obtaining on alloy state with a constant composition from one metal particle to another ; 5 variations in catalytic activity due ta the addition of Mell to Pt, reflecting one or several of the following effects a increase in the dispersion of Pt with (or without a change in its intrinsic properties by weak-valence ions of W, Mo, Cr, etc. ; b formation of Mell in a metallic state, eventually producing an alloy with Pt ; c the rote of promoter carbon

  10. Synthesis of subnanometer-diameter vertically aligned single-walled carbon nanotubes with copper-anchored cobalt catalysts.

    Science.gov (United States)

    Cui, Kehang; Kumamoto, Akihito; Xiang, Rong; An, Hua; Wang, Benjamin; Inoue, Taiki; Chiashi, Shohei; Ikuhara, Yuichi; Maruyama, Shigeo

    2016-01-21

    We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high-quality SWNTs are expected to pave the way to replace silicon for next-generation optoelectronic and photovoltaic devices. PMID:26690843

  11. Platinum-ruthenium bimetallic clusters on graphite: a comparison of vapor deposition and electroless deposition methods.

    Science.gov (United States)

    Galhenage, Randima P; Xie, Kangmin; Diao, Weijian; Tengco, John Meynard M; Seuser, Grant S; Monnier, John R; Chen, Donna A

    2015-11-14

    Bimetallic Pt-Ru clusters have been grown on highly ordered pyrolytic graphite (HOPG) surfaces by vapor deposition and by electroless deposition. These studies help to bridge the material gap between well-characterized vapor deposited clusters and electrolessly deposited clusters, which are better suited for industrial catalyst preparation. In the vapor deposition experiments, bimetallic clusters were formed by the sequential deposition of Pt on Ru or Ru on Pt. Seed clusters of the first metal were grown on HOPG surfaces that were sputtered with Ar(+) to introduce defects, which act as nucleation sites for Pt or Ru. On the unmodified HOPG surface, both Pt and Ru clusters preferentially nucleated at the step edges, whereas on the sputtered surface, clusters with relatively uniform sizes and spatial distributions were formed. Low energy ion scattering experiments showed that the surface compositions of the bimetallic clusters are Pt-rich, regardless of the order of deposition, indicating that the interdiffusion of metals within the clusters is facile at room temperature. Bimetallic clusters on sputtered HOPG were prepared by the electroless deposition of Pt on Ru seed clusters from a Pt(+2) solution using dimethylamine borane as the reducing agent at pH 11 and 40 °C. After exposure to the electroless deposition bath, Pt was selectively deposited on Ru, as demonstrated by the detection of Pt on the surface by XPS, and the increase in the average cluster height without an increase in the number of clusters, indicating that Pt atoms are incorporated into the Ru seed clusters. Electroless deposition of Ru on Pt seed clusters was also achieved, but it should be noted that this deposition method is extremely sensitive to the presence of other metal ions in solution that have a higher reduction potential than the metal ion targeted for deposition. PMID:26018140

  12. Preparation and characterization of silica-supported Ni/Pt catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Raab, C.; Lercher, J.A. (Universitaet Wien, Vienna (Austria)); Goodwin, J.G. Jr. (Univ. of Pittsburgh, PA (USA)); Shyu, J.Z. (Amoco Research Center, Naperville, IL (USA))

    1990-04-01

    The formation of a series of Ni/Pt catalysts was investigated by means of temperature programmed reduction (TPR) of the chloride precursor, hydrogen chemisorption, x-ray diffraction, scanning electron microscopy, XPS, and magnetic measurements. An alloy between Pt and Ni was formed. The minority constituent of the series of bimetallic catalysts was always found to be quantitatively alloyed or in close contact with the more abundant metal. For several samples, the stoichiometric NiPt compound was observed. With Ni-rich samples a nonstoichiometric alloy (rich in Ni) was concluded to exist. At all concentration levels the presence of Pt facilitated the reduction of Ni{sup 2+} significantly. Temperature-programmed reduction of the Ni/Pt catalyst with 50 mol% and higher concentrations of Pt did not differ from that of pure Pt. Based on XPS and magnetic measurements it is concluded that a constant fraction (approximately 10-15%) of Ni was highly dispersed and interacted strongly with the support. 30 refs.

  13. Synchrotron radiation studies of supported metal catalysts

    International Nuclear Information System (INIS)

    Metallic clusters supported on refractory oxides have been used extensively for several decades in the production of chemicals and petroleum derived transportation fuels. Catalysts containing more than one metal component are of particular interest since the addition of a second metal provides a method of controlling the selectivity of the catalyst. That is, the second metal can alter the rates of competing reactions in a complex reaction sequence and thus alter the final product distribution of the reaction. In this work the reactions of cyclohexane in hydrogen over silica supported ruthenium and osmium catalysts were studied. Bimetallic catalysts represent an important class of materials that are of interest both scientifically and technologically. Despite the importance and long-standing use of supported metal catalysts, detailed information on the structure of the metal clusters has been difficult to obtain. The development of x-ray absorption spectroscopy with the increasing availability of synchrotron radiation, however, has provided a powerful and versatile tool for studying the structure of these complex systems. Using the Extended X-ray Absorption Fine Structure (EXAFS) technique, it is possible to obtain information on the local atomic structure of supported monometallic catalytic metals and their interaction with the support. In the discussion that follows the authors will focus on results that have been obtained on the structure of supported bimetallic cluster catalysts

  14. Preparation of Ag{sub core}/Au{sub shell} bimetallic nanoparticles from physical mixtures of Au clusters and Ag ions under dark conditions and their catalytic activity for aerobic glucose oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); Toshima, Naoki; Takasaki, Kanako [Department of Applied Chemistry, Tokyo University of Science Yamaguchi, SanyoOnoda-shi, Yamaguchi 756-0884 (Japan); Okumura, Mitsutaka [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama, Toyonaka, Osaka 560-0043 (Japan)

    2014-02-15

    Graphical abstract: The synthesis, characterization and catalytic activities for glucose oxidation of AgAu bimetallic nanoparticles (BNPs) with size of less than 2 nm are reported. The catalytic activity of Ag{sub 10}Au{sub 90} BNPs was about two times higher than that of Au NPs, even the BNPs have a larger particle size than that of Au NPs. -- Highlights: • Ag{sub core}/Au{sub shell} BNPs with size of less than 2.0 nm were prepared. • No any reducing reagents and lights were used for the preparation of the BNPs. • The catalytic activity of the BNPs is about two times higher than that of Au NPs. -- Abstract: AgAu bimetallic nanoparticles (BNPs), one of the most extensively studied bimetallic systems in the literatures, could have various structures and compositions depending on their preparation conditions. In the present work, catalytically highly active PVP-protected Ag{sub core}/Au{sub shell} BNPs of about 2.5 nm in diameter were fabricated from physical mixtures of aqueous dispersions of Au nanoparticles and Ag{sup +} ions under dark conditions without using any reducing agents. The prepared Ag{sub core}/Au{sub shell} BNP colloidal catalysts, which possessed a high activity for aerobic glucose oxidation, were characterized by Ultraviolet–visible spectrophotometry (UV–Vis), Inductive coupled plasma emission spectrometer (ICP), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Energy disperse spectroscopy (EDS) in High-resolution scanning transmission electron microscopy (HR-STEM). The highest activity (11,360 mol-glucose h{sup −1} mol-metal{sup −1}) was observed for the BNPs with the Ag/Au atomic ratio of 1/9, the TOF value of which is about two times higher than that of Au nanoparticles with the particle size of 1.3 nm. The enhanced catalytic activity of the prepared Ag{sub core}/Au{sub shell} BNPs compared to Au NPs can be ascribed to the presence of negatively charged Au atoms resulted from electron donations

  15. Tetranuclear Zn/4f coordination clusters as highly efficient catalysts for Friedel-Crafts alkylation.

    Science.gov (United States)

    Griffiths, Kieran; Kumar, Prashant; Akien, Geoffrey R; Chilton, Nicholas F; Abdul-Sada, Alaa; Tizzard, Graham J; Coles, Simon J; Kostakis, George E

    2016-06-14

    A series of custom-designed, high yield, isoskeletal tetranuclear Zn/4f coordination clusters showing high efficiency as catalysts with low catalytic loadings in Friedel-Crafts alkylation are described for the first time. The possibility of altering the 4f centers in these catalysts without altering the core topology allows us to further confirm their stability via EPR and NMR, as well to gain insights into the plausible reaction mechanism, showcasing the usefulness of these bimetallic systems as catalysts. PMID:27248829

  16. Stainless Steel to Titanium Bimetallic Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Kaluzny, J. A. [Fermilab; Grimm, C. [Fermilab; Passarelli, D. [Fermilab

    2015-01-01

    In order to use stainless steel piping in an LCLS-II (Linac Coherent Light Source Upgrade) cryomodule, stainless steel to titanium bimetallic transitions are needed to connect the stainless steel piping to the titanium cavity helium vessel. Explosion bonded stainless steel to titanium transition pieces and bimetallic transition material samples have been tested. A sample transition tube was subjected to tests and x-ray examinations between tests. Samples of the bonded joint material were impact and tensile tested at room temperature as well as liquid helium temperature. The joint has been used successfully in horizontal tests of LCLS-II cavity helium vessels and is planned to be used in LCLS-II cryomodules. Results of material sample and transition tube tests will be presented.

  17. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    Directory of Open Access Journals (Sweden)

    Jianlong Ji

    2014-03-01

    Full Text Available Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM, energy dispersive X-ray spectrometer (EDS, transmission electron microscopy (TEM and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS activity, using 4-mercaptopyridine (4-MP as model molecules.

  18. Synthesis and characterization of highly conductive Sn–Ag bimetallic nanoparticles for printed electronics

    International Nuclear Information System (INIS)

    To synthesize low-cost, highly conductive metal nanoparticles for inkjet printing materials, we synthesized Sn–Ag bimetallic nanoparticles using a polyol process with poly(vinyl pyrrolidone). Because a surface oxidation layer forms on Sn nanoparticles, various compositions of Sn–xAg [x = 0, 20, 40, 60, 80, 100 (wt%)] nanoparticles were synthesized and characterized for the purpose of removing the β-Sn phase. The results of XPS, TEM, and XRD analyses confirm that the formation of a bimetallic phase, such as Ag4Sn or Ag3Sn, hinders the β-Sn phase and, consequently, leads to the removal of the surface oxidation layer. To measure the sheet resistance of various compositions of Sn–Ag nanoparticles, we made the ink that contains Sn–Ag by dispersing 10 wt% of Sn–Ag nanoparticles in methanol. The sheet resistance is decreased by the conductive Sn–Ag phases, such as the fcc, Ag4Sn, and Ag3Sn phases, but sharply increased by the low-conductive Sn nanoparticles and the surface oxidation layer on the Sn nanoparticles. The sheet resistance results confirm that 80Ag20Sn and 60Ag40Sn bimetallic nanoparticles are suitable candidates for inkjet printing materials.

  19. Method for the determination of Pd-catalyst residues in active pharmaceutical ingredients by means of high-energy polarized-beam energy dispersive X-ray fluorescence.

    Science.gov (United States)

    Marguí, E; Van Meel, K; Van Grieken, R; Buendía, A; Fontàs, C; Hidalgo, M; Queralt, I

    2009-02-15

    In medicinal chemistry, Pd is perhaps the most-widely utilized precious metal, as catalyst in reactions which represent key transformations toward the synthesis of new active pharmaceutical ingredients (APIs). The disadvantage of this metal-catalyzed chemistry is that expensive and toxic metal residues are invariably left bound to the desired product. Thus, stringent regulatory guidelines exist for the amount of residual Pd that a drug candidate is allowed to contain. In this work, a rapid and simple method for the determination of Pd in API samples by high-energy polarized-beam energy dispersive X-ray fluorescence spectrometry has been developed and validated according to the specification limits of current legislation (10 mg kg(-1) Pd) and the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH guidelines). Sample and calibration standards preparation includes a first step of homogenization and then, in a second step, the pressing of the powdered material into pellets without any chemical treatment. The use of several synthetic calibration standards made of cellulose to simulate the API matrix appears to be an effective means to obtain reliable calibration curves with a good spread of data points over the working range. With the use of the best measuring conditions, the limit of detection (0.11 mg kg(-1) Pd) as well as the limit of quantitation (0.37 mg kg(-1) Pd) achieved meet rigorous requirements. The repeatability of the XRF measurement appeared to be less than 2%, while the precision of the whole method was around 7%. Trueness was evaluated by analyzing spiked API samples at the level of the specification limit and calculating the recovery factor, which was better than 95%. To study the applicability of the developed methodology for the intended purpose, three batches of the studied API were analyzed for their Pd content, and the attained results were comparable to those obtained by the

  20. RuCu nanoparticles supported on graphene: A highly efficient catalyst for hydrolysis of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Nan; Hu, Kai [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072 (China); Luo, Wei, E-mail: wluo@whu.edu.cn [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072 (China); Suzhou Institute of Wuhan University, Suzhou, Jiangsu, 215123 (China); Cheng, Gongzhen, E-mail: gzcheng@whu.edu.cn [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072 (China)

    2014-03-25

    Graphical abstract: Well dispersed RuCu/graphene nanoparticles exerted satisfied catalytic activity and recycle stability towards the hydrolysis of ammonia borane. Highlights: • One-step in situ synthesis of graphene supported RuCu NPs. • The catalysts exhibit excellent catalytic activity toward hydrolysis of AB. • Graphene supported NPs exhibit the highest catalytic activity. -- Abstract: Well dispersed RuCu nanoparticles (NPs) supported on graphene were in situ synthesized by a one-step co-reduction of aqueous solution of ruthenium (III) chloride, cupric (II) chloride, and graphite oxide (GO) with ammonia borane (AB) under ambient condition. The nature of the NPs was fully characterized by TEM, HRTEM, XRD, energy dispersive spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). The as-synthesized NPs exhibit much higher catalytic activity for hydrolytic dehydrogenation of AB than the monometallic Ru and Cu, bimetallic RuCu/graphene reduced by NaBH{sub 4}, and graphene free RuCu counterparts. Additionally, the as-synthesized NPs supported on graphene exhibit higher catalytic activity than the catalysts with other conventional supports, such as SiO{sub 2}, γ-Al{sub 2}O{sub 3}, and carbon black. The activity of Ru{sub 1}Cu{sub 7.5}/graphene NPs in terms of turnover frequency (TOF) is 135 mol H{sub 2} min{sup −1} (mol Ru){sup −1}, which is higher than Ru/graphene, and most reported Ru-based or other noble metal-based NPs for the catalytic hydrolysis of AB. The activation energy for hydrolysis of AB in the presence of Ru{sub 1}Cu{sub 7.5}/graphene NPs was determined as 30.59 kJ mol{sup −1}, which is lower than most of the reported catalysts. Furthermore, the as-prepared NPs exert satisfied durable stability for the hydrolytic dehydrogenation of AB.

  1. SYNTHESIS OF POLYMER-STABILIZED PLATINUM/RUTHENIUM BIMETALLIC COLLOIDS AND THEIR CATALYTIC PROPERTIES FOR SELECTIVE HYDROGENATION OF CROTONALDEHYDE

    Institute of Scientific and Technical Information of China (English)

    Wei-xia Tu; Han-fan Liu

    2005-01-01

    Polymer-stabilized platinum/ruthenium bimetallic colloids (Pt/Ru) were synthesized by polyol reduction with microwave irradiation and characterized by TEM and XPS. The colloidal nanoparticles have small and narrow size distributions. Catalytic performance of the Pt/Ru colloidal catalysts was investigated on the selective hydrogenation of crontonaldehyde (CRAL). A suitable amount of the added metal ions and base can improve the selectivity of CRAL to crotylalcohol (CROL) remarkably. The catalytic activity and the selectivity are dependent on the compositions of bimetallic colloids. Thereinto, PVP-stabilized 9Pt/1Ru colloid with a molar ratio of metals Pt:Ru = 9:1 shows the highest catalytic selectivity 77.3% to CROL at 333 K under 4.0 MPa of hydrogen.

  2. Controlled reduction of LaFe xMn yMo zO3/Al2O3 composites to produce highly dispersed and stable Fe0 catalysts: a Mössbauer investigation

    Directory of Open Access Journals (Sweden)

    Juliana Cristina Tristão

    2008-06-01

    Full Text Available In this work, controlled reduction of perovskites supported on Al2O3 was used to prepare thermally stable nanodispersed iron catalysts based on Fe0/La2O3/Al2O3. The perovskites composites LaFe0.90Mn0.08Mo0.02O3(25, 33 and 50 wt (% /Al2O3 and LaFe0.90Mn0.1O3(25 wt (% /Al2O3 were prepared and characterized by XRD, BET, TPR, SEM and Mössbauer spectroscopy. XRD for unsupported perovskite showed the formation of a single phase perovskite structure. The Mössbauer spectra of the perovskites were fitted with hyperfine field distribution model for the perovskite. Supported perovskites on Al2O3 showed a decrease of the hyperfine field in respect to unsupported perovskite, due to decrease of particle size and dispersion of the Fe3+ specimens on the support. Also showed broaden lines and relaxation effects due to the small particle size. To produce the Fe0 catalyst, the composite perovskite(25%/Al2O3 was reduced with H2 at 900, 1000 and 1100 °C for 1 hour. XRD data indicated the formation of Fe0 catalyst with particles sizes of ca. 35 nm. The Mössbauer spectrum showed the formation of metallic iron and doublets corresponding to species of octahedric Fe2+ and Fe3+ sites dispersed on Al2O3. These catalysts showed improved stability towards sintering even upon treatment at 1000 and 1100 °C under H2.

  3. Comparing and Optimizing Nitrate Adsorption from Aqueous Solution Using Fe/Pt Bimetallic Nanoparticles and Anion Exchange Resins

    OpenAIRE

    Muhammad Daud; Zahiruddin Khan; Aisha Ashgar; M. Ihsan Danish; Ishtiaq A. Qazi

    2015-01-01

    This research work was carried out for the removal of nitrate from raw water for a drinking water supply. Nitrate is a widespread ground water contaminant. Methodology employed in this study included adsorption on metal based nanoparticles and ion exchange using anionic resins. Fe/Pt bimetallic nanoparticles were prepared in the laboratory, by the reduction of their respective salts using sodium borohydride. Scanning electron microscope, X-ray diffraction, energy dispersive spectrometry, and ...

  4. Removal of trichloroethylene DNAPL trapped in porous media using nanoscale zerovalent iron and bimetallic nanoparticles: Direct observation and quantification

    International Nuclear Information System (INIS)

    Highlights: ► TCE DNAPL removal inside pores using NZVI or bimetals in a 2-D system was visualized. ► Presence of nitrate and humic substances decrease the TCE DNAPL removal efficiency. ► Presence of ethanol increases the TCE DNAPL removal efficiency. ► Metal catalysts enhance the TCE DNAPL removal using NZVI in a short term reaction. ► Metal catalysts do not increase the DNAPL removal efficiency for a long term reaction. - Abstract: Direct trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) removal inside pore areas using nanoscale zerovalent iron (NZVI) and bimetallic nanoparticles were first investigated in a water-saturated porous glass micromodel. Effects of nitrate, aqueous ethanol co-solvent, humic substance, and elapsed time on TCE DNAPL removal using NZVI were studied by direct visualization. The removal efficiency was then quantified by directly measuring the remaining TCE DNAPL blobs area using an image analyzer. As ethanol content of co-solvent increased, TCE DNAPL removal by NZVI was also increased implying sequential TCE DNAPL removal mechanisms: as dissolved TCE was degraded by NZVI, TCE dissolution from TCE blobs would be then facilitated and the TCE blob areas would be eventually reduced. The presence of nitrate and humic substance hindered the NZVI reactivity for the TCE DNAPL removal. In contrast, the TCE DNAPL removal efficiency was enhanced using bimetallic nanoparticles in a short-term reaction by generating atomic hydrogen for catalytic hydro-dechlorination. However, all TCE DNAPL removal efficiencies reached the same level after long-term reaction using both NZVI and bimetallic nanoparticles. Direct TCE DNAPL observation clearly implied that TCE blobs existed for long time even though all TCE blobs were fully exposed to NZVI and bimetallic nanoparticles.

  5. Bimetallic electrocatalysts on titanium dioxide-based supports for methanol oxidation and oxygen evolution

    Science.gov (United States)

    Fuentes, Roderick Eliel

    Electrocatalysts are essential for the development of active and durable fuel cells and hydrogen production technologies. Generally, electrochemical processes of energy conversion and hydrogen generation in a Proton Exchange Membrane (PEM) utilize precious metals, such as platinum, iridium and ruthenium, as electrocatalysts. For the methanol oxidation and oxygen evolution reaction, a bimetallic structure can be used to enhance kinetics and increase stability. It is desired to support electrocatalysts to disperse nanoparticles on the surface and promote better catalyst utilization. Traditionally, carbon has been used as an electrochemical support because it has a high surface area and high electrical conductivity. The problem with carbon is that it is not a very stable material and can corrode at voltages more than 0.9 V, affecting performance of the electrochemical reaction. Therefore, it would be useful to support electrocatalysts in a stable material with suitable conductivity. Using titanium dioxide as a support can be advantageous due to its corrosion-resistant capability. TiO2 exhibit different crystalline structures, such as anatase and rutile, which can have an effect on catalytic activity. Unfortunately, it is not conductive; hence, it is not used in electrochemical applications. However, it can be doped with niobium to increase electronic conductivity; but, it usually come at the expense of surface area. In this work, TiO 2 and Nb-TiO2 were studied as platinum/ruthenium and iridium/ruthenium nanoparticles supports for the electrochemical oxidation of methanol and oxygen evolution, respectively. Even though the conductivity of our supports was very low, adding a considerable loading of nanoparticles increased conductivity of the composite material (support + catalyst) to acceptable levels. Using cyclic voltammetry (CV) and direct methanol fuel cell tests creating a membrane electrode assembly (MEA), Pt-Ru supported on Nb-TiO2 and TiO 2 showed superior

  6. Squeezing and stretching Pd thin films: A high-resolution STM study of Pd/Au(111) and Pd/Cu(111) bimetallics

    Science.gov (United States)

    Blecher, Mishan E.; Lewis, Emily A.; Pronschinske, Alex; Murphy, Colin J.; Mattera, Michael F. G.; Liriano, Melissa L.; Sykes, E. Charles H.

    2016-04-01

    Pd bimetallic alloys are promising catalysts, especially for heterogeneous reactions involving hydrogen, as they exhibit increased activity and reduced demand for expensive precious metals. Using scanning tunneling microscopy, we examine the structure of Pd thin films on Cu(111) and Au(111) and demonstrate compression and expansion, respectively, of the bulk Pd lattice constant in the film. The relative binding strength of H to the two surfaces, inferred via tip-induced diffusion barriers, suggests that the strain in these systems may alter adsorbate binding and corroborates well-known trends in d-band shifts calculated by the density functional theory. Modification to the topography and activity of Pd films based on the choice of substrate metal illustrates the value of bimetallic systems for designing less expensive, tunable catalysts.

  7. Synthesis and characterization of Fe-Co catalyst prepared via reverse microemulsion method

    Science.gov (United States)

    Mohd Zabidi, Noor Asmawati; Abdul Aziz, Muhammad Nur Azizi; Ali, Sardar; Taha, Mohd Faisal

    2012-09-01

    This paper reports the characterization of bimetallic catalyst systems comprising cobalt and iron on CNTs support prepared via reverse microemulsion method. The properties of the bimetallic catalyst were characterized using TEM, FESEM and N2 adsorption. Based on TEM analyses, the calculated average particle sizes ranged from 4.6 nm to 5.2 nm for the various catalyst compositions. The performance of the Co-based catalyst in a Fischer-Tropsch reaction was evaluated in a fixed-bed reactor at 220°C, 1 atm and H2/CO v/v ratio of 2:1 v/v and space velocity of 12 L/g.h. Amongst the catalysts tested, the 90Co10Fe/CNTs resulted in the highest CO conversion of 14.1% whereas the 100Co/CNTs resulted in the highest C5+ hydrocarbon selectivity.

  8. Analysis of Manufacturing Bimetallic Tubes by the Cold Drawing Process

    Directory of Open Access Journals (Sweden)

    Halaczek D.

    2016-03-01

    Full Text Available Drawing processes apply to obtain the bimetallic tubes from the different metals and alloys, combined in the solid state, which significantly affects the specificity of this process. The manufacturing of bimetallic tubes by drawing process depends on many factors which include: preparation of the surface of materials joined in the solid state, the geometric parameters of the working tool, technological parameters of the drawing process (drawing speed, type of lubricant, the use of back pull etc.. Generally, the cold drawing process of producing the bimetallic tubes refers to metals which have high ductility (copper, aluminum, etc.. The tube sinking (tube drawing without a mandrel of bimetallic tubes together with joining them at the interface of the two metal in the solid-state is applied for tubes of the diameter range between 6 to 20 mm and based on of the reducing the diameter of the tube. However, a slight increase of wall thickness ca. 0.05 ÷ 0.10 mm can appear, which is not dangerous phenomenon in case of producing the bimetallic tubes by joining in the solid-state. The aim of the research was to investigate the technology of tubes drawing process from non-ferrous metal, drawing process of bimetallic tubes and the production of bimetallic tubes in layers composition: cooper Cu-ETP - brass CuZn37 and CuZn37 brass - copper Cu-ETP in the tube sinking process. The research program included: production of bimetallic tubes with a different composition (Cu- ETP-CuZn37 and CuZn37-Cu-ETP and a different percentage of the cross-section components; analysis of changes of tube wall thickness and the layer composition of the bimetallic tube, based on measurements on the workshop microscope; analysis of the material flow in the process of the bimetallic tubes production based on the measurements results of a profilograph CP-200.

  9. Steam reforming of ethanol over bimetallic RhPt/La2O3: Long-term stability under favorable reaction conditions

    OpenAIRE

    Cobo, Martha; Pieruccini, Diana; Abello, Ricardo; Ariza, Laura; Córdoba, Luis Fernando; Conesa Ferrer, Juan Antonio

    2013-01-01

    Recently, the steam reforming of biofuels has been presented as a potential hydrogen source for fuel cells. Because this scenario represents an interesting opportunity for Colombia (South America), which produces large amounts of bioethanol, the steam reforming of ethanol was studied over a bimetallic RhPt/La2O3 catalyst under bulk mass transfer conditions. The effect of temperature and the initial concentrations of ethanol and water were evaluated at space velocities above 55,000 h−1 to dete...

  10. Insight into the Catalytic Mechanism of Bimetallic Platinum–Copper Core–Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Lu; Luo, Xiangyi; Kropf, A. Jeremy; Wen, Jianguo; Wang, Xiaoping; Lee, Sungsik; Myers, Deborah J.; Miller, Dean; Wu, Tianpin; Lu, Jun; Amine, Khalil

    2016-01-01

    The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt–Cu core–shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li–O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt–Cu core–shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

  11. Low Pt content on the Pd{sub 45}Pt{sub 5}Sn{sub 50} cathode catalyst for PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Salvador-Pascual, J.J.; Solorza-Feria, O. [Depto. Quimica, Centro de Investigacion y de Estudios Avanzados del IPN, A. Postal 14-740, 07360 Mexico D.F. (Mexico); Collins-Martinez, V.; Lopez-Ortiz, A. [Centro de Investigacion en Materiales Avanzados, Miguel de Cervantes 120, 31109 Chihuahua (Mexico)

    2010-06-01

    Pd{sub 45}Pt{sub 5}Sn{sub 50} electrocatalyst was prepared by a NaBH{sub 4} reduction of PdCl{sub 2}, H{sub 2}PtCl{sub 6} and SnCl{sub 2} in THF at 0 C. This catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) microanalysis and hydrodynamic electrochemical technique. XRD, SEM and TEM results demonstrate that the borohydrate reduction methodology enable the synthesis of conglomerated particles nanometric in size ranging from 1 to 6 nm. Oxygen reduction reaction (ORR) activity was investigated on carbon dispersed catalyst by rotating disk electrode (RDE) technique in H{sub 2}SO{sub 4} 0.5 M. The effect of temperature on the kinetics was analyzing resulting in an apparent activation energy of 42.54 {+-} 1 kJ mol{sup -1}, value which is less than the obtained for the nanostructured bimetallic PdSn electrocatalyst under the same experimental condition. The Pd{sub 45}Pt{sub 5}Sn{sub 50} electrocatalyst dispersed on a carbon powder was tested as cathode electrocatalyst in a membrane-electrode assembly (MEA) arriving to a power density of 210 mW cm{sup -2} at 0.35 V and 80 C. (author)

  12. Enhanced Dry Reforming of Methane on Ni and Ni-Pt Catalysts Synthesized by Atomic Layer Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Gould, Troy D.; Montemore, Matthew M.; Lubers, Alia M.; Ellis, Lucas D.; Weimer, Alan; Falconer, John L.; Medlin, James W.

    2015-02-25

    Atomic layer deposition (ALD) was used to deposit Ni and Pt on alumina supports to form monometallic and bimetallic catalysts with initial particle sizes of 1–2.4 nm. The ALD catalysts were more active (per mass of metal) than catalysts prepared by incipient wetness (IW) for dry reforming of methane (DRM), and they did not form carbon whiskers during reaction due to their sufficiently small size. Catalysts modified by Pt ALD had higher rates of reaction per mass of metal and inhibited coking, whereas NiPt catalysts synthesized by IW still formed carbon whiskers. Temperature-programmed reduction of Ni catalysts modified by Pt ALD indicated the presence of bimetallic interaction. Density functional theory calculations suggested that under reaction conditions, the NiPt surfaces form Ni-terminated surfaces that are associated with higher DRM rates (due to their C and O adsorption energies, as well as the CO formation and CH4 dissociation energies).

  13. Bimetallic nanoparticles of copper and indium by borohydride reduction

    International Nuclear Information System (INIS)

    This study investigated the preparation of copper-indium bimetallic nanoparticles through the borohydride reduction in an alcohol solution for application in ink-coating and sputtering target materials. Copper, indium metal and copper-indium intermetallic materials were synthesized by reacting CuCl2 and InCl3 with NaBH4 in 2-propanol (IPA) and tetraethylene glycol (TEG) at room temperature. The Cu-In samples contained Cu2In and CuIn phases with particle sizes of 10-100 nm and 30-200 nm in both the IPA and TEG solutions, respectively. The nanoparticulate Cu-In precursor layer was coated onto a soda-lime glass through spin-casting, where the Cu-In intermetallic phases of Cu2In and Cu11In9 were produced through heat treatment in Ar gas and a microstructured CuInSe2 layer was produced in a selenium atmosphere. Cu, In, Cu-In intermetallic nanoparticles and the films were characterized using powder X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analyses.

  14. DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

    OpenAIRE

    Leng, Jing; Wang, Wen-Min; Lu, Li-min; Bai, Ling; Qiu, Xin-Lan

    2014-01-01

    In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR ...

  15. Ultrasound assisted dispersion of different amount of Ni over ZSM-5 used as nanostructured catalyst for hydrogen production via CO2 reforming of methane

    International Nuclear Information System (INIS)

    Graphical abstract: A series of Ni/ZSM-5 nanocatalysts with different amount of Ni were prepared via ultrasound assisted method and characterized with XRD, FESEM, TEM, BET and FTIR techniques. The research deals with catalyst development for dry reforming of methane with the aim of reaching the most stable catalyst specifically over nano-sized catalysts. About more than 99% of Ni particles size is less than 100 nm for the sample prepared with 8% Ni, which is essential to the relative suppression of the carbon formation on catalysts. Catalyst prepared with 8% Ni content showed superior activity in process expected due to its better catalytic properties. - Highlights: • Using ZSM-5 zeolite in dry reforming of methane. • Employing ultrasound energy in synthesis of Ni/ZSM-5 nanocatalyst. • Enhancement of Ni particles size to meet desired catalyst at lower amount of Ni loading. • Dry reforming of methane over Ni/ZSM-5 nanocatalyst with different Ni-loading. • Superior activity of Ni/ZSM-5 nanocatalyst synthesized with 8% Ni content. - Abstract: Carbon dioxide reforming of methane is an interesting route for synthesis gas production especially over nanostructured catalysts. The present research deals with nanocatalyst development by sonochemical method for dry reforming of methane with the aim of reaching the most efficient nanocatalyst. Effect of Ni metal content, one of the most significant variables, on the properties of the ZSM-5 supported nanocatalysts was taken into account. The Ni/ZSM-5 nanocatalysts were prepared via assisted traditional impregnation method via ultrasound irradiation and characterized with XRD, FESEM, TEM, BET and FTIR techniques. Comparison of XRD patterns implies that the peaks related to NiO become sharper by increasing metal content over the support. In the case of nanocatalysts with lower metal content (3% and 8%), the beneficial influence of ultrasound assisted procedure become more pronounced and the observed reduction in

  16. Development of Cu and Ni catalysts supported on ZrO{sub 2} for the generation of H{sub 2} by means of the reaction of reformed methanol in atmosphere oxidizer; Desarrollo de catalizadores de Cu y Ni soportados en ZrO{sub 2} para la generacion de H{sub 2} mediante la reaccion de reformado de metanol en atmosfera oxidante

    Energy Technology Data Exchange (ETDEWEB)

    Lopez C, P.

    2012-07-01

    ZrO{sub 2} was prepared by the sol-gel method and calcined at 450 C. The prepared zirconia was impregnated with an aqueous solution of Cu(CH{sub 3}CO{sub 2}){sub 2}{center_dot}H{sub 2}O or NiNO{sub 3}{center_dot}6H{sub 2}O at an appropriate concentration to yield 3 wt % of copper or nickel, respectively, in the mono metallic catalysts. Three bimetallic samples were prepared at 80% Cu and 20% Ni respectively to obtain 3 wt % of total metallic phase. Surface area of the Cu-Ni base catalysts supported on ZrO{sub 2} oxide showed differences as a function of the metal addition. Between them, the Cu/ZrO{sub 2} catalyst had the lowest surface area than other catalysts. X-ray diffraction patterns of the bimetallic catalysts did not show diffraction peaks of the Cu, Ni or bimetallic Cu-Ni alloys. In addition, TPR profiles of the bimetallic catalysts had the lowest reduction temperature compared with the mono metallic samples. The reactivity of the catalysts in the range of 250-350 C showed that the samples prepared by successive impregnation had the highest catalytic activity than the other catalysts studied. Also the selectivity for H{sub 2} production was higher for these catalysts. This finding was associated to the presence of the bimetallic Cu-Ni nanoparticles, as was evidenced by Tem-EDX analysis. (Author)

  17. PdPt bimetallic nanoparticles enabled by shape control with halide ions and their enhanced catalytic activities.

    Science.gov (United States)

    Zhang, Jinfeng; Wan, Lei; Liu, Lei; Deng, Yida; Zhong, Cheng; Hu, Wenbin

    2016-02-11

    In this study, a new and convenient one step approach is described for synthesizing shape controlled PdPt bimetallic nanoparticles. It is found that the resultant morphologies of these PdPt nanoparticles can be well controlled by simply altering the participation of different halide ions that serve as shape controlling agents in the reaction solution. The dendritic core-shell PdPt bimetallic nanoparticles generated with Pt atoms adopt usual island growth pattern in the presence of Cl(-) ions, whereas the introduction of Br(-) ions with a relatively strong adsorption effect facilitate the formation of a layered core-shell structure due to the layered growth mode of Pt atoms on the exterior surface of the central Pd core. Moreover, the stronger adsorption function of I(-) ions and the resulting fast atomic diffusion promoted the generation of mesoporous core-shell PdPt bimetallic nanoparticles with many pore channels. In addition, the size of these synthesized PdPt nanoparticles exhibited a significant dependence on the concentration of the halide ions involved. Due to their specific structural features and synergistic effects, these PdPt catalysts exhibited shape-dependent catalytic performance and drastically enhanced electrocatalytic activities relative to that of commercial Pt black and Pt/C toward methanol oxidation. PMID:26511671

  18. Atomic structure and thermal stability of Pt-Fe bimetallic nanoparticles: from alloy to core/shell architectures.

    Science.gov (United States)

    Huang, Rao; Wen, Yu-Hua; Shao, Gui-Fang; Sun, Shi-Gang

    2016-06-22

    Bimetallic nanoparticles comprising noble metal and non-noble metal have attracted intense interest over the past few decades due to their low cost and significantly enhanced catalytic performances. In this article, we have explored the atomic structure and thermal stability of Pt-Fe alloy and core-shell nanoparticles by molecular dynamics simulations. In Fe-core/Pt-shell nanoparticles, Fe with three different structures, i.e., body-centered cubic (bcc), face-centered cubic (fcc), and amorphous phases, has been considered. Our results show that Pt-Fe alloy is the most stable configuration among the four types of bimetallic nanoparticles. It has been discovered that the amorphous Fe cannot stably exist in the core and preferentially transforms into the fcc phase. The phase transition from bcc to hexagonal close packed (hcp) has also been observed in bcc-Fe-core/Pt-shell nanoparticles. In contrast, Fe with the fcc structure is the most preferred as the core component. These findings are helpful for understanding the structure-property relationships of Pt-Fe bimetallic nanoparticles, and are also of significance to the synthesis and application of noble metal based nanoparticle catalysts. PMID:27297782

  19. BIMETALLIC LITHIUM BOROHYDRIDES TOWARD REVERSIBLE HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Au, M.

    2010-10-21

    Borohydrides such as LiBH{sub 4} have been studied as candidates for hydrogen storage because of their high hydrogen contents (18.4 wt% for LiBH{sub 4}). Limited success has been made in reducing the dehydrogenation temperature by adding reactants such as metals, metal oxides and metal halides. However, full rehydrogenation has not been realized because of multi-step decomposition processes and the stable intermediate species produced. It is suggested that adding second cation in LiBH{sub 4} may reduce the binding energy of B-H. The second cation may also provide the pathway for full rehydrogenation. In this work, several bimetallic borohydrides were synthesized using wet chemistry, high pressure reactive ball milling and sintering processes. The investigation found that the thermodynamic stability was reduced, but the full rehydrogenation is still a challenge. Although our experiments show the partial reversibility of the bimetallic borohydrides, it was not sustainable during dehydriding-rehydriding cycles because of the accumulation of hydrogen inert species.

  20. Homogeneity and elemental distribution in self-assembled bimetallic Pd-Pt aerogels prepared by a spontaneous one-step gelation process.

    Science.gov (United States)

    Oezaslan, M; Liu, W; Nachtegaal, M; Frenkel, A I; Rutkowski, B; Werheid, M; Herrmann, A-K; Laugier-Bonnaud, C; Yilmaz, H-C; Gaponik, N; Czyrska-Filemonowicz, A; Eychmüller, A; Schmidt, T J

    2016-07-27

    a commercially available unsupported Pt black catalyst. We show that the Pd-Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity. PMID:27411594

  1. Renovation and Reuse of Reactive Dyeing Effluent by a Novel Heterogeneous Fenton System Based on Metal Modified PTFE Fibrous Catalyst/H2O2

    OpenAIRE

    Bing Li; Yongchun Dong; Zhizhong Ding; Yiming Xu; Chi Zou

    2013-01-01

    Cu-Fe bimetallic grafted polytetrafluoroethylene (PTFE) fiber complexes were prepared and optimized as the novel heterogeneous Fenton catalysts for the degradation of reactive dyes under UV irradiation. Cotton fabrics were dyed with three reactive dyes, namely, Reactive Red 195, Reactive Yellow 145, and Reactive Blue 222, in tap fresh water using exhaustion process. The spent dyeing effluents were then collected and degraded with the optimized Cu-Fe bimetallic grafted PTFE fiber complex/H2O2 ...

  2. Simultaneous Detection of Electronic Structure Changes from Two Elements of a Bifunctional Catalyst Using Wavelength-Dispersive X-ray Emission Spectroscopy and in situ Electrochemistry

    OpenAIRE

    Gul, Sheraz; Desmond Ng, Jia Wei; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H.; Zhang, Jin Z.; Bergmann, Uwe; Yachandra, Vittal K.; Jaramillo, Thomas F.; Yano, Junko

    2015-01-01

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of char...

  3. Silver doped catalysts for treatment of exhaust

    Energy Technology Data Exchange (ETDEWEB)

    Park, Paul Worn (Peoria, IL); Hester, Virgil Raymond (Edelstein, IL); Ragle, Christie Susan (Havana, IL); Boyer, Carrie L. (Shiloh, IL)

    2009-06-02

    A method of making an exhaust treatment element includes washcoating a substrate with a slurry that includes a catalyst support material. At least some of the catalyst support material from the slurry may be transferred to the substrate, and silver metal (Ag) is dispersed within the catalyst support material.

  4. Supported Copper, Nickel and Copper-Nickel Nanoparticle Catalysts for Low Temperature Water-Gas-Shift Reaction

    Science.gov (United States)

    Lin, Jiann-Horng

    Hydrogen is being considered worldwide as a future replacement for gasoline, diesel fuel, natural gas in both the transportation and non-transportation sectors. Hydrogen is a versatile energy carrier that can be produced from a variety of widely available primary energy sources, including coal, natural gas, biomass, solar, wind, and nuclear power. Coal, the most abundant fossil fuel on the planet, is being looked at as the possible future major source of H2, due to the development of the integrated gasification combined cycle (IGCC) and integrated gasification fuel cell technologies (IGFC). The gasification of coal produces syngas consisting of predominately carbon monoxide and hydrogen with some remaining hydrocarbons, carbon dioxide and water. Then, the water-gas shift reaction is used to convert CO to CO2 and additional hydrogen. The present work describes the synthesis of model Cu, Ni and Cu-Ni catalysts prepared from metal colloids, and compares their behavior in the WGS reaction to that of traditional impregnation catalysts. Initially, we systematically explored the performance of traditional Cu, Ni and Cu-Ni WGS catalysts made by impregnation methods. Various bimetallic Cu-Ni catalysts were prepared by supported impregnation and compared to monometallic Cu and Ni catalysts. The presence of Cu in bimetallic catalysts suppressed undesirable methanation side reaction, while the Ni component was important for high WGS activity. Colloidal Cu, Ni and Cu-Ni alloy nanoparticles obtained by chemical reduction were deposited onto alumina to prepare supported catalysts. The resulting Cu and Ni nanoparticle catalysts were found to be 2.5 times more active in the WGS reaction per unit mass of active metal as compared to catalysts prepared by the conventional impregnation technique. The powder XRD and HAADF-STEM provided evidence supporting the formation of Cu-Ni particles containing the Cu core and Cu-Ni alloy shell. The XPS data indicated surface segregation of Cu in

  5. Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanol

    DEFF Research Database (Denmark)

    Sharafutdinov, Irek; Elkjær, Christian Fink; de Carvalho, Hudson Wallace Pereira;

    2014-01-01

    In this work, we present a detailed study of the formation of supported intermetallic Ni–Ga catalysts for CO2 hydrogenation to methanol. The bimetallic phase is formed during a temperature-programmed reduction of the metal nitrates. By utilizing a combination of characterization techniques, in...

  6. Dispersion state and catalytic properties of vanadia species on the surface of V2O5/TiO2 catalysts

    Institute of Scientific and Technical Information of China (English)

    许波连; 陈懿; 范以宁; 刘浏; 林明

    2002-01-01

    The dispersion state and catalytic properties of anatase-supported vanadia species are studied by means of X-ray diffraction (XRD), laser Raman spectroscopy (LRS), H2 temperature-programmed reduction (TPR) and the selective oxidation of o-xylene to phthalic anhydride. The almost identical values of the experimental dispersion capacity of V2O5 on anatase and the surface vacant sites available on the preferentially exposed (001) plane of anatase suggest that the highly dispersed vanadium cations are bonded to the vacant sites on the surface of anatase as derived by the incorporation model. When the loading amount of V2O5 is far below its dispersion capacity, the dispersed vanadia species might mainly consist of isolated VOx species bridging to the surface through V-O-Ti bonds. With the increase of V2O5 loading the isolated vanadia species interact with their nearest neighbors (either isolated or polymerized vanadia) through bridging V-O-V at the expenses of V-O-Ti bonds, resulting in the increase of the ra

  7. Charge distribution and Fermi level in bimetallic nanoparticles

    OpenAIRE

    Holmberg, Nico; Laasonen, Kari; Peljo, Pekka Eero

    2016-01-01

    Upon metal-metal contact, a transfer of electrons will occur between the metals until the Fermi levels in both phases are equal, resulting in a net charge difference across the metal-metal interface. Here, we have examined this contact electrification in bimetallic model systems composed of mixed Au-Ag nanoparticles containing ca. 600 atoms using density functional theory calculations. We present a new model to explain this charge transfer by considering the bimetallic system as a nanocapacit...

  8. Interaction of sulfur and bimetallic surfaces: Fe-promoted sulfidation of Mo(110)

    International Nuclear Information System (INIS)

    Iron promotes the interaction between S2 and Mo(110). The exposure of Mo(110) to large amounts of S2 produces only a chemisorbed layer of sulfur, without forming molybdenum sulfides. The sulfidation of Mo occurs after exposing Fe/Mo(110) surfaces to S2 gas. Fe promotes the rate of formation of molybdenum sulfides by transferring charge to Mo (favoring in this way an electrophilic attack of S on Mo) and by changing the structure of the surface (making the penetration of S into the bulk of the sample easier). The thermal stabilities of the MoSx/Mo(110) and FeSy/MoSx/Mo(110) systems are comparable, with the bimetallic sulfide showing a somewhat lower decomposition temperature (∼1200 K). The behavior of FeMoS catalysts in hydrodesulfurization processes is discussed in light of these results. copyright 1996 American Vacuum Society

  9. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  10. A New Class of Highly Dispersed VOx Catalysts on Mesoporous Silica: Synthesis, Characterization, and Catalytic Activity in the Partial Oxidation of Ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Herrera, Jose E.; Hu, Jian Zhi; Wang, Yong; Peden, Charles HF

    2006-01-26

    The morphology of vanadium oxide supported on a titania-modified mesoporous silica (MCM-41), obtained by means of a careful grafting process through atomic layer deposition, was studied using a variety of characterization techniques. The XRD together with TEM, 51V-NMR, Raman, FTIR and DRS-UV-Vis results showed that the vanadia species are extremely well dispersed onto the surface of the mesoporous support; the dispersion being stable upon thermal treatments up to 400 °C. Studies of the catalytic activity of these materials were performed using the partial oxidation of ethanol as a probe reaction. The results indicate an intrinsic relationship between dispersion, the presence of a TiO2-VOx phase, and catalytic activity for oxidation and dehydration.

  11. Synchrotron radiation applied to the study of heterogeneous model catalyst surfaces

    International Nuclear Information System (INIS)

    The application of synchrotron radiation-based experimental techniques for the characterization of model catalyst surfaces is reviewed. The planar model systems considered are distinguished by their heterogeneous surface character. Prototypical examples are discussed to illustrate various aspects of model catalyst surfaces and they include oxide thin films on metal single crystal substrates, metal nanoparticles deposited on ordered oxide films, thin layers of oxides on oxide substrates, heterogeneous bimetallic surfaces and metal single crystal surfaces decorated by oxide nanoparticles. (author)

  12. New synthesis ways of supported metallic catalysts and structure-reactivity relations in catalysis by metals; Nouvelles voies de syntheses de catalyseurs metalliques supportes et relations structure-reactivite en catalyse par les metaux

    Energy Technology Data Exchange (ETDEWEB)

    Uzio, D.

    2006-01-15

    This work deals with some research studies in the field of supported metallic catalysts. In all these works have been studied the characteristics bound to the active sites and the relations between these characteristics and the catalytic performances. The genesis of colloidal suspensions of transition metallic oxide has been used for the preparation of selective hydrogenation catalysts. At first studied in the case of palladium, this new synthesis way has been used for other metals such as Pt, Ni or Co. These studies have then been developed for preparing bimetallic catalysts (PdSn) with as supplementary aim the control of the homogeneity of the bimetallic character at the scale of nano-metric particles. These works have particularly allowed to specify the chemistry of the solutions of some metallic complexes and to rationalize the chemical processes carried out in the usual fabrication processes. Studies on size effects and the study of the reactivity of the nano and sub nano-metric particle have then been developed. Indeed, the clusters containing some atoms can see their intrinsic properties varied very strongly under the influence of several parameters as the number of atoms, the nature of the support, the reactional atmosphere. Using the knowledge acquired during the preceding works (chemistry of palladium aqueous solutions), the study of new methods of preparation of particles containing very few atoms has brought new data on the properties of hyper dispersed particles as well as on the principle of sensitivity to structure. The contribution of the support to the catalytic process for the hydrogenation of different substrates has been studied too. (O.M.)

  13. Multiply twinned AgNi alloy nanoparticles as highly active catalyst for multiple reduction and degradation reactions.

    Science.gov (United States)

    Kumar, Mukesh; Deka, Sasanka

    2014-09-24

    Size dependent surface characteristics of nanoparticles lead to use of these nanomaterials in many technologically important fields, including the field of catalysis. Here Ag(1-x)Ni(x) bimetallic alloy nanoparticles have been developed having a 5-fold twinned morphology, which could be considered as an important alloy because of their excellent and unique catalytic and magnetic properties. Alloying between Ag and Ni atoms on a nanoscale has been confirmed with detailed X-ray diffraction, high resolution transmission electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, and magnetization measurements. Although introduced for the first time as a catalyst due to having high active surface sites, the as-synthesized nanoparticles showed one of the best multiple catalytic activity in the industrially important (electro)-catalytic reduction of 4-nitrophenol (4-NP) and 4-nitroaniline (4-NA) to corresponding amines with noticeable reduced reaction time and increased rate constant without the use of any large area support. Additionally the same catalyst showed enhanced catalytic activity in degradation of environment polluting dye molecules. The highest ever activity parameter we report here for Ag0.6Ni0.4 composition is 156 s(-1)g(-1) with an apparent rate constant of 31.1 × 10(-3) s(-1) in a 4-NP reduction reaction where the amount of catalyst used was 0.2 mg and the time taken for complete conversion of 4-NP to 4-aminophenol was 60 s. Similarly, an incredible reaction rate constant (115 s(-1)) and activity parameter (576.6 s(-1)g(-1)) were observed for the catalytic degradation of methyl orange dye where 15 s is the maximum time for complete degradation of the dye molecules. The high catalytic performance of present AgNi alloy NPs over the other catalysts has been attributed to size, structural (twinned defect) and electronic effects. This study may lead to use of these bimetallic nanostructures with excellent recyclable catalytic

  14. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    Science.gov (United States)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  15. Shaped Ir-Ni bimetallic nanoparticles for minimizing Ir utilization in oxygen evolution reaction.

    Science.gov (United States)

    Lim, Jinkyu; Yang, Sungeun; Kim, Chanyeon; Roh, Chi-Woo; Kwon, Yongwoo; Kim, Yong-Tae; Lee, Hyunjoo

    2016-04-12

    Shaped Ir-Ni bimetallic nanoparticles were synthesized and used for electrocatalytic oxygen evolution reaction (OER). The obtained bimetallic nanoparticles showed significantly enhanced Ir mass activity and durability compared with Ir nanoparticles. PMID:27034092

  16. Theoretical and experimental aspects of the bimetallic reinforcement bars steel - steel resistant to corrosion rolling process

    Directory of Open Access Journals (Sweden)

    S. Sawicki

    2010-11-01

    Full Text Available Purpose: Bimetallic bars which possess higher corrosion resistance and mechanical properties, it is the new kind of bimetallic bars, which are better than standard bars. The bimetallic bars are more often applied in concrete construction.Design/methodology/approach: The simulations of the bar rolling were carried out using the Forge2007® commercial program.Findings: The use of non-corrosive steel on plating layer assures receipt on a high durability and esthetics bimetallic bars.Practical implications: Bimetallic bars are chiefly used in the building industry at production of concrete constructions, and as working elements in bridge building in aggressive environment.Originality/value: Production of bimetallic bars is very difficult. One from many problems during production bimetallic bars is assurance good strength of bimetallic layer bond.

  17. Shape-control and electrocatalytic activity-enhancement of Pt-based bimetallic nanocrystals.

    Science.gov (United States)

    Porter, Nathan S; Wu, Hong; Quan, Zewei; Fang, Jiye

    2013-08-20

    Due to the increasing worldwide energy demand and environ-mental concerns, the need for alternative energy sources is growing stronger, and platinum catalysts in fuel cells may help make the technologies a reality. However, the pursuit of highly active Pt-based electrocatalysts continues to be a challenge. Scientists developing electrocatalysts continue to focus on characterizing and directing the construction of nanocrystals and advancing their electrochemical applications. Although chemists have worked on Pt-based bimetallic (Pt-M) preparations in the past, more recent research shows that both shape-controlled Pt-M nanocrystals and the assembly of these nanocrystals into supercrystals are promising new directions. A solution-based synthesis approach is an effective technique for preparing crystallographic facet-directed nanocatalysts. This is aided by careful selection of the metal precursor, capping ligand, reducing agent, and solvent. Incorporating a secondary metal M into the Pt lattice and manipulating the crystal facets on the surface cooperatively alter the electrocatalytic behavior of these Pt-M bimetallic nanocrystals. Specifically, chemists have extensively studied the {111}- and {100}-terminated crystal facets because they show unique atomic arrangement on surfaces, exhibit different catalytic performance, and possess specific resistance to toxic adsorbed carbon monoxide (COads). For catalysts to have maximum efficiency, they need to have resistance to COads and other poisonous carbon-containing intermediates when the catalysts operate under harsh conditions. A necessary design to any synthesis is to clearly understand and utilize the role of each component in order to successfully induce shape-controlled growth. Since chemists began to understand Pt nanocrystal shape-dependent electrocatalytic activity, the main obstacles blocking proton exchange membrane fuel cells are anode poisoning, sluggish kinetics at the cathode, and low activity. In this

  18. Radiation formation of Al-Ni bimetallic nanoparticles in aqueous system

    International Nuclear Information System (INIS)

    This work concerns the study of Al-Ni bimetallic nanoparticles synthesized by gamma-radiolysis of aqueous solution containing aluminium chloride hexahydrate, nickel chloride hexahydrate, polyvinyl alcohol for capping colloidal nanoparticles, and isopropanol as radical scavenger. While the Al/Ni molar ratio is kept constant, size of the nanoparticles can be well controlled by varying the radiation dose. The products were characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD). Observations of UV-vis absorption spectra and TEM images showed that as the radiation dose increases from 50 to 100 kGy the particle size decreases and the number particles distribution increases. It may be explained due to the competition between nucleation and aggregation processes in the formation of metallic nanoparticles under irradiation. The EDX and XRD analysis confirmed directly the formation of Al-Ni bimetallic nanoparticles in form of alloy nanoparticles. (author)

  19. Ammonia Decomposition over Bimetallic Nitrides Supported on γ-Al2O3

    Institute of Scientific and Technical Information of China (English)

    Chun Shan LU; Xiao Nian LI; Yi Feng ZHU; Hua Zhang LIU; Chun Hui ZHOU

    2004-01-01

    A series of monometallic nitrides and bimetallic nitrides were prepared by temperature-programmed reaction with NH3. The effects of Co, Ni and Fe additives and the synergic action between Fe, Co, Ni and Mo on the ammonia decomposition activity were investigated. TPR-MS, XRD were also carried out to obtain better insight into the structure of the bimetallic nitride. The results of ammonia decomposition activity show that bimetallic nitrides are more active than monometallic nitrides or bimetallic oxides.

  20. Fe/Al bimetallic particles for the fast and highly efficient removal of Cr(VI) over a wide pH range: Performance and mechanism.

    Science.gov (United States)

    Fu, Fenglian; Cheng, Zihang; Dionysiou, Dionysios D; Tang, Bing

    2015-11-15

    The iron/aluminum (Fe/Al) bimetallic particles with high efficiency for the removal of Cr(VI) were prepared. Fe/Al bimetallic particles were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). SEM mapping showed that the core of bimetal was Al, and the planting Fe was deposited on the surface of Al. In acidic and neutral conditions, Fe/Al bimetal can completely remove Cr(VI) from wastewater in 20 min. Even at pH 11.0, the Cr(VI) removal efficiency achieved was 93.5%. Galvanic cell effect and high specific surface area are the main reasons for the enhanced removal of Cr(VI) by bimetallic particles. There were no iron ions released in solutions at pH values ranging from 3.0 to 11.0. The released Al(3+) ions concentrations in acidic and neutral conditions were all less than 0.2mg/L. The bimetal can be used 4 times without losing activity at initial pH 3.0. XPS indicated that the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)-Fe(III) hydroxide/oxyhydroxide on the surface of Fe/Al bimetal. The Fe/Al bimetallic particles are promising for further testing for the rapid and effective removal of contaminants from water. PMID:26073381

  1. Effect of Cu2+/Al3+ mole ratio on structure of Cu-Al bimetallic nanoparticles prepared by radiation induced method

    International Nuclear Information System (INIS)

    Cu-Al bimetallic nanoparticles were synthesized by gamma irradiation technique in aqueous solutions containing metal chlorides as precursors, polyvinyl alcohol (PVA) as a capping agent, isopropanol as a radical scavenger, and distilled water as a solvent. The Cu-Al bimetallic nanoparticles were characterized by transmission electron microscopy (TEM), UV-visible absorption spectrometry, powder X-ray diffractometer (XRD), and Energy-dispersive X-ray spectroscopy (EDX). The TEM, XRD, EDX, and absorption analyses confirmed the formation of core-shell structure of Cu-Al bimetallic nanoparticles at lower Cu2+/Al3+ mole ratio, and the formation of Cu-Al alloy nanoparticles at higher Cu2+/Al3+ mole ratio. The TEM analysis for particle size and size distribution revealed that the average particle size of Cu-Al bimetallic nanoparticles decreased with the increase of absorbed dose. It may be explained due to the competition between nucleation and aggregation processes in the formation of metallic nanoparticles under irradiation. (orig.)

  2. Effect of Cu{sup 2+}/Al{sup 3+} mole ratio on structure of Cu-Al bimetallic nanoparticles prepared by radiation induced method

    Energy Technology Data Exchange (ETDEWEB)

    Abedini, Alam; Larki, Farhad; Saion, Elias; Noroozi, Monir [Putra Malaysia Univ., Serdang, Selangor (Malaysia). Dept. of Physics

    2013-07-15

    Cu-Al bimetallic nanoparticles were synthesized by gamma irradiation technique in aqueous solutions containing metal chlorides as precursors, polyvinyl alcohol (PVA) as a capping agent, isopropanol as a radical scavenger, and distilled water as a solvent. The Cu-Al bimetallic nanoparticles were characterized by transmission electron microscopy (TEM), UV-visible absorption spectrometry, powder X-ray diffractometer (XRD), and Energy-dispersive X-ray spectroscopy (EDX). The TEM, XRD, EDX, and absorption analyses confirmed the formation of core-shell structure of Cu-Al bimetallic nanoparticles at lower Cu{sup 2+}/Al{sup 3+} mole ratio, and the formation of Cu-Al alloy nanoparticles at higher Cu{sup 2+}/Al{sup 3+} mole ratio. The TEM analysis for particle size and size distribution revealed that the average particle size of Cu-Al bimetallic nanoparticles decreased with the increase of absorbed dose. It may be explained due to the competition between nucleation and aggregation processes in the formation of metallic nanoparticles under irradiation. (orig.)

  3. Effect of surface structure on the catalytic behavior of Ni:Cu/Al and Ni:Cu:K/Al catalysts for methane decomposition

    Institute of Scientific and Technical Information of China (English)

    S.Tajammul Hussain; Sheraz Gul; Muhammed Mazhar; Dalaver H.Anjum; Faical Larachi

    2008-01-01

    Methane decomposition using nickel, copper, and aluminum (Ni:Cu/Al) and nickel, copper, potassium, and alu-minum (Ni:Cu:K/Al) modified nano catalysts has been investigated for carbon fibers, hydrogen and hydrocarbon production. X-ray photoelectron spectroscopy (XPS), static secondary ion mass spectrometry (SSIMS), thermal gravimetric analysis (TGA),Fourier transform infrared (FT-IR), secondary electron microscopy/X-ray energy dispersive (SEM-EDX), and temperature pro-grammed desorption (TPD) were used to depict the chemistry of the catalytic results. These techniques revealed the changes in surface morphology and structure of Ni, Cu, Al, and K, and formation of bimetallic and trimetallic surface cationic sites with sifferent cationic species, which resulted in the production of graphitic form of pure carbon on Ni:Cu/Al catalyst. The addition of K has a marked effect on the product selectivity and reactivity of the catalyst system. K addition restricts the formation of carbon on the surface and increases the production of hydrogen and C2, C3 hydrocarbons during the catalytic reaction whereas no hydrocarbons are produced on the sample without K. This study completely maps the modified surface structure and its re-lationship with the catalytic behavior of both systems. The process provides a flexible route for the production of carbon fibers and hydrogen on Ni:Cu/Al catalyst and hydrogen along with hydrocarbons on Ni:Cu:K/Al catalyst. The produced carbon fibers are imaged using a transmission electron microscope (TEM) for diameter size and wall structure determination. Hydrogen produced is COx free, which can be used directly in the fuel cell system. The effect of the addition of Cu and its transformation and interaction with Ni and K is responsible for the production of CO/CO2 free hydrogen, thus producing an environmental friendly clean energy.

  4. Hydroformylation and kinetics of 1-hexene over ruthenium, cobalt and rhodium zerolite catalysts

    International Nuclear Information System (INIS)

    In this paper, six kinds of catalysts were prepared by cation exchange with rhodium, ruthenium and cobalt chloropentaamino dichoride and zeolites. Effects such as support materials, PPH3 to metal ratio, reaction temperature, total pressure, H2/CO ratio, reaction time and solvents have been investigated in an autoclave. The most favorable results of 1-hexene hydroformylation were obtained in the temperature range 100-150 degrees C at a pressure of 5.0MPa (H2/CO=1:1) and the addition of free PPh3. The bimetallic catalysts showed high catalytic activing for hydroformylation because of the synergistic effect of bimetallic systems. This paper reports the results of experiments and catalysts characterization by means of IR and XRD spectroscopy

  5. Spatial Bimetallic Castings Manufactured from Iron Alloys

    Directory of Open Access Journals (Sweden)

    M. Cholewa

    2007-07-01

    Full Text Available In this paper a conception for manufacturing method of skeleton castings with composite features was shown. Main application of such castings are the working organs of machines subjected to intensive abrasive and erosive wear. Skeleton geometry was based on three-dimensional cubic net consisting of circular connectors and nodes joining 6 connectors according to Cartesian co-ordinate system. Dimension of an elementary cell was equal to 10 mm and diameter of single connector was equal to 5 mm. For bimetallic castings preparation two Fe based alloys were used: L25SHMN cast steel for skeleton substrate and ZlCr15NiMo cast iron for working part of the casting. In presented work obtained structure was analyzed with indication of characteristic regions. Authors described phenomena occurring at the alloys interface and phases in transition zone. A thesis was formulated concerning localization of transition zone at the cast iron matrix – cast steel reinforcement interface. Direction of further studies were indicated.

  6. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Volume 2, appendices. Final technical report, October 1, 1991--September 30, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States); Chander, S. [Pennsylvania State Univ., College Park, PA (United States); Gutterman, C.

    1995-04-01

    Liquefaction experiments were undertaken using subbituminous Black Thunder mine coal to observe the effects of aqueous SO{sub 2} coal beneficiation and the introduction of various coal swelling solvents and catalyst precursors. Aqueous SO{sub 2} beneficiation of Black Thunder coal removed alkali metals and alkaline earth metals, increased the sulfur content and increased the catalytic liquefaction conversion to THF solubles compared to untreated Black Thunder coal. The liquefaction solvent had varying effects on coal conversion, depending upon the type of solvent added. The hydrogen donor solvent, dihydroanthracene, was most effective, while a coal-derived Wilsonville solvent promoted more coal conversion than did relatively inert 1-methylnaphthalene. Swelling of coal with hydrogen bonding solvents tetrahydrofuran (THF), isopropanol, and methanol, prior to reaction resulted in increased noncatalytic conversion of both untreated and SO{sub 2} treated Black Thunder coals, while dimethylsulfoxide (DMSO), which was absorbed more into the coal than any other swelling solvent, was detrimental to coal conversion. Swelling of SO{sub 2} treated coal before liquefaction resulted in the highest coal conversions; however, the untreated coal showed the most improvements in catalytic reactions when swelled in either THF, isopropanol, or methanol prior to liquefaction. The aprotic solvent DMSO was detrimental to coal conversion.

  7. Low-temperature steam-reforming of ethanol over ZnO-supported Ni and Cu catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Homs, Narcis; Llorca, Jordi; De la Piscina, Pilar Ramirez [Departament de Quimica Inorganica, Universitat de Barcelona, C/Marti i Franques 1-11, 08028 Barcelona (Spain)

    2006-08-15

    ZnO-supported Ni and Cu as well as bimetallic Co-Ni and Co-Cu catalysts containing ca. 0.7wt% sodium promoter and prepared by the co-precipitation method were tested in the ethanol steam-reforming reaction at low temperature (523-723K), using a bioethanol-like mixture diluted in Ar. Monometallic ZnO-supported Cu or Ni samples do not exhibit good catalytic performance in the steam-reforming of ethanol for hydrogen production. Copper catalyst mainly dehydrogenates ethanol to acetaldehyde, whereas nickel catalyst favours ethanol decomposition. However, the addition of Ni to ZnO-supported cobalt has a positive effect both on the production of hydrogen at low temperature (<573K), and on catalyst stability. Evidence for alloy formation as well as mixed oxides at the microstructural level was found in the bimetallic systems after running the ethanol steam-reforming reaction by HRTEM-EELS. (author)

  8. Preparation of Supported Metal Catalysts by Atomic and Molecular Layer Deposition for Improved Catalytic Performance

    Science.gov (United States)

    Gould, Troy D.

    Creating catalysts with enhanced selectivity and activity requires precise control over particle shape, composition, and size. Here we report the use of atomic layer deposition (ALD) to synthesize supported Ni, Pt, and Ni-Pt catalysts in the size regime (number of ALD cycles, Ni weight loadings were varied from 4.7 wt% to 16.7 wt% and the average particle sizes ranged from 2.5 to 3.3 nm, which increased the selectivity for C 3H6 hydrogenolysis by an order of magnitude over a much larger Ni/Al2O3 catalyst. Pt particles were deposited by varying the number of ALD cycles and the reaction chemistry (H2 or O 2) to control the particle size from approximately 1 to 2 nm, which allowed lower-coordinated surface atoms to populate the particle surface. These Pt ALD catalysts demonstrated some of the highest oxidative dehydrogenation of propane selectivities (37%) of a Pt catalyst synthesized by a scalable technique. Dry reforming of methane (DRM) is a reaction of interest due to the recent increased recovery of natural gas, but this reaction is hindered from industrial implementation because the Ni catalysts are plagued by deactivation from sintering and coking. This work utilized Ni ALD and NiPt ALD catalysts for the DRM reaction. These catalysts did not form destructive carbon whiskers and had enhanced reaction rates due to increased bimetallic interaction. To further limit sintering, the Ni and NiPt ALD catalysts were coated with a porous alumina matrix by molecular layer deposition (MLD). The catalysts were evaluated for DRM at 973 K, and the MLD-coated Ni catalysts outperformed the uncoated Ni catalysts in either activity (with 5 MLD cycles) or stability (with 10 MLD cycles). In summary, this thesis developed a new Ni nanoparticle ALD chemistry, explored possibilities for changing Pt ALD particle size, brought the two techniques together to create enhanced bimetallic catalysts, and stabilized the catalysts using MLD.

  9. Examples of material solutions in bimetallic layered castings

    Directory of Open Access Journals (Sweden)

    S. Tenerowicz

    2011-07-01

    Full Text Available In paper is presented technology of bimetallic layered castings based on founding method of layer coating directly in cast process so-called method of mould cavity preparation. Prepared castings consist two fundamental parts i.e. bearing part and working part (layer. The bearing part of bimetallic layered casting is typical foundry material i.e. pearlitic grey cast iron, whereas working part (layer is depending on accepted variant plates of alloy steels sort X6Cr13, X12Cr13, X10CrNi18-8 and X2CrNiMoN22-5-3. The ratio of thickness between bearing and working part is 8:1. The verification of the bimetallic layered castings was evaluated on the basis of ultrasonic NDT (non-destructive testing, structure and macro- and microhardness researches.

  10. Spin waves in antiferromagnetically coupled bimetallic oxalates.

    Science.gov (United States)

    Reis, Peter L; Fishman, Randy S

    2009-01-01

    Bimetallic oxalates are molecule-based magnets with transition-metal ions M(II) and M(')(III) arranged on an open honeycomb lattice. Performing a Holstein-Primakoff expansion, we obtain the spin-wave spectrum of antiferromagnetically coupled bimetallic oxalates as a function of the crystal-field angular momentum L(2) and L(3) on the M(II) and M(')(III) sites. Our results are applied to the Fe(II)Mn(III), Ni(II)Mn(III) and V(II)V(III) bimetallic oxalates, where the spin-wave gap varies from 0 meV for quenched angular momentum to as high as 15 meV. The presence or absence of magnetic compensation appears to have no effect on the spin-wave gap. PMID:21817242

  11. Synthesis of bimetallic nanoshells by an improved electroless plating method.

    Science.gov (United States)

    Liu, J B; Dong, W; Zhan, P; Wang, S Z; Zhang, J H; Wang, Z L

    2005-03-01

    In the Letter, we demonstrate an improved electroless plating method for the synthesis of bimetallic shell particles. The procedure involves a combination of surface reaction, seeding growth, and removal of supporting cores. We modified ammonical AgNO3 in ethanol with a controlled amount of HCHO in the seeding process and a uniform and relatively dense coverage of silver nanoparticle seeds on colloid cores was achieved. Following the second kind of metal plating, we extended this method to prepare continuous bimetallic core-shell and hollow particles with a submicrometer diameter. The morphologies of the bimetallic Cu/Ag and Pt/Ag particles were studied with transmission electron microscopy and scanning electron microscopy, and their crystallinity and chemical composition were confirmed by X-ray diffraction. The prepared materials may be of applied value in areas such as catalysis, optics, and plasmonics. PMID:15723456

  12. TOPICAL REVIEW: Nanostructured catalysts in fuel cells

    Science.gov (United States)

    Zhong, Chuan-Jian; Luo, Jin; Fang, Bin; Wanjala, Bridgid N.; Njoki, Peter N.; Loukrakpam, Rameshwori; Yin, Jun

    2010-02-01

    One of the most important challenges for the ultimate commercialization of fuel cells is the preparation of active, robust, and low-cost catalysts. This review highlights some findings of our investigations in the last few years in developing advanced approaches to nanostructured catalysts that address this challenge. Emphasis is placed on nanoengineering-based fabrication, processing, and characterization of multimetallic nanoparticles with controllable size (1-10 nm), shape, composition (e.g. MlnM2100-n, M1nM2mM3100-n-m, M1@M2, where M (1 or 2) = Pt, Co, Ni, V, Fe, Cu, Pd, W, Ag, Au etc) and morphology (e.g. alloy, core@shell etc). In addition to an overview of the fundamental issues and the recent progress in fuel cell catalysts, results from evaluations of the electrocatalytic performance of nanoengineered catalysts in fuel cell reactions are discussed. This approach differs from other traditional approaches to the preparation of supported catalysts in the ability to control the particle size, composition, phase, and surface properties. An understanding of how the nanoscale properties of the multimetallic nanoparticles differ from their bulk-scale counterparts, and how the interaction between the nanoparticles and the support materials relates to the size sintering or evolution in the thermal activation process, is also discussed. The fact that the bimetallic gold-platinum nanoparticle system displays a single-phase character different from the miscibility gap known for its bulk-scale counterpart serves as an important indication of the nanoscale manipulation of the structural properties, which is useful for refining the design and preparation of the bimetallic catalysts. The insight gained from probing how nanoparticle-nanoparticle and nanoparticle-substrate interactions relate to the size evolution in the activation process of nanoparticles on planar substrates serves as an important guiding principle in the control of nanoparticle sintering on different

  13. Structural, spectral and mechanical studies of bimetallic crystal: cadmium manganese thiocyanate single crystals

    Science.gov (United States)

    Manikandan, M.; Vijaya Prasath, G.; Bhagavannarayan, G.; Vijayan, N.; Mahalingam, T.; Ravi, G.

    2012-09-01

    A nonlinear optical bimetallic thiocyanate complex crystal, cadmium manganese thiocyanate (CMTC) has been successfully synthesized. The growth of single crystals of cadmium manganese thiocyanate has been accomplished from aqueous solution using slow evaporation method. The presence of manganese and cadmium in the synthesized material was confirmed through energy dispersive spectrum (EDS) analysis. Structural analysis was carried out using powder X-ray diffractometer (PXRD) and crystalline perfection of the grown crystals was ascertained by high-resolution X-ray diffraction (HRXRD) analysis. Fourier transform infrared (FTIR) spectrum was taken to confirm the functional groups. The transmittance spectrum of the crystal in the UV-visible region has been recorded and the cutoff wavelength has been determined. The dielectric measurements for the crystals were performed for various frequencies and temperatures. The mechanical properties were evaluated by Vickers microhardness testing, which reveals hardness and stiffness constant of the crystals.

  14. Structural, spectral and mechanical studies of bimetallic crystal: cadmium manganese thiocyanate single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Manikandan, M.; Vijaya Prasath, G.; Mahalingam, T.; Ravi, G. [Alagappa University, Department of Physics, Karaikudi (India); Bhagavannarayan, G.; Vijayan, N. [National Physical Laboratory, Materials Characterization Division, New Delhi (India)

    2012-09-15

    A nonlinear optical bimetallic thiocyanate complex crystal, cadmium manganese thiocyanate (CMTC) has been successfully synthesized. The growth of single crystals of cadmium manganese thiocyanate has been accomplished from aqueous solution using slow evaporation method. The presence of manganese and cadmium in the synthesized material was confirmed through energy dispersive spectrum (EDS) analysis. Structural analysis was carried out using powder X-ray diffractometer (PXRD) and crystalline perfection of the grown crystals was ascertained by high-resolution X-ray diffraction (HRXRD) analysis. Fourier transform infrared (FTIR) spectrum was taken to confirm the functional groups. The transmittance spectrum of the crystal in the UV-visible region has been recorded and the cutoff wavelength has been determined. The dielectric measurements for the crystals were performed for various frequencies and temperatures. The mechanical properties were evaluated by Vickers microhardness testing, which reveals hardness and stiffness constant of the crystals. (orig.)

  15. Chemical selforganization of composite catalysts during catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Imbihl, Ronald, E-mail: imbihl@pci.uni-hannover.de [Institut fuer Physikalische Chemie und Elektrochemie, Leibniz-Universitaet Hannover, Callinstrasse 3-3a, D-30167 Hannover (Germany)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer Selforganization of composite catalysts under reaction conditions. Black-Right-Pointing-Pointer Reactive phase separation causes demixing of catalysts. Black-Right-Pointing-Pointer Condensation patterns in supported oxide catalysts. -- Abstract: Recent progress in the study of selforganization phenomena in catalytic reactions on multi-component surfaces is reviewed. As chemically more complex systems a Rh(1 1 1) surface with ultra-thin vanadium oxide layers ({theta}{sub V} < 0.5 MLE) and a bimetallic Rh(1 1 1)/Ni surface, both subjected to the H{sub 2} + O{sub 2} reaction, were chosen. Applying spatially resolving methods in situ, it is shown that under reaction conditions a reversible redistribution of the components of the catalyst occurs. The redistribution processes are essentially driven by the different chemical affinities of the components to reacting species.

  16. Magnetic bimetallic nanoparticles supported reduced graphene oxide nanocomposite: Fabrication, characterization and catalytic capability

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lei; Wu, Tao; Xu, Xiaoyang; Xia, Fengling; Na, Heya [School of Science, Tianjin University, Tianjin 300072 (China); Liu, Yu, E-mail: liuyuls@163.com [School of Science, Tianjin University, Tianjin 300072 (China); Qiu, Haixia [School of Science, Tianjin University, Tianjin 300072 (China); Wang, Wei [School of Chemical Engineering, Tianjin University, Tianjin 300072 (China); Gao, Jianping, E-mail: jianpinggao2012@126.com [School of Science, Tianjin University, Tianjin 300072 (China)

    2015-04-15

    Highlights: • Ni and Ag nanoparticles loaded on RGO (Ni–Ag@RGO) were fabricated in a one-pot reaction. • The Ni–Ag@RGO were excellent catalysts for the reduction of 4-nitrophenol. • The Ni–Ag@RGO showed superior catalytic activity for photodegradation of methyl orange. • The Ni–Ag@RGO exhibit good reusability in a magnetic field. - Abstract: A facile method for preparing Ni–Ag bimetallic nanoparticles supported on reduced graphene oxide (Ni–Ag@RGO hybrid) has been established. Hydrazine hydrate was used as the reducing agent to reduce the graphene oxide, Ni{sup 2+} and Ag{sup +} to form Ni–Ag@RGO hybrid. The prepared hybrid was further characterized by X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, and transmission electron microscopy. Interestingly, the prepared material shown good magnetic properties, which were determined by vibrating sample magnetometer. In addition, the Ni–Ag@RGO hybrid exhibited excellent catalytic activity for the reduction of 4-nitrophenol and the photodegradation of methyl orange. The catalytic process was monitored by determining the change in the concentration of the reactants with time using ultraviolet–visible absorption spectroscopy. After completion of the reaction, the catalyst can be separated from the reaction system simply under a magnet field and shows good recyclability.

  17. Fe/Al bimetallic particles for the fast and highly efficient removal of Cr(VI) over a wide pH range: Performance and mechanism

    International Nuclear Information System (INIS)

    Highlights: • Bimetallic particles with different Fe/Al mass ratios were prepared. • High removal rate of Cr(VI) was achieved in acidic, neutral, and alkaline pH. • No total iron ions at pH 3.0–11.0 and nearly no Al3+ at pH 3.0–7.0 were released. • Galvanic cell effect and high specific surface area contributed to Cr(VI) removal. - Abstract: The iron/aluminum (Fe/Al) bimetallic particles with high efficiency for the removal of Cr(VI) were prepared. Fe/Al bimetallic particles were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). SEM mapping showed that the core of bimetal was Al, and the planting Fe was deposited on the surface of Al. In acidic and neutral conditions, Fe/Al bimetal can completely remove Cr(VI) from wastewater in 20 min. Even at pH 11.0, the Cr(VI) removal efficiency achieved was 93.5%. Galvanic cell effect and high specific surface area are the main reasons for the enhanced removal of Cr(VI) by bimetallic particles. There were no iron ions released in solutions at pH values ranging from 3.0 to 11.0. The released Al3+ ions concentrations in acidic and neutral conditions were all less than 0.2 mg/L. The bimetal can be used 4 times without losing activity at initial pH 3.0. XPS indicated that the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III) hydroxide/oxyhydroxide on the surface of Fe/Al bimetal. The Fe/Al bimetallic particles are promising for further testing for the rapid and effective removal of contaminants from water

  18. Characterization measurements of Ti-SS bimetallic transition joint samples

    International Nuclear Information System (INIS)

    A small set of bimetallic tubes has been investigated for the purpose to determine characteristics of samples at different conditions of tests for more statistics. Nine bimetallic samples have been manufactured at the Russian Federal Nuclear Center - VNIIEF (Sarov, Russia) using explosion technology for welding titanium and stainless steel tubes. During the tests eight samples have shown an excellent behaviour. This result is very good and we believe that these samples can be used for the construction of the cavity vessels. A preliminary measurement on the residual magnetic moment around junction line between the two materials has been carried out

  19. 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...

  20. Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Huang, Zhen-Feng; Song, Jiajia; Li, Ke; Tahir, Muhammad; Wang, Yu-Tong; Pan, Lun; Wang, Li; Zhang, Xiangwen; Zou, Ji-Jun

    2016-02-01

    The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion. PMID:26777119

  1. Synthesis of Pt-Pd bimetallic nanoparticles anchored on graphene for highly active methanol electro-oxidation

    Science.gov (United States)

    Zhang, Yuting; Chang, Gang; Shu, Honghui; Oyama, Munetaka; Liu, Xiong; He, Yunbin

    2014-09-01

    A simple, one-step reduction route was employed to synthesize bimetallic Pt-Pd nanoparticles (Pt-PdNPs) supported on graphene (G) sheets, in which the reduction of graphite oxide and metal precursor was carried out simultaneously using ascorbic acid as a soft reductant. The morphology and structure of Pt-PdNPs/G composites were characterized using X-ray diffraction, Transmission Electron Microscopy, Field Emission Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy analysis. The results show that Pt-Pd bimetallic nanoparticles were successfully synthesized and evenly anchored on the graphene sheets. Electrochemical experiments, including cyclic voltammetry and chronoamperometric measurements, were performed to investigate the electrochemical and electrocatalytic properties of the Pt-PdNPs/G composites. It was found that Pt-PdNPs/G composites show better electrocatalytic activity and stability towards the electro-oxidation of methanol than its counterparts such as composites composed of graphene-supported monometallic nanoparticles (PtNPs/G, PdNPs/G) and free-standing (Pt-PdNPs) and Vulcan-supported bimetallic Pt-Pd nanoparticles (Pt-PdNPs/V). The results could be attributed to the synergetic effects of the Pt-Pd nanoparticles and the enhanced electron transfer of graphene. The electrocatalytic activity of Pt-PdNPs/G changed with the Pd content in the Pt-Pd alloy, and the best performance was achieved with a Pt-Pd ratio of 1/3 in an alkaline environment. Our study indicates the potential use of Pt-PdNPs/G as new anode catalyst materials for direct methanol fuel cells.

  2. Electrochemical oxidation of ammonia on carbon-supported bi-metallic PtM (M = Ir, Pd, SnO{sub x}) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Lomocso, Thegy L. [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada); Baranova, Elena A., E-mail: elena.baranova@uottawa.ca [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada)

    2011-10-01

    Highlights: > Oxidation of NH{sub 3} is investigated on carbon-supported Pt and PtM (M = Pd, Ir, SnO{sub x}) nanoparticles. > Carbon supported PtPd and PtIr nanoparticles show higher catalytic activity if compared to Pt nanocatalyst. > Pt{sub 7}Ir{sub 3} nanoparticles combine good catalytic activity and enhanced stability for NH{sub 3} oxidation. > Electronic effect between two metals in PtIr is responsible for increase in the catalytic activity. - Abstract: Ammonia electro-oxidation was studied in alkaline solution on carbon-supported Pt and bimetallic Pt{sub y}M{sub 1-y} (M = Pd, Ir, SnO{sub x} and y = 70, 50 at.%) nanoparticles. Catalysts were synthesized using the modified polyol method and deposited on carbon, resulting in 20 wt.% of metal loading. Particle size, structure and surface composition of the particles were investigated using TEM, XRD and XPS. Mean size of PtM bi-metallic nanoparticles varied between 2.0 and 4.7 nm, depending on the second metal (M). XRD revealed the structure of all bi-metallic particles to be face-centered cubic and confirmed alloy formation for Pt{sub y}Pd{sub 1-y} (y = 70, 50 at.%) and Pt{sub 7}Ir{sub 3}nanoparticles, as well as partial alloying between Pt and SnO{sub x}. Electrochemical behaviour of ammonia on Pt and PtM nanoparticles is comparable to that expected for bulk Pt and PtM alloys. Addition of Pd to Pt at the nanoscale decreased the onset potential of ammonia oxidation if compared to pure platinum nanoparticles; however stability of the catalyst was poor. For Pt{sub 7}(SnO{sub x}){sub 3}, current densities were similar to Pt, whereas catalyst stability against deactivation was improved. It is found that carbon supported Pt{sub 7}Ir{sub 3} nanoparticles combine good catalytic activity with enhanced stability for ammonia electro-oxidation. Electronic effect generated between two metals in the bimetallic nanoparticles might be responsible for increase in the catalytic activity of Pd- and Ir-containing catalysts, causing

  3. Charge distribution and Fermi level in bimetallic nanoparticles.

    Science.gov (United States)

    Holmberg, Nico; Laasonen, Kari; Peljo, Pekka

    2016-01-28

    Upon metal-metal contact, a transfer of electrons will occur between the metals until the Fermi levels in both phases are equal, resulting in a net charge difference across the metal-metal interface. Here, we have examined this contact electrification in bimetallic model systems composed of mixed Au-Ag nanoparticles containing ca. 600 atoms using density functional theory calculations. We present a new model to explain this charge transfer by considering the bimetallic system as a nanocapacitor with a potential difference equal to the work function difference, and with most of the transferred charge located directly at the contact interface. Identical results were obtained by considering surface contacts as well as by employing a continuum model, confirming that this model is general and can be applied to any multimetallic structure regardless of geometry or size (going from nano- to macroscale). Furthermore, the equilibrium Fermi level was found to be strongly dependent on the surface coverage of different metals, enabling the construction of scaling relations. We believe that the charge transfer due to Fermi level equilibration has a profound effect on the catalytic, electrocatalytic and other properties of bimetallic particles. Additionally, bimetallic nanoparticles are expected to have very interesting self-assembly for large superstructures due to the surface charge anisotropy between the two metals. PMID:26788999

  4. Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

    Science.gov (United States)

    Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

    2016-01-26

    Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

  5. New bimetallic EMF cell shows promise in direct energy conversion

    Science.gov (United States)

    Hesson, J. C.; Shimotake, H.

    1968-01-01

    Concentration cell, based upon a thermally regenerative cell principle, produces electrical energy from any large heat source. This experimental bimetallic EMF cell uses a sodium-bismuth alloy cathode and a pure liquid sodium anode. The cell exhibits reliability, corrosion resistance, and high current density performance.

  6. Structural disordering of de-alloyed Pt bimetallic nanocatalysts

    DEFF Research Database (Denmark)

    Spanos, Ioannis; Dideriksen, Knud; Kirkensgaard, Jacob Judas Kain;

    2015-01-01

    Platinum bimetallic alloys are well-known for their ability to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). PtxCo1-x colloidal nanoparticles were synthesized with varying initial Pt : Co ratios, but constant size to investigate how the initial metal...

  7. Carbon nanofiber supported bimetallic PdAu nanoparticles for formic acid electrooxidation

    Science.gov (United States)

    Qin, Yuan-Hang; Jiang, Yue; Niu, Dong-Fang; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2012-10-01

    Carbon nanofiber (CNF) supported PdAu nanoparticles are synthesized with sodium citrate as the stabilizing agent and sodium borohydride as the reducing agent. High resolution transmission electron microscopy (HRTEM) characterization indicates that the synthesized PdAu particles are well dispersed on the CNF surface and X-ray diffraction (XRD) characterization indicates that the alloying degree of the synthesized PdAu nanoparticles can be improved by adding tetrahydrofuran to the synthesis solution. The results of electrochemical characterization indicate that the addition of Au can promote the electrocatalytic activity of Pd/C catalyst for formic acid oxidation and the CNF supported high-alloying PdAu catalyst possesses better electrocatalytic activity and stability for formic acid oxidation than either the CNF supported low-alloying PdAu catalyst or the CNF supported Pd catalyst.

  8. Three-Dimensional Graphene Supported Bimetallic Nanocomposites with DNA Regulated-Flexibly Switchable Peroxidase-Like Activity.

    Science.gov (United States)

    Yuan, Fang; Zhao, Huimin; Zang, Hongmei; Ye, Fei; Quan, Xie

    2016-04-20

    A synergistic bimetallic enzyme mimetic catalyst, three-dimensional (3D) graphene/Fe3O4-AuNPs, was successfully fabricated which exhibited flexibly switchable peroxidase-like activity. Compared to the traditional 2D graphene-based monometallic composite, the introduced 3D structure, which was induced by the addition of glutamic acid, and bimetallic anchoring approach dramatically improved the catalytic activity, as well as the catalysis velocity and its affinity for substrate. Herein, Fe3O4NPs acted as supporters for AuNPs, which contributed to enhance the efficiency of electron transfer. On the basis of the measurement of Mott-Schottky plots of graphene and metal anchored hybrids, the catalysis mechanism was elucidated by the decrease of Fermi level resulted from the chemical doping behavior. Notably, the catalytic activity was able to be regulated by the adsorption and desorption of single-stranded DNA molecules, which laid a basis for its utilization in the construction of single-stranded DNA-based colorimetric biosensors. This strategy not only simplified the operation process including labeling, modification, and imprinting, but also protected the intrinsic affinity between the target and biological probe. Accordingly, based on the peroxidase-like activity and its controllability, our prepared nanohybrids was successfully adopted in the visualized and label-free sensing detections of glucose, sequence-specific DNA, mismatched nucleotides, and oxytetracycline. PMID:27018504

  9. Homogeneous catalysts

    CERN Document Server

    Chadwick, John C; Freixa, Zoraida; van Leeuwen, Piet W N M

    2011-01-01

    This first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste.The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.

  10. Characterization and Dehydrogenation Activity of SBA-15 and HMS Supported Chromia Catalysts

    Institute of Scientific and Technical Information of China (English)

    YUE,Hong-Yong(乐洪咏); ZHENG,Bo(郑波); YUE,Ying-Hong(乐英红); ZHANG,Xue-Zheng(张雪峥); HUA,Wei-Ming(华伟明); GAO,Zi(高滋)

    2002-01-01

    SBA-15 and HMS supported chromia catalysts were prepared and characterized. Chromia is highly dispersed on the mesoporous supports when its loading is ≤7 wt%. The supported catalysts display high activity, selectivity and stability for dehydrogenation of ethyibenzene and propane. ESR measurement of the catalysts before and after reaction shows that the active species for dehydrogenation reaction might be Cr3 + species on the catalyst surface, and the activity of the catalyst is probably correlated with the dispersion of Cr3+ species.

  11. Fabrication of electrically conductive nickel-silver bimetallic particles via polydopamine coating.

    Science.gov (United States)

    Kim, Sung Yeop; Kim, Jieun; Choe, Jaehoon; Byun, Young Chang; Seo, Jung Hyun; Kim, Do Hyun

    2013-11-01

    Inspired by adhesive proteins excreted by marine mussels, dopamine can act as a versatile surface modification agent for various organic and inorganic materials. By using adhesive polydopamine (PDA) as an intermediate layer, a simple and novel method for fabricating nickel-PDA-silver (Ni-PDA-Ag) bimetallic composite particles was developed. Ni-PDA-Ag bimetallic particles were fabricated by dispersing Ni particles in an aqueous dopamine solution followed by electroless Ag plating on the prepared Ni-PDA particles. A PDA layer with nano-meter thickness was deposited spontaneously on the surface of the Ni particles by oxidative self-polymerization of dopamine under alkaline conditions. Electroless Ag plating on the prepared Ni-PDA particles was carried out in the presence of a glucose solution as a reducing agent. Ni-PDA particles and Ni-PDA-Ag composite particles with a PDA intermediate layer were characterized by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), field-emission transmission electron microscopy (FE-TEM), and X-ray diffraction (XRD). In addition, the electrical conductivity of as-prepared composite particles was evaluated by a 4-point probe. The PDA layer deposited on the surface of Ni was confirmed by XPS spectra, FT-IR spectroscopy, and FE-TEM. FE-SEM images demonstrated that Ag nanoparticles were successfully plated on the PDA layer-coated Ni particles after the electroless Ag plating process. XRD patterns also confirmed the presence of Ag in a metallic state. In addition, the sheet resistance of as-prepared composite particles showed a tendency to decrease with increasing AgNO3 concentration. PMID:24245300

  12. Moessbauer study of function of magnesium in iron oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    YangJie-Xin; MaoLian-Sheng; 等

    1997-01-01

    Moessbauer spectroscopy has been utilized for studying the action of Mg element in iron oxide catalysts used for the dehydrogenation of ethylbenzene to sytrene.The experimental results show that the presence of opportune amount of Mg can enhance the stability and dispersion of catalysts,i.e.Mg is an sueful structure promoter in this kind of catalysts.

  13. In/Co-ferrierite. A highly active catalyst for the CH4-SCR NO process under presence of steam

    International Nuclear Information System (INIS)

    A series of monometallic (In, Co) and bimetallic (In/Co and Co/In) catalysts supported on ferrierite type zeolite were tested in the selective catalytic reduction of nitric oxide, in the presence of methane and excess of oxygen. All the catalysts were prepared by contact-induced ion exchange. A strong synergistic effect was observed for the catalysts containing both indium and cobalt, in comparison with the monometallic samples. For these bimetallic catalysts, a very high selectivity to nitrogen and rather efficient fuel economy were observed under the standard reaction conditions (NO=1000ppm, CH4=2000ppm, O2=4%, H2O=2500ppm). Moreover, the In/Co-ferrierite catalyst displays significant stability under a prolonged test (≅200h) in the presence of 2.5% of steam: the activity dropped rather moderately but was completely restored if steam supply was cut off, while the selectivity of the reaction was not affected in the whole temperature range scanned (300-500oC). The study suggests that a redox-type promotional effect of Co species on NO oxidation may be responsible of the strong synergistic effect detected in bimetallic In-Co formulations. (author)

  14. 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

  15. The effect of chemical reducing agents in the synthesis of sol-gel Ru-Sn catalysts: Selective hydrogenation of cinnamaldehyde

    Czech Academy of Sciences Publication Activity Database

    Hájek, J.; Mäki-Arvela, P.; Toukoniitty, E.; Kumar, N.; Salmi, T.; Murzin, DY.; Červený, L.; Paseka, Ivo; Laine, E.

    2004-01-01

    Roč. 30, č. 3 (2004), s. 187-195. ISSN 0928-0707 R&D Projects: GA ČR GA104/03/0409 Institutional research plan: CEZ:AV0Z4032918 Keywords : chemical reduction- sol-gel bimetallic catalyst * cinnamaldehyde Subject RIV: CA - Inorganic Chemistry Impact factor: 1.150, year: 2004

  16. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    OpenAIRE

    Zhen Yin; Yining Zhang; Kai Chen; Jing Li; Wenjing Li; Pei Tang; Huabo Zhao; Qingjun Zhu; Xinhe Bao; Ding Ma

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the s...

  17. Multiphase catalysts for selective reduction of NOx with hydrocarbons

    International Nuclear Information System (INIS)

    Among the existing proposed solutions to reduce emission of NOx there is a promising alternative, the so-called (HC-SCR) selective catalytic reduction of NOx using hydrocarbons as reductant. This thesis is part of a worldwide effort devoted to gain knowledge on the selective catalytic reduction of NOx with hydrocarbons with the final goal to contribute to the development of suitable catalysts for the above mentioned process. Chapter 2 describes the details of the experimental set-up and of the analytical methods employed. Among the catalyst for HC-SCR, Co-based catalyst are known to be active and selective, thus, a study on a series of Co-based catalysts, supported on zeolites, was undertaken and the results are presented in Chapter 3. Correlation between catalytic characteristics and kinetic results are employed to understand the working catalyst and this is used as a basis for catalyst optimization. With the intention to prepare a multi-functional catalyst that will preserve the desired characteristics of the individual components, minimizing their negative aspects, catalysts based on Co-Pt, supported on ZSM-5, were investigated. In Chapter 4 the results of this study are discussed. A bimetallic Co-Pt/ZSM-5 catalysts with low Pt contents (0.1 wt %) showed a synergistic effect by combining high stability and activity of Pt catalysts with the high N2 selectivity of Co catalysts. Furthermore, it was found to be sulfur- and water-tolerant. Its positive qualities brought us to study the mechanism that takes place over this catalyst during HC-SCR. The results of an in-situ i.r mechanistic study over this catalyst is reported in Chapter 5. From the results presented in Chapter 5 a mechanism operating over the Co-Pt/ZSM-5 catalyst is proposed. The modification of Co catalyst with Pt improved the catalysts. However, further improvement was found to be hindered by high selectivity to N2O. Since Rh catalysts are generally less selective to N2O, the modification of Co

  18. Facile growth of Ag@Pt bimetallic nanorods on electrochemically reduced graphene oxide for an enhanced electrooxidation of hydrazine

    Indian Academy of Sciences (India)

    Jeena S E; Selvaraju T

    2016-03-01

    An efficient transducer was constructed by the direct growth of bimetallic Ag@Pt nanorods (NRDs) on L−tryptophan functionalized electrochemically reduced graphene oxide (L−ERGO) modified electrode using galvanic displacement method for the electrooxidation of hydrazine.Initially, one dimensionalbimetallic Ag@Cu core−shell NRDs were grown on L−ERGO modified electrode by simple seed mediated growth method. Then, the Cu shells at bimetallic NRDs were exchanged by Pt through galvanic displacement method. Accordingly, the synergetic effect produced by the combination of Ag and Pt as NRDs at L−ERGO surface enabled an enhancement in the electrocatalytic efficiency for hydrazine oxidation. L−ERGO supported bimetallic Ag@Pt NRDs were characterised by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and cyclic voltammetric techniques. Finally, the modified electrode was successfully used for the electrooxidation of hydrazine in PB (pH 7.4)with a detection limit of 6*10−7M(SdivN=3). Importantly, the presence of Pt on Ag surface plays a vital role in the electrooxidation of [N2H4] at−0.2 V with an onset potential at−0.5 V where its overpotential has decreased. On the other hand, L−ERGO nanosheets tend to facilitate an effective immobilization of low density Ag seeds (Agseeds) on its surface. Chronoamperometric studies were used to study the linear correlation of [N2H4] between 1 mM and 10 mM. The modified electrode shows a high sensitivity and selectivity for a trace amount of N2H4 in the presence of different interfering cations and anions

  19. Characterization of the impregnated iron based catalyst for direct coal liquefaction by EXAFS

    Institute of Scientific and Technical Information of China (English)

    JianliYang; JishengZhun; 等

    2001-01-01

    Catalyst plays an important role in direct cola liquefaction(DCL)[1],Due to relatively high activity,low cost and environmentally benign for disposal,iron catalysts are regarded as the most attractive catalysts for DCL.To maximize catalytic effect and minimize catalyst usage,ultra-fine size catalysts are preferred.The most effective catalysts are found to be those impregnated onto coal because of their high dispersion on coal surface and intimate contact with coal particles.

  20. Sulfide Catalysts Supported on Porous Aromatic Frameworks for Naphthalene Hydroprocessing

    Directory of Open Access Journals (Sweden)

    Eduard Karakhanov

    2016-08-01

    Full Text Available This paper describes the first example of using porous aromatic frameworks as supports for sulfide catalysts for the hydrogenation of aromatic hydrocarbons. The synthesis of bimetallic Ni-W and Ni-Mo sulfides was performed by in situ decomposition of [(n-Bu4N]2[Ni(MeS42] (Me = W, Mo complexes, supported on mesoporous aromatic framework with a diamond-like structure. It is shown that the highest naphthalene conversions were achieved in the case of additional sulfidation with sulfur. After the reaction, catalysts were characterized by X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The activity of synthesized catalysts has been studied using naphthalene as a model substrate. The materials used in this study were substantially active in hydrogenation and slightly in hydrocracking of naphthalene.

  1. Mg-AI Mixed Oxides Supported Bimetallic Au-Pd Nanoparticles with Superior Catalytic Properties in Aerobic Oxidation of Benzyl Alcohol and Glycerol

    Institute of Scientific and Technical Information of China (English)

    王亮; 张伟; 曾尚景; 苏党生; 孟祥举; 肖丰收

    2012-01-01

    Nano-sized Au and Pd catalysts are favorable for oxidations with molecular oxygen, and the preparation of this kind of nanoparticles with high catalytic activities is strongly desirable. We report a successful synthesis of bimetal- lic Au-Pd nanoparticles with rich edge and comer sites on unique support of Mg-AI mixed oxides (Au-Pd/MAO), which are favorable for producing metal nanoparticles with high degree of coordinative unsaturation of metal atoms The systematic microscopic characterizations confirm the bimetallic Au-Pd nanoparticles are present as Au-Pd alloy The irregular shape of the bimetallic nanoparticles are directly observed in HRTEM images. As we expected, Au-Pd/MAO gives very excellent catalytic performances in the aerobic oxidation of benzyl alcohol and glycerol. For example, Au-Pd/MAO shows very high TOF of 91000 h i at 433 K with molecular oxygen at air pressure in solvent-free oxidation of benzyl alcohol; this catalyst also shows relatively high selectivity for tartronic acid (TA- RAC, 36.6%) at high conversion (98.5%) in aerobic oxidation of glycerol. The superior catalytic properties of Au-Pd/MAO would be potentially important tbr production of fine chemicals.

  2. Preparation of MoO3/MgO Catalysts with Eggshell and Uniform Mo Distribution by Methanol Assisted Spreading: Effect of MoO3 Dispersion on Rate of Spreading

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    2006-01-01

    Roč. 7, č. 5 (2006), s. 276-280. ISSN 1566-7367 R&D Projects: GA AV ČR(CZ) IAA4072306 Institutional research plan: CEZ:AV0Z40720504 Keywords : magnesium oxide * molybdenum catalyst * eggshell catalyst Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.878, year: 2006

  3. Compositional changes of Pd-Au bimetallic nanoclusters upon hydrogenation

    OpenAIRE

    Di Vece, M; Bals, S.; Verbeeck, J.; Lievens, P.; van Tendeloo, G.

    2009-01-01

    Changes in the size distribution and composition of bimetallic Pd-Au nanoclusters have been observed after hydrogen exposure. This effect is caused by hydrogen-induced Ostwald ripening whereby the hydrogen reduces the binding energy of the cluster atoms leading to their detachment from the cluster. The composition changes due to a difference in mobility of the detached palladium and gold atoms on the surface. Fast palladium atoms contribute to the formation of larger nanoclusters, while the s...

  4. Thermoelastic stability of bimetallic shallow shells of revolution

    OpenAIRE

    Batista, Milan; Kosel, Franc

    2015-01-01

    This article considers the thermoelastic stability of bimetallic shallow shells of revolution. Basic equations are derived from Reissner's non-linear theory of shells by assuming that deformations and rotations are small and that materials are linear elastic. The equations are further specialized for the case of a closed spherical cup. For this case the perturbated initial state is considered and it is shown that only in the cases when the cup edge is free or simply supported buckling under h...

  5. Titania Supported Pt and Pt/Pd Nano-particle Catalysts for the Oxidation of Sulfur Dioxide

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Johannessen, Tue; Eriksen, Kim Michael;

    2006-01-01

    Several types of titania (anatase) were used as supports for pure platinum and Pt–Pd bimetallic alloy catalysts. The preparation methods, normal wet impregnation technique and flame aerosol synthesis, obtained metal loadings of 2% by weight. The prepared catalysts were tested for SO2 oxidation...... activity at atmospheric pressure in the temperature range 250–600 °C. The SO2 to SO3 conversion efficiency of the Pt–Pd alloy was significantly higher than that of the individual metals. The effects of the preparation method and the titania type used on the properties and activity of the resulting catalyst...

  6. Advances in HDS catalysts design: relation between catalyst structure and feed composition

    OpenAIRE

    Kagami, Narinobu

    2006-01-01

    The aim of this work is to propose a better understanding of ultra deep HDS for diesel, to contribute to the development of advanced catalysts. The characterization of catalyst structure was examined by XRD, TPR, TPS and Raman spectroscopy. The ranking of catalytic activities were tested using various model compounds, such as thiophenes and dibenzothiophenes. The catalyst with higher stacking type active phase has weaker interaction with the support and can maintain high metal dispersion at h...

  7. Synergistic Effects of Alloying and Thiolate Modification in Furfural Hydrogenation over Cu-Based Catalysts.

    Science.gov (United States)

    Pang, Simon H; Love, Nicole E; Medlin, J Will

    2014-12-01

    Control of bimetallic surface composition and surface modification with self-assembled monolayers (SAMs) represent two methods for modifying catalyst activity and selectivity. However, possible synergistic effects of employing these strategies in concert have not been previously explored. We investigated the effects of modifying Cu/Al2O3 catalysts by alloying with Ni and modifying with octadecanethiol (C18) SAMs, using furfural hydrogenation as a probe reaction. Incorporation of small amounts of Ni (Cu4Ni) improved catalytic activity while slightly reducing hydrogenation selectivity. Further incorporation of Ni resulted in high rates for decarbonylation and ring-opening. Modification of the Cu4Ni catalyst with C18-SAMs resulted in improvement in both the activity and hydrogenation selectivity. X-ray photoelectron spectroscopy experiments on bimetallic thin films and density functional theory calculations revealed that the C18-SAM kinetically stabilized Cu at the surface under hydrogenation conditions. These results indicate that thiolate monolayers can be used to control surface bimetallic composition to improve catalytic performance. PMID:26278941

  8. Preparation and Reactivity of Niobium-Containing Hydrotreating Catalysts

    OpenAIRE

    Schwartz, Viviane

    2000-01-01

    A series of niobium-containing nitride and carbides were prepared by a temperature-programmed synthesis method. The catalysts synthesized comprised a monometallic niobium oxynitride and a new bimetallic oxycarbide supported system, Nb-Mo-O-C/Al2O3 (Mo/Nb = 1.2; 1.6; 2.0).In the case of the niobium oxynitride, the progress of formation was analyzed by interrupting the synthesis at various stages. The effect of the heating rate on product properties was also investigated. The solid intermedi...

  9. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  10. Steam gasification of carbon: Catalyst properties

    Energy Technology Data Exchange (ETDEWEB)

    Falconer, J.L.

    1991-09-16

    This research uses several techniques to measure the concentration of catalyst sites and determine their stoichiometry for the catalyzed gasification of carbon. Both alkali and alkaline earth oxides are effective catalysts for accelerating the gasification rate of coal chars, but only a fraction of the catalyst appears to be in a form that is effective for gasification, and the composition of that catalyst is not established. Transient techniques, with {sup 13}C labeling, are being used to study the surface processes, to measure the concentration of active sites, and to determine the specific reaction rates. We have used secondary ion mass spectroscopy (SIMS) for both high surface area samples of carbon/alkali carbonate mixtures and for model carbon surfaces with deposited alkali atoms. SIMS provides a direct measure of surface combination of these results can provide knowledge of catalyst dispersion and composition, and thus indicate the way to optimally utilize carbon gasification catalysts.

  11. Development of Novel Resid Hydrometallization Catalyst RDM-3

    Institute of Scientific and Technical Information of China (English)

    Hu Dawei; Niu Chuanfeng; Yang Qinghe; Liu Tao

    2007-01-01

    Based on the reaction mechanism of resid hydrodemetallization,a new catalyst carrier was designed and prepared.As compared with the similar type of catalyst carder,the said new carrier featured a higher pore volume,a larger pore diameter and a weaker surface acidity,which could improve the diffusion performance and stable reaction performance of the catalyst.The active metal components were loaded on the said carrier by a new technique for better metal dispersion,thus the impurity removal rate of the new catalyst,RDM-3,was improved significantly.The commercial test of the RDM-3 catalyst showed that the process of catalyst preparation was stable,the catalyst performance was slightly better than the catalyst prepared in the lab,therefore,the catalyst could be manufactured in commercial scale.

  12. Pt5Gd as a Highly Active and Stable Catalyst for Oxygen Electroreduction

    DEFF Research Database (Denmark)

    Escribano, Maria Escudero; Verdaguer-Casadevall, Arnau; Verdaguer Casadevall, Arnau;

    2012-01-01

    -fold increase in ORR activity, relative to pure Pt at 0.9 V, approaching the most active in the literature for catalysts prepared in this way. AR-XPS profiles after electrochemical measurements in 0.1 M HClO4 show the formation of a thick Pt overlayer on the bulk Pt5Gd, and the enhanced ORR activity...... can be explained by means of compressive strain effects. Furthermore, these novel bimetallic electrocatalysts are highly stable, which, in combination with their enhanced activity, makes them very promising for the development of new cathode catalysts for fuel cells....

  13. Alumina supported model Pd Ag catalysts: A combined STM, XPS, TPD and IRAS study

    Science.gov (United States)

    Khan, N. A.; Uhl, A.; Shaikhutdinov, S.; Freund, H.-J.

    2006-05-01

    The bimetallic Pd-Ag model catalysts were prepared by physical vapor deposition on thin alumina films. The morphology and structure of the Pd-Ag particles were studied by STM, XPS, and by TPD and IRAS of CO. The results showed the formation of true alloy particles with Ag segregated at the surface. The addition of Ag first suppresses the most strongly bonded CO on threefold hollow sites of Pd. With further increasing Ag coverage, only isolated Pd atoms surrounded by Ag atoms are likely present on the surface. The results on CO adsorption suggest that the model Pd-Ag system mimics the structure of the real Pd-Ag catalysts.

  14. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran

    Science.gov (United States)

    Mulvey, Robert E.; Blair, Victoria L.; Clegg, William; Kennedy, Alan R.; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC4) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C4 fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

  15. Formation of bimetallic nanoalloys by Au coating of size-selected Cu clusters

    International Nuclear Information System (INIS)

    Bimetallic clusters display new characteristics that could not be obtained by varying either the size of pure metallic systems or the composition of bulk bimetals alone. Coating of pre-deposited clusters by vapour deposition is a typical synthesis process of bimetallic clusters. Here, we have demonstrated that hierarchical, gold cluster-decorated copper clusters as well as both heterogeneous and homogeneous Cu–Au bimetallic clusters (4.6 to 10.7 nm) can be prepared by coating pre-deposited, size-selected Cu5000 (4.6 ± 0.2 nm) with Au evaporation at various temperatures. These bimetallic clusters were analyzed by aberration-corrected scanning transmission electron microscopy and associated electron energy loss spectroscopy. The results indicate that the growth of bimetallic clusters is controlled by a competition between nucleation and diffusion of the coating Au atoms.

  16. Photocatalytic Degradation of DIPA Using Bimetallic Cu-Ni/TiO2 Photocatalyst under Visible Light Irradiation

    Directory of Open Access Journals (Sweden)

    Nadia Riaz

    2014-01-01

    Full Text Available Bimetallic Cu-Ni/TiO2 photocatalysts were synthesized using wet impregnation (WI method with TiO2 (Degussa-P25 as support and calcined at different temperatures (180, 200, and 300°C for the photodegradation of DIPA under visible light. The photocatalysts were characterized using TGA, FESEM, UV-Vis diffuse reflectance spectroscopy, fourier transform infrared spectroscopy (FTIR and temperature programmed reduction (TPR. The results from the photodegradation experiments revealed that the Cu-Ni/TiO2 photocatalysts exhibited much higher photocatalytic activities compared to bare TiO2. It was found that photocatalyst calcined at 200°C had the highest photocatalyst activities with highest chemical oxygen demand (COD removal (86.82%. According to the structural and surface analysis, the enhanced photocatalytic activity could be attributed to its strong absorption into the visible region and high metal dispersion.

  17. Fabrication a new modified electrochemical sensor based on Au-Pd bimetallic nanoparticle decorated graphene for citalopram determination.

    Science.gov (United States)

    Daneshvar, Leili; Rounaghi, Gholam Hossein; Es'haghi, Zarrin; Chamsaz, Mahmoud; Tarahomi, Somayeh

    2016-12-01

    This paper proposes a simple approach for sensing of citalopram (CTL) using gold-palladium bimetallic nanoparticles (Au-PdNPs) decorated graphene modified gold electrode. Au-PdNPs were deposited at the surface of a graphene modified gold electrode with simple electrodeposition method. The morphology and the electrochemical properties of the modified electrode were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), energy dispersion spectroscopy (EDS), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and square wave voltammetry (SWV). The novel sensor exhibited an excellent catalytic activity towards the oxidation of CTL. The oxidation peak current of CTL, was linear in the range of 0.5-50μM with a detection limit 0.049μM with respect to concentration of citalopram. The proposed sensor was successfully applied for determination of CTL tablet and human plasma samples with satisfactory results. PMID:27612758

  18. Computational Chemistry-Based Identification of Ultra-Low Temperature Water-Gas-Shift Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis

    2008-08-31

    The current work seeks to identify novel, catalytically-active, stable, poison-resistant LWGS catalysts that retain the superior activity typical of conventional Cu catalysts but can be operated at similar or lower temperatures. A database for the Binding Energies (BEs) of the LWGS relevant species, namely CO, O and OH on the most-stable, close-packed facets of a set of 17 catalytically relevant transition metals was established. This BE data and a database of previously established segregation energies was utilized to predict the stability of bimetallic NSAs that could be synthesized by combinations of the 17 parent transition metals. NSAs that were potentially stable both in vacuo and under the influence of strong-binding WGS intermediates were then selected for adsorption studies. A set of 40 NSAs were identified that satisfied all three screener criteria and the binding energies of CO, O and OH were calculated on a set of 66, 43 and 79 NSA candidates respectively. Several NSAs were found that bound intermediates weaker than the monometallic catalysts and were thus potentially poison-resistant. Finally, kinetic studies were performed and resulted in the discovery of a specific NSA-based bimetallic catalyst Cu/Pt that is potentially a promising LWGS catalyst. This stable Cu/Pt subsurface alloy is expected to provide facile H{sub 2}O activation and remain relatively resistant from the poisoning by CO, S and formate intermediates.

  19. Preparation of Dispersive Cobalt Naphthenate Catalyst and Its Application in Suspended-Bed Hydrocracking of Heavy Oil%分散型环烷酸钴催化剂的制备及其在重油悬浮床加氢裂化中的应用

    Institute of Scientific and Technical Information of China (English)

    李传; 尚猛; 邓文安; 阙国和

    2011-01-01

    采用皂化反应和复分解反应合成了适用于重油悬浮床加氧裂化反应的分散型环烷酸钴催化剂,并优化了合成条件;通过光学显微镜、激光粒度仪、XRD和SEM方法对硫化后的催化剂进行了表征;通过釜式反应评价了该催化剂在委内瑞拉380号燃料油悬浮床加氢裂化反应中的性能.实验结果表明,合成分散型环烷酸钴催化剂的优化条件为:在皂化反应中,NaOH质量分数15%,环烷酸与NaOH摩尔比1:0.995,皂化温度95℃,皂化时间3h;在复分解反应中,CoSO4溶液质量分数15%,以滴加方式加入CoSO4溶液,复分解反应温度90℃,复分解反应时间2h.该催化剂硫化后颗粒分散度较大,团聚不明显,表面粗糙,有较大的比表而积,主要以立方晶系Co9S8晶型存在,并对重油悬浮床加氢裂化反应有较好的抑焦效果.%A dispersive cobalt naphthenate catalyst which was used in suspended-bed hydrocracking of heavy oil was prepared through saponification and double-decomposition, and the catalyst after sulfurization was characterized by means of optical microscopy, laser scattering particle analyzer, XRD and SEM. The effect of the catalyst on the suspended-bed hydrocracking of Venezuela 380* fuel oil was studied in a autoclave. The results showed that the optimal preparation conditions for the dispersive cobalt naphthenate catalyst were mass content of NaOH 15% , mole ratio of naphthenic acid to NaOH1: 0.995, saponification temperature 95 t, saponification time 3 h, mass content of CoSO4 solution (distributive droplets) 15% , double-decomposition temperature 90 t and double-decomposition time2 h. The dispersive cobalt naphthenate catalyst after sulfurization had the advantages of high particle dispersion, slight particle aggregation, coarse surface and big specific surface area, and the catalyst particles mainly existed in the form of Co9S8 cubic crystal. And the catalyst showed a good ability of inhibiting coke formation.

  20. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    How can architecture promote the enriching experiences of the tolerant, the democratic, and the learning city - a city worth living in, worth supporting and worth investing in? Catalyst Architecture comprises architectural projects, which, by virtue of their location, context and their combination...... of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city...

  1. Atomic Structure of Au−Pd Bimetallic Alloyed Nanoparticles

    KAUST Repository

    Ding, Yong

    2010-09-08

    Using a two-step seed-mediated growth method, we synthesized bimetallic nanoparticles (NPs) having a gold octahedron core and a palladium epitaxial shell with controlled Pd-shell thickness. The mismatch-release mechanism between the Au core and Pd shell of the NPs was systematically investigated by high-resolution transmission electron microscopy. In the NPs coated with a single atomic layer of Pd, the strain between the surface Pd layer and the Au core is released by Shockley partial dislocations (SPDs) accompanied by the formation of stacking faults. For NPs coated with more Pd (>2 nm), the stacking faults still exist, but no SPDs are found. This may be due to the diffusion of Au atoms into the Pd shell layers to eliminate the SPDs. At the same time, a long-range ordered L11 AuPd alloy phase has been identified in the interface area, supporting the assumption of the diffusion of Au into Pd to release the interface mismatch. With increasing numbers of Pd shell layers, the shape of the Au-Pd NP changes, step by step, from truncated-octahedral to cubic. After the bimetallic NPs were annealed at 523 K for 10 min, the SPDs at the surface of the NPs coated with a single atomic layer of Pd disappeared due to diffusion of the Au atoms into the surface layer, while the stacking faults and the L11 Au-Pd alloyed structure remained. When the annealing temperature was increased to 800 K, electron diffraction patterns and diffraction contrast images revealed that the NPs became a uniform Au-Pd alloy, and most of the stacking faults disappeared as a result of the annealing. Even so, some clues still support the existence of the L11 phase, which suggests that the L11 phase is a stable, long-range ordered structure in Au-Pd bimetallic NPs. © 2010 American Chemical Society.

  2. Possibilities of implementing bimetallic hammer castings in crushing industries

    Directory of Open Access Journals (Sweden)

    S. Žic

    2009-01-01

    Full Text Available For decades manganese steel casts have been most used materials for manufacturing elements subjected to impact and high stress abrasion. These materials are used in countless industrial applications that involve crushing of raw material by impact. Some of most important characteristics of manganese cast steels are work-hardening and high strength. Opposite from manganese steels, highly alloyed white cast irons are materials with high amount of hard carbide phases that shows better abrasion resistance but have lower strength and impact energy. Aim of this paper is to investigate possibilities to reduce costs and maintenance periods by implementing bimetallic materials.

  3. Bimetallic FeNi concave nanocubes and nanocages.

    Science.gov (United States)

    Moghimi, Nafiseh; Abdellah, Marwa; Thomas, Joseph Palathinkal; Mohapatra, Mamata; Leung, K T

    2013-07-31

    Concave nanostructures are rare because of their thermodynamically unfavorable shapes. We prepared bimetallic FeNi concave nanocubes with high Miller index planes through controlled triggering of the different growth kinetics of Fe and Ni. Taking advantage of the higher activity of the high-index planes, we then fabricated monodispersed concave nanocages via a material-independent electroleaching process. With the high-index facets exposed, these concave nanocubes and nanocages are 10- and 100-fold more active, respectively, toward electrodetection of 4-aminophenol than cuboctahedrons, providing a label-free sensing approach for monitoring toxins in water and pharmaceutical wastes. PMID:23837524

  4. 1D antiferromagnetism in spin‐alternating bimetallic chains

    OpenAIRE

    Coronado Miralles, Eugenio; Sapiña Navarro, Fernando; Drillon, M.; De Jongh, L.J.

    1990-01-01

    The magnetic and thermal properties of the ordered bimetallic chain CoNi(EDTA)⋅6H2O in the very low‐temperature range are reported. The magnetic behavior does not exhibit the characteristic features of 1D ferrimagnets, but a continuous decrease of χmT towards zero at absolute zero. This 1D antiferromagnetic behavior results from an accidental compensation between the moments located at the two sublattices. This behavior, as well as the specific‐heat results, are modeled on the basis of an Isi...

  5. Preparation of Co/Pd alloy particles dispersed multiwalled carbon nanotube supported nanocatalysts via gamma irradiation

    International Nuclear Information System (INIS)

    New multiwalled carbon nanotube/silica supported cobalt-palladium bimetallic nanocatalysts (MWNT-silica/Co–Pd NPs) were prepared by a simple one step gamma irradiation method. The method involves the in-situ surface modification of MWNT with silica (MWNT-silica) and simultaneous formation of Co–Pd bimetallic NPs using gamma irradiation. The bimetallic NPs were stabilized by silica particles formed over the surface of MWNT. Extensive characterization studies have been performed on structural, morphological, and electrochemical, aspects of MWNT-silica/Co–Pd NPs. MWNT-silica/Co–Pd NPs were characterized by field emission scanning microscopy (FESEM), UV–visible spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and Raman spectroscopy. The influence of irradiation dosage levels on the stabilizing effect of silica particles has been studied. The electrolytic activities of the MWNT-silica/Co–Pd NPs were investigated by cyclic voltammetry. - Highlights: ► New supported cobalt–palladium bimetallic nanocatalysts were prepared. ► Structural, morphological and electrochemical properties are reported. ► Electrocatalytic reduction of oxygen has been demonstrated for the new catalysts.

  6. Bimetallic Ag-Pd nanoparticles-decorated graphene oxide: a fascinating three-dimensional nanohybrid as an efficient electrochemical sensing platform for vanillin determination

    International Nuclear Information System (INIS)

    Highlights: • A 3D Ag-Pd/GO nanohybrid was fabricated via a green and in situ chemical route. • Ag-Pd/GO shows excellent electro-catalytic properties for the oxidation of vanillin. • The 3D hybrid-based sensor shows excellent performances for the vanillin detection. • This proposed method was successfully used to detect vanillin in children’s snacks. - Abstract: In this work, a fascinating hybrid based on Ag-Pd bimetallic nanoparticles-decorated graphene oxide (Ag-Pd/GO) has been successfully synthesized by a green and in situ chemical reduction strategy. The resultant hybrid was particularly characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, ultraviolet-visible spectroscopy and electrochemical techniques. The morphological results illustrate that Ag-Pd nanoparticles in microspheric appearances are highly dispersed and embedded on the GO layers, resulting in a rough surface and three-dimensional (3D) microstructure with a high Ag-Pd content in the matrix. The as-synthesized 3D Ag-Pd/GO hybrid displays distinctly enhanced electrocatalytic activity for the vanillin oxidation in comparison with that of the monometal-decorated GO, revealing a synergistic effect of the matrix GO and the doped bimetallic Ag-Pd. Therefore, the Ag-Pd/GO composite can be used as an enhanced electrochemical sensing platform for the sensitive determination of vanillin, and the fabricated sensor displays a wide detection range of 0.02–45 μmol dm−3, low detection limit of 5 nmol dm−3 and satisfactory recoveries between 98.8 % and 103.5 %. All the results demonstrate that the 3D hybrids integrated graphene with bimetallic nanoparticles are promising candidates for the development of high-performance electrochemical sensors

  7. Fe/Al bimetallic particles for the fast and highly efficient removal of Cr(VI) over a wide pH range: Performance and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Fenglian, E-mail: fufenglian2006@163.com [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China); Environmental Engineering and Science Program, Department of Biomedical, Chemical and Environmental Engineering (DBCEE), University of Cincinnati, OH 45221-0012 (United States); Cheng, Zihang [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, Department of Biomedical, Chemical and Environmental Engineering (DBCEE), University of Cincinnati, OH 45221-0012 (United States); Tang, Bing [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China)

    2015-11-15

    Highlights: • Bimetallic particles with different Fe/Al mass ratios were prepared. • High removal rate of Cr(VI) was achieved in acidic, neutral, and alkaline pH. • No total iron ions at pH 3.0–11.0 and nearly no Al{sup 3+} at pH 3.0–7.0 were released. • Galvanic cell effect and high specific surface area contributed to Cr(VI) removal. - Abstract: The iron/aluminum (Fe/Al) bimetallic particles with high efficiency for the removal of Cr(VI) were prepared. Fe/Al bimetallic particles were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). SEM mapping showed that the core of bimetal was Al, and the planting Fe was deposited on the surface of Al. In acidic and neutral conditions, Fe/Al bimetal can completely remove Cr(VI) from wastewater in 20 min. Even at pH 11.0, the Cr(VI) removal efficiency achieved was 93.5%. Galvanic cell effect and high specific surface area are the main reasons for the enhanced removal of Cr(VI) by bimetallic particles. There were no iron ions released in solutions at pH values ranging from 3.0 to 11.0. The released Al{sup 3+} ions concentrations in acidic and neutral conditions were all less than 0.2 mg/L. The bimetal can be used 4 times without losing activity at initial pH 3.0. XPS indicated that the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III) hydroxide/oxyhydroxide on the surface of Fe/Al bimetal. The Fe/Al bimetallic particles are promising for further testing for the rapid and effective removal of contaminants from water.

  8. Glycerol oxidation using gold-containing catalysts.

    Science.gov (United States)

    Villa, Alberto; Dimitratos, Nikolaos; Chan-Thaw, Carine E; Hammond, Ceri; Prati, Laura; Hutchings, Graham J

    2015-05-19

    Glycerol is an important byproduct of biodiesel production, and it is produced in significant amounts by transesterification of triglycerides with methanol. Due to the highly functionalized nature of glycerol, it is an important biochemical that can be utilized as a platform chemical for the production of high-added-value products. At present, research groups in academia and industry are exploring potential direct processes for the synthesis of useful potential chemicals using catalytic processes. Over the last 10 years, there has been huge development of potential catalytic processes using glycerol as the platform chemical. One of the most common processes investigated so far is the catalytic oxidation of glycerol at mild conditions for the formation of valuable oxygenated compounds used in the chemical and pharmaceutical industry. The major challenges associated with the selective oxidation of glycerol are (i) the control of selectivity to the desired products, (ii) high activity and resistance to poisoning, and (iii) minimizing the usage of alkaline conditions. To address these challenges, the most common catalysts used for the oxidation of glycerol are based on supported metal nanoparticles. The first significant breakthrough was the successful utilization of supported gold nanoparticles for improving the selectivity to specific products, and the second was the utilization of supported bimetallic nanoparticles based on gold, palladium, and platinum for improving activity and controlling the selectivity to the desired products. Moreover, the utilization of base-free reaction conditions for the catalytic oxidation of glycerol has unlocked new pathways for the production of free-base products, which facilitates potential industrial application. The advantages of using gold-based catalysts are the improvement of the catalyst lifetime, stability, and reusability, which are key factors for potential commercialization. In this Account, we discuss the advantages of the

  9. Clean Catalysts for Water Recovery Systems in Long-Duration Missions Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Oxidation catalysts based on innovative, physically-robust activated carbon materials containing dispersed noble metals are essential in process optimization for...

  10. Morphology and structural stability of Pt-Pd bimetallic nanoparticles

    Science.gov (United States)

    Liu, Tun-Dong; Zheng, Ji-Wen; Shao, Gui-Fang; Fan, Tian-E.; Wen, Yu-Hua

    2015-03-01

    The morphologies and structures of Pt-Pd bimetallic nanoparticles determine their chemical and physical properties. Therefore, a fundamental understanding of their morphologies and structural stabilities is of crucial importance to their applications. In this article, we have performed Monte Carlo simulations to systematically explore the structural stability and structural features of Pt-Pd alloy nanoparticles. Different Pt/Pd ratios, and particle sizes and shapes were considered. The simulated results reveal that the truncated octahedron, which has the remarkably lowest energy among all the considered shapes, exhibits the best structural stability while the tetrahedron has the worst invariably. Furthermore, all the structures of Pt-Pd alloy nanoparticles present Pd-rich in the outmost layer but Pt-rich in the sub-outmost layer. Especially, atomic distribution and chemical short-range order parameter were applied to further characterize the structural features of Pt-Pd alloy nanoparticles. This study provides a significant insight not only into the structural stability of Pt-Pd alloy nanoparticles with different compositions, and particle sizes and shapes but also to the design of bimetallic nanoparticles. Project supported by the National Natural Science Foundation of China (Grant No. 51271156) and the Natural Science Foundation of Fujian Province, China (Grant Nos. 2013J01255 and 2013J06002).

  11. Geometry optimization of bimetallic clusters using an efficient heuristic method

    Science.gov (United States)

    Lai, Xiangjing; Xu, Ruchu; Huang, Wenqi

    2011-10-01

    In this paper, an efficient heuristic algorithm for geometry optimization of bimetallic clusters is proposed. The algorithm is mainly composed of three ingredients: the monotonic basin-hopping method with guided perturbation (MBH-GP), surface optimization method, and iterated local search (ILS) method, where MBH-GP and surface optimization method are used to optimize the geometric structure of a cluster, and the ILS method is used to search the optimal homotop for a fixed geometric structure. The proposed method is applied to Cu38-nAun (0 ≤ n ≤ 38), Ag55-nAun (0 ≤ n ≤ 55), and Cu55-nAun (0 ≤ n ≤ 55) clusters modeled by the many-body Gupta potential. Comparison with the results reported in the literature indicates that the present method is highly efficient and a number of new putative global minima missed in the previous papers are found. The present method should be a promising tool for the theoretical determination of ground-state structure of bimetallic clusters. Additionally, some key elements and properties of the present method are also analyzed.

  12. Analysis for the synergy effects in bimetallic ferrierite catalysts for N2O decomposition

    Czech Academy of Sciences Publication Activity Database

    Tabor, Edyta; Jíša, Kamil; Nováková, Jana; Vondrová, Alena; Tvarůžková, Zdenka; Jakubec, Ivo; Závěta, K.; Lančok, A.; Sobalík, Zdeněk

    Salamanca : panish Catalysis Society and the Catalysis Division of the Portuguese Chemical Society, 2011. s. 376-376. [EuropaCat IX. Catalysis for a Sustainable World. 30.08.2009-04.09.2009, Salamanca] Institutional research plan: CEZ:AV0Z40400503 Keywords : N2O decomposition * synergy * Mössbauer spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry

  13. Characterization of platinum–iron catalysts supported on MCM-41 synthesized with rice husk silica and their performance for phenol hydroxylation

    OpenAIRE

    Jitlada Chumee, Nurak Grisdanurak, Arthit Neramittagapong and Jatuporn Wittayakun

    2009-01-01

    Mesoporous material RH-MCM-41 was synthesized with rice husk silica by a hydrothermal method. It was used as a support for bimetallic platinum−iron catalysts Pt–Fe/RH-MCM-41 for phenol hydroxylation. The catalysts were prepared by co-impregnation with Pt and Fe at amounts of 0.5 and 5.0 wt.%, respectively. The RH-MCM-41 structure in the catalysts was studied with x-ray diffraction, and their surface areas were determined by nitrogen adsorption. The oxidation number of Fe supported on RH-MCM-4...

  14. Studies of Heterogeneous Catalyst Selectivity and Stability for Biorefining Applications

    Science.gov (United States)

    O'Neill, Brandon J.

    The conversion of raw resources into value-added end products has long underlain the importance of catalysts in economic and scientific development. In particular, the development of selective and stable heterogeneous catalysts is a challenge that continues to grow in importance as environmental, sociological, and economic concerns have motivated an interest in sustainability and the use of renewable raw materials. Within this context, biomass has been identified as the only realistic source of renewable carbon for the foreseeable future. The development of processes to utilize biomass feedstocks will require breakthroughs in fundamental understanding and practical solutions to the challenges related to selectivity and stability of the catalysts employed. Selectivity is addressed on multiple fronts. First, the selectivity for C-O bond scission reactions of a bifunctional, bimetallic RhRe/C catalyst is investigated. Using multiple techniques, the origin of Bronsted acidity in the catalyst and the role of pretreatment on the activity, selectivity, and stability are explored. In addition, reaction kinetics experiments and kinetic modeling are utilized to understand the role of chemical functional group (i.e. carboxylic acid versus formate ester) in determining the decarbonylation versus decarboxylation selectivity over a Pd/C catalyst. Finally, kinetic studies over Pd/C and Cu/gamma-Al2O3 were performed so that that may be paired with density functional theory calculations and microkinetic modeling to elucidate the elementary reaction mechanism, identify the active site, and provide a basis for future rational catalyst design. Next, the issue of catalyst stability, important in the high-temperature, liquid-phase conditions of biomass processing, is examined, and a method for stabilizing the base-metal nanoparticles of a Cu/gamma-Al2O 3 catalyst using atomic layer deposition (ALD) is developed. This advancement may facilitate the development of biorefining by enabling

  15. Physical and Numerical Analysis of Extrusion Process for Production of Bimetallic Tubes

    Energy Technology Data Exchange (ETDEWEB)

    Misiolek, W.Z.; Sikka, V.K.

    2006-08-10

    Bimetallic tubes are used for very specific applications where one of the two metals provides strength and the other provides specific properties such as aqueous corrosion and carburization, coking resistance, and special electrical and thermal properties. Bimetallic tubes have application in pulp and paper industry for heat-recovery boilers, in the chemical industry for ethylene production, and in the petrochemical industry for deep oil well explorations. Although bimetallic tubes have major applications in energy-intensive industry, they often are not used because of their cost and manufacturing sources in the United States. This project was intended to address both of these issues.

  16. Catalysts development to base of Cu and Ni supported in ZrO2 for the H2 generation by the methanol reformed in oxidizing atmosphere

    International Nuclear Information System (INIS)

    The search of new alternating sources of energy is at the present time one of the primordial objectives to world level because of the global heating caused by the high emissions of CO2 at the atmosphere. In this sense the employment of H2 through the fuel cells offers a more viable alternative for the use of the energy coming from the connection H-H that can be appointed for use of mobile, industrial and homemade applications. However, to generate H2 in enough quantities is a great challenge at technological level for the necessity of to count with highly selective and efficient catalysts to low reaction temperatures as well as a source that comes from renewable resources. Under this context the methanol reformed in oxidizing atmosphere offers great ecological as energetics and industrial advantages; inside this investigation plane, the Cu seems to be one of the suitable candidates for this reaction due to its high capacity to generate H2, besides the great potential of improvement in its physical-chemical properties when being worked in nano metric size and /or associated with other materials. On the other hand, it is known that the Ni addition improvement the catalytic properties because of a better material dispersion, what offers big possibilities of being applied in the H2 generation in situ by means of the methanol reformed reaction in oxidizing atmosphere; and that the conformation of bimetallic particles Cu/Ni presented high selectivity and catalytic activity for the reaction in question. (Author)

  17. Microwave-assisted synthesis and characterization of bimetallic PtRu alloy nanoparticles supported on carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Rahsepar, Mansour, E-mail: rahsepar@shirazu.ac.ir [Department of Materials Science and Engineering, School of Engineering, Shiraz University, Zand Boulevard, Shiraz, 7134851154 (Iran, Islamic Republic of); Kim, Hasuck, E-mail: hasuckim@snu.ac.kr [Department of Chemistry, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul, 151-747 (Korea, Republic of); Department of Energy Systems Engineering, Daegu Gyeongbuk Institute of Science & Technology, Daegu, 711-873 (Korea, Republic of)

    2015-11-15

    Multiwalled carbon nanotube (MWCNT) supported PtRu nanoparticles were synthesized by using a microwave-assisted improved impregnation technique. X-ray diffraction, transmission electron microscopy and X-ray photo electron spectroscopy were used to characterize the prepared PtRu/MWCNT nanoparticles. The PtRu nanoparticles with a satisfactory dispersion were formed on the external surface of MWCNTs. The CO stripping experiment was performed to evaluate the poisoning resistance of the prepared PtRu/MWCNT nanoparticles. Results of electrochemical measurements indicate that the prepared PtRu/MWCNTs shows an enhanced performance toward CO poisoning. The results of characterization revealed that microwave-assisted improved impregnation technique have a high yield of alloy phase formation and could be effectively used as a simple, quick and efficient technique for preparation of bimetallic PtRu/MWCNT nanoparticles. - Highlights: • Highly dispersed PtRu/MWCNTs were formed without use of any stabilizing agent. • Microwave irradiation enhances the uniform dispersion of the PtRu nanoparticles. • Microwave-assisted improved impregnation have a high yield of alloy phase formation. • The prepared PtRu/MWCNTs shows an enhanced performance toward CO poisoning.

  18. Microwave-assisted synthesis and characterization of bimetallic PtRu alloy nanoparticles supported on carbon nanotubes

    International Nuclear Information System (INIS)

    Multiwalled carbon nanotube (MWCNT) supported PtRu nanoparticles were synthesized by using a microwave-assisted improved impregnation technique. X-ray diffraction, transmission electron microscopy and X-ray photo electron spectroscopy were used to characterize the prepared PtRu/MWCNT nanoparticles. The PtRu nanoparticles with a satisfactory dispersion were formed on the external surface of MWCNTs. The CO stripping experiment was performed to evaluate the poisoning resistance of the prepared PtRu/MWCNT nanoparticles. Results of electrochemical measurements indicate that the prepared PtRu/MWCNTs shows an enhanced performance toward CO poisoning. The results of characterization revealed that microwave-assisted improved impregnation technique have a high yield of alloy phase formation and could be effectively used as a simple, quick and efficient technique for preparation of bimetallic PtRu/MWCNT nanoparticles. - Highlights: • Highly dispersed PtRu/MWCNTs were formed without use of any stabilizing agent. • Microwave irradiation enhances the uniform dispersion of the PtRu nanoparticles. • Microwave-assisted improved impregnation have a high yield of alloy phase formation. • The prepared PtRu/MWCNTs shows an enhanced performance toward CO poisoning

  19. Towards the Rational Design of Nanoparticle Catalysts

    Science.gov (United States)

    Dash, Priyabrat

    This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall "greenness" of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle

  20. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

    Science.gov (United States)

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-12-01

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

  1. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1996-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  2. Surface organometallic chemistry on metals. III. Formation of a bimetallic Ni-Sn phase generated by reaction of a Sn(n-C sub 4 H sub 9 ) sub 4 and silica-supported nickel oxide

    Energy Technology Data Exchange (ETDEWEB)

    Agnelli, M.; Candy, J.P.; Basset, J.M. (l' Universite Claude Bernard, Villeurbanne (France)); Bournonville, J.P.; Ferretti, O.A. (Institut Francais du Petrole, Rueil-Malmaison (France))

    1990-02-01

    Reaction of Sn(n-C{sub 4}H{sub 9}){sub 4} with NiO/SiO{sub 2} occurs above 423 K according to the apparent following stoichiometry: NiO + xSn(n-C{sub 4}H{sub 9}){sub 4} {yields} NiSn{sub x} + (2x + 1)C{sub 4}H{sub 8} + (2x {minus} 1)C{sub 4}H{sub 10} + H{sub 2}O. Various compositions of the bimetallic phase can be achieved by changing the initial Sn/Ni ratio. The obtained catalysts were very active and selective in the hydrogenation of ethyl acetate to ethanol. Characterization of the bimetallic phase has shown that the particles are bimetallic (STEM). As a result of chemisorption IR, and magnetic measurements, it appears that the presence of tin has four effects: (i) it decreases significantly the amount of CO and H{sub 2} adsorbed; (ii) it isolates nickel atoms from their neighbors; (iii) it increases electron density on nickel; and (IV) it suppresses the magnetic properties of nickel. Redox behavior of Ni-Sn/SiO{sub 2} toward surface OH indicates that surface hydroxyls can oxidize Sn{sup (0)}, probably to Sn{sup (II)} with evolution of H{sub 2}, the process being reversible with H{sub 2}. It is suggested that during this oxidation process, tin migrates to the periphery of the bimetallic particle with formation of (chemical bond Si-O){sub 2}Sn{sup (II)} surface species.

  3. Nonchromophoric halide ligand variation in polyazine-bridged Ru(II),Rh(III) bimetallic supramolecules offering new insight into photocatalytic hydrogen production from water.

    Science.gov (United States)

    Rogers, Hannah Mallalieu; White, Travis A; Stone, Brittany N; Arachchige, Shamindri M; Brewer, Karen J

    2015-04-01

    The new bimetallic complex [(Ph2phen)2Ru(dpp)RhBr2(Ph2phen)](PF6)3 (1) (Ph2phen = 4,7-diphenyl-1,10-phenanthroline; dpp = 2,3-bis(2-pyridyl)pyrazine) was synthesized and characterized to compare with the Cl(-) analogue [(Ph2phen)2Ru(dpp)RhCl2(Ph2phen)](PF6)3 (2) in an effort to better understand the role of halide coordination at the Rh metal center in solar H2 production schemes. Electrochemical properties of complex 1 display a reversible Ru(II/III) oxidation, and cathodic scans indicate multiple electrochemical mechanisms exist to reduce Rh(III) by two electrons to Rh(I) followed by a quasi-reversible dpp(0/-) ligand reduction. The weaker σ-donating ability of Br(-) vs Cl(-) impacts the cathodic electrochemistry and provides insight into photocatalytic function by these bimetallic supramolecules. Complexes 1 and 2 exhibit identical light-absorbing properties with UV absorption dominated by intraligand (IL) π → π* transitions and visible absorption by metal-to-ligand charge transfer (MLCT) transitions to include a lowest energy Ru(dπ) → dpp(π*) (1)MLCT transition (λ(abs) = 514 nm; ε = 16 000 M(-1) cm(-1)). The relatively short-lived, weakly emissive Ru(dπ) → dpp(π*) (3)MLCT excited state (τ = 46 ns) for both bimetallic complexes is attributed to intramolecular electron transfer from the (3)MLCT excited state to populate a low-energy Ru(dπ) → Rh(dσ*) triplet metal-to-metal charge transfer ((3)MMCT) excited state that allows photoinitiated electron collection. Complex 1 outperforms the related Cl(-) bimetallic analogue 2 as a H2 photocatalyst despite identical light-absorbing and excited-state properties. Additional H2 experiments with added halide suggest ion pairing plays a role in catalyst deactivation and provides new insight into observed differences in H2 production upon halide variation in Ru(II),Rh(III) supramolecular architectures. PMID:25782053

  4. Bimetallic alloys in action: dynamic atomistic motifs for electrochemistry and catalysis

    Czech Academy of Sciences Publication Activity Database

    Mueller, J. E.; Krtil, Petr; Kubler, L. A.; Jacob, T.

    2014-01-01

    Roč. 16, č. 29 (2014), s. 15029-15042. ISSN 1463-9076 Institutional support: RVO:61388955 Keywords : Bimetallic alloys * electrochemistry * catalysis Subject RIV: CG - Electrochemistry Impact factor: 4.493, year: 2014

  5. Bioinspired Design of Ultrathin 2D Bimetallic Metal-Organic-Framework Nanosheets Used as Biomimetic Enzymes.

    Science.gov (United States)

    Wang, Yixian; Zhao, Meiting; Ping, Jianfeng; Chen, Bo; Cao, Xiehong; Huang, Ying; Tan, Chaoliang; Ma, Qinglang; Wu, Shixin; Yu, Yifu; Lu, Qipeng; Chen, Junze; Zhao, Wei; Ying, Yibin; Zhang, Hua

    2016-06-01

    With the bioinspired design of organic ligands and metallic nodes, novel ultrathin 2D bimetallic metal-organic-framework nanosheets are successfully synthesized, which can serve as advanced 2D biomimetic nanomaterials to mimic heme proteins. PMID:27008574

  6. Microbially supported synthesis of catalytically active bimetallic Pd-Au nanoparticles

    DEFF Research Database (Denmark)

    Hosseinkhani, Baharak; Søbjerg, Lina Sveidal; Rotaru, Amelia-Elena;

    2012-01-01

    Bimetallic nanoparticles are considered the next generation of nanocatalysts with increased stability and catalytic activity. Bio-supported synthesis of monometallic nanoparticles has been proposed as an environmentally friendly alternative to the conventional chemical and physical protocols. In ...

  7. Analysis of Al-Cu Bimetallic Bars Properties After Explosive Welding and Rolling in Modified Passes

    Directory of Open Access Journals (Sweden)

    Mróz S.

    2015-04-01

    Full Text Available The paper presents the results of the experimental tests of Al-Cu bimetallic bars rolling process in multi-radial modified passes. The bimetallic bars consist of aluminium core, grade 1050A and copper outer layer, grade M1E. The stocks were round bars with diameter 22 mm with a copper layer share of 15 and 30%. As a result of rolling in four passes, bars of a diameter of about 16.0 mm were obtained. A bimetallic stock was manufactured using an explosive welding method. The use of the designed arrangement of multi-radial modified stretching passes resulted in obtaining Al-Cu bimetallic bars with the required lateral dimensions, an uniform distribution of the cladding layer over the bar perimeter and high quality of shear strength between individual layers.

  8. Levelling the playing field: screening for synergistic effects in coalesced bimetallic nanoparticles

    Science.gov (United States)

    Tan, Rachel Lee Siew; Song, Xiaohui; Chen, Bo; Chong, Wen Han; Fang, Yin; Zhang, Hua; Wei, Jun; Chen, Hongyu

    2016-02-01

    Depending on the synthetic methods, bimetallic nanoparticles can have either core-shell, phase segregated, alloy, or partially coalesced structures, presenting different degrees of atomic mixing on their surface. Along with the variations of size and morphology, the structural differences make it difficult to compare the catalytic activity of bimetallic nanoparticles. In this article, we developed a facile screening method that can focus on the synergistic effects rather than structural differences. Prefabricated nanoparticles are mixed together to form linear aggregates and coalesced to form bimetallic junctions. Their hollow silica shells allow materials transport but prevent further aggregation. With a level playing field, this screening platform can identify the best bimetallic combination for a catalytic reaction, before optimizing the synthesis. This approach is more advantageous than the conventional approaches where structural difference may have dominant effects on the catalytic performance.Depending on the synthetic methods, bimetallic nanoparticles can have either core-shell, phase segregated, alloy, or partially coalesced structures, presenting different degrees of atomic mixing on their surface. Along with the variations of size and morphology, the structural differences make it difficult to compare the catalytic activity of bimetallic nanoparticles. In this article, we developed a facile screening method that can focus on the synergistic effects rather than structural differences. Prefabricated nanoparticles are mixed together to form linear aggregates and coalesced to form bimetallic junctions. Their hollow silica shells allow materials transport but prevent further aggregation. With a level playing field, this screening platform can identify the best bimetallic combination for a catalytic reaction, before optimizing the synthesis. This approach is more advantageous than the conventional approaches where structural difference may have dominant

  9. Studies of the transition zone in steel – chromium cast iron bimetallic casting

    Directory of Open Access Journals (Sweden)

    S. Tenerowicz

    2010-01-01

    Full Text Available In this work authors presented the results of transition zone studies on steel – cast iron interface in bimetallic casting. During the investigations cylindrical castings with different diameter were prepared of cast iron with steel rods placed in the center. From each bimetallic casting a microsection was prepared for microhardness tests and metalographic analysis, consisting of transition zone measurement, point and linear analysis as well as quantitative analysis.

  10. Admittance Loci Based Design of a Plasmonic Structure Using Ag-Au Bimetallic Alloy Film

    OpenAIRE

    Kaushik Brahmachari; Mina Ray

    2013-01-01

    A theoretical study based on the use of admittance loci method in the design of surface plasmon resonance (SPR) based structure using Ag-Au bimetallic alloy film of different alloy fractions and nanoparticle sizes has been reported along with some interesting performance related simulated results at 633 nm wavelength. The sensitivity and other performance parameter issues of the structure based on the choice of correct alloy fraction and nanoparticle size of Ag-Au bimetallic alloy film have a...

  11. Application of carbon supported base metal carburized catalyst to fuel cell electrocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Izhar, S.; Otsuka, S.; Nagai, M. [Tokyo Univ. of Agriculture and Technology, Tokyo (Japan). Graduate School of Bio-applications and Systems Engineering

    2006-07-01

    Due to the high cost and potential for carbon monoxide poisoning, polymer electrolyte fuel cells using platinum (Pt) base catalysts pose serious problems. Transition metal carbides are highly regarded because of their high conductivity, high activity in hydrogenolysis reactions and high resistance to poisoning of the catalyst. A study was conducted in which nickel (Ni) molybdenum (Mo)/Ketjen carbon (KC) carbides were prepared with various Ni compositions and carburization temperatures. XRD, TPR and the cyclic voltammetric method were used to evaluate these catalysts through comparative evaluations with a Pt/C catalyst. These Ni-Mo/KC catalysts were evaluated for their electrocatalytic activity using a H{sub 2}O{sub 2} single stack cell and a 3-electrode cell in order to identify the active species. It was found that Ni{sub 0.5}Mo{sub 0.5} carbided at 873 K achieved the current density of 17 per cent of the Pt/C catalyst. Cyclic voltammetry measurements indicated that the Ni-Mo/KC carbide catalysts have a high activity towards the anodic electrooxidation of hydrogen. The activity is due to the amorphous Ni-Mo carbide measured by XRD and TPR. It was concluded that bimetallic carbides can reduce the manufacturing cost of fuel cells and are therefore a suitable material for Pt/C catalysts.

  12. EFFECT OF CONCENTRATION METAL PRECURSOR Co AND Mo ON CHARACTER OF CoMo / USY CATALYST

    Directory of Open Access Journals (Sweden)

    Khoirina Dwi Nugrahaningtyas

    2016-08-01

    Full Text Available The preparation and characterization of bimetallic catalysts using impregnation method with a variation of concentration of precursor sequence Co and Mo metal obtained catalyst K 1 [Co (0.018 M - Mo (0.037 M/USY]. K 2 [Co (0.026 M - Mo (0.055 M/USY], K 3 [Co (0.035 M - Mo (0.074 M/USY], K 4 [Co (0.05 M - Mo (0.11 M /USY] and K 5 [Co (0.107 M - Mo (0.22 M/USY]. Character of the catalyst in terms of crystallinity was analyzed by XRD. The result shows that there is no cristalinity damage of USY after impregnation but the amorphous cristalin structure was obtained. Amount of metal content was analyzed by XRF and the catalyst morphology by SEM-EDS. The result shows that the higher the concentration of Co and Mo so that find the higher content of metal in catalyst of the prepared catalyst increase. K 4 shows the best characteristic of catalysts prepared in this research. Analysis of K 4 is proving that Co and Mo are presented in catalyst.

  13. Nickel/ruthenium catalyst and method for aqueous phase reactions

    Science.gov (United States)

    Elliott, Douglas C.; Sealock, John L.

    1998-01-01

    A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

  14. Gas-Phase Growth of Heterostructures of Carbon Nanotubes and Bimetallic Nanowires

    Directory of Open Access Journals (Sweden)

    Whi Dong Kim

    2011-01-01

    Full Text Available A simple, inexpensive, and viable method for growing multiple heterostructured carbon nanotubes (CNTs over the entire surface of Ni-Al bimetallic nanowires (NWs in the gas phase was developed. Polymer-templated bimetallic nitrate NWs were produced by electrospinning in the first step, and subsequent calcination resulted in the formation of bimetallic oxide NWs by thermal decomposition. In the second step, free-floating bimetallic NWs were produced by spray pyrolysis in an environment containing hydrogen gas as a reducing gas. These NWs were continuously introduced into a thermal CVD reactor in order to grow CNTs in the gas phase. Scanning electron microscopy (SEM, transmission electron microscopy (TEM, and Raman spectrometry analyses revealed that the catalytic Ni sites exposed in the non-catalytic Al matrix over the entire surface of the bimetallic NWs were seeded to radially grow highly graphitized CNTs, which resembled “foxtail” structures. The grown CNTs were found to have a relatively uniform diameter of approximately 10±2 nm and 10 to 15 walls with a hollow core. The average length of the gas-phase-grown CNTs can be controlled between 100 and 1000 nm by adjusting the residence time of the free-floating bimetallic NWs in the thermal CVD reactor.

  15. Analysis of a bimetallic micro heat engine for energy harvesting

    International Nuclear Information System (INIS)

    Micro heat engines have been proposed as an alternative to thermoelectric generators, to harvest thermal energy. Recently, we proposed a micro heat engine fabricated using a buckled bimetallic beam. In this paper, we present a finite element as well as an analytical model to predict the static behavior of such a heat engine. A lumped parameter model to predict the dynamic behavior of the engine has been discussed as well. Finally, the engine has been fabricated and tested to validate all models presented. The analytical model corroborates the finite element model accurately. In addition, a good correlation has been observed between the simulations and measurements. The engine is capable of operating at up to 10.4 Hz from a temperature difference of 44 K. (paper)

  16. Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water

    Science.gov (United States)

    Darabdhara, Gitashree; Boruah, Purna K.; Borthakur, Priyakshree; Hussain, Najrul; Das, Manash R.; Ahamad, Tansir; Alshehri, Saad M.; Malgras, Victor; Wu, Kevin C.-W.; Yamauchi, Yusuke

    2016-04-01

    Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles are successfully prepared via a chemical approach consisting of reducing the metal precursors using ascorbic acid as reductant at an elevated temperature. The prepared nanocomposite is employed as a photocatalyst for the degradation of organic contaminants such as phenol, 2-chlorophenol (2-CP), and 2-nitrophenol (2-NP). The complete degradation of phenol is achieved after 300 min under natural sunlight irradiation whereas the degradation of 2-CP and 2-NP is completed after 180 min. The activity of the photocatalyst is evaluated considering several parameters such as the initial phenol concentration, the photocatalyst loading, and the pH of the solution. The degradation kinetics of all the compounds is carefully studied and found to follow a linear Langmuir-Hinshelwood model. Furthermore, the reusability of the photocatalyst is successfully achieved up to five cycles and the catalyst exhibits an excellent stability.Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles are successfully prepared via a chemical approach consisting of reducing the metal precursors using ascorbic acid as reductant at an elevated temperature. The prepared nanocomposite is employed as a photocatalyst for the degradation of organic contaminants such as phenol, 2-chlorophenol (2-CP), and 2-nitrophenol (2-NP). The complete degradation of phenol is achieved after 300 min under natural sunlight irradiation whereas the degradation of 2-CP and 2-NP is completed after 180 min. The activity of the photocatalyst is evaluated considering several parameters such as the initial phenol concentration, the photocatalyst loading, and the pH of the solution. The degradation kinetics of all the compounds is carefully studied and found to follow a linear Langmuir-Hinshelwood model. Furthermore, the reusability of the photocatalyst is successfully achieved up to five cycles and the catalyst

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    Fe/TiO2 based catalysts were prepared by incipient wetness impregnation and deposition–precipitation (DP). The catalysts were characterized by activity measurements, N2 physisorption, X-ray powder diffraction, electron paramagnetic resonance spectroscopy, energy dispersive X-ray spectroscopy, H2-.......Relative SCR activity of catalysts at 450 °C....

  18. Sol-gel based oxidation catalyst and coating system using same

    Science.gov (United States)

    Watkins, Anthony N. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor)

    2010-01-01

    An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

  19. Preparation methods of mixed metal sulfide catalysts for deep hydrogenation of crude oils%原油深度加氢复合多金属硫化物催化剂的制备方法

    Institute of Scientific and Technical Information of China (English)

    蒋丽娟; 李来平; 张文钲

    2014-01-01

    复合多金属硫化物( MMS)催化剂主要用于原油的深度加氢,用于生产高十六烷值、低硫和低芳族化合物柴油。MMS催化剂包含NiMoS、NiWS、NiMoO、NiWO、NiMoWS和ZnMoWS催化剂等。综述MMS催化剂中二元复合金属硫化物催化剂和三元复合金属硫化物催化剂的制备方法,采用二步法即添加有机物作孔成形剂先制得催化剂前驱体,再由前驱体制得的MMS催化剂结构更松散,具有较大的比表面积(90 m2·g-1)和大孔容(大于0.3 cm3·g-1),因而具有更好的催化活性。对比不同MMS催化剂对重质柴油、焦油等的加氢裂解、加氢脱硫和加氢脱氮性能,认为NiMoW三元复合金属硫化物催化剂(50%Ni25%Mo25%W)的活性最优。%Mixed metal sulfide catalyst( MMS)catalysts are mainly used for deep hydroprocessing of refractory crudes to produce diesel oil with higher cetane number,lower sulfur and lower aromatic compounds. MMS catalysts include NiMoS,NiWS,NiMoO,NiWO,NiMoWS and ZnMoWS,etc. The preparation methods of MMS catalysts,including bi-metallic sulfide catalysts and tri-metallic sulfide catalysts,were summarized in this paper. The catalyst precursors were prepared by adding organic compounds as pore forming agents,and then the catalysts were prepared. The catalysts prepared by the two-steps method possessed dispersive structure. The attained catalyst with BET specific surface area of 90 m2·g-1 and pore volume of 0. 3 cm3 ·g-1 exhibited better catalytic activity. Compared with other several MMS catalysts,the hydrocracking,hydrodesulfurization and hydrodenitrification activities of NiMoW(50mol%Ni,25mol%Mo,25mol%W)tri-metallic sulfide catalysts for processing heavy diesel oil and tar were the best.

  20. Promotion Effects of Nickel Catalysts of Dry Reforming with Methane

    Institute of Scientific and Technical Information of China (English)

    YAN,Zi-Feng(阎子峰); DING,Rong-Gang(丁荣刚); LIU,Xin-Mei(刘欣梅); SONG,Lin-Hua(宋林花)

    2001-01-01

    The promotion effects of nickel catalyst of dry reforming with methane were extensively investigated by means of XRD,SEM, EDX, N2-adsorption and H2-adsorption. XRD characterization indicated that good dispersion of nickel oxide and MgO promoter is achieved over γ-Al2O3 support. Addition of MgO promoter effectively retards the formation of NiS12O4 phase. SEM and EDX analysis exhibited that the addition ofrare-earth metal oxide CeO2 effectively promotes the Ni metal dispersion on the surface of the catalysts despite of undesirable self-dispersion of CeO2 promoter. Furthermore, the nickel component is gradually dispersed on the surface of the support following the exposure to reaction gas mixture for a period of time. The addition of MgO inhibited the self-dispersion and promotion effect of CeO2 on Ni dispersion on the catalysts. H2 chemisorption revealed that the addition of the alkaline oxide MgO promoter significantly prohibits the metal dispersion on the catalyst. Inappropriate promoter addition can result in sharp decrease of the metal dispersion. N2-adsorption indicated that oxide promoter was mostly concentrated on the outer layer of the alumina support while the nickel metal was generally dispersed in the support pores. Addition of promoters contributed to more reduction in mesopore volume.

  1. Synthesis and Characterization of Platinum-Ruthenium-Tin Catalysts

    Science.gov (United States)

    Uffalussy, Karen

    Magnesia-supported trimetallic Pt-Ru-Sn catalysts prepared through a cluster and a conventional synthetic route have been investigated in terms of their structural properties and their catalytic activity for the hydrogenation of citral and crotonaldehyde. FTIR results indicate that the majority of the stabilizing ligands remain attached to the PtRu5(μ-SnPh 2)(C)(CO)15 cluster used following impregnation onto the MgO support. Under H2 reduction conditions, partial and full ligand removal are both observed at 473 and 573 K, respectively. HRSTEM analysis shows that cluster-derived samples exhibit significantly smaller average metal particle sizes, as well as narrower particle size distributions than the corresponding conventionally prepared ones. EDX measurements show that in the cluster-derived catalysts, the majority of the metal particles present are trimetallic in nature, with metal compositions similar to those of the original cluster. In contrast, the conventionally prepared materials contain mostly bimetallic and monometallic particles with variable compositions. XPS was used to determine how the variation in method of Sn addition to bimetallic Pt-Ru affects the electronic state for the trimetallic Pt-Ru-Sn/MgO system prepared by impregnation using multimetallic clusters, metal-salts, and the combination of both precursor types. Results show that the PtRu5Sn/MgO material has a significantly higher percentage of Sn0 in comparison to Pt-Ru-Sn/MgO and PtRu5-Sn/MgO, and a corresponding shift in both Pt and Ru peaks can be correlated to this relative change in Sn oxidation state. The formation of smaller metal particles and electronic modification of Pt and Ru by Sn in the cluster-derived catalysts and the presence of the three metals in these particles in close proximity result in higher activity and selectivity to the unsaturated alcohols for the hydrogenation of both citral and crotonaldehyde.

  2. Dispersion Forces

    CERN Document Server

    Buhmann, Stefan Yoshi

    2012-01-01

    In this book, a modern unified theory of dispersion forces on atoms and bodies is presented which covers a broad range of advanced aspects and scenarios. Macroscopic quantum electrodynamics is shown to provide a powerful framework for dispersion forces which allows for discussing general properties like their non-additivity and the relation between microscopic and macroscopic interactions. It is demonstrated how the general results can be used to obtain dispersion forces on atoms in the presence of bodies of various shapes and materials. Starting with a brief recapitulation of volume I, this volume II deals especially with bodies of irregular shapes, universal scaling laws, dynamical forces on excited atoms, enhanced forces in cavity quantum electrodynamics, non-equilibrium forces in thermal environments and quantum friction. The book gives both the specialist and those new to the field a thorough overview over recent results in the field. It provides a toolbox for studying dispersion forces in various contex...

  3. DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

    Science.gov (United States)

    Leng, Jing; Wang, Wen-Min; Lu, Li-Min; Bai, Ling; Qiu, Xin-Lan

    2014-02-01

    In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR nanocomposites (GOD/PtAuNPs/ss-DNA/GR). The nanocomposites provided a suitable microenvironment for GOD to retain its biological activity. The direct and reversible electron transfer process between the active site of GOD and the modified electrode was realized without any extra electron mediator. Thus, the prepared GOD/PtAuNP/ss-DNA/GR electrode was proposed as a biosensor for the quantification of glucose. The effects of pH, applied potential, and temperature on the performance of the biosensor were discussed in detail and were optimized. Under optimal conditions, the biosensor showed a linearity with glucose concentration in the range of 1.0 to 1,800 μM with a detection limit of 0.3 μM (S/N = 3). The results demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors.

  4. Growth Mechanism of Single-Walled Carbon Nanotubes on Iron–Copper Catalyst and Chirality Studies by Electron Diffraction

    DEFF Research Database (Denmark)

    He, Maoshuai; Liu, Bilu; Chernov, Alexander I.;

    2012-01-01

    Chiralities of single-walled carbon nanotubes grown on an atomic layer deposition prepared bimetallic FeCu/MgO catalyst were evaluated quantitatively using nanobeam electron diffraction. The results reveal that the growth yields nearly 90% semiconducting tubes, 45% of which are of the (6,5) type....... The growth mechanisms as well as the roles of different components in the catalyst were studied in situ using environmental transmission electron microscopy and infrared spectroscopy. On the basis of the understanding of carbon nanotube growth mechanisms, an MgO-supported FeCu catalyst was prepared by...... impregnation, showing similar catalytic performance as the atomic layer deposition-prepared catalyst, yielding single-walled carbon nanotubes with a similar narrow chirality distribution....

  5. Synthesis and properties of catalysts prepared from silicomolybdovanadium heteropoly acid

    International Nuclear Information System (INIS)

    Catalytic properties of samples prepared of silicomolybdovanadium heteropoly acid (HPA) have been investigated. The massive catalyst is shown to be comparatively low effective in the reaction of acrolein oxidation to acrylic acid. Impregnation of coarse-dispersed silica gel by the HPA solution results in the formation of active and selective catalyst, whereas low-active catalyst of deep oxidation is formed on the base of high-dispersed silica gel. The obtained data are explained by the formation and stabilization of different forms of vanadium- and molybdenum-containing compounds on the carrier surface

  6. Quantitative study of catalytic activity and catalytic deactivation of Fe–Co/Al2O3 catalysts for multi-walled carbon nanotube synthesis by the CCVD process

    OpenAIRE

    Pirard, Sophie; Heyen, Georges; Pirard, Jean-Paul

    2010-01-01

    The catalytic deactivation during multi-walled carbon nanotube (MWNT) synthesis by the CCVD process and the influence of hydrogen on it were quantified. Initial specific reaction rate, relative specific productivity and catalytic deactivation were studied. Carbon source was ethylene, and a bimetallic iron–cobalt catalyst supported on alumina was used. The catalytic deactivation was modeled by a decreasing hyperbolic law, reflecting the progressive accumulation of amorphous carbon on active si...

  7. Ion irradiation synthesis of Ag–Au bimetallic nanospheroids in SiO{sub 2} glass substrate with tunable surface plasmon resonance frequency

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Xuan; Yu, Ruixuan; Takayanagi, Shinya [Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido 060–8628 (Japan); Shibayama, Tamaki; Watanabe, Seiichi [Center for Advanced Research of Energy and Materials, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060–8628 (Japan)

    2013-08-07

    Ag–Au bimetallic nanospheroids with tunable localized surface plasmon resonance (LSPR) were synthesized by 100 keV Ar–ion irradiation of 30 nm Ag–Au bimetallic films deposited on SiO{sub 2} glass substrates. A shift of the LSPR peaks toward shorter wavelengths was observed up to an irradiation fluence of 1.0 × 10{sup 17} cm{sup −2}, and then shifted toward the longer wavelength because of the increase of fragment volume under ion irradiation. Further control of LSPR frequency over a wider range was realized by modifying the chemical components. The resulting LSPR frequencies lie between that of the pure components, and an approximate linear shift of the LSPR toward the longer wavelength with the Au concentration was achieved, which is in good agreement with the theoretical calculations based on Gans theory. In addition, the surface morphology and compositions were examined with a scanning electron microscope equipped with an energy dispersive spectrometer, and microstructural characterizations were performed using a transmission electron microscope. The formation of isolated photosensitive Ag–Au nanospheroids with a FCC structure partially embedded in the SiO{sub 2} substrate was confirmed, which has a potential application in solid-state devices.

  8. Facile synthesis of Pt–Pd bimetallic nanoparticles by plasma discharge in liquid and their electrocatalytic activity toward methanol oxidation in alkaline media

    International Nuclear Information System (INIS)

    The Pt–Pd bimetallic nanoparticles for direct methanol fuel cell applications were successfully prepared by plasma discharge in aqueous solution. The obtained nanoparticles were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, and transmission electron microscopy. During plasma discharge, the nanoparticles were produced from the erosion of electrodes. It was noted that the erosion amount of anode electrodes was much greater than that of cathode electrodes so that the composition of Pt–Pd bimetallic nanoparticles could be changed with different power types and electrode configurations. Diffraction patterns fitted from Gaussian devolution indicated that the crystalline phase of Pt40Pd60 products was composed of pure Pt, pure Pd and Pt–Pd alloy phases. The morphology of synthesized nanoparticles showed that nanowires connected with quasi-spherical nanoparticles with 2–3 nm in diameter were observed and large spherical particles with > 50 nm in diameter were also detected intermittently. The cyclic voltammetric measurement and continuous potential scan demonstrated that Pt40Pd60 had much higher catalytic activity and better resistance to CO poisoning than Pt94Pd6 and Pt1Pd99 for methanol oxidation. These results indicate that the Pt40Pd60 could be an excellent candidate for the direct methanol fuel cell applications

  9. Green synthesis of Pt-on-Pd bimetallic nanodendrites on graphene via in situ reduction, and their enhanced electrocatalytic activity for methanol oxidation

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Porous 3D dendrite-like structure of Pt-on-Pd bimetallic nanostructures supported on graphene were prepared. • The surface of nanostructures was very “clean” because of the surfactant-free formation process and the use of green reagent. • The hetero-nanostructures showed excellent electrocatalytic performance in methanol oxidation. - Abstract: A green synthesis of Pt-on-Pd bimetallic nanodendrites supported on graphene (GPtPdNDs) with a Pd interior and a dendrite-like Pt exterior was achieved using a two-step preparation, mixing graphene and PdCl42− first, then adding PtCl42− and ethanol without any other solvent. The morphology, structure and composition of the thus-prepared GPtPdNDs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no halide ions (refer in particular to Br-, I−) or surfactant was involved in the synthesis, the prepared GPtPdNDs were directly modified onto a glassy carbon electrode and showed excellent electrocatalytic performance in methanol oxidation without any pretreatments. Moreover, with the special structure of PtPdNDs and the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the GPtPdNDs composites exhibited higher electrocatalytic activity and better tolerance to Pt nanoparticles supported on graphene (GPtNPs) and Pt/C for methanol oxidation

  10. Characterization of bimetallic Fe/Pd nanoparticles by grape leaf aqueous extract and identification of active biomolecules involved in the synthesis.

    Science.gov (United States)

    Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

    2016-08-15

    This paper reports the detailed composition and morphology of one-step green synthesized bimetallic Fe/Pd nanoparticles (NPs) using grape leaf aqueous extract and identification of active biomolecules involved in the synthesis employing various techniques. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) revealed that Fe/Pd NPs were polydispersed and quasi-spherical with a diameter ranging from 2 to 20nm. X-ray Photoelectron Spectroscopy (XPS) and Energy Dispersive X-ray Spectroscopy (EDS) provided evidence for the composition of Fe and Pd and for their species existing on the surface of Fe/Pd NPs. In addition, biomolecules in the grape leaf aqueous extract were identified but their functions are still unclear. Biomolecules in the aqueous extract such as methoxy-phenyl-oxime, N-benzoyl-2-cyano-histamine, 2-ethyl-phenol, 1,2-benzenediol, β-hydroxyquebracamine, hydroquinone, 2-methoxy-4-vinylphenol, 5-methyl-2-furancarboxaldehyde, 4-(3-hydroxybutyl)-3,5,5-trimethyl-2-cyclohexen and some polyphenolic compounds were identified as reducing and capping agents, which were studied by Chromatography-Mass Spectroscopy (GC-MS), XPS and Fourier Transform Infrared Spectroscopy (FTIR). Our finding suggests a new insight into cost-effective, simple, and environmentally benign production of bimetallic Fe/Pd NPs. PMID:27110966

  11. Polymer nanocomposite membranes with hierarchically structured catalysts for high throughput dehalogenation

    Science.gov (United States)

    Crock, Christopher A.

    Halogenated organics are categorized as primary pollutants by the Environmental Protection Agency. Trichloroethylene (TCE), which had broad industrial use in the past, shows persistence in the environment because of its chemical stability. The large scale use and poor control of TCE resulted in its prolonged release into the environment before the carcinogenic risk associated with TCE was fully understood. TCE pollution stemmed from industrial effluents and improper disposal of solvent waste. Membrane reactors are promising technology for treating TCE polluted groundwater because of the high throughput, relatively low cost of membrane fabrication and facile retrofitting of existing membrane based water treatment facilities with catalytic membrane reactors. Compared to catalytic fluidized or fixed bed reactors, catalytic membrane reactors feature minimal diffusional limitation. Additionally, embedding catalyst within the membrane avoids the need for catalyst recovery and can prevent aggregation of catalytic nanoparticles. In this work, Pd/xGnP, Pd-Au/xGnP, and commercial Pd/Al2O3 nanoparticles were employed in batch and flow-through membrane reactors to catalyze the dehalogenation of TCE in the presence of dissolved H2. Bimetallic Pd-Au/xGnP catalysts were shown to be more active than monometallic Pd/xGnP or commercial Pd/Al 2O3 catalysts. In addition to synthesizing nanocomposite membranes for high-throughput TCE dehalogenation, the membrane based dehalogenation process was designed to minimize the detrimental impact of common catalyst poisons (S2-, HS-, and H2S -) by concurrent oxidation of sulfide species to gypsum in the presence of Ca2+ and removal of gypsum through membrane filtration. The engineered membrane dehalogenation process demonstrated that bimetallic Pd-Au/xGnP catalysts resisted deactivation by residual sulfide species after oxidation, and showed complete removal of gypsum during membrane filtration.

  12. Probing hydrodesulfurization over bimetallic phosphides using monodisperse Ni2-xMxP nanoparticles encapsulated in mesoporous silica

    Science.gov (United States)

    Danforth, Samuel J.; Liyanage, D. Ruchira; Hitihami-Mudiyanselage, Asha; Ilic, Boris; Brock, Stephanie L.; Bussell, Mark E.

    2016-06-01

    Metal phosphide nanoparticles encapsulated in mesoporous silica provide a well-defined system for probing the fundamental chemistry of the hydrodesulfurization (HDS) reaction over this new class of hydrotreating catalysts. To investigate composition effects in bimetallic phosphides, the HDS of dibenzothiophene (DBT) was carried out over a series of Ni-rich Ni2-xMxP@mSiO2 (M = Co, Fe) nanocatalysts (x ≤ 0.50). The Ni2-xMxP nanoparticles (average diameters: 11-13 nm) were prepared by solution-phase arrested precipitation and encapsulated in mesoporous silica, characterized by a range of techniques (XRD, TEM, IR spectroscopy, BET surface area, CO chemisorption) and tested for DBT HDS activity and selectivity. The highest activity was observed for a Ni1.92Co0.08P@mSiO2 nanocatalyst, but the overall trend was a decrease in HDS activity with increasing Co or Fe content. In contrast, the highest turnover frequency (TOF) was observed for the most Co- and Fe-rich compositions based on sites titrated by CO chemisorption. IR spectral studies of adsorbed CO on the Ni2-xMxP@mSiO2 catalysts indicate that an increase in electron density occurs on Ni sites as the Co or Fe content is increased, which may be responsible for the increased TOFs of the catalytic sites. The Ni2-xMxP@mSiO2 nanocatalysts exhibit a strong preference for the direct desulfurization pathway (DDS) for DBT HDS that changes only slightly with increasing Co or Fe content.

  13. Bifunctional Catalysts for Upgrading of Biomass-Derived Oxygenates: A Review

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

    2016-08-05

    Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the different types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. These studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.

  14. Application of carbon supported NiMo carburized catalyst to fuel cell anode electrocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Izhar, S.; Otsuka, S.; Nagai, M. [Tokyo Univ. of Agriculture and Technology, Tokyo (Japan). Graduate School of Bio-applications and Systems Engineering

    2008-01-15

    The fabrication of polymer electrolyte fuel cells using platinum (Pt) base catalysts is a challenge due to the high cost of Pt and the potential for carbon monoxide poisoning. Transition metal carbides are highly regarded as a material substitute because of their high conductivity, high activity in hydrogenolysis reactions and high resistance to poisoning of the catalyst. A study was conducted in which nickel (Ni) molybdenum (Mo)/Ketjen carbon (KC) carbides were prepared with various Ni compositions and carburization temperatures. XRD, temperature programmed reduction and the cyclic voltammetric method were used to evaluate these catalysts through comparative evaluations with a Pt/C catalyst. The Ni-Mo/KC catalysts were evaluated for their electrocatalytic activity using a H{sub 2}O{sub 2} single stack cell and a 3-electrode cell in order to identify the active species. Cyclic voltammetry measurements indicated that the Ni-Mo/KC carbide catalysts have a high activity towards the anodic electrooxidation of hydrogen. The activity was attributed to the amorphous Ni-Mo carbide measured by XRD and temperature programmed reduction techniques. It was concluded that bimetallic carbides can reduce the manufacturing cost of fuel cells and are therefore a suitable material for Pt/C catalysts. 17 refs., 3 tabs., 7 figs.

  15. Research advances in the catalysts for the selective oxidation of ethane to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhe; ZHAO Zhen; XU Chunming

    2005-01-01

    Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

  16. The kinetics of CO poisoning in simulated reformate and effect of Ru island morphology on PtRu fuel cell catalysts as determined by operando XANES

    Energy Technology Data Exchange (ETDEWEB)

    Scott, F.; Roth, C; Ramaker, D

    2007-01-01

    In situ X-ray absorption spectroscopy (XAS) measurements, including both X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS), were carried out on commercially produced Pt and PtRu bimetallic electrocatalysts as well as on a mechanically mixed PtRu bimetallic electrocatalyst in an operating fuel cell in H{sub 2} doped with 150 ppm CO. By use of the novel {Delta}XANES technique, the coverages of CO and ontop and n-fold H (overpotential deposited and underpotential deposited hydrogen) are obtained and compared for the three catalysts, and the results are correlated with PtRu cluster morphology. The mechanical mixing process used to create the bimetallic PtRu catalyst is found to maximize CO tolerance, although the PtRu commercial electrocatalyst exhibits an increased electronic effect, most probably due to the presence of Ru(O){sub x} islands at the catalyst surface. The mobility of the CO on both Ru and Pt is found to be sharply dependent on the CO coverage, decreasing dramatically beyond 0.4 fractional coverage.

  17. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method.

    Science.gov (United States)

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-12-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and O(I)) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles. PMID:27456502

  18. Cr(VI) reduction in wastewater using a bimetallic galvanic reactor

    Energy Technology Data Exchange (ETDEWEB)

    Lugo-Lugo, Violeta [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico); Barrera-Diaz, Carlos, E-mail: cbarrera@uaemex.mx [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico); Bilyeu, Bryan [Xavier University of Louisiana, Department of Chemistry, 1 Drexel Drive, New Orleans, LA 70125 (United States); Balderas-Hernandez, Patricia [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico); Urena-Nunez, Fernando [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, Col. Escandon, Delegacion Miguel Hidalgo, C.P. 11801, Mexico, D.F. (Mexico); Sanchez-Mendieta, Victor [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico)

    2010-04-15

    The electrochemical reduction of Cr(VI)-Cr(III) in wastewater by iron and copper-iron bimetallic plates was evaluated and optimized. Iron has been used as a reducing agent, but in this work a copper-iron galvanic system in the form of bimetallic plates is applied to reducing hexavalent chromium. The optimal pH (2) and ratio of copper to iron surface areas (3.5:1) were determined in batch studies, achieving a 100% reduction in about 25 min. The Cr(VI) reduction kinetics for the bimetallic system fit a first order mechanism with a correlation of 0.9935. Thermodynamic analysis shows that the Cr(VI) reduction is possible at any pH value. However, at pH values above 3.0 for iron and 5.5 for chromium insoluble species appear, indicating that the reaction will be hindered. Continuous column studies indicate that the bimetallic copper-iron galvanic system has a reduction capacity of 9.5890 mg Cr(VI) cm{sup -2} iron, whereas iron alone only has a capacity of 0.1269 mg Cr(VI) cm{sup -2}. The bimetallic copper-iron galvanic system is much more effective in reducing hexavalent chromium than iron alone. The exhausted plates were analyzed by SEM, EDS, and XRD to determine the mechanism and the surface effects, especially surface fouling.

  19. Effect of Synthesis Techniques on Crystallization and Optical Properties of Ag-Cu Bimetallic Nanoparticles

    Science.gov (United States)

    Xiong, Ziye; Qin, Fen; Huang, Po-Shun; Nettleship, Ian; Lee, Jung-Kun

    2016-04-01

    Silver (Ag)-copper (Cu) bimetallic nanoparticles (NPs) were synthesized by the reduction of silver nitrate and copper (II) acetate monohydrate using ethylene glycol in a microwave (MW) heating system with controlled reaction times ranging from 5 min to 30 min. The molar ratio Ag/Cu was varied from 1:1 to 1:3. The effect of reaction conditions on the bimetallic NPs structures and compositions were characterized by x-ray photoelectron spectroscopy, x-ray diffraction and transmission electron microscopy. The average particle size was approximately 150 nm. The surface plasmon resonance (SPR) of Ag-Cu bimetallic NPs was investigated by monitoring the SPR band peak behavior via UV/Vis spectrophotometry. The resonance peak positions and peak widths varied due to the different structures of the bimetallic NPs created under the synthesis conditions. In the MW heating method, the reduction of Cu was increased and Cu was inhomogeneously deposited over the Ag cores. As the composition of Cu becoming higher in the Ag-Cu bimetallic NPs, the absorption between 400 nm to 600 nm was greatly enhanced.

  20. Cr(VI) reduction in wastewater using a bimetallic galvanic reactor

    International Nuclear Information System (INIS)

    The electrochemical reduction of Cr(VI)-Cr(III) in wastewater by iron and copper-iron bimetallic plates was evaluated and optimized. Iron has been used as a reducing agent, but in this work a copper-iron galvanic system in the form of bimetallic plates is applied to reducing hexavalent chromium. The optimal pH (2) and ratio of copper to iron surface areas (3.5:1) were determined in batch studies, achieving a 100% reduction in about 25 min. The Cr(VI) reduction kinetics for the bimetallic system fit a first order mechanism with a correlation of 0.9935. Thermodynamic analysis shows that the Cr(VI) reduction is possible at any pH value. However, at pH values above 3.0 for iron and 5.5 for chromium insoluble species appear, indicating that the reaction will be hindered. Continuous column studies indicate that the bimetallic copper-iron galvanic system has a reduction capacity of 9.5890 mg Cr(VI) cm-2 iron, whereas iron alone only has a capacity of 0.1269 mg Cr(VI) cm-2. The bimetallic copper-iron galvanic system is much more effective in reducing hexavalent chromium than iron alone. The exhausted plates were analyzed by SEM, EDS, and XRD to determine the mechanism and the surface effects, especially surface fouling.

  1. Thermal diffusivity of nanofluids containing Au/Pd bimetallic nanoparticles of different compositions.

    Science.gov (United States)

    Sánchez-Ramírez, J F; Jiménez Pérez, J L; Cruz Orea, A; Gutierrez Fuentes, R; Bautista-Hernández, A; Pal, U

    2006-03-01

    Colloidal suspensions of bimetallic Au/Pd nanoparticles were prepared by simultaneous reduction of the metal ions from their corresponding chloride salts with polymer (PVP) stabilizer. Thermal properties of water containing bimetallic nanoparticles with different nominal compositions (Au/Pd = 12/1, 5/1, 1/1, 1/5) were measured using the mode mismatched dual-beam thermal lens technique to determine the effect of particle composition on the thermal diffusivity of the nanofluids. The characteristic time constant of the transient thermal lens was estimated by fitting the experimental data to the theoretical expression for transient thermal lens. The thermal diffusivity of the nanofluids (water, containing Au/Pd bimetallic nanoparticles) is seen to be strongly dependent on the composition of the particles. The maximum diffusivity was achieved for the nanoparticles with highest Au/Pd molar ratio. A possible mechanism for such high thermal diffusivity of the nanofluids with bimetallic particles is given. UV-Vis spectroscopy, TEM and high-resolution electron microscopy (HREM) techniques were used to characterize the Au/Pd bimetallic nanoparticles. PMID:16573121

  2. Ni-based heterogeneous catalyst from a designed molecular precursor for the efficient electrochemical water oxidation.

    Science.gov (United States)

    Kuznetsov, Denis A; Konev, Dmitry V; Komarova, Natal'ya S; Ionov, Andrey M; Mozhchil, Rais N; Fedyanin, Ivan V

    2016-07-28

    Bimetallic Ni-Mo alkoxide was synthesized and exploited as the single-source precursor for the solution-processed deposition of the mixed-oxide layers on different conducting surfaces. Upon potential cycling in 1 M NaOH, these composites convert, in situ, into highly porous NiOx/NiOOH catalysts characterized by the high electrocatalytic activity for water oxidation under both basic (pH 13.6) and near neutral (pH 9.2) conditions. PMID:27354324

  3. Design strategies for the molecular level synthesis of supported catalysts.

    Science.gov (United States)

    Wegener, Staci L; Marks, Tobin J; Stair, Peter C

    2012-02-21

    Supported catalysts, metal or oxide catalytic centers constructed on an underlying solid phase, are making an increasingly important contribution to heterogeneous catalysis. For example, in industry, supported catalysts are employed in selective oxidation, selective reduction, and polymerization reactions. Supported structures increase the thermal stability, dispersion, and surface area of the catalyst relative to the neat catalytic material. However, structural and mechanistic characterization of these catalysts presents a formidable challenge because traditional preparations typically afford complex mixtures of structures whose individual components cannot be isolated. As a result, the characterization of supported catalysts requires a combination of advanced spectroscopies for their characterization, unlike homogeneous catalysts, which have relatively uniform structures and can often be characterized using standard methods. Moreover, these advanced spectroscopic techniques only provide ensemble averages and therefore do not isolate the catalytic function of individual components within the mixture. New synthetic approaches are required to more controllably tailor supported catalyst structures. In this Account, we review advances in supported catalyst synthesis and characterization developed in our laboratories at Northwestern University. We first present an overview of traditional synthetic methods with a focus on supported vanadium oxide catalysts. We next describe approaches for the design and synthesis of supported polymerization and hydrogenation catalysts, using anchoring techniques which provide molecular catalyst structures with exceptional activity and high percentages of catalytically significant sites. We then highlight similar approaches for preparing supported metal oxide catalysts using atomic layer deposition and organometallic grafting. Throughout this Account, we describe the use of incisive spectroscopic techniques, including high

  4. Chemical and electrochemical promotion of supported rhodium catalyst

    OpenAIRE

    Baranova, Olena; Comninellis, Christos

    2007-01-01

    The chemical and electrochemical promotion of highly dispersed nanofilm Rh catalysts (dispersion: about 10 %, film thickness: 40 nm) has been investigated for the first time. To this end Rh metal was sputter-deposited, either on a purely ionic conductor (8 % Y2O3-stabilized ZrO2) or on a mixed ionic-electronic conductor (TiO2), the latter being a highly dispersed layer of TiO2 (4 µm) deposited on YSZ. These catalysts are designated as Rh/YSZ and Rh/TiO2/YSZ, respectively. It was established a...

  5. Chemical dispersants

    NARCIS (Netherlands)

    Rahsepar, Shokouhalsadat; Smit, Martijn P.J.; Murk, Albertinka J.; Rijnaarts, Huub H.M.; Langenhoff, Alette A.M.

    2016-01-01

    Chemical dispersants were used in response to the Deepwater Horizon oil spill in the Gulf of Mexico, both at the sea surface and the wellhead. Their effect on oil biodegradation is unclear, as studies showed both inhibition and enhancement. This study addresses the effect of Corexit on oil biodeg

  6. Sulfentrazone dechlorination by iron-nickel bimetallic nanoparticles.

    Science.gov (United States)

    Nascimento, Mayra A; Lopes, Renata P; Cruz, Jean C; Silva, Antônio A; Lima, Claudio F

    2016-04-01

    The sulfentrazone dechlorination using bimetallic nanoparticles of Fe/Ni was studied. Different variables that could influence the sulfentrazone conversion were investigated, such as nitrogen atmosphere, pH and dosage of the nanoparticles and initial concentration of sulfentrazone. The best results were obtained using controlled pH (pH 4.0) and 1.0 g L(-1) of nanomaterials, resulting in 100 % conversion in only 30 min. Kinetic studies were also conducted, evaluating the influence of different nanoparticle dosages (1.0 to 4.0 g L(-1)), system temperatures (20 to 35 °C) and nickel levels in the composition of the nanomaterials (0.025 to 0.10 gNi/gFe). The mechanism of sulfentrazone conversion has changed due a direct reduction on the catalytic activity sites and indirect reduction by atomic hydrogen. Both mechanisms have followed pseudo-first order models. The conversion rate improved when the dosage of the nanomaterials, system temperature and nickel content in the composition of the nanocomposites were increased. Finally, the conversion products were elucidated by mass spectrometry and toxicity assays were performed using Daphnia Similis. The results showed that the dechlorination product is less toxic than sulfentrazone. PMID:26802513

  7. Vibrational spectroscopic studies of adsorbates on bimetallic surfaces. Doctoral thesis

    Energy Technology Data Exchange (ETDEWEB)

    Kuhn, W.K.

    1992-12-01

    In this work, well-defined bimetallic surfaces have been studied using carbon monoxide adsorption in conjunction with infrared reflection absorption spectroscopy (IRAS). These studies have indicated that for CO adsorbed on Cu overlayers, the bond between the CO and the Cu adatoms is comprised of both pi-back-donation and polarization interaction components. The sum of the contributions from these effects determines the observed bond strength with the observed CO stretching frequency being determined by the relative contributions of the components. In addition, it was determined that IR spectra of adsorbed CO show a remarkable sensitivity to surface structure. Three-dimensional Cu clusters, well-ordered two dimensional Cu islands and isolated Cu atoms are distinctively characterized by their CO IR peaks. In addition, both disorder-order and order-order transitions are observed for the metal overlayers on the single crystal metal substrates. It was also observed that localized segregation and ordering of mixed Co and S overlayers on a Mo(110) substrate occurs upon annealing.

  8. Synthesis and characterization of Ni-Mo bimetallic nitride from the mixture of nitrogen and hydrogen

    International Nuclear Information System (INIS)

    A new method for the synthesis of Ni-Mo bimetallic nitrides was reported in the present paper. The bimetallic nitrides were successfully prepared by a temperature-programmed reaction between bimetallic oxide precursors and the mixed gases of N2 and H2 instead of NH3. By adjusting pH values of the solution in the process of co-precipitation, pure NiMoO4 or NiMoO4 with excess MoO3 was obtained, and then pure Ni3Mo3N or Ni3Mo3N with γ-Mo2N was synthesized by nitriding the precursors. The structural properties of the precursors and their corresponding nitrides were investigated by means of X-ray diffraction (XRD), ultraviolet laser Raman spectroscopy, thermogravimetric (TG) analysis and chemical analysis of total nitrogen content

  9. Plasmonic emission enhancement of colloidal quantum dots in the presence of bimetallic nanoparticles

    International Nuclear Information System (INIS)

    We studied plasmonic features of bimetallic nanostructures consisting of gold nanoisland cores semi-coated with a chromium layer and explored how they influence emission of CdSe/ZnS quantum dots. We showed that, compared with chromium-covered glass substrates without the gold cores, the bimetallic nanostructures could significantly enhance the emission of the quantum dots. We studied the impact of the excitation intensity and thickness of the chromium layer on this process and utilized numerical means to identify the mechanisms behind it. Our results suggest that when the chromium layer is thin, the enhancement process is the result of the bimetallic plasmonic features of the nanostructures. As the chromium layer becomes thick, the impact of the gold cores is screened and the enhancement mostly happens mostly via the field enhancement of chromium nanoparticles in the absence of significant energy transfer from the quantum dots to these nanoparticles

  10. The quality of the joint between alloy steel and unalloyed cast steel in bimetallic layered castings

    Directory of Open Access Journals (Sweden)

    T. Wróbel

    2012-01-01

    Full Text Available In paper is presented technology of bimetallic layered castings based on founding method of layer coating directly in cast process so-called method of mould cavity preparation. Prepared castings consist two fundamental parts i.e. bearing part and working part (layer. The bearing part of bimetallic layered casting is typical foundry material i.e. ferritic-pearlitic unalloyed cast steel, whereas working part (layer is plate of austenitic alloy steel sort X2CrNi 18-9. The ratio of thickness between bearing and working part is 8:1. The aim of paper was assessed the quality of the joint between bearing and working part in dependence of pouring temperature and carbon concentration in cast steel. The quality of the joint in bimetallic layered castings was evaluated on the basis of ultrasonic non-destructive testing, structure and microhardness researches.

  11. Description of the performances of a thermo-mechanical energy harvester using bimetallic beams

    Science.gov (United States)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2016-06-01

    Many recent researches have been focused on the development of thermal energy harvesters using thermo-mechanical or thermo-electrical coupling phenomena associated to a first-order thermodynamic transition. In the case of the bimetallic strip heat engine, the exploitation of the thermo-mechanical instability of bimetallic membranes placed in a thermal gradient enables to convert heat into kinetic energy. This paper is a contribution to the modeling and the comprehension of these heat engines. By restraining the study to the simply-supported bimetallic beams and using a Ritz approximation of the beam shape, this paper aims to give an analytical solution to the first mode of the composite beams and then to evaluate the efficiency of the harvesters exploiting these kinds of instability.

  12. Melting Behaviour of Core-Shell Structured Ag-Rh Bimetallic Clusters

    Institute of Scientific and Technical Information of China (English)

    PAN Yang; CHENG Dao-Jian; HUANG Shi-Ping; WANG Wen-Chuan

    2007-01-01

    The me/ting behaviour of four typical core-shell structured 309-atom Ag-Rh bimetallic clusters, with decahedral and icosahedral geometric configurations, is investigated by using molecular dynamics simulation, based on the Sutton-Chen potential. The initial atomic configurations are obtained from semi-grand canonical ensemble Monte Carlo simulations. It is found that the melting point temperature Tm increases with the mole fraction of Rh in the bimetallic clusters, and Tm of Ag-Rh icosahedral clusters is higher than those of Ag-Rh decahedral clusters with the same Rh mole fraction. It is also found that the Ag atoms lie on the surface of Ag-Rh bimetallic clusters even after melting.

  13. Design and performance benchmark of various architectures of a piezoelectric bimetallic strip heat engine

    Science.gov (United States)

    Boughaleb, J.; Arnaud, A.; Monfray, S.; Cottinet, P. J.; Quenard, S.; Boeuf, F.; Guyomar, D.; Skotnicki, T.

    2016-06-01

    This paper deals with an investigation of a thermal energy harvester based on the coupling of a piezoelectric membrane and a bimetallic strip heat engine. The general working principle of the device consists of a double conversion mechanism: the thermal energy is first converted into mechanical energy by means of a bimetallic strip, then the mechanical energy is converted into electricity with a piezoelectric membrane. This paper deals with the study and optimization of the harvester's design. First, the piezoelectric membrane configuration is studied to find the most efficient way to convert mechanical energy into electricity. A benchmark of various piezoelectric materials is then presented to point out the most efficient materials. Finally, our study focuses on the bimetallic strip's properties: the effect of its dimensions of its thermal hysteresis on the harvester's performances are studied and compared. Thanks to these different steps, we were able to point out the best configuration to convert efficiently thermal heat flux into electricity.

  14. Plasmonic emission enhancement of colloidal quantum dots in the presence of bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sadeghi, S. M., E-mail: seyed.sadeghi@uah.edu [Department of Physics, University of Alabama in Huntsville, Huntsville, Alabama 35899 (United States); Nano and Micro Device Center, University of Alabama in Huntsville, Huntsville, Alabama 35899 (United States); Hatef, A.; Meunier, M. [Ecole Polytechnique de Montreal, Laser Processing and Plasmonics Laboratory, Engineering Physics Department, Montreal, Quebec H3C 3A7 (Canada); Nejat, A. [Department of Electrical and Computer Engineering, Boston University, 8 Saint Marys Street, Boston, Massachusetts 02215 (United States); Campbell, Q. [Department of Physics, University of Alabama in Huntsville, Huntsville, Alabama 35899 (United States)

    2014-04-07

    We studied plasmonic features of bimetallic nanostructures consisting of gold nanoisland cores semi-coated with a chromium layer and explored how they influence emission of CdSe/ZnS quantum dots. We showed that, compared with chromium-covered glass substrates without the gold cores, the bimetallic nanostructures could significantly enhance the emission of the quantum dots. We studied the impact of the excitation intensity and thickness of the chromium layer on this process and utilized numerical means to identify the mechanisms behind it. Our results suggest that when the chromium layer is thin, the enhancement process is the result of the bimetallic plasmonic features of the nanostructures. As the chromium layer becomes thick, the impact of the gold cores is screened and the enhancement mostly happens mostly via the field enhancement of chromium nanoparticles in the absence of significant energy transfer from the quantum dots to these nanoparticles.

  15. Foundation Flash Catalyst

    CERN Document Server

    Goralski, Greg

    2010-01-01

    This book offers an introduction to Flash Catalyst for designers with intermediate to advanced skills. It discusses where Catalyst sits within the production process and how it communicates with other programs. It covers all of the features of the Flash Catalyst workspace, teaching you how to create designs from scratch, how to build application designs and add functionality, and how to master the Catalyst/Flex workflow. * Introduces Flash Catalyst * Focuses on production process * Covers the interrelation between Flash Catalyst and Photoshop/Illustrator/Flex/Flash What you'll learn Starting f

  16. Solvent-Mediated Eco-Friendly Synthesis and Characterization of Monodispersed Bimetallic Ag/Pd Nano composites for Sensing and Raman Scattering Applications

    International Nuclear Information System (INIS)

    The solvent-mediated eco-friendly monodispersed Ag/Pd bimetallic nano composites (BNCs) having thick core and thin shell have been prepared through novel green chemical solvent reduction method. Reducing solvent, dimethyl formamide (DMF) is employed for the controlled green synthesis. Characterization of the synthesized Ag/Pd BNCs has been done by x-ray diffraction (XRD) studies, high-resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray analysis (EDX), and high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction (SAED) pattern. The nature of the interaction of L-cysteine with Ag/Pd BNCs has been studied by using surface plasmon spectroscopy, Fourier transform-infrared spectroscopy (FT-IR), cyclic voltammetry (CV), and theoretical methods.

  17. 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

  18. Development of structural characterisation tools for catalysts; Developpement d'outils de caracterisation structurale de catalyseurs

    Energy Technology Data Exchange (ETDEWEB)

    Lynch, J.

    1999-10-01

    Because of the diversity of their compositions and structures, and the treatments needed to render them active, heterogeneous catalysts present a major challenge in structural characterisation. Electron microscopy provides textural and structural information at the scale of the individual particle. We have been able to analyse epitaxial relationships between nanometer size particles and their support and to determine which crystal faces are most exposed. Chemical analysis can be carried out on individual particles in a bimetallic catalyst. Limitations of this technique are shown for characterisation of catalysts at the atomic scale or in reactive conditions. Here, global analysis methods based on X-ray absorption and diffraction provide more information. W-ray absorption fine structure analysis has been applied to sub-nanometer size particles in platinum based catalysts to explore interactions between the metal and reactive gases such as hydrocarbons and H{sub 2}S. Differences observed between mono-metallic and bimetallic solids lead to structural models to explain differences in catalyst reactivity. X-ray diffraction, combined with electron microscopy, shows the presence of different forms of extra-framework aluminium is steamed zeolites. Quantification of some these forms has been possible and a study of their reactivity towards different de-aluminating agents has been achieved. Work in progress shows the advantages of a combination of X-ray diffraction and absorption to study decomposition of hydrotalcites to form mixed oxides as well as possibilities in infra-red spectroscopy of adsorbed CO to determine surface sites in Fischer Tropsch catalysts. Use of in-situ analysis cells enables a detailed description of catalyst structure in reactive atmospheres and opens the possibility of correlating structure with catalytic activity. (author)

  19. Structure analysis of bimetallic Co-Au nanoparticles formed by sequential ion implantation

    Science.gov (United States)

    Chen, Hua-jian; Wang, Yu-hua; Zhang, Xiao-jian; Song, Shu-peng; chen, Hong; Zhang, Ke; Xiong, Zu-zhao; Ji, Ling-ling; Dai, Hou-mei; Wang, Deng-jing; Lu, Jian-duo; Wang, Ru-wu; Zheng, Li-rong

    2016-08-01

    Co-Au alloy Metallic nanoparticles (MNPs) are formed by sequential ion implantation of Co and Au into silica glass at room temperature. The ion ranges of Au ions implantation process have been displayed to show the ion distribution. We have used the atomic force microscopy (AFM) and transmission electron microscopy (TEM) to investigate the formation of bimetallic nanoparticles. The extended X-ray absorption fine structure (EXAFS) has been used to study the local structural information of bimetallic nanoparticles. With the increase of Au ion implantation, the local environments of Co ions are changed enormously. Hence, three oscillations, respectively, Co-O, Co-Co and Co-Au coordination are determined.

  20. Resonance parameters based analysis for metallic thickness optimization of a bimetallic plasmonic structure

    Science.gov (United States)

    Bera, Mahua; Banerjee, Jayeta; Ray, Mina

    2014-02-01

    Metallic film thickness optimization in mono- and bimetallic plasmonic structures has been carried out in order to determine the correct device parameters. Different resonance parameters, such as reflectivity, phase, field enhancement, and the complex amplitude reflectance Argand diagram (CARAD), have been investigated for the proposed optimization procedure. Comparison of mono- and bimetallic plasmonic structures has been carried out in the context of these resonance parameters with simultaneous angular and spectral interrogation. Differential phase analysis has also been performed and its application to sensing has been discussed along with a proposed interferometric set-up.

  1. Polyfunctional two- (2D) and three- (3D) dimensional oxalate bridged bimetallic magnets

    CERN Document Server

    Clément, R; Gruselle, M; Train, C

    2003-01-01

    We report major results concerning polyfunctional two- (2D) and three- (3D) dimensional oxalate bridged bimetallic magnets. As a consequence of their specific organization they are composed of an anionic sub-lattice and a cationic counter-part. These bimetallic polymers can accommodate various counter-cations possessing specific physical properties in addition to the magnetic ones resulting from the interactions between the metallic ions in the anionic sub-lattice. Thus, molecular magnets possessing paramagnetic, conductive and optical properties are presented in this review. Refs. 60 (author)

  2. Characterization of hydrophobic catalysts for hydrogen isotope exchange

    International Nuclear Information System (INIS)

    Domestic hydrophobic catalysts, KC-1 and KC-2, which were developed for the liquid phase catalytic exchange process separating hydrogen isotopes, were tested against Japanese catalyst, Kogel, which is being used in the Fugen's heavy water upgrader in Japan. KC-1 and KC-2 have different characteristics due to the differences of the solvent and solvent composition used. The test results of domestic hydrophobic catalysts characteristics such as pore distribution, specific surface area, platinum loading, and platinum dispersion from AECL agreed well with the results obtained by KEPRI/KAERI. The shape of KC-1 and KC-2 were 4x4 mm cylindrial pellet and that of Kogel catalyst was 4∼5.5mm sphere. The platinum loading of all catalysts were 0.8 wt%. The BET surface areas were 442, 247, 514m2 ·g-1 for KC-1, KC-2, and Kogel respectively, among which the BET surface area of KC-2 was the smallest. The platinum dispersion area was 2.47, 2.07, 1.90 m2g-1 and the platinum dispersion was 100, 100, 92% for KC-1, KC-2, and Kogel respectively, which showed domestic catalysts had higher values than Kogel catalyst. The average pore size was the largest in KC-2

  3. Ni Catalysts Supported on Modified Alumina for Diesel Steam Reforming

    Directory of Open Access Journals (Sweden)

    Antonios Tribalis

    2016-01-01

    Full Text Available Nickel catalysts are the most popular for steam reforming, however, they have a number of drawbacks, such as high propensity toward coke formation and intolerance to sulfur. In an effort to improve their behavior, a series of Ni-catalysts supported on pure and La-, Ba-, (La+Ba- and Ce-doped γ-alumina has been prepared. The doped supports and the catalysts have been extensively characterized. The catalysts performance was evaluated for steam reforming of n-hexadecane pure or doped with dibenzothiophene as surrogate for sulphur-free or commercial diesel, respectively. The undoped catalyst lost its activity after 1.5 h on stream. Doping of the support with La improved the initial catalyst activity. However, this catalyst was completely deactivated after 2 h on stream. Doping with Ba or La+Ba improved the stability of the catalysts. This improvement is attributed to the increase of the dispersion of the nickel phase, the decrease of the support acidity and the increase of Ni-phase reducibility. The best catalyst of the series doped with La+Ba proved to be sulphur tolerant and stable for more than 160 h on stream. Doping of the support with Ce also improved the catalytic performance of the corresponding catalyst, but more work is needed to explain this behavior.

  4. Exploring the decomposition pathways of iron asymmetric transfer hydrogenation catalysts.

    Science.gov (United States)

    Lagaditis, Paraskevi O; Sues, Peter E; Lough, Alan J; Morris, Robert H

    2015-07-21

    Our group has developed a series of iron-based asymmetric transfer hydrogenation (ATH) catalysts for the reduction of polar double bonds. The activation of the precatalysts as well as the catalytic mechanism have been thoroughly investigated, but the decomposition pathways of these systems are poorly understood. Herein, we report a study of the deactivation pathways for an iron ATH catalyst under catalytically relevant conditions. The decomposition pathways were examined using experimental techniques and density functional theory (DFT) calculations. The major decomposition products that formed, Fe(CO)((Et)2PCH2CH2CHCHNCH2CH2P(Et)2) (3a) and Fe(CO)((Et)2PCH2CH2C(Ph)C(Ph)NCH2CH2P(Et)2) (3b), had two amido donors as well as a C=C bond on the diamine backbone of the tetradentate ligand. These species were identified by NMR studies and one was isolated as a bimetallic complex with Ru(II)Cp*. Two minor iron hydride species also formed concurrently with 3a, as determined by NMR studies, one of which was isolated and contained a fully saturated ligand as well as a hydride ligand. None of the compounds that were isolated were found to be active ATH catalysts. PMID:25373607

  5. Supported Molten Metal Catalysis. A New Class of Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ravindra Datta; Ajeet Singh; Manuela Serban; Istvan Halasz

    2006-06-02

    We describe a new class of heterogeneous catalysts called supported molten metal catalysis (SMMC), in which molten metal catalysts are dispersed as nanodroplets on the surface of porous supports, allowing much larger active surface area than is possible in conventional contacting techniques for catalytic metals that are molten under reaction conditions, thus greatly enhancing their activity and potential utility. Specific examples of different types of reactions are provided to demonstrate the broad applicability of the technique in designing active, selective, and stable new catalysts. It is shown that dispersing the molten metal on a support in the suggested manner can enhance the rate of a reaction by three to four orders of magnitude as a result of the concomitant increase in the active surface area. New reaction examples include {gamma}-Al{sub 2}O{sub 3} supported molten Te (melting point 450 C) and Ga (MP 30 C) catalysts for bifunctional methylcyclohexane dehydrogenation. These catalysts provide activity similar to conventional Pt-based catalysts for this with better resistance to coking. In addition, results are described for a controlled pore glass supported molten In (MP 157 C) catalyst for the selective catalytic reduction of NO with ethanol in the presence of water, demonstrating activities superior to conventional catalysts for this reaction. A discussion is also provided on the characterization of the active surface area and dispersion of these novel supported catalysts. It is clear based on the results described that the development of new active and selective supported molten metal catalysts for practical applications is entirely plausible.

  6. Noble metal catalysts in the production of biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, A.

    2013-11-01

    The energy demand is increasing in the world together with the need to ensure energy security and the desire to decrease greenhouse gas emissions. While several renewable alternatives are available for the production of electricity, e.g. solar energy, wind power, and hydrogen, biomass is the only renewable source that can meet the demand for carbon-based liquid fuels and chemicals. The technology applied in the conversion of biomass depends on the type and complexity of the biomass, and the desired fuel. Hydrogen and hydrogen-rich mixtures (synthesis gas) are promising energy sources as they are more efficient and cleaner than existing fuels, especially when they are used in fuel cells. Hydrotreatment is a catalytic process that can be used in the conversion of biomass or biomass-derived liquids into fuels. In autothermal reforming (ATR), catalysts are used in the production of hydrogen-rich mixtures from conventional fuels or bio-fuels. The different nature of biomass and biomass-derived liquids and mineral oil makes the use of catalysts developed for the petroleum industry challenging. This requires the improvement of available catalysts and the development of new ones. To overcome the limitations of conventional hydrotreatment and ATR catalysts, zirconia-supported mono- and bimetallic rhodium, palladium, and platinum catalysts were developed and tested in the upgrading of model compounds for wood-based pyrolysis oil and in the production of hydrogen, using model compounds for gasoline and diesel. Catalysts were also tested in the ATR of ethanol. For comparative purposes commercial catalysts were tested and the results obtained with model compounds were compared with those obtained with real feedstocks (hydrotreatmet tests with wood-based pyrolysis oil and ATR tests with NExBTL renewable diesel). Noble metal catalysts were active and selective in the hydrotreatment of guaiacol used as the model compound for the lignin fraction of wood-based pyrolysis oil and wood

  7. Cobalt-Lead-Manganese oxides combined cathode catalyst for air electrode in Zinc –air battery

    International Nuclear Information System (INIS)

    Highlights: • Bi and trimetallic oxides based on Mn, Pb and Co were prepared and characterized. • Introduction of Pb and Co in MnOx catalyst promote four electron ORR. • Zinc air battery with Mn2Pb2CoOx catalyst displays much smaller charge transfer resistance in contrast to the pure MnOx. • Mn2Pb2CoOx catalyst has lower loss of performance after 500C-D cycles than the rest of the catalysts. • Zinc air battery containing Mn2Pb2CoOx has promising current and power density and also discharge capacity. - Abstract: Bi and tri metalic oxides based on Mn, Pb and Co composite catalysts were prepared by oxidation of metal acetates with KMnO4. The structure of the catalysts was characterized by X-ray diffraction (XRD). It is found that the Mn2Pb2CoOx catalyst has amorphous structure and contains various oxides of Mn, Pb and Co. Electrocatalytic activity of catalysts in 6 M KOH was studied using Cyclic Voltammetry (CV) and polarization. Cyclic Voltammetry plot of Mn2Pb2CoOx catalyst showed higher electrocatalytic activity towards the Oxygen Reduction Reaction (ORR) compared to other tri and bimetallic composite catalysts. The kinetics of ORR on the catalysts was investigated using the rotating disk electrode technique in 6 M KOH solution. From the slope of Koutecky–Levich plots, it is evident that the ORR on Mn2Pb2CoOx is a 4-electron transfer process. With these inherent features, the zinc–air battery was fabricated using various catalysts and their performance was examined for practical applications

  8. 镁铝复合氧化物负载铜催化剂上甘油选择性氢解合成丙二醇%Selective Hydrogenolysis of Glycerol to Propylene Glycol on MgO-Al2O3 Dispersed Cu Catalysts

    Institute of Scientific and Technical Information of China (English)

    王帅; 李洋; 刘海超

    2012-01-01

    我们通过乙醇溶液浸渍法合成出了具有高分散度金属Cu的Cu/MgO-Al2O3(Mg/Al原子比=1/1,3/1,4/1)、Cu/MgO和Cu/Al2O3等催化剂.在200℃,6.0 MPa H2和二氧六环溶剂中,这些催化剂高选择性地将甘油氢解为1,2-丙二醇(选择性〉90%),而单位表面Cu原子的甘油转化速率则随催化剂表面碱中心与Cu原子比例的提高而增大.N2O化学吸附-H2程序升温还原实验表明Cu粒子的本征氢解能力不随其负载量以及载体中的Mg/Al原子比发生明显改变,加之碱性MgO-Al2O3载体本身不催化甘油的转化,我们推测在甘油氢解反应中金属Cu粒子与载体界面处的碱中心辅助Cu粒子活化甘油分子的α位C—H键,从而加速甘油脱氢为甘油醛步骤以及甘油氢解反应的进行.CO2程序升温脱附实验以及对甘油氢解反应中Cu/MgO-Al2O3催化剂稳定性的考察结果暗示在甘油氢解反应中起主要作用的碱中心是载体表面上与Mg2+键连的羟基基团(即B碱OH-).这些对甘油氢解反应中金属中心与碱性中心协同作用的认识对进一步理性设计高效的甘油或其它多元醇分子氢解催化剂具有重要指导意义.%Cu/MgO-Al2O3(Mg/Al atomic ratio=1/1,3/1,4/1),Cu/MgO and Cu/Al2O3 catalysts with high Cu dispersions were prepared by an impregnation method using ethanol as solvent instead of water.Compared to water,ethanol as solvent was favorable not only for obtaining the high dispersions of the Cu clusters on the basic oxide supports,but also for retaining the basicity and structures of the supports during the catalyst preparation.The density of the basic sites for the dispersed Cu catalysts increased with increasing the MgO contents in the basic supports.These catalysts catalyzed glycerol hydrogenolysis to propylene glycol with a high selectivity(〉90%),and showed slight deactivation in dioxane at 200 ℃ and 6.0 MPa H2.Their reaction rates normalized by per exposed Cu atom increased

  9. Organophilic worm-like ruthenium nanoparticles catalysts by the modification of CTAB on montmorillonite supports.

    Science.gov (United States)

    Zhou, Limei; Qi, Xiaolong; Jiang, Xiaohui; Zhou, Yafen; Fu, Haiyan; Chen, Hua

    2013-02-15

    A supported Ru catalyst was prepared by using cetyltrimethylammonium bromide (CTAB) intercalated montmorillonite as the supporting matrix. The as-prepared Ru catalyst was subsequently characterized by XRD, XPS, N(2) sorption, TEM, and dispersibility measurement. The results showed that the Ru nanoparticles were in the modified montmorillonite interlayers, and the morphology of Ru nanoparticle was worm-like. Moreover, this supported Ru catalyst could be well dispersed in organic solvents such as toluene. The catalyst exhibited high activity and selectivity in the hydrogenation of quinoline even without stirring. PMID:23141762

  10. Synthesis and characterization of platinum supported on alumina doped with cerium catalyst

    International Nuclear Information System (INIS)

    The synthesis and characterization of gamma-alumina doped with cerium as platinum support for the automobile exhaust catalyst are described. Platinum/alumina/ceria catalyst were prepared by impregnation of hexachloroplatinic acid and sintered at 500 degree Celsius to obtain metal dispersions of 1.0 wt%. Catalyst distribution inside the powder and the effects of the addition of cerium to alumina were analyzed by the scanning electron microscopy (SEM) and x-ray fluorescence spectroscopy (XRF). The results showed that the alumina - supported catalysts contained well dispersion of the noble metal

  11. Studies on Macro—kinetics of Gas Phase Polymerization of Butadiene with Rare—earch Catalyst

    Institute of Scientific and Technical Information of China (English)

    FANGDonyu; SUNJianzhong; 等

    2002-01-01

    The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium(Nd) was carried out.The effects of reaction temperature,reaction pressure,dispersing medium, and types of catalyst on kinetics of polymerization were investigated .A kinetic model with two kinds of active sites was proposed.The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant,and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.

  12. Pd Close Coupled Catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhong Hua SHI; Mao Chu GONG; Yao Qiang CHEN

    2006-01-01

    A catalyst comprised novel high surface area alumina support was prepared to control emission of automobiles. The results showed that prepared catalyst could satisfy the requirements of a high performance close coupled catalyst for its good catalytic activity at low temperature and good stability at high temperature.

  13. Productions of palm oil bio diesel whit heterogeneous basic catalysts compared to conventional homogeneous catalysts

    International Nuclear Information System (INIS)

    The conventional process to produce biodiesel involves the presence of homogeneous basic catalysts. However, these catalysts have disadvantages associated to the need of purification steps, which increase the cost of the final product and generate pollution problems caused by the effluents. This paper compares different homogeneous and heterogeneous catalysts for the biodiesel production from palm oil. For this, heterogeneous catalysts supported on alumina were prepared and characterized by nitrogen adsorption, scanning electron microscopy, energy dispersive X ray spectroscopy and X ray diffraction. Transesterification of palm oil with methanol was accomplished at 60 celsius degrade and one hour, varying methanol/oil ratio, the type of catalyst and its concentration. Yields of the reaction and purity of the so obtained biodiesel were evaluated. Comparing the catalysts performance, based on the amount, was found that sodium methoxide (CH3 ONa) and potassium carbonate supported on alumina (K2 CO3 /Al2O3) were the catalysts that give the higher purity of biodiesel (96.8 and 95.85% respectively). When was determined the active site quality, by dividing the performance by each mole of active sites, it was found that calcined Na2SO4 /Al2O3 has the most active sites.

  14. An Exploration of Geometric and Electronic Effects in Metal Nanoparticle Catalysts

    Science.gov (United States)

    Childers, David

    The goal of this thesis is to investigate the influence geometric and electronic effects on metal nanoparticle catalysis. There are three main methods which alter a catalyst's properties: changing support material, changing nanoparticle size and alloying a second metal. This work will focus on the latter two methods using Pt-group metals and alloys. Platinum and palladium were chosen as the active metals due to a large amount of industry significance and prior literature to draw upon. Neopentane conversion and propane dehydrogenation were the two probe reactions used to evaluate these catalysts mainly due to their relative simplicity and ease of operation on a laboratory scale. The effect of particle size was studied with Pt and Pd monometallic catalysts using neopentane hydrogenolysis/isomerization as the probe reaction. Particle size studies have been done previously using this reaction so there is literature data to compare this study's results. This data will also be used as comparison for the bimetallic studies conducted later so that particle size effects can be accounted for when attempting to determine the effect of alloying a second metal. Bimetallic catalysts have several different possible structures depending on a number of factors from the identity of the two metals to the synthesis procedure. Homogeneous, core-shell and intermetallic alloys are the three structures evaluated in this work. Determining the surface composition of a homogeneous alloy can be difficult especially if both metals adsorb CO. PtPd homogeneous alloys were used to evaluate the ability of EXAFS to give information about surface composition using CO adsorption. These catalysts were also tested using neopentane conversion to evaluate changes in catalytic performance. Core-shell catalysts can also exhibit unique properties although it is not clear whether the identity of the core metal is relevant or if surface changes are most important to changing catalytic behavior. PdAu catalysts

  15. Electronic characterization and reactivity of bimetallic clusters of the Ti(Mg){sub n} type for hydrogen storage applications

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Wilber [Institute of Chemistry, University of Antioquia, A.A. 1226, Medellin (Colombia); Truong, Thanh N. [Henry Eyring, Center for Theoretical Chemistry, Department of Chemistry, University of Utah, 315 South 1400 East, Rm 2020, Salt Lake City, UT 84112 (United States); Mondragon, Fanor, E-mail: fmondra@udea.edu.co [Institute of Chemistry, University of Antioquia, A.A. 1226, Medellin (Colombia)

    2011-08-25

    Highlights: > Magnesium-titanium clusters were modeled employing DFT and MP2. > Bimetallic systems have larger stability than monometallic magnesium clusters. > Reactivity of the bimetallic cluster is centered in the transition metal. > Bimetallic clusters are more reactive towards hydrogen to produce more stable hydrides. > Magnesium titanium systems are better for hydrogen storage than pure magnesium systems. - Abstract: This paper describes the variations in the properties, characteristics and hydrogenation energy barriers of magnesium clusters induced by titanium. DFT approach was used to determine the most stable structures at this theory level and then MP2 was used to refine the energy calculations with the basis set 6-311g(d) for magnesium and hydrogen, and pseudopotential lanl2dz for titanium. Bimetallic clusters showed higher stability and reactivity than the corresponding magnesium ones. Titanium induces a change in the magnesium atoms in their electronic configuration reflected in an increase of the population of their orbitals. At the same time titanium electronic populations is modified. These changes cause variations in some reactivity parameters such as the Fukui indexes which modify the hydrogenation of the magnesium clusters and bimetallic clusters. For example, there is a reduction in the energy barrier for dissociation of the H{sub 2} molecule in the bimetallic clusters. In the hydrogenated cluster the hydrogen atoms form bridges between all of the magnesium or magnesium-titanium atoms. These results indicate that, energetically, bimetallic systems can be more promising systems for hydrogen storage.

  16. Fabrication of Cu/Pd bimetallic nanostructures with high gas sorption ability towards development of LPG sensor

    International Nuclear Information System (INIS)

    A one-step synthesis of bimetallic Cu/Pd nanorods with rod's diameter ∼3 nm and their length in the range 10–15 nm is presented. The average size, size distribution, surface morphology and structure of the bimetallic Cu/Pd have been determined by transmission electron microscope (TEM), acoustic particle sizer (APS), scanning electron microscope (SEM) and X-ray diffraction (XRD), respectively. Further, thin films of bimetallic Cu/Pd nanostructures have been fabricated via spin-coating method. Fabricated films are, then, investigated for humidity and liquefied petroleum gas (LPG) sensors for the first time. The sensitivity and sensor response of the films towards the LPG are found better in comparison to the humidity. The investigated sensing parameters demonstrate that the fabricated LPG sensor using Cu/Pd bimetallic nanostructures is challenging for the detection of LPG at room temperature. - Highlights: • Fabrication of Cu/Pd meso-porous bimetallic thin film. • Cu/Pd nanostructures were characterized by SEM, TEM, APS and XRD. • Bimetallic nanostructures with smaller sizes and narrower size distributions. • First report on Cu/Pd bimetallic nanostructures as sensors. • Sensitivity of the sensor was simply enhanced by Cu-incorporation

  17. Coating powdered copper catalyst with yttria sol

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Kuan-Ying [Department of Chemical and Engineering and Materials Science, Yuan Ze University, Chung-Li, Taiwan (China); Fuel Cell Center, Yuan Ze University, Chung-Li, Taiwan (China); Shen, Chia-Chieh, E-mail: ccshen@saturn.yzu.edu.tw [Fuel Cell Center, Yuan Ze University, Chung-Li, Taiwan (China); Department of Mechanical Engineering, Yuan Ze University, Chung-Li, Taiwan (China); Graduate School of Renewable Energy Engineering, Yuan Ze University, Chung-Li, Taiwan (China); Lee, Chi-Yuan; Lee, Shuo-Jen [Fuel Cell Center, Yuan Ze University, Chung-Li, Taiwan (China); Department of Mechanical Engineering, Yuan Ze University, Chung-Li, Taiwan (China); Graduate School of Renewable Energy Engineering, Yuan Ze University, Chung-Li, Taiwan (China); Leu, Chih-Hsing [Energy and Environment Research Laboratories, Industrial Technology Research Institute, Hsinchu, Taiwan (China); Wang, Jung-Hui [Fuel Cell Center, Yuan Ze University, Chung-Li, Taiwan (China); Yeh, Chuin-Tih [Department of Chemical and Engineering and Materials Science, Yuan Ze University, Chung-Li, Taiwan (China); Fuel Cell Center, Yuan Ze University, Chung-Li, Taiwan (China)

    2011-07-15

    Research highlights: {yields} The neutral Y{sub 2}O{sub 3} sol is an effective binder for coating powders of CuZnAl catalyst. {yields} A particle size ratio of 15 for catalyst to binder is suggested for stable coating. {yields} Sufficient stirring is an important step in the catalyst slurry preparation. - Abstract: A commercial Y{sub 2}O{sub 3} sol was tested as a binder for coating CuZnAl catalyst powder onto microchannels of a stainless steel plate (SSP). Coated plates were used to fabricate microchannel reactors that generate hydrogen via the steam reforming of methanol (SRM). Washcoating slurries were prepared by suspending catalyst powders into the sol. Slurry parameters, such as solid content, binder content, pH value, and stir time, were optimized to achieve a stable catalyst coating and good SRM performance. The expected stable coating could be obtained from neutral (pH 7) Y{sub 2}O{sub 3} slurry that is required for a negligible dissolution of the copper component of the catalyst. The experimental coating stability generally improved with the slurry stir time. Observed improvements were attributed to a dispersion of catalyst powders in the slurry through a two-step mechanism: the mechanical disassembly of agglomerated CuZnAl powders into primary particles, and the repelling of dissembled particles through adsorption of positively charged Y{sub 2}O{sub 3} binders. A reasonable reaction temperature of 280 deg. C was found for 95% conversion of methanol in SRM from the resulted microchannel reactors. A low CO fraction of 0.3% was also found in the hydrogen-rich gas reformed.

  18. Carbon supported Cu-Pd nanoparticles as anode catalyst for direct borohydride-hydrogen peroxide fuel cells

    International Nuclear Information System (INIS)

    Carbon supported Cu-Pd bimetallic nanoparticles were prepared by a successive reduction method in aqueous solution and used as anode electrocatalyst for direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the as-prepared electrocatalysts are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV), chronopotentiometry (CP), linear sweep voltammetry (LSV) and fuel cell test. The results show that the size of the crystallite is around 12.5 nm, the Cu1Pd1/C catalyst presents the highest catalytic activity among all the resultant catalysts, and the DBHFC using Cu1Pd1/C as anode catalyst and Pt mesh (1 cm × 1 cm) as cathode electrode obtains the maximum power density as high as 39.8 mW cm-2 at a discharge current density of 80.1 mA cm-2 at 20 °C

  19. Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H2 and characterized by X-ray diffraction (XRD),BET,temperature-programmed desorption of ammonia (NH3-TPD) and X-ray photoelectron spectroscopy (XPS).The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined.The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene,pyridine,dibenzothiophene,carbazole and diesel oil as the feed-stock.The TiO2,γ-Al2O3 supports and the Ni,Co promoters could remarkably increase and stabilize active W species on the catalyst surface.A suitable amount of Ni (3%-5%),Co (5%-7%) and V (1%-3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al2O3 catalyst.The WP/γ-Al2O3 catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO2 catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities.The Ni,Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al2O3 catalyst.The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al2O3 catalyst.In general,a support or promoter in the WP/γ-Al2O3 catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.

  20. Structure, Mobility, and Composition of Transition Metal Catalyst Surfaces. High-Pressure Scanning Tunneling Microscopy and Ambient-Pressure X-ray Photoelectron Spectroscopy Studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zhongwei [Univ. of California, Berkeley, CA (United States)

    2013-12-06

    Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

  1. A Highly Efficient Bifunctional Catalyst for Alkaline Air-Electrodes Based on a Ag and Co3O4 Hybrid: RRDE and Online DEMS Insights

    International Nuclear Information System (INIS)

    Enhanced catalytic activity towards oxygen reduction (ORR) and evolution (OER) reactions has been achieved by combination of spinel Co3O4 nanoparticles with Ag particles. Quasi-stationary polarization curves showed that the mixed catalyst, Ag + Co3O4 (10 wt%), outperformed its components. Rotating ring-disc electrode (RRDE) measurements revealed a negligible peroxide species formation and a 4-electron pathway for ORR. A tafel slope of ca. 75 mV dec−1 has been observed. The overpotential for ORR at 10% Co3O4 catalyst is ca. 70 mV lower than that of Ag and only ca. 80 mV higher than that of the commercial Pt catalyst. DEMS technique provided a direct evidence for oxygen evolution at these bimetallic catalysts. This hybrid is therefore one of the (or even the) most active, carbon-free, durable, non-precious ORR and OER electrocatalysts reported to date

  2. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than...... turned out to work well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used...

  3. Density and Shape Effects in the Acoustic Propulsion of Bimetallic Nanorod Motors.

    Science.gov (United States)

    Ahmed, Suzanne; Wang, Wei; Bai, Lanjun; Gentekos, Dillon T; Hoyos, Mauricio; Mallouk, Thomas E

    2016-04-26

    Bimetallic nanorods are propelled without chemical fuels in megahertz (MHz) acoustic fields, and exhibit similar behaviors to single-metal rods, including autonomous axial propulsion and organization into spinning chains. Shape asymmetry determines the direction of axial movement of bimetallic rods when there is a small difference in density between the two metals. Movement toward the concave end of these rods is inconsistent with a scattering mechanism that we proposed earlier for acoustic propulsion, but is consistent with an acoustic streaming model developed more recently by Nadal and Lauga ( Phys. Fluids 2014 , 26 , 082001 ). Longer rods were slower at constant power, and their speed was proportional to the square of the power density, in agreement with the acoustic streaming model. The streaming model was further supported by a correlation between the disassembly of spinning chains of rods and a sharp decrease in the axial speed of autonomously moving motors within the levitation plane of the cylindrical acoustic cell. However, with bimetallic rods containing metals of different densities, a consistent polarity of motion was observed with the lighter metal end leading. Speed comparisons between single-metal rods of different densities showed that those of lower density are propelled faster. So far, these density effects are not explained in the streaming model. The directionality of bimetallic rods in acoustic fields is intriguing and offers some new possibilities for designing motors in which shape, material, and chemical asymmetry might be combined for enhanced functionality. PMID:26991933

  4. VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

    Science.gov (United States)

    Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

  5. Bimetallic lanthanide complexes that display a ratiometric response to oxygen concentrations

    OpenAIRE

    Sørensen, TJ; Kenwright, AM; Faulkner, S.

    2015-01-01

    A pair of hetero-bimetallic lanthanide complexes containing terbium and europium ions have been prepared by coupling kinetically stable complexes together using an Ugi methodology to incorporate a naphthyl chromophore. Both complexes exhibit emission from terbium and europium in solution. The terbium centred emission varies with dissolved oxygen concentration, while the europium intensity remains essentially constant in one of the complexes.

  6. Theoretical studies of the work functions of Pd-based bimetallic surfaces

    International Nuclear Information System (INIS)

    Work functions of Pd-based bimetallic surfaces, including mainly M/Pd(111), Pd/M, and Pd/M/Pd(111) (M = 4d transition metals, Cu, Au, and Pt), are studied using density functional theory. We find that the work function of these bimetallic surfaces is significantly different from that of parent metals. Careful analysis based on Bader charges and electron density difference indicates that the variation of the work function in bimetallic surfaces can be mainly attributed to two factors: (1) charge transfer between the two different metals as a result of their different intrinsic electronegativity, and (2) the charge redistribution induced by chemical bonding between the top two layers. The first factor can be related to the contact potential, i.e., the work function difference between two metals in direct contact, and the second factor can be well characterized by the change in the charge spilling out into vacuum. We also find that the variation in the work functions of Pd/M/Pd(111) surfaces correlates very well with the variation of the d-band center of the surface Pd atom. The findings in this work can be used to provide general guidelines to design new bimetallic surfaces with desired electronic properties

  7. Selective Oxidations using Nanostructured Heterogeneous Catalysts

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen

    chapter focuses on the use of supported metal catalysts for the selective oxidation of alcohols, which are currently dominated by the platinum group metals. Chapter 2 deals with the most important methods to characterise heterogeneous catalysts, including X-ray powder diffraction, physisorption analysis...... supported gold nanoparticles with particular emphasis on the nature of the active site and the requirements needed to be considered when designing new catalytic systems. Furthermore, the chapter describes some of the most important methods to synthesise small and disperse gold nanoparticles on different...... pressure) without any additives or co-catalysts and afforded the desired imines with high selectivity (up to 99%). The highest catalytic activity was obtained with 5 wt% Ag/Al2O3 in toluene with air as oxidant, although the reaction also occurred under inert atmosphere by releasing H2 into the gas...

  8. Pyrochlore catalysts for hydrocarbon fuel reforming

    Science.gov (United States)

    Berry, David A.; Shekhawat, Dushyant; Haynes, Daniel; Smith, Mark; Spivey, James J.

    2012-08-14

    A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A2B2-y-zB'yB"zO7-.DELTA., where y>0 and z.gtoreq.0. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H2+CO) for fuel cells, among other uses.

  9. Tuning the surface electronic structure of a Pt3Ti(111) electro catalyst.

    Science.gov (United States)

    Paßens, M; Caciuc, V; Atodiresei, N; Moors, M; Blügel, S; Waser, R; Karthäuser, S

    2016-07-21

    Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the preparation conditions. PMID:26865393

  10. A hydrophobic catalyst for recombining H2/D2 and O2 in nuclear reactors

    International Nuclear Information System (INIS)

    A catalyst is developed for efficient recombination of hydrogen and oxygen in presence of water vapor and without requirement of an external heat source. The catalyst, comprising of finely dispersed platinum on a large area polymeric sheet, is hydrophobic in nature and is therefore resistant to water poisoning. The recombination reaction is exothermic which results in the rise of catalyst temperature and hence in its high and automatically sustained catalytic activity. In order to prevent catalyst overheating, the catalyst sheet is sandwiched between the two perforated metallic plates, which help in maintaining the catalyst panel at an isothermal temperature below its melting point. The performance of this catalyst, evaluated on both bench and pilot plant scale, is found to be long lasting. Due to the flexible nature of this catalyst material, different convenient recombiner designs may be envisaged for use in nuclear reactors, either for reaction of radiolytically generated hydrogen and oxygen or for mitigation of hydrogen under severe accident conditions

  11. Autothermal reforming of propane over Ni-based hydrotalcite catalysts.

    Science.gov (United States)

    Park, Sun-Young; Kim, Jong-Ho; Moon, Dong-Ju; Park, Nam-Cook; Kim, Young-Chul

    2010-05-01

    Ni-based hydrotalcite catalysts were investigated for ATR of propane in a fixed-bed flow reactor. The reactions were carried out with a H2O/C/O2 stream ratio of 3/1/0.73 at temperatures ranging from 300 to 700 degrees C. The solvents used in the manufacture of Ni-based catalysts noble metal/Ni/MgAl catalysts or substituted active material were changed in order to decrease the level of catalyst deactivation. The use of a mixture of ethanol and water during the formation of the Pd-Ni/MgAl catalyst produced a higher hydrogen yield than that using water only. In addition, the use of acetone in the synthesis of Ru-Ni/MgAl catalyst produced a higher hydrogen yield than using water only. This shows that the solvents used for the noble metals affect the degree of dispersion and particle size of the nickel and prevented carbon deposition resulting in the enhanced hydrogen selectivity and catalyst activity. Active metals were substituted during the preparation of hydrotalcite catalysts. Among the catalysts prepared with various ratio (Ni:Fe) tested at high temperature, the ratio, Ni:Fe = 75:25, showed best performance. There was less sintering of Ni particles due to substitution of the active metal at the optimal ratio. PMID:20358916

  12. Surface coatings and catalyst production by electrodeposition

    Science.gov (United States)

    May, Chester B.; Riley, Clyde; Coble, H. Dwain; Loo, Boon H.

    1987-01-01

    Electrodeposition and electrocodeposition in low gravity are discussed. The goal is to provide a better understanding of the role of convection and buoyancy in the mechanisms of formation of some electrodeposited surfaces, fluid flow in the vicinity of electrodepositing surfaces, the influence of a moving medium upon codeposition, the effect of gravity upon the dispersion (coagulation) of neutral particles that are desired for codeposition and preparation of improved surface coatings and metal catalysts.

  13. Pt-Re-Sn/Al{sub 2}O{sub 3} trimetallic catalysts for naphtha reforming processes without presulfiding step

    Energy Technology Data Exchange (ETDEWEB)

    Mazzieri, V.A.; Grau, J.M.; Vera, C.R.; Yori, J.C.; Parera, J.M.; Pieck, C.L. [Instituto de Investigaciones en Catalisis y Petroquimica, INCAPE, FIQ-UNL, CONICET, Santiago del Estero 2654, 3000 Santa Fe (Argentina)

    2005-12-12

    The n-heptane reforming and the cyclopentane hydrogenolysis reactions over noble metal monometallic catalysts (0.3% Pt), bimetallic catalysts (0.3% Pt, x% Re, x=0.1, 0.3, 0.9 and 2.0, sulfided) and trimetallic catalysts (0.3% Pt, 0.3% Re, y% Sn, y=0.1, 0.3, 0.6 and 0.9, unsulfided) were studied. The metal function was supported over a chlorided {gamma}-alumina that provided the acid function. The reforming of n-heptane was performed at 450{sup o}C, molar ratio H{sub 2}/n-C{sub 7}=4 and WHSV=7.3 while the hydrogenolysis of cyclopentane was performed at 350{sup o}C, H{sub 2}/CP=20 and WHSV=2.4. The sulfided 0.3Pt-0.3Re catalyst (with 0.06% S) was found to be the best performing bimetallic one. It had a great stability, typical of this kind of catalysts, and also produced a reformate with a high iso-heptanes/toluene ratio. This is advantageous for fulfilling the current environmental regulations that limit the amount of aromatic hydrocarbons in reformulated gasolines. The best trimetallic catalyst was 0.3Pt-0.3Re-0.6Sn which had a similar activity and selectivity as sulfided 0.3Pt-0.3Re, though it displayed a higher stability and a lower hydrogenolysis activity, without the need of presulfidation. Tin affected the metal and acid functions of the catalyst simultaneously and inhibited them to such different degrees that a very convenient metal/acid activity ratio was obtained, resulting in an improvement of the activity, selectivity and stability of the catalysts. It can be concluded that it is possible to prepare trimetallic naphtha reforming catalysts of the Pt-Re-Sn kind with a better performance than conventional sulfided Pt-Re catalysts and with the additional advantage that they do not need complicated sulfiding pretreatments. This simplifies the commercial operation of the reformer unit and enables the application of this catalyst to continuously operated processes.

  14. Tuning the surface electronic structure of a Pt3Ti(111) electro catalyst

    Science.gov (United States)

    Paßens, M.; Caciuc, V.; Atodiresei, N.; Moors, M.; Blügel, S.; Waser, R.; Karthäuser, S.

    2016-07-01

    Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the preparation conditions.Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the

  15. Phytogenic silver, gold, and bimetallic nanoparticles as novel antitubercular agents

    Directory of Open Access Journals (Sweden)

    Singh R

    2016-05-01

    Full Text Available Richa Singh,1 Laxman Nawale,2 Manisha Arkile,2 Sweety Wadhwani,1 Utkarsha Shedbalkar,1 Snehal Chopade,1 Dhiman Sarkar,2 Balu Ananda Chopade1,3 1Department of Microbiology, Savitribai Phule Pune University, 2Combichem-Bioresource Center, Organic Chemistry Division, National Chemical Laboratory, Pune, 3Dr Babasaheb Ambedkar Marathwada University, Aurangabad, Maharashtra, India Purpose: Multi- and extensively drug-resistant tuberculosis (TB is a global threat to human health. It requires immediate action to seek new antitubercular compounds and devise alternate strategies. Nanomaterials, in the present scenario, have opened new avenues in medicine, diagnosis, and therapeutics. In view of this, the current study aims to determine the efficacy of phytogenic metal nanoparticles to inhibit mycobacteria. Methods: Silver (AgNPs, gold (AuNPs, and gold–silver bimetallic (Au–AgNPs nanoparticles synthesized from medicinal plants, such as Barleria prionitis, Plumbago zeylanica, and Syzygium cumini, were tested against Mycobacterium tuberculosis and M. bovis BCG. In vitro and ex vivo macrophage infection model assays were designed to determine minimum inhibitory concentration (MIC and half maximal inhibitory concentration of nanoparticles. Microscopic analyses were carried out to demonstrate intracellular uptake of nanoparticles in macrophages. Besides this, biocompatibility, specificity, and selectivity of nanoparticles were also established with respect to human cell lines. Results: Au–AgNPs exhibited highest antitubercular activity, with MIC of <2.56 µg/mL, followed by AgNPs. AuNPs did not show such activity at concentrations of up to 100 µg/mL. In vitro and ex vivo macrophage infection model assays revealed the inhibition of both active and dormant stage mycobacteria on exposure to Au–AgNPs. These nanoparticles were capable of entering macrophage cells and exhibited up to 45% cytotoxicity at 30 µg/mL (ten times MIC concentration after 48 hours

  16. Phytogenic silver, gold, and bimetallic nanoparticles as novel antitubercular agents

    Science.gov (United States)

    Singh, Richa; Nawale, Laxman; Arkile, Manisha; Wadhwani, Sweety; Shedbalkar, Utkarsha; Chopade, Snehal; Sarkar, Dhiman; Chopade, Balu Ananda

    2016-01-01

    Purpose Multi- and extensively drug-resistant tuberculosis (TB) is a global threat to human health. It requires immediate action to seek new antitubercular compounds and devise alternate strategies. Nanomaterials, in the present scenario, have opened new avenues in medicine, diagnosis, and therapeutics. In view of this, the current study aims to determine the efficacy of phytogenic metal nanoparticles to inhibit mycobacteria. Methods Silver (AgNPs), gold (AuNPs), and gold–silver bimetallic (Au–AgNPs) nanoparticles synthesized from medicinal plants, such as Barleria prionitis, Plumbago zeylanica, and Syzygium cumini, were tested against Mycobacterium tuberculosis and M. bovis BCG. In vitro and ex vivo macrophage infection model assays were designed to determine minimum inhibitory concentration (MIC) and half maximal inhibitory concentration of nanoparticles. Microscopic analyses were carried out to demonstrate intracellular uptake of nanoparticles in macrophages. Besides this, biocompatibility, specificity, and selectivity of nanoparticles were also established with respect to human cell lines. Results Au–AgNPs exhibited highest antitubercular activity, with MIC of <2.56 μg/mL, followed by AgNPs. AuNPs did not show such activity at concentrations of up to 100 μg/mL. In vitro and ex vivo macrophage infection model assays revealed the inhibition of both active and dormant stage mycobacteria on exposure to Au–AgNPs. These nanoparticles were capable of entering macrophage cells and exhibited up to 45% cytotoxicity at 30 μg/mL (ten times MIC concentration) after 48 hours. Among these, Au–AgNPs synthesized from S. cumini were found to be more specific toward mycobacteria, with their selectivity index in the range of 94–108. Conclusion This is the first study to report the antimycobacterial activity of AuNPs, AgNPs, and Au–AgNPs synthesized from medicinal plants. Among these, Au–AgNPs from S. cumini showed profound efficiency, specificity, and

  17. Role of clay as catalyst in Friedel–Craft alkylation

    Indian Academy of Sciences (India)

    Tanushree Choudhury; Nirendra M Misra

    2011-10-01

    Solid acids have become increasingly important for many liquid-phase industrial reactions these days. Montmorillonite clays (2:1 clay mineral) have been used as efficient solid acid catalysts for a number of organic and liquid phase reactions and offer several advantages over classic acids. Tailor made catalysts can be prepared from clays by suitably adjusting their acidity and surface area by acid activation. In the present work, preparation, characterization and performance of Pt (II) clays, Cu (II) clays, acid clay, and sol–gel hybrids of Cu (II) clays as solid catalysts in a test Friedel–Craft alkylation reaction of benzyl chloride with toluene using differential scanning calorimeter (DSC) are reported. Product formation has been analysed by FTIR spectroscopy. The main objective of this work is to show how clay as a solid catalyst affects reaction rates and activation energies. Acidity and dispersion of solid catalysts are twomain factors which govern a catalysis reaction. Kinetic parameter analysis and XRD studies confirm that acid Pt (II) clay and Pt (II) clay dispersed by natural dispersants aremore effective catalysts. In contrast to the reactions using AlCl3, the experimental conditions are non-polluting and the final work up does not require any aqueous treatment.

  18. Thermo-mechanical efficiency of the bimetallic strip heat engine at the macro-scale and micro-scale

    Science.gov (United States)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2015-10-01

    Bimetallic strip heat engines are energy harvesters that exploit the thermo-mechanical properties of bistable bimetallic membranes to convert heat into mechanical energy. They thus represent a solution to transform low-grade heat into electrical energy if the bimetallic membrane is coupled with an electro-mechanical transducer. The simplicity of these devices allows us to consider their miniaturization using MEMS fabrication techniques. In order to design and optimize these devices at the macro-scale and micro-scale, this article proposes an explanation of the origin of the thermal snap-through by giving the expressions of the constitutive equations of composite beams. This allows us to evaluate the capability of bimetallic strips to convert heat into mechanical energy whatever their size is, and to give the theoretical thermo-mechanical efficiencies which can be obtained with these harvesters.

  19. Thermo-mechanical efficiency of the bimetallic strip heat engine at the macro-scale and micro-scale

    International Nuclear Information System (INIS)

    Bimetallic strip heat engines are energy harvesters that exploit the thermo-mechanical properties of bistable bimetallic membranes to convert heat into mechanical energy. They thus represent a solution to transform low-grade heat into electrical energy if the bimetallic membrane is coupled with an electro-mechanical transducer. The simplicity of these devices allows us to consider their miniaturization using MEMS fabrication techniques. In order to design and optimize these devices at the macro-scale and micro-scale, this article proposes an explanation of the origin of the thermal snap-through by giving the expressions of the constitutive equations of composite beams. This allows us to evaluate the capability of bimetallic strips to convert heat into mechanical energy whatever their size is, and to give the theoretical thermo-mechanical efficiencies which can be obtained with these harvesters. (paper)

  20. BIODIESEL PRODUCTION FROM MICROALGAE OVER HETEROGENEOUS CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    M. Tuncer; E. S. Umdu; E. Kursat; G. Yilmaz; E. Seker [Izmir Institute of Technology, Faculty of Engineering, Department of Chemical Engineering, Guelbahce Campus, Izmir (Turkey); Y. Durmaz; S. Gokpinar [Ege University, Faculty of Fisheries, Department of Aquaculture, Izmir (Turkey)

    2008-09-30

    The aim of this study is to produce biodiesel from yellow green algae (Nannochloropsis oculata) by using heterogeneous catalysts. Nannochloropsis oculata was preferred due to its high triglyceride content. N. oculata were grown in a batch culture using a flat plate type photobioreactor. After reaching the stationary phase, the algae were harvested, centrifuged and vacuum dried. Its lipid was extracted by using n-hexane. Finally, lipid-hexane mixture was subjected to the transesterification at 50 C using methanol and alumina supported CaO and MgO catalysts. We found that CaO nano-crystals were obtained on 80 wt.% CaO/Al{sub 2}O{sub 3} catalysts, hence resulting in a high CaO dispersion. Our activity results show that the biodiesel yield obtained using CaO and MgO on Al{sub 2}O{sub 3} catalysts was a factor of two higher than that obtained with NaOH catalyst under the same reaction condition.