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Sample records for bimetallic model catalysts

  1. Bi-metallic catalysts, methods of making, and uses thereof

    KAUST Repository

    Basset, Jean-Marie

    2017-01-19

    Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

  2. 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)

  3. Naphtha reforming on mono and bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Querini, C.A.; Figoli, N.S.; Parera, J.M.

    1987-07-15

    Catalytic activity, selectivity and stability in the reforming of several naphtha cuts on Pt/Al/sub 2/O/sub 3/, Pt-Re-S/Al/sub 2/O/sub 3/ and Pt-Ge/Al/sub 2/O/sub 3/ were studied by carrying out activity-deactivation tests which consist of three periods. During the first and third periods, industrial conditions were reproduced, and during the second one, pressure and H/sub 2//hydrocarbon ratio were decreased in order to accelerate the deactivation. The results are compared with those obtained in the reforming of n-paraffins and cyclopentanes, showing an agreement with the qualitative performance of the catalysts. Pt-Re-S/Al/sub 2/O/sub 3/ is the most active catalyst; Pt-Ge/Al/sub 2/O/sub 3/ is the one showing the largest liquid yield, and Pt/Al/sub 2/O/sub 3/ is the catalyst producing the largest volume of gas. Coke deposited on the catalysts shows a minimum for a feed with a mean boiling point of 100 C. This minimum, on one hand is the result of the greater coking capacity of the naphthenes with five carbon atom rings present in the lighter cuts and, on the other hand, is caused by the presence of 8, 9 and 10 carbon atom paraffins and aromatics present in the heavier cuts. From the results obtained on each of the catalysts, reactor performance can be improved using simultaneously two bimetallic catalysts in separate beds. 13 refs.

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

    Science.gov (United States)

    Marks, Tobin J [Evanston, IL; Rodriguez, Brandon A [Evanston, IL; Delferro, Massimiliano [Chicago, IL

    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.

  5. NOVEL SUPPORTED BIMETALLIC CARBIDE CATALYSTS FOR COPROCESSING OF COAL WITH WASTE METERIALS

    Energy Technology Data Exchange (ETDEWEB)

    S. Ted Oyama; David F. Cox; Chunshan Song; Fred Allen; Weilin Wang; Viviane Schwartz; Xinqin Wang; Jianli Yang

    2001-01-01

    The overall objectives of this project are to explore the potential of novel monometallic and bimetallic Mo-based carbide catalysts for heavy hydrocarbon coprocessing, and to understand the fundamental chemistry related to the reaction pathways of coprocessing and the role of the catalysts in the conversion of heavy hydrocarbon resources into liquid fuels based on the model compound reactions.

  6. 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.

  7. Efficient utilization of bimetallic catalyst in low environment syngas ...

    Indian Academy of Sciences (India)

    Sonal

    2017-10-26

    Oct 26, 2017 ... Special Issue on Recent Trends in the Design and Development of Catalysts and their Applications. Efficient utilization of bimetallic catalyst ... norms, the research is diverted towards Fisher Tropsch synthesis route. .... was done in GCMS and quantitative analysis was done using simulative distillation taking ...

  8. Balance of Nanostructure and Bimetallic Interactions in Pt Model Fuel Cell Catalysts

    DEFF Research Database (Denmark)

    Friebel, Daniel; Viswanathan, Venkatasubramanian; Miller, Daniel J.

    2012-01-01

    We have studied the effect of nanostructuring in Pt monolayer model electrocatalysts on a Rh(111) single-crystal substrate on the adsorption strength of chemisorbed species. In situ high energy resolution fluorescence detection X-ray absorption spectroscopy at the Pt L3 edge reveals characteristi...

  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, flat...... 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....

  10. Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

    Science.gov (United States)

    Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

    2016-01-01

    This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated. PMID:28773672

  11. Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

    Directory of Open Access Journals (Sweden)

    Magda Blosi

    2016-07-01

    Full Text Available This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF to 2,5-furandicarboxylic acid (FDCA. The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    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.......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...

  13. 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.

  14. 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

    , we report a more detailed catalytic study aimed at optimizing the catalyst performance. For this purpose, two series of mono and bimetallic Ni-Fe catalysts supported on MgAl2O4 and Al2O3, respectively, were prepared. All catalysts were tested in the CO methanation reaction in the temperature interval...

  15. Decomposition kinetics of ammonia in gaseous stream by a nanoscale copper-cerium bimetallic catalyst.

    Science.gov (United States)

    Hung, Chang-Mao

    2008-01-15

    This study performance is to examine the kinetics over nanoscale copper-cerium bimetallic catalyst under selective catalytic oxidation (SCO) of ammonia to N(2) in a tubular fixed-bed reactor (TFBR) at temperatures from 150 to 400 degrees C in the presence of oxygen. The nanoscale copper-cerium bimetallic catalyst was prepared by co-precipitation with Cu(NO(3))(2) and Ce(NO(3))(3) at molar ratio of 6:4. Experimental results showed that the catalyst with transmission electron microscopy (TEM) revealed that copper and cerium are well dispersed and catalyst in the form of nanometer-sized particles. Moreover, the kinetic behavior of NH(3) oxidation with catalysis can be accounted by using the rate expression of the Langmuir-Hinshelwood type kinetic model. Kinetic parameters are also developed on the basis of the differential reactor data. Also, experimental results are compared with those of the model predicted.

  16. Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction.

    Science.gov (United States)

    Hansgen, Danielle A; Vlachos, Dionisios G; Chen, Jingguang G

    2010-06-01

    The facile decomposition of ammonia to produce hydrogen is critical to its use as a hydrogen storage medium in a hydrogen economy, and although ruthenium shows good activity for catalysing this process, its expense and scarcity are prohibitive to large-scale commercialization. The need to develop alternative catalysts has been addressed here, using microkinetic modelling combined with density functional studies to identify suitable monolayer bimetallic (surface or subsurface) catalysts based on nitrogen binding energies. The Ni-Pt-Pt(111) surface, with one monolayer of Ni atoms residing on a Pt(111) substrate, was predicted to be a catalytically active surface. This was verified using temperature-programmed desorption and high-resolution electron energy loss spectroscopy experiments. The results reported here provide a framework for complex catalyst discovery. They also demonstrate the critical importance of combining theoretical and experimental approaches for identifying desirable monolayer bimetallic systems when the surface properties are not a linear function of the parent metals.

  17. 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.

  18. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schoeb, Ann M. [Iowa State Univ., Ames, IA (United States)

    1997-10-17

    The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO2 catalysts for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO2, Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.

  19. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    Science.gov (United States)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

  20. Bimetallic Pt-Ru Nanoparticle Catalyst for Hydrogen Peroxide Detection

    Directory of Open Access Journals (Sweden)

    Metini Janyasupab

    2011-01-01

    Full Text Available A bimetallic Pt-Ru nanoparticle catalyst was prepared and characterized for the enhancement of hydrogen peroxide (H2O2 detection in biosensing applications. The particles were synthesized via sodium borohydride reduction, with low heat treatment, and characterized by TEM and HRTEM. The chemical composition analyses were performed by EDX. The bimetallic particle diameters ranged from 2 to 12 nm, with an average of 4.5 nm. The Pt-Ru catalyst exhibited an improved performance at low overpotential (+0.2 V versus Ag/AgCl reference electrode in H2O2 detection, suggesting a sensitivity value of 78.95 μA⋅mM-1 (or 402.1 μA⋅mM-1⋅cm-2 which was 30% higher than that for the single Pt catalyst. The major contribution of this enhancement comes from the stronger oxygen adsorption on Ru metal. The Pt-Ru catalyst also showed a more stable signal at the high overpotential (+0.4 V versus Ag/AgCl, providing better accuracy in the detection of H2O2.

  1. Regeneration of sulfur-fouled bimetallic Pd-based catalysts.

    Science.gov (United States)

    Chaplin, Brian P; Shapley, John R; Werth, Charles J

    2007-08-01

    Pd-based catalysts provide efficient and selective reduction of several drinking water contaminants, but their long-term application requires effective treatments for catalyst regeneration following fouling by constituents in natural waters. This studytested alumina-supported Pd-Cu and Pd-In bimetallic catalysts for nitrate reduction with H2 after sulfide fouling and oxidative regeneration procedures. Both catalysts were severely deactivated after treatment with microM levels of sulfide. Regeneration was attempted with dissolved oxygen, hydrogen peroxide, sodium hypochlorite, and heated air. Only sodium hypochlorite and heated air were effective regenerants, specifically restoring nitrate reduction rates for a Pd-In/gamma-Al2O3 catalyst from 20% to between 39 and 60% of original levels. Results from ICP-MS revealed that sodium hypochlorite caused dissolution of Cu from the Pd-Cu catalyst but that the Pd-In catalyst was chemically stable over a range of sulfide fouling and oxidative regenerative conditions. Analysis byXPS indicated that PdS and In2S3 complexes form during sulfide fouling, where sulfur is present as S2-, and that regeneration with sodium hypochlorite converts a portion of the S2- to S6+, with a corresponding increase in reduction rates. These results indicate that Pd-In catalysts show exceptional promise for being robust under fouling and regeneration conditions that may occur when treating natural waters.

  2. Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

    International Nuclear Information System (INIS)

    Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

    2016-01-01

    Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N 2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d 5/2 shifted to higher positions while that of Au 4f 7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity

  3. Catalytic reforming of glycerol in supercritical water over bimetallic Pt-Ni catalyst

    NARCIS (Netherlands)

    Chakinala, A.G.; van Swaaij, Willibrordus Petrus Maria; Kersten, Sascha R.A.; de Vlieger, Dennis; Seshan, Kulathuiyer; Brilman, Derk Willem Frederik

    2013-01-01

    Catalytic reforming of pure glycerol for the production of hydrogen at low temperature and short residence times in supercritical water was investigated using a bimetallic Pt–Ni catalyst supported on alumina. Initial tests were carried out to study the reforming activity of bimetallic Pt–Ni

  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. Structural Characteristics of Bimetallic Catalysts Supported on Nano-Ceria

    Directory of Open Access Journals (Sweden)

    J. F. Bozeman

    2011-01-01

    Full Text Available Cu-Pt bimetal catalysts supported on nanocrystalline CeO2 (nano-ceria are synthesized via the low-cost sol-gel approach followed by impregnation processing. The average particle size of the catalytic composites is 63 nm. Ceria nanopowders sequentially impregnated in copper solution and then in Pt solution transformed into Pt-skin-structured Cu-Pt/ceria nanocomposite, based on the surface elemental and bulk compositional analyses. The ceria supporter has a fluorite structure, but the structure of Cu and Pt catalytic contents, not detected by X-ray diffraction spectroscopy due to the low loading level, is yet conclusive. The bimetallic catalytic nanocomposites may potentially serve as sulfur-tolerant anode in solid oxide fuel cells.

  6. Fundamental studies of hydrogen interaction with supported meta and bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bhatia, Sandeep [Iowa State Univ., Ames, IA (United States)

    1993-12-07

    The thesis is divided into 3 parts: interaction of H with silica supported Ru catalysts (high pressure in situ NMR), in situ NMR study of H interaction with supported Ru-group IB bimetallic catalysts, and in-situ NMR study of H effects on silica-supported Pt, Rh and Ru catalysts.

  7. Balance of Nanostructure and Bimetallic Interactions in Pt Model Fuel Cell Catalysts: An in Situ XAS and DFT Study

    Energy Technology Data Exchange (ETDEWEB)

    Friebel, Daniel; Viswanathan, Venkatasubramanian; Miller, Daniel James; Anniyev, Toyli; Ogasawara, Hirohito; Larsen, Ask Hjorth; O' Grady, Christopher P.; Norskov, Jens K.; Nilsson, Anders

    2012-05-31

    We have studied the effect of nanostructuring in Pt monolayer model electrocatalysts on a Rh(111) single-crystal substrate on the adsorption strength of chemisorbed species. In situ high energy resolution fluorescence detection X-ray absorption spectroscopy at the Pt L(3) edge reveals characteristic changes of the shape and intensity of the 'white-line' due to chemisorption of atomic hydrogen (H(ad)) at low potentials and oxygen-containing species (O/OH(ad)) at high potentials. On a uniform, two-dimensional Pt monolayer grown by Pt evaporation in ultrahigh vacuum, we observe a significant destabilization of both H(ad) and O/OH(ad) due to strain and ligand effects induced by the underlying Rh(111) substrate. When Pt is deposited via a wet-chemical route, by contrast, three-dimensional Pt islands are formed. In this case, strain and Rh ligand effects are balanced with higher local thickness of the Pt islands as well as higher defect density, shifting H and OH adsorption energies back toward pure Pt. Using density functional theory, we calculate O adsorption energies and corresponding local ORR activities for fcc 3-fold hollow sites with various local geometries that are present in the three-dimensional Pt islands.

  8. 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

  9. 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.

  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. A Review on Bimetallic Nickel-Based Catalysts for CO2Reforming of Methane.

    Science.gov (United States)

    Bian, Zhoufeng; Das, Sonali; Wai, Ming Hui; Hongmanorom, Plaifa; Kawi, Sibudjing

    2017-11-17

    In recent years, CO 2 reforming of methane (dry reforming of methane, DRM) has become an attractive research area because it converts two major greenhouse gasses into syngas (CO and H 2 ), which can be directly used as fuel or feedstock for the chemical industry. Ni-based catalysts have been extensively used for DRM because of its low cost and good activity. A major concern with Ni-based catalysts in DRM is severe carbon deposition leading to catalyst deactivation, and a lot of effort has been put into the design and synthesis of stable Ni catalysts with high carbon resistance. One effective and practical strategy is to introduce a second metal to obtain bimetallic Ni-based catalysts. The synergistic effect between Ni and the second metal has been shown to increase the carbon resistance of the catalyst significantly. In this review, a detailed discussion on the development of bimetallic Ni-based catalysts for DRM including nickel alloyed with noble metals (Pt, Ru, Ir etc.) and transition metals (Co, Fe, Cu) is presented. Special emphasis has been provided on the underlying principles that lead to synergistic effects and enhance catalyst performance. Finally, an outlook is presented for the future development of Ni-based bimetallic catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Catalytic reduction of N2O over Ag-Pd/Al2O3 bimetallic catalysts.

    Science.gov (United States)

    Tzitzios, V K; Georgakilas, V

    2005-05-01

    A study of the catalytic conversion of N2O to N2 over a bimetallic Ag-Pd catalyst is described in this article. Several Ag-Pd catalytic systems were prepared supported on Al2O3 with different ratios and their catalytic activity for the direct decomposition of N2O and their reduction with CO was measured. Based on the experimental results, it was observed that Ag-Pd bimetallic catalyst (5-0.5%) was the most active for both nitrous oxide reduction and direct decomposition. This high activity seems to be connected with a synergistic effect between Ag and Pd.

  13. From First Principles Design to Realization of Bimetallic Catalysts for Ultrahigh Selectivity - Final Project Report

    Energy Technology Data Exchange (ETDEWEB)

    Richard M. Crooks

    2007-04-11

    (A) Synthesis, Characterization, and Fundamental Properties of Bimetallic DENs. AuAg alloy and core/shell bimetallic DENs were synthesized and characterized. Selective extraction was used as a structural characterization tool for these bimetallic nanoparticles. This is significant because there are few easily accessible methods for structure elucidation of bimetallic nanoparticles in this size regime. As a first step towards the synthesis of catalytically active, bimetallic heterogeneous materials we reported the incorporation of Au and Pd monometallic DENs and AuPd bimetallic DENs into amorphous titania networks. The compositional fidelity of the original DENs, and to some extent their size, is retained following dendrimer removal. Gas-phase catalytic activity for CO oxidation is higher for the bimetallic catalysts than for the corresponding Pd-only and Au-only monometallics. (B) Electrocatalysts based on dendrimer-encapsulated nanoparticles. Platinum dendrimer-encapsulated nanoparticles (DENs) were prepared within fourth-generation, hydroxyl-terminated, poly(amidoamine) dendrimers and immobilized on glassy carbon electrodes using an electrochemical immobilization strategy. X-ray photoelectron spectroscopy, electron microscopy, and electrochemical experiments confirm that the Pt DENs are about 1.4 nm in diameter and that they remain within the dendrimer following surface immobilization. The resulting Pt DEN films were electrocatalytically active for the oxygen reduction reaction (ORR). The films are also robust, surviving up to 50 consecutive cyclic voltammograms and sonication. Monometallic Pd DENs were also prepared and found to have little catalytic activity for the ORR. However, PtPd bimetallic DENs had catalytic activity nearly identical to that found for Pt-only DENs. This indicates an overall catalytic enhancement for the bimetallic electrocatalysts.

  14. Efficient low-temperature soot combustion by bimetallic Ag-Cu/SBA-15 catalysts.

    Science.gov (United States)

    Wen, Zhaojun; Duan, Xinping; Hu, Menglin; Cao, Yanning; Ye, Linmin; Jiang, Lilong; Yuan, Youzhu

    2018-02-01

    In this study, the effects of copper (Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag-Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5Ag 1 -Cu 0.1 /SBA-15 catalyst, on which the soot combustion starts at T ig =225°C with a T 50 =285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C (Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag-Cu nanolloy particles, downsizing the mean particle size from 3.7nm in monometallic catalyst to 2.6nm in bimetallic Ag-Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance. Copyright © 2017. Published by Elsevier B.V.

  15. 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

  16. Bimetallic catalysts for HI decomposition in the iodine-sulfur thermochemical cycle

    International Nuclear Information System (INIS)

    Wang Laijun; Hu Songzhi; Xu Lufei; Li Daocai; Han Qi; Chen Songzhe; Zhang Ping; Xu Jingming

    2014-01-01

    Among the different kinds of thermochemical water-splitting cycles, the iodine-sulfur (IS) cycle has attracted more and more interest because it is one of the promising candidates for economical and massive hydrogen production. However, there still exist some science and technical problems to be solved before industrialization of the IS process. One such problem is the catalytic decomposition of hydrogen iodide. Although the active carbon supported platinum has been verified to present the excellent performance for HI decomposition, it is very expensive and easy to agglomerate under the harsh condition. In order to decrease the cost and increase the stability of the catalysts for HI decomposition, a series of bimetallic catalysts were prepared and studied at INET. This paper summarized our present research advances on the bimetallic catalysts (Pt-Pd, Pd-Ir and Pt-Ir) for HI decomposition. In the course of the study, the physical properties, structure, and morphology of the catalysts were characterized by specific surface area, X-ray diffractometer; and transmission electron microscopy, respectively. The catalytic activity for HI decomposition was investigated in a fixed bed reactor under atmospheric pressure. The results show that due to the higher activity and better stability, the active carbon supported bimetallic catalyst is more potential candidate than mono metallic Pt catalyst for HI decomposition in the IS thermochemical cycle. (author)

  17. 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.

  18. Modeling of a bimetallic MEMS-based infrared detector

    Science.gov (United States)

    Pevtsov, E. Ph; Breev, S. V.; Demenkova, T. A.

    2018-01-01

    In work techniques of calculations of the key parameters of the bimetal capacitive IR detectors matrix are presented. Sensitivity characteristics of the bimetal detector were calculated and prototype model of detector in the form of bimetallic console was produced. The possibility of use of capacitive MEMS-receivers on basis of bimetallic effect as an alternative to pyroelectric and microbolometer IR detectors is shown.

  19. Activity and selectivity modifications produced by coke deposition on mono- and bimetallic reforming catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Querini, C.A.; Figoli, N.S.; Parera, J.M.

    1989-08-15

    Modifications of the activity and selectivity of mono- and bimetallic catalysts induced by coke were studied. A mixture of cyclohexane and n-pentane was used as the feed in order to follow typical reforming reactions such as hydrogenolysis, dehydrogenation, isomerization and ring contraction. The catalysts were previously coked by means of accelerated deactivation tests. There were significant modifications to the catalyst selectivity with coke content. The ring contraction of cyclohexane into methylcyclopentane was the only reaction for which the coked catalysts were more active than the fresh catalysts. The concept of 'indirect control' of the metal function in the conversion of cyclohexane into methylcyclopentane is introduced in order to explain that the metal is not the location where the slowest step in the above conversion occurs, but that where cyclohexane is rapidly converted into benzene. 4 figs., 20 refs., 4 tabs.

  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. Bimetallic platinum group metal-free catalysts for high power generating microbial fuel cells.

    Science.gov (United States)

    Kodali, Mounika; Santoro, Carlo; Herrera, Sergio; Serov, Alexey; Atanassov, Plamen

    2017-10-31

    M1-M2-N-C bimetallic catalysts with M1 as Fe and Co and M2 as Fe, Co, Ni and Mn were synthesized and investigated as cathode catalysts for oxygen reduction reaction (ORR). The catalysts were prepared by Sacrificial Support Method in which silica was the template and aminoantipyrine (AAPyr) was the organic precursor. The electro-catalytic properties of these catalysts were investigated by using rotating ring disk (RRDE) electrode setup in neutral electrolyte. Fe-Mn-AAPyr outperformed Fe-AAPyr that showed higher performances compared to Fe-Co-AAPyr and Fe-Ni-AAPyr in terms of half-wave potential. In parallel, Fe-Co-AAPyr, Co-Mn-AAPyr and Co-Ni-AAPyr outperformed Co-AAPyr. The presence of Co within the catalyst contributed to high peroxide production not desired for efficient ORR. The catalytic capability of the catalysts integrated in air-breathing cathode was also verified. It was found that Co-based catalysts showed an improvement in performance by the addition of second metal compared to simple Co- AAPyr. Fe-based bimetallic materials didn't show improvement compared to Fe-AAPyr with the exception of Fe-Mn-AAPyr catalyst that had the highest performance recorded in this study with maximum power density of 221.8 ± 6.6 μWcm -2 . Activated carbon (AC) was used as control and had the lowest performances in RRDE and achieved only 95.6 ± 5.8 μWcm -2 when tested in MFC.

  2. Study of selective Fischer-Tropsch catalysts synthesized by the destruction of bimetallic carbonyl complexes on activated γ-Al2O3 support

    International Nuclear Information System (INIS)

    Maksimov, Yu.V.; Matveev, V.V.; Suzdalev, I.P.; Khomenko, T.I.; Kadushin, A.A.

    1990-01-01

    The bimetallic catalysts obtained by the deposition of a Fe-Co binuclear cluster on the dehydroxylated γ-Al 2 O 3 are studied and compared to some other relative systems. These bimetallic catalysts are found to be active and selective in olefin synthesis. This is connected with the formation of Fe-Co contact which is detectable by Moessbauer spectroscopy. (orig.)

  3. Preparation of Pt–Ru bimetallic catalyst supported on carbon ...

    Indian Academy of Sciences (India)

    Unknown

    ssion electron microscopic investigation reveals that Pt–Ru nanoparticles are highly dispersed inside the tube with an average particle size of 1⋅7 nm. Keywords. Carbon nanotubes; template synthesis; fuel cell catalyst; nanoparticles. 1. Introduction. There is a considerable interest currently in developing nanostructured ...

  4. 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.

  5. Bimetallic Ag–Ni/C particles as cathode catalyst in AFCs (alkaline fuel cells)

    International Nuclear Information System (INIS)

    Song, Xingjuan; Zhang, Dongming

    2014-01-01

    AFCs (alkaline fuel cells) is one of the promising fuel cells, due to their low working temperature and less corrosive environment. However, decreasing the catalyst cost and improving its performance are still the challenges in its application. Transition metal as the catalyst for AFCs not only can reduce its cost, but also has great electro-catalytic efficiency. In this paper, Carbon supported Ag–Ni bimetallic catalysts with differential Ag/Ni atomic ratios were prepared by chemically reducing silver and nickel salts. Ag 3 Ni/C shows the relatively higher ORR (oxygen reduction reaction) activity among the differential Ag/Ni bimetallic particles. In order to improve the activity and stability, the catalysts were heat-treated at the temperature of 500 °C. The results indicate that the limiting current density has been improved greatly for Ag 3 Ni/C-500 °C, which is as high as 2.5× that of Ag/C. The microstructure investigation show that the non-equilibrium state of Ag–Ni alloy by heat treatment is confirmed by HRTEM (high-resolution transmission electron microscopy) images, and Ag(111) surfaces are decreased in XRD pattern, which results in the ORR activity improved and overpotential decreased. Heat treatment also has contributed to Ag–Ni/C electrochemistry stability in some degree. - Highlights: • Ag–Ni/C is applied as cathode catalyst for AFCs (alkaline fuel cells). • Ag 3 Ni/C-500 °C shows the best performance. • Non-equilibrium state of Ag–Ni alloy by heat treatment is observed. • The decreased Ag(111) surfaces are favor to improve the catalyst activity

  6. 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.

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

    International Nuclear Information System (INIS)

    Huang, Chao; Yang, Xu; Yang, Hui; Huang, Peiyan; Song, Huiyu; Liao, Shijun

    2014-01-01

    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

  8. 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.

  9. Catalyst design for carbon nanotube growth using atomistic modeling

    International Nuclear Information System (INIS)

    Pint, Cary L; Bozzolo, Guillermo; Hauge, Robert

    2008-01-01

    The formation and stability of bimetallic catalyst particles, in the framework of carbon nanotube growth, is studied using the Bozzolo-Ferrante-Smith (BFS) method for alloys. Monte Carlo-Metropolis simulations with the BFS method are utilized in order to predict and study equilibrium configurations for nanoscale catalyst particles which are directly relevant to the catalyst state prior to growth of carbon nanotubes. At the forefront of possible catalyst combinations is the popular Fe-Mo bimetallic catalyst, which we have recently studied experimentally. We explain our experimental results, which indicate that the growth observed is dependent on the order of co-catalyst deposition, in the straightforward interpretation of BFS strain and chemical energy contributions toward the formation of Fe-Mo catalyst prior to growth. We find that the competition between the formation of metastable inner Mo cores and clusters of surface-segregated Mo atoms in Fe-Mo catalyst particles influences catalyst formation, and we investigate the role of Mo concentration and catalyst particle size in this process. Finally, we apply the same modeling approach to other prominent bimetallic catalysts and suggest that this technique can be a powerful tool to understand and manipulate catalyst design for highly efficient carbon nanotube growth

  10. Synthesis of Highly Dispersed and Highly Stable Supported Au–Pt Bimetallic Catalysts by a Two-Step Method

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaofeng; Zhao, Haiyan; Wu, Tianpin; Liu, Yuzi; Liang, Xinhua

    2016-11-01

    Highly dispersed and highly stable supported bimetallic catalysts were prepared using a two-step process. Pt nanoparticles (NPs) were first deposited on porous γ-Al2O3 particles by atomic layer deposition (ALD). Au NPs were synthesized by using gold(III) chloride as the Au precursor, and then immobilized on ALD Pt/γ-Al2O3 particles. The Au–Pt bimetallic catalysts were highly active and highly stable in a vigorously stirred liquid phase reaction of glucose oxidation.

  11. 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.

  12. 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.

  13. 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.

  14. Electrocatalysis of fuel cells reaction on Pt and Pt-bimetallic anode catalysts: A selective review

    Directory of Open Access Journals (Sweden)

    Stamenković Vojislav

    2002-01-01

    Full Text Available In this review we selectively summarize recent progress, primarily from our laboratory, in the development of interrelationships between the kinetics of the fuel cells reactions and the structure/composition of anode catalysts. The focus is placed on two types of metallic surfaces: platinum single crystals and bimetallic surfaces based on Pt. In the first part it was illustrated that the hydcogen reaction is structure sensitive process, with Pt(110 being an order of magnitude more active than either of the atomically "flatter" (100 and (111 surfaces. The hydrogen reaction on Pt(hkl modified by pseudomorphic Pd (submonolayers shows the "volcano-like" behavior, having the maximum rate on Pt(111 modified by 1 ML of Pd. The Pt(111-Pd system is used to demonstrate how the energetics of intermediates formed in the hydrogen reaction is affected by interfacial bonding and energetic constraints produced between pseudomorphic Pd films and the Pt(111 substrate. In the second part it was shown that the oxidation of Ha in the presence of CO occurs concurrently with CO oxidation on Pt and Pt bimetallic surfaces. The Pt-Ru system is used to demonstrate that both the bifunctional effect and the ligand effect contribute to the influence of Ru on the CO oxidation rate and for Hz oxidation process in the presence of CO. The knowledge is then used to create the real-life catalyst with the catalytic activities which are, to the greatest extend possible similar to the tailor-made surface.

  15. Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz

    2009-12-01

    Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

  16. Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

    Energy Technology Data Exchange (ETDEWEB)

    Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

    2015-03-24

    Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

  17. 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.

  18. Developing a Thermal- and Coking-Resistant Cobalt-Tungsten Bimetallic Anode Catalyst for Solid Oxide Fuel Cells

    NARCIS (Netherlands)

    Yan, N.; Pandey, J.; Zeng, Y.; Amirkhiz, B.S.; Hua, B.; Geels, N.J.; Luo, J.L.; Rothenberg, G.

    2016-01-01

    We report the development of a novel Co–W bimetallic anode catalyst for solid oxide fuel cells (SOFCs) via a facile infiltration-annealing process. Using various microscopic and spectroscopic measurements, we find that the formed intermetallic nanoparticles are highly thermally stable up to 900 °C

  19. Effects of doping in 25-atom bimetallic nanocluster catalysts for carbon–carbon coupling reaction of iodoanisole and phenylacetylene

    Directory of Open Access Journals (Sweden)

    Zhimin Li

    2016-10-01

    Full Text Available We here report the catalytic effects of foreign atoms (Cu, Ag, and Pt doped into well-defined 25-gold-atom nanoclusters. Using the carbon-carbon coupling reaction of p-iodoanisole and phenylacetylene as a model reaction, the gold-based bimetallic MxAu25−x(SR18 (–SR=–SCH2CH2Ph nanoclusters (supported on titania were found to exhibit distinct effects on the conversion of p-iodoanisole as well as the selectivity for the Sonogashira cross-coupling product, 1-methoxy-4-(2-phenylethynylbenzene. Compared to Au25(SR18, the centrally doped Pt1Au24(SR18 causes a drop in catalytic activity but with the selectivity retained, while the AgxAu25−x(SR18 nanoclusters gave an overall performance comparable to Au25(SR18. Interestingly, CuxAu25−x(SR18 nanoclusters prefer the Ullmann homo-coupling pathway and give rise to product 4,4′-dimethoxy-1,1′-biphenyl, which is in opposite to the other three nanocluster catalysts. Our overall conclusion is that the conversion of p-iodoanisole is largely affected by the electronic effect in the bimetallic nanoclusters’ 13-atom core (i.e., Pt1Au12, CuxAu13−x, and Au13, with the exception of Ag doping, and that the selectivity is primarily determined by the type of atoms on the MxAu12−x shell (M=Ag, Cu, and Au in the nanocluster catalysts.

  20. Investigation of Pt-Ti doped carbon aerogel as bi-metallic catalyst for H/D exchange process

    Science.gov (United States)

    Bhartiya, Sushmita; Kohli, D. K.; Singh, Ashish; Singh, Rashmi; Singh, M. K.

    2017-05-01

    Platinum (Pt) carbon based catalyst for hydrogen-deuterium (H/D) exchange between hydrogen and water is one of the benign processes being explored for heavy water production. Platinum being precious, presents a significant contribution on overall cost of catalyst. Titanium (Ti), a potential catalyst was explored for the H/D exchange to reduce the cost of catalyst. Titanium oxide co-doped with platinum in carbon aerogel (CA) was investigated for the exchange process. The present studies involve synthesis and characterization of TiO2 nanoparticles doped in carbon aerogel. Pt and TiO2 doping (5% by weight for both) in CA was used to prepare the bimetallic PtTi-CA catalyst. The H/D exchange efficiency obtained for the PtTi-CA catalyst (with 50% Pt economy) was 57% which compares well with Pt-CA catalyst having exchange efficiency of 67%.

  1. 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.

  2. Isospecific, Chain Shuttling Polymerization of Propylene Oxide Using a Bimetallic Chromium Catalyst: A New Route to Semicrystalline Polyols.

    Science.gov (United States)

    Childers, M Ian; Vitek, Andrew K; Morris, Lilliana S; Widger, Peter C B; Ahmed, Syud M; Zimmerman, Paul M; Coates, Geoffrey W

    2017-08-16

    Hydroxy-telechelic poly(propylene oxide) (PPO) is widely used industrially as a midsegment in polyurethane synthesis. These atactic polymers are produced from racemic propylene oxide using chain shuttling agents and double-metal cyanide catalysts. Unlike atactic PPO, isotactic PPO is semicrystalline with a melting temperature of approximately 67 °C. Currently there is no practical route to hydroxy-telechelic isotactic PPO using racemic propylene oxide as the monomer. In this paper, hydroxy-telechelic isotactic PPO is synthesized from racemic propylene oxide with control of molecular weight using enantioselective and isoselective bimetallic catalysts in conjunction with chain shuttling agents. The discovery of an easily accessible bimetallic chromium catalyst is reported for this transformation. Diol, triol, and polymeric chain shuttling agents are used to give hydroxy-telechelic isotactic PPO of varying functionality and structure. Detailed quantum chemical studies are used to reveal the polymerization mechanism and origin of stereoselectivity.

  3. 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.

  4. Synthesis of Bimetallic Ni-Cr Nano-Oxides as Catalysts for Methanol Oxidation in NaOH Solution.

    Science.gov (United States)

    Gu, Yingying; Luo, Jing; Liu, Yicheng; Yang, Haihong; Ouyang, Ruizhou; Miao, Yuqing

    2015-05-01

    Bimetallic Ni-Cr nano-oxide catalysts were synthesized by thermal decomposition method and were investigated as the anode electrocatalysts for the oxidation of methanol. The catalysts were characterized by X-ray diffraction and transmission electron microscopy. The electroactivity of the catalysts towards methanol oxidation in a solution containing 0.25 M NaOH and 1.0 M MeOH was examined using cyclic voltammetry and chronoamperometry. The results indicate that a mixture of rhombohedral-structured NiO and Cr2O3 nanocrystals generated at the calcination temperature of 500-700 degrees C while octahedral-structured spinel NiCr2O4 formed at higher temperature. The influence of metallic molar ratio on the electrocatalytic performance of the catalysts was studied. The Ni-Cr nano-oxides prepared at comparatively low temperature displayed significantly higher catalytic activity and durability in alkaline solution toward electrooxidation of methanol compared with the pure nano NiO. The results indicate a synergy effect between NiO and Cr2O3 enhancing the electrocatalytic properties of the bimetallic Ni-Cr nano-oxide catalysts. Meanwhile, NiCr2O4 hardly increased the activity and durability of the catalyst. In addition, the Ni-Cr catalyst also exhibited excellent stability and good reproducibility. Therefore, Ni-Cr nano-oxide catalyst may be a suitable and cheap electrocatalyst for methanol oxidation in alkaline medium.

  5. 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.

  6. A general approach for the synthesis of bimetallic M–Sn (M = Ru, Rh and Ir) catalysts for efficient hydrogenolysis of ester

    KAUST Repository

    Samal, Akshaya Kumar

    2016-11-24

    A versatile synthetic method was applied for the preparation of Sn containing bimetallic catalysts. The synthesis was performed by simply mixing the super hydride [LiB(C2H5)(3)H], with a metal (Ru, Rh or Ir) salt and an organotin complex in tetrahydrofuran solvent without using any surfactant. This leads to the formation of monodispersed M-Sn (M = Ru, Rh or Ir) bimetallic nanoparticles (NPs). These bimetallic catalysts show high performances in the hydrogenolysis of ester to the corresponding alcohol.

  7. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Ruan, Hao [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Feng, Maoqi [Chemistry & Chemical Engineering Division, Southwest Research Institute, San Antonio TX 78238 USA; Qin, Yuling [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Job, Heather [Pacific Northwest National Laboratory, 902 Battelle Blvd Richland WA 99354 USA; Luo, Langli [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Wang, Chongmin [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Kuhn, Erik [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Chen, Xiaowen [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-03-16

    The synthesis of high-efficiency and low-cost multifunctional catalysts for hydrodeoxygenation (HDO) of waste lignin into advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low molecular weight gaseous side-products. Among all the prepared catalysts, Ru-Cu/HY showed the best HDO performance, giving the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably due to the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all the bifunctional catalysts were proven to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite, and this could be attributed to the “intimacy criterion”. The practical use of the designed catalysts would be promising in lignin valorization.

  8. Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran and 2-Methyltetrahydrofuran over Bimetallic Copper-Palladium Catalysts.

    Science.gov (United States)

    Chang, Xin; Liu, An-Feng; Cai, Bo; Luo, Jin-Yue; Pan, Hui; Huang, Yao-Bing

    2016-12-08

    The catalytic transfer hydrogenation of furfural to the fuel additives 2-methylfuran (2-MF) and 2-methyltetrahydrofuran (2-MTHF) was investigated over various bimetallic catalysts in the presence of the hydrogen donor 2-propanol. Of all the as-prepared catalysts, bimetallic Cu-Pd catalysts showed the highest catalytic activities towards the formation of 2-MF and 2-MTHF with a total yield of up to 83.9 % yield at 220 °C in 4 h. By modifying the Pd ratios in the Cu-Pd catalyst, 2-MF or 2-MTHF could be obtained selectively as the prevailing product. The other reaction conditions also had a great influence on the product distribution. Mechanistic studies by reaction monitoring and intermediate conversion revealed that the reaction proceeded mainly through the hydrogenation of furfural to furfuryl alcohol, which was followed by deoxygenation to 2-MF in parallel to deoxygenation/ring hydrogenation to 2-MTHF. Finally, the catalyst showed a high reactivity and stability in five catalyst recycling runs, which represents a significant step forward toward the catalytic transfer hydrogenation of furfural. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

    Science.gov (United States)

    Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

    2017-04-22

    The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2 O 3 and HY zeolite. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Versatile nickel–tungsten bimetallics/carbon nanofiber catalysts for direct conversion of cellulose to ethylene glycol

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ying; Zhang, Wen; Yang, Feng; Brown, Dennis E.; Ren, Yang; Lee, Sungsik; Zeng, Dehong; Gao, Qiang; Zhang, Xin

    2016-01-01

    We herein propose a novel synthetic methodology for a series of nickel–tungsten bimetallics/carbon nanofiber catalysts (Ni, 0.37–2.08 wt%; W, 0.01–0.06 wt%) in situ fabricated by pyrolysis (950 °C) of Ni, W and Zn-containing metal organic framework (Ni0.6-x–Wx–ZnBTC, x = 0–0.6) fibers. The resulting catalysts (Ni0.6-x–Wx/CNF) have uniform particles (ca. 68 nm), evenly dispersed onto the hierarchically porous carbon nanofibers formed simultaneously. All of the Ni0.6-x–Wx/CNF catalysts prove to be highly active towards direct conversion of cellulose to ethylene glycol (EG). A large productivity ranging from 15.3 to 70.8 molEG h-1 gW-1 is shown, two orders of magnitude higher than those by using other W-based catalysts reported.

  11. Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

    Science.gov (United States)

    Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

    2017-08-30

    Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

  12. 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.

  13. Hydrodesulfurization and hydrogenation of model compounds on silica alumina supported bimetallic systems

    Energy Technology Data Exchange (ETDEWEB)

    V.L. Barrio; P.L. Arias; J.F. Cambra; M.B. Guemez; B. Pawelec; J.L.G. Fierro [University of the Basque Country, Bilbao (Spain). School of Engineering

    2003-03-01

    Silica alumina supported Pd catalysts with a second metal such as Cu, Ru or Pt have been prepared (nominal content: 1 wt%) and tested in the naphthalene hydrogenation (HYD) and dibenzothiophene hydrodesulfurization (HDS) model reactions. These catalysts were characterized by means of temperature-programmed reduction, NH{sub 3} temperature-programmed desorption and photoelectron spectroscopy techniques. The combined use of all these techniques revealed that only in the case of PtPd system a rather uniform distribution of the metals across the pore network is achieved. Another important observation was that the PtPd system exhibited strong Broensted acid sites. The highest HYD and HDS activities of the PtPd bimetallic catalyst can be related not only to a high dispersion of the metals and their uniform distribution but also to its strong Broensted acidity. The PtPd system presented the highest DBT conversion (83.1%) and the highest C S hydrogenolysis activity as illustrated by the lowest S-containing products (21.9 wt%) as compared with the much higher S-containing products (54.8 wt%) obtained with the monometallic Pd/ASA catalyst under the same experimental conditions. 28 refs., 8 figs., 4 tabs.

  14. Direct hydrogenation of biomass-derived butyric acid to n-butanol over a ruthenium-tin bimetallic catalyst.

    Science.gov (United States)

    Lee, Jong-Min; Upare, Pravin P; Chang, Jong-San; Hwang, Young Kyu; Lee, Jeong Ho; Hwang, Dong Won; Hong, Do-Young; Lee, Seung Hwan; Jeong, Myung-Geun; Kim, Young Dok; Kwon, Young-Uk

    2014-11-01

    Catalytic hydrogenation of organic carboxylic acids and their esters, for example, cellulosic ethanol from fermentation of acetic acid and hydrogenation of ethyl acetate is a promising possibility for future biorefinery concepts. A hybrid conversion process based on selective hydrogenation of butyric acid combined with fermentation of glucose has been developed for producing biobutanol. ZnO-supported Ru-Sn bimetallic catalysts exhibits unprecedentedly superior performance in the vapor-phase hydrogenation of biomass-derived butyric acid to n-butanol (>98% yield) for 3500 h without deactivation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Samantaray, Manoja

    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.

  16. In Situ Exsolution of Bimetallic Rh-Ni Nanoalloys: a Highly Efficient Catalyst for CO2Methanation.

    Science.gov (United States)

    Arandiyan, Hamidreza; Wang, Yuan; Scott, Jason; Mesgari, Sara; Dai, Hongxing; Amal, Rose

    2018-03-22

    Unique CO 2 methanation catalysts comprising bimetallic Ni-Rh nanoalloy/3DOM LaAlO 3 have been successfully prepared via a poly(methyl methacrylate) microsphere colloidal crystal-templating route, followed by the in situ growth of Ni nanoparticles (NPs). Here, we show that unlike traditional Ni particles deposited on a perovskite support, the exsolution of Ni occurs on both the external and internal surface of the porous perovskite substrate, leading to a strong metal-support interaction. Owing to the exsolution of Ni and the formation of Ni-Rh nanoalloys, a 52% enhancement in the methanation turnover frequency was obtained over the Ni-Rh/3DOM LaAlO 3 [13.9 mol/(mol h)] compared to Rh/3DOM LaNi 0.08 Al 0.92 O 3 [9.16 mol/(mol h)] before reduction treatment. The results show that the low-temperature reducibility, rich surface adsorbed oxygen species, and basic sites of the catalyst greatly improve its activity toward CO 2 methanation. The hierarchically porous structure of the perovskite support provides a high dispersion of bimetallic Ni-Rh NPs.

  17. Catalytic activity of mono and bimetallic Zn/Cu/MWCNTs catalysts for the thermocatalyzed conversion of methane to hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Erdelyi, B. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Institute of Physics, Faculty of Science, P.J. Šafárik University, Park Angelium 9, 040 01 Košice (Slovakia); Oriňak, A., E-mail: andrej.orinak@upjs.sk [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Oriňaková, R. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Lorinčík, J. [Research Center Rez, Hlavní 130, 250 68 Husinec-Řež (Czech Republic); Jerigová, M. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); Velič, D. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); International Laser Centre, Ilkovičová 3, 841 01 Bratislava (Slovakia); Mičušík, M. [Polymer institute, Slovak Academy of Sciences, Dubravská cesta 9, 84541 Bratislava (Slovakia); and others

    2017-02-28

    Highlights: • Zn/Cu/MWCNTs catalyst with good activity. • Methane conversion to hydrogen with high effectivity. • ZnO/Cu responsible for catalytic activity. - Abstract: Mono and bimetallic multiwalled carbon nanotubes (MWCNTs) fortified with Cu and Zn metal particles were studied to improve the efficiency of the thermocatalytic conversion of methane to hydrogen. The surface of the catalyst and the dispersion of the metal particles were studied by scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS) and with energy-dispersive X-ray spectroscopy (EDS). It was confirmed that the metal particles were successfully dispersed on the MWCNT surface and XPS analysis showed that the Zn was oxidised to ZnO at high temperatures. The conversion of methane to hydrogen during the catalytic pyrolysis was studied by pyrolysis gas chromatography using different amounts of catalyst. The best yields of hydrogen were obtained using pyrolysis conditions of 900 °C and 1.2 mg of Zn/Cu/MWCNT catalyst for 1.5 mL of methane.The initial conversion of methane to hydrogen obtained with Zn/Cu/MWCNTs was 49%, which represent a good conversion rate of methane to hydrogen for a non-noble metal catalyst.

  18. Exploratory catalyst screening studies on the base free conversion of glycerol to lactic acid and glyceric acid in water using bimetallic Au-Pt compounds on acidic zeolites

    NARCIS (Netherlands)

    Pazhavelikkakath Purushothaman, Rajeesh Kumar; van Haveren, J.; Mayoral, A.; Melian Cabrera, I.; Heeres, H.J.

    2014-01-01

    The base free oxidation of glycerol with molecular oxygen in water using bimetallic Au-Pt catalysts on three different acidic zeolite supports (H-mordenite, H-beta and H-USY) was explored in a batch setup. At temperatures between 140 and 180 degrees C, lactic acid formation was significant and

  19. Exploratory Catalyst Screening Studies on the Base Free Conversion of Glycerol to Lactic Acid and Glyceric Acid in Water Using Bimetallic Au–Pt Nanoparticles on Acidic Zeolites

    NARCIS (Netherlands)

    Purushothaman, R.K.P.; Haveren, van J.; Mayoral, A.; Melian-Cabrera, I.; Heeres, H.J.

    2014-01-01

    The base free oxidation of glycerol with molecular oxygen in water using bimetallic Au-Pt catalysts on three different acidic zeolite supports (H-mordenite, H-beta and H-USY) was explored in a batch setup. At temperatures between 140 and 180 degrees C, lactic acid formation was significant and

  20. Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Ramulifho, T

    2012-01-01

    Full Text Available -MWCNT-Pd and its "mixed" bimetallic electrocatalysts (i.e., SF-MWCNT-PdSn mix and SF-MWCNT-PdNi) towards ethanol oxidation in alkaline medium was investigated. The result shows that the mixed Pd-based catalysts (obtained by simple ultrasonic...

  1. Catalytic hydrotreatment of fast pyrolysis liquids in batch and continuous set-ups using a bimetallic Ni-Cu catalyst with a high metal content

    NARCIS (Netherlands)

    Yin, Wang; Kloekhorst, Arjan; Venderbosch, Robertus H.; Bykova, Maria V.; Khromova, Sofia A.; Yakovlev, Vadim A.; Heeres, Hero J.

    2016-01-01

    In this paper, an experimental study on the hydrotreatment of fast pyrolysis liquids is reported in both batch and continuous set-ups using a novel bimetallic Ni-Cu based catalyst with high Ni loading (up to 50%) prepared by a sol-gel method. The experiments were carried out in a wide temperature

  2. Effect of nanoparticle metal composition: mono- and bimetallic gold/copper dendrimer stabilized nanoparticles as solvent-free styrene oxidation catalysts

    Science.gov (United States)

    Blanckenberg, A.; Kotze, G.; Swarts, A. J.; Malgas-Enus, R.

    2018-02-01

    A range of mono- and bimetallic AumCun nanoparticles (NPs), with varying metal compositions, was prepared by using a third-generation diaminobutane poly(propylene imine) (G3 DAB-PPI) dendrimer, modified with alkyl chains, as a stabilizer. It was found that the length of the peripheral alkyl chain, ( M1 (C15), M2 (C11), and M3 (C5)), had a direct influence on the average nanoparticle size obtained, confirming the importance of the nanoparticle stabilizer during synthesis. The Au NPs showed the highest degree of agglomeration and polydispersity, whereas the Cu NPs were the smallest and most monodisperse of the NPs. The bimetallic NPs sizes were found to vary between those of the monometallic NPs, depending on the metal composition. Interestingly, the bimetallic NPs were found to be the most stable, showing very little variation in size over time, even up to 9 months. The DSNs were evaluated in the catalytic oxidation of styrene, using either H2O2 or TBHP as oxidant. Here, we show that the bimetallic DSNs are indeed the superior catalysts when compared to their monometallic analogues, under the same reaction conditions, since a good compromise between stability and activity can be achieved where the Au provides catalytic activity and the Cu serves as a stabilizer. These AumCun bimetallic DSNs present a less expensive and more stable catalyst with negligible loss of activity, opening the door to green catalysis.

  3. Aerobic Oxidation of Cyclohexane on Catalysts Based on Twinned and Single-Crystal Au75Pd25 Bimetallic Nanocrystals.

    Science.gov (United States)

    Wang, Liangbing; Zhao, Songtao; Liu, Chenxuan; Li, Chen; Li, Xu; Li, Hongliang; Wang, Youcheng; Ma, Chao; Li, Zhenyu; Zeng, Jie

    2015-05-13

    Bimetallic Au75Pd25 nanocrystals with shapes of icosahedron and octahedron were synthesized by adding different amounts of iodide ions, and were employed as catalysts for solvent-free aerobic oxidation of cyclohexane. Although both icosahedrons and octahedrons were bounded by {111} facets, the turnover frequency number of Au75Pd25 icosahedrons reached 15,106 h(-1), almost three times as high as that of Au75Pd25 octahedrons. The conversion of cyclohexane reached 28.1% after 48 h using Au75Pd25 icosahedrons, with the selectivity of 84.3% to cyclohexanone. Density functional theory calculations along with X-ray photoelectron spectroscopy examinations reveal that the excellent catalytic performance of AuPd icosahedrons could be ascribed to twin-induced strain and highly negative charge density of Au atoms on the surface.

  4. Elucidating the Origin of Hydrogen Evolution Reaction Activity in Mono- and Bimetallic Metal- and Nitrogen-Doped Carbon Catalysts (Me-N-C).

    Science.gov (United States)

    Shahraei, Ali; Moradabadi, Ashkan; Martinaiou, Ioanna; Lauterbach, Stefan; Klemenz, Sebastian; Dolique, Stephanie; Kleebe, Hans-Joachim; Kaghazchi, Payam; Kramm, Ulrike I

    2017-08-02

    In this work, we present a comprehensive study on the role of metal species in MOF-based Me-N-C (mono- and bimetallic) catalysts for the hydrogen evolution reaction (HER). The catalysts are investigated with respect to HER activity and stability in alkaline electrolyte. On the basis of the structural analysis by X-ray diffraction, X-ray-induced photoelectron spectroscopy, and transmission electron microscopy, it is concluded that MeN 4 sites seem to dominate the HER activity of these catalysts. There is a strong relation between the amount of MeN 4 sites that are formed and the energy of formation related to these sites integrated at the edge of a graphene layer, as obtained from density functional theory (DFT) calculations. Our results show, for the first time, that the combination of two metals (Co and Mo) in a bimetallic (Co,Mo)-N-C catalyst allows hydrogen production with a significantly improved overpotential in comparison to its monometallic counterparts and other Me-N-C catalysts. By the combination of experimental results with DFT calculations, we show that the origin of the enhanced performance of our (Co,Mo)-N-C catalyst seems to be provided by an improved hydrogen binding energy on one MeN 4 site because of the presence of a second MeN 4 site in its close vicinity, as investigated in detail for our most active (Co,Mo)-N-C catalyst. The outstanding stability and good activity make especially the bimetallic Me-N-C catalysts interesting candidates for solar fuel applications.

  5. Thermodynamic guidelines for the design of bimetallic catalysts for oxygen electroreduction and rapid screening by scanning electrochemical microscopy. M-co (M: Pd, Ag, Au).

    Science.gov (United States)

    Fernández, José L; Walsh, Darren A; Bard, Allen J

    2005-01-12

    We propose guidelines for the design of improved bimetallic (and related) electrocatalysts for the oxygen reduction reaction (ORR) in acidic media. This guide is based on simple thermodynamic principles assuming a simple mechanism where one metal breaks the oxygen-oxygen bond of molecular O(2) and the other metal acts to reduce the resulting adsorbed atomic oxygen. Analysis of the Gibbs free energies of these two reactions guides the selection of combinations of metals that can produce alloy surfaces with enhanced activity for the ORR when compared to the constituent metals. Selected systems have been tested by fabricating arrays of metallic catalysts consisting of various binary and ternary combinations of Pd, Au, Ag, and Co deposited on glassy carbon (GC) substrates. The electrocatalytic activity of these materials for the ORR in acidic medium was examined using scanning electrochemical microscopy (SECM) in a new rapid-imaging mode. This was used to rapidly screen arrays covering a wide range of catalyst compositions for their activity for the ORR in 0.5 M H(2)SO(4). Using the SECM technique, we have identified combinations of metals with enhanced electrocatalytic activities when compared with the constituent, pure metals. Addition of Co to Pd, Au, and Ag clearly decreases the ORR overpotential, in agreement with the proposed model. Catalyst spots that exhibited enhanced electrocatalytic activity in the SECM screening technique were then examined using classical rotating disk electrode (RDE) experiments. The activity of carbon black supported catalyst mixtures on a GC RDE and the electrocatalytic activity determined using the SECM screening technique showed excellent agreement. C/Pd-Co electrodes (10-30% Co) exhibited remarkable activity for ORR catalysis, close to that of carbon-supported Pt.

  6. Oxide Nanocrystal Model Catalysts.

    Science.gov (United States)

    Huang, Weixin

    2016-03-15

    Model catalysts with uniform and well-defined surface structures have been extensively employed to explore structure-property relationships of powder catalysts. Traditional oxide model catalysts are based on oxide single crystals and single crystal thin films, and the surface chemistry and catalysis are studied under ultrahigh-vacuum conditions. However, the acquired fundamental understandings often suffer from the "materials gap" and "pressure gap" when they are extended to the real world of powder catalysts working at atmospheric or higher pressures. Recent advances in colloidal synthesis have realized controlled synthesis of catalytic oxide nanocrystals with uniform and well-defined morphologies. These oxide nanocrystals consist of a novel type of oxide model catalyst whose surface chemistry and catalysis can be studied under the same conditions as working oxide catalysts. In this Account, the emerging concept of oxide nanocrystal model catalysts is demonstrated using our investigations of surface chemistry and catalysis of uniform and well-defined cuprous oxide nanocrystals and ceria nanocrystals. Cu2O cubes enclosed with the {100} crystal planes, Cu2O octahedra enclosed with the {111} crystal planes, and Cu2O rhombic dodecahedra enclosed with the {110} crystal planes exhibit distinct morphology-dependent surface reactivities and catalytic properties that can be well correlated with the surface compositions and structures of exposed crystal planes. Among these types of Cu2O nanocrystals, the octahedra are most reactive and catalytically active due to the presence of coordination-unsaturated (1-fold-coordinated) Cu on the exposed {111} crystal planes. The crystal-plane-controlled surface restructuring and catalytic activity of Cu2O nanocrystals were observed in CO oxidation with excess oxygen. In the propylene oxidation reaction with O2, 1-fold-coordinated Cu on Cu2O(111), 3-fold-coordinated O on Cu2O(110), and 2-fold-coordinated O on Cu2O(100) were identified

  7. Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

    Science.gov (United States)

    Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

    2016-11-09

    Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

  8. 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.

  9. 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.

  10. Mono- and bimetallic Rh and Pt NSR-catalysts prepared by controlled deposition of noble metals on support or storage component

    Science.gov (United States)

    Büchel, Robert; Pratsinis, Sotiris E.; Baiker, Alfons

    2013-01-01

    Mono- and bimetallic Rh and Pt based NOx storage-reduction (NSR) catalysts, where the noble metals were deposited on the Al2O3 support or BaCO3 storage component, have been prepared using a twin flame spray pyrolysis setup. The catalysts were characterized by nitrogen adsorption, CO chemisorption combined with diffuse reflectance infrared Fourier transform spectroscopy, X-ray diffraction, and scanning transmission electron microscopy combined with energy dispersive X-ray spectroscopy. The NSR performance of the catalysts was investigated by fuel lean/rich cycling in the absence and presence of SO2 (25 ppm) as well as after H2 desulfation at 750 °C. The performance increased when Rh was located on BaCO3 enabling good catalyst regeneration during the fuel rich phase. Best performance was observed for bimetallic catalysts where the noble metals were separated, with Pt on Al2O3 and Rh on BaCO3. The Rh-containing catalysts generally showed much higher tolerance to SO2 during fuel rich conditions and lost only little activity during thermal aging at 750 °C. PMID:23741085

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

    Science.gov (United States)

    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.

  12. Reaction between carbonyl compound and ammonia on the bimetallic catalyst the Eu, Yb system; Eu, Yb kei baimetarikku shokubaijo deno karuboniru kagobutsu to anmonia tono hanno

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-09-01

    Ln-Cu/Al{sub 2}O{sub 3}, Ln-Fe/SiO{sub 2}, Ln-Ni/SiO{sub 2}, Ln-Co/SiO{sub 2} bimetallic catalyst are obtained Cu/Al{sub 2}O{sub 3}, Fe/SiO{sub 2} and Ni/SiO{sub 2} and Co/SiO{sub 2}, when it reacted with the rare metal which dissolved in the liquid ammonia. Using it, the reaction between carbonyl compound and ammonia was examined at 473-523K reaction temperature. In the reaction between carbonyl compound and ammonia, these bimetallic catalysts can be developed to amination and reductive alkylation, those relation reactions and in order to show the activity for hydrogenation, dehydrogenation and conversion hydrogenation, which made the ammonia to be the hydrogen source. The catalysis greatly changed with the rare earth metal composition in the catalyst. Especially, the Ln-Cu/Al{sub 2}O{sub 3} catalyst showed the activity for the reaction between methyl acetate and ammonia. By adding the rare earth metal at Cu/Al{sub 2}O{sub 3}, the Eu-Cu/Al{sub 2}O{sub 3} catalyst was more activated, and the acetonitrile was given. Eu-Cu /Al{sub 2}O{sub 3}, since it has the high activity for the conversion hydrogenation from the ammonia, the reductive amination progressed acetone ammonia hydrogen, and isopropylamine was formed. (translated by NEDO)

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

    International Nuclear Information System (INIS)

    Xie, Hong; Ye, Xiaoliang; Duan, Kaiyue; Xue, Muyin; Du, Yongling; Ye, Weichun; Wang, Chunming

    2015-01-01

    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 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

  14. 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.

  15. 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.

  16. 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.

  17. High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

    Science.gov (United States)

    Jung, Won Suk

    2018-03-15

    In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr Catalysts Supported on SBA-15 Silica

    Directory of Open Access Journals (Sweden)

    Alicia Carrero

    2017-02-01

    Full Text Available Glycerol steam reforming (GSR is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES, N2-physisorption, X-ray powder diffraction (XRD, hydrogen temperature programmed reduction (H2-TPR, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and thermogravimetric analyses (TGA, and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material.

  19. 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 Shari; Hensley, Alyssa J.; 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.

  20. Bimetallic catalysts performance during ethanol steam reforming: Influence of support materials

    Energy Technology Data Exchange (ETDEWEB)

    Furtado, Andreia Cristina; Alonso, Christian Goncalves; Fernandes-Machado, Nadia Regina Camargo [Department of Chemical Engineering, State University of Maringa (UEM), Colombo Avenue, 5790, CEP 87020-900 Maringa, Parana (Brazil); Cantao, Mauricio Pereira [LACTEC - Institute of Technology for Development, BR 116, KM 98 S/N, CEP 81531-980 Curitiba, Parana (Brazil)

    2009-09-15

    Ni-Cu catalysts supported on different materials were tested in ethanol steam reforming reaction for hydrogen production. These catalysts were evaluated at reaction temperature of 400 C under atmospheric pressure. The reagents, with a water/ethanol molar ratio equal to 10, were fed at 70 dm{sup 3}/(h g{sub cat}) (after vaporization). Analysis of the ethanol conversion, as well as evaluation and quantification of the reaction products, indicated the catalyst 10% Ni-1% Cu/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} as the most appropriate for the ethanol steam reforming under investigated reaction conditions, among the studied catalysts. During 8 h of reaction this catalyst presented an average ethanol conversion of 43%, producing a high amount of H{sub 2} by steam reforming and by ethanol decomposition and dehydrogenation parallel reactions. Steam reforming, among the observed reactions, was quantified by the presence of carbon dioxide. About 60% of the hydrogen was produced from ethanol steam reforming and 40% from parallel reactions. (author)

  1. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  2. Vapor phase synthesis and characterization of bimetallic alloy and supported nanoparticle catalysts

    Science.gov (United States)

    Abdelsayed, V.; Saoud, K. M.; El-Shall, M. Samy

    2006-08-01

    The laser vaporization controlled condensation (LVCC) technique coupled with a differential mobility analyzer (DMA) is used to synthesize size-selected alloy nanoparticles and nanoparticle catalyst systems. The formation of Au-Ag alloy nanoparticles is concluded from the observation of only one plasmon band. The maximum of the plasmon absorption is found to vary linearly with the gold mole fraction. For the Au-Pd system, the XRD data confirms the formation of the alloy nanoparticles with no evidence of any of the pure components. The Au/CeO2 nanoparticle catalyst prepared by the LVCC method is a promising catalyst for low temperature CO oxidation due to its high activity and stability.

  3. Combining CO2 reduction with propane oxidative dehydrogenation over bimetallic catalysts.

    Science.gov (United States)

    Gomez, Elaine; Kattel, Shyam; Yan, Binhang; Yao, Siyu; Liu, Ping; Chen, Jingguang G

    2018-04-11

    The inherent variability and insufficiencies in the co-production of propylene from steam crackers has raised concerns regarding the global propylene production gap and has directed industry to develop more on-purpose propylene technologies. The oxidative dehydrogenation of propane by CO 2 (CO 2 -ODHP) can potentially fill this gap while consuming a greenhouse gas. Non-precious FeNi and precious NiPt catalysts supported on CeO 2 have been identified as promising catalysts for CO 2 -ODHP and dry reforming, respectively, in flow reactor studies conducted at 823 K. In-situ X-ray absorption spectroscopy measurements revealed the oxidation states of metals under reaction conditions and density functional theory calculations were utilized to identify the most favorable reaction pathways over the two types of catalysts.

  4. Preparation of Rh/Ag bimetallic nanoparticles as effective catalyst for hydrogen generation from hydrolysis of KBH4

    Science.gov (United States)

    Huang, Liang; Jiao, Chengpeng; Wang, Liqiong; Huang, Zili; Liang, Feng; Liu, Simin; Wang, Yuhua; Zhang, Haijun; Zhang, Shaowei

    2018-01-01

    ISOBAM-104 protected Rh/Ag bimetallic nanoparticles (NPs) with average diameter less than 3.0 nm were synthesized by a co-reduction method. Ultraviolet–visible spectroscopy, transmission electron microscopy (TEM), high-resolution TEM and x-ray photoelectron spectroscopy (XPS) were employed to characterize the structure, particle size, and electronic structure of the prepared bimetallic NPs. The catalytic activities of prepared bimetallic NPs for hydrogen generation from hydrolysis of a basic KBH4 solution were evaluated in detail. The results indicated that as-prepared Rh/Ag bimetallic NPs showed a higher catalytic activity than corresponding monometallic NPs. Among all the monometallic NPs and bimetallic NPs, Rh80Ag20 bimetallic NPs exhibited the highest catalytic activity with a value of 6010 mol-H2·h‑1·mol-catalyst‑1 at pH = 12 and 303 K. The high catalytic activities of Rh/Ag bimetallic NPs could be attributed to presence of negatively charged Rh atoms and positively charged Ag atoms, which is supported by the results of XPS and density functional theory calculation. Based on the kinetic study, the apparent activation energy for the hydrolysis reaction of the basic KBH4 solution catalyzed by Rh80Ag20 bimetallic NPs was about 47.0 ± 3.9 kJ mol‑1.

  5. Tuning the Composition of Electrodeposited Bimetallic Tin-Lead Catalysts for Enhanced Activity and Durability in Carbon Dioxide Electroreduction to Formate.

    Science.gov (United States)

    Moore, Colin E; Gyenge, Előd L

    2017-09-11

    Bimetallic Sn-Pb catalysts with five different Sn/Pb atomic ratios were electrodeposited on Teflonated carbon paper and non-Teflonated carbon cloth using both fluoroborate- and oxide-containing deposition media to produce catalysts for the electrochemical reduction of CO 2 (ERC) to formate (HCOO - ). The interaction between catalyst composition, morphology, substrate, and deposition media was investigated by using cyclic voltammetry and constant potential electrolysis at -2.0 V versus Ag/AgCl for 2 h in 0.5 m KHCO 3 . The catalysts were analyzed before and after electrolysis by using SEM and XRD to determine the mechanisms of Faradaic efficiency loss and degradation. Catalysts that are mainly Sn with 15-35 at % Pb generated Faradaic efficiencies up to 95 % with a stable performance. However, pure Sn catalysts showed high initial stage formate production rates but experienced an extensive (up to 30 %) decrease of the Faradaic efficiency. The XRD results demonstrated the presence of polycrystalline SnO 2 after electrolysis using Sn-Pb catalysts with 35 at % Pb and its absence in the case of pure Sn. It is proposed that the presence of Pb (15-35 at %) in mainly Sn catalysts stabilized SnO 2 , which is responsible for the enhanced Faradaic efficiency and catalytic durability in the ERC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Volcano Plot for Bimetallic Catalysts in Hydrogen Generation by Hydrolysis of Sodium Borohydride

    Science.gov (United States)

    Koska, Anais; Toshikj, Nikola; Hoett, Sandra; Bernaud, Laurent; Demirci, Umit B.

    2017-01-01

    In the field of "hydrogen energy", sodium borohydride (NaBH[subscript 4]) is a potential hydrogen carrier able to release H[subscript 2] by hydrolysis in the presence of a metal catalyst. Our laboratory experiment focuses on this. It is intended for thirdyear undergraduate students in order to have hands-on laboratory experience through…

  7. NEXAFS characterization and reactivity studies of bimetallic vanadium molybdenum oxynitride hydrotreating catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, R.; Oyama, S.T. [Virginia Polytechnic Inst., Blacksburg, VA (United States); Fruehberger, B.; Chen, J.G. [Exxon Research and Engineering Company, Annandale, NJ (United States)

    1997-02-27

    The surface and bulk compositions of vanadium molybdenum oxynitride (V{sub 2}MoO{sub 1.7}N{sub 2.4}), prepared by temperature-programmed reaction (TPR) of vanadium molybdenum oxide (V{sub 2}MoO{sub 8}) with ammonia, have been characterized using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS data were recorded at the K-edges of nitrogen and oxygen, the L-edge of vanadium, and the M-edge of molybdenum. The nitrogen K-edge region of V-Mo oxynitride shows the characteristic NEXAFS features of early-transition-metal nitrides, although these features are different from those of either VN or Mo{sub 2}N. Furthermore, comparison of the electron yield and fluorescence yield measurements also reveals that the oxidation state is different for vanadium near the surface region and for vanadium in the bulk, which is estimated to be 2.8 {+-} 0.3 and 3.8 {+-} 0.3, respectively. The oxidation state of bulk molybdenum is also estimated to be 4.4 {+-} 0.3. The X-ray diffraction pattern shows that the bulk phase of the bimetallic oxide is different from the pure monometallic oxide phases but the oxynitride has a cubic structure that resembles the pure vanadium and molybdenum nitride phases. The V-Mo oxide as prepared shows a preferential orientation of [001] crystallographic planes which is lost during the nitridation process. This shows that the solid state transformation V{sub 2}MoO{sub 8} {yields} V{sub 2}MoO{sub 1.7}N{sub 2.4} is not topotactic. 27 refs., 8 figs., 1 tab.

  8. 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.

  9. Selective hydrogenation of acetylene on SiO{sub 2} supported Ni-In bimetallic catalysts: Promotional effect of In

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yanjun; Chen, Jixiang, E-mail: jxchen@tju.edu.cn

    2016-11-30

    Graphical abstract: A suitable Ni/In ratio remarkably enhanced the acetylene conversion, the selectivity to ethylene and the catalyst stability. Display Omitted - Highlights: • There was a promotional effect of In on the performance of Ni/SiO{sub 2}. • A suitable Ni/In ratio was required for good performance of Ni{sub x}In/SiO{sub 2}. • Both geometrical and electronic effects of In contributed to good performance. • Ni/SiO{sub 2} deactivation is mainly owing to phase change from Ni to nickel carbide. • The carbonaceous deposit was the main reason for Ni{sub x}In/SiO{sub 2} deactivation. - Abstract: Ni/SiO{sub 2} and the bimetallic Ni{sub x}In/SiO{sub 2} catalysts with different Ni/In ratios were tested for the selective hydrogenation of acetylene, and their physicochemical properties before and after the reaction were characterized by means of N{sub 2}-sorption, H{sub 2}-TPR, XRD, TEM, XPS, H{sub 2} chemisorption, C{sub 2}H{sub 4}-TPD, NH{sub 3}-TPD, FT-IR of adsorbed pyridine, and TG/DTA and Raman. A promotional effect of In on the performance of Ni/SiO{sub 2} was found, and Ni{sub x}In/SiO{sub 2} with a suitable Ni/In ratio gave much higher acetylene conversion, ethylene selectivity and catalyst stability than Ni/SiO{sub 2}. This is ascribed to the geometrical isolation of the reactive Ni atoms with the inert In ones and the charge transfer from the In atoms to Ni ones, both of which are favorable for reducing the adsorption strength of ethylene and restraining the C−C hydrogenolysis and the polymerizations of acetylene and the intermediate compounds. On the whole, Ni{sub 6}In/SiO{sub 2} and Ni{sub 10}In/SiO{sub 2} had better performance. Nevertheless, with increasing the In content, the selectivity to the C4+ hydrocarbons tended to increase due to the enhanced catalyst acidity because of the charge transfer from the In atoms to Ni ones. As the Lewis acid ones, the In sites could promote the polymerization. The catalyst deactivation was also analyzed

  10. Bimetallic Ag-Pt Sub-nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Negreiros, Fabio R. [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Halder, Avik [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Yin, Chunrong [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Singh, Akansha [Harish-Chandra Research Institute, HBNI, Chhatnag Road Jhunsi Allahabad 211019 India; Barcaro, Giovanni [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Sementa, Luca [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Tyo, Eric C. [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Pellin, Michael J. [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Bartling, Stephan [Institut für Physik, Universität Rostock, Rostock Germany; Meiwes-Broer, Karl-Heinz [Institut für Physik, Universität Rostock, Rostock Germany; Seifert, Sönke [X-ray Science Division, Argonne National Laboratory, Lemont IL USA; Sen, Prasenjit [Harish-Chandra Research Institute, HBNI, Chhatnag Road Jhunsi Allahabad 211019 India; Nigam, Sandeep [Chemistry Division, Bhabha Atomic Research Centre, Trombay Mumbai- 400 085 India; Majumder, Chiranjib [Chemistry Division, Bhabha Atomic Research Centre, Trombay Mumbai- 400 085 India; Fukui, Nobuyuki [East Tokyo Laboratory, Genesis Research Institute, Inc., Ichikawa Chiba 272-0001 Japan; Yasumatsu, Hisato [Cluster Research Laboratory, Toyota Technological Institute: in, East Tokyo Laboratory, Genesis Research Institute, Inc. Ichikawa, Chiba 272-0001 Japan; Vajda, Stefan [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Nanoscience and Technology Division, Argonne National Laboratory, Lemont IL USA; Institute for Molecular Engineering, University of Chicago, Chicago IL USA; Fortunelli, Alessandro [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Materials and Process Simulation Center, California Institute of Technology, Pasadena CA USA

    2017-12-29

    A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO -> CO2 reaction (COox) is presented. Ag9Pt2 and Ag9Pt3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. Insitu GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O-2, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.

  11. Mono- and Bimetallic Ruthenium—Arene Catalysts for Olefin Metathesis: A Survey

    Science.gov (United States)

    Borguet, Yannick; Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

    In this chapter, we summarize the main achievements of our group toward the development of easily accessible, highly efficient ruthenium—arene catalyst precursors for olefin metathesis. Major advances in this field are presented chronologically, with an emphasis on catalyst design and mechanistic details. The first part of this survey focuses on monometallic complexes with the general formula RuCl2(p-cymene)(L), where L is a phosphine or N-heterocyclic carbene ancillary ligand. In the second part, we disclose recent developments in the synthesis and catalytic applications of homobimetallic ruthenium—arene complexes of generic formula (p-cymene)Ru(μ-Cl)3RuCl(η2-C2H4)(L) and their derivatives resulting from the substitution of the labile ethylene moiety with vinylidene, allenylidene, or indenylidene units

  12. Efficient utilization of bimetallic catalyst in low H₂/CO environment ...

    Indian Academy of Sciences (India)

    Application of Fischer-Tropsch synthesis (FTS) in the utilization of low H ₂/CO ratio (0.5–1.5) gas obtained from coal and biomass gasification can be done by selecting a catalyst system active for both FTS and WGS reaction. The enhancement of H ₂ content depends on the extent of water gas shift (WGS) reaction and can ...

  13. 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.

  14. 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.

  15. 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.

  16. Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States)

    2017-01-06

    An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources such as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.

  17. Developments of modeling tools for the ultrasonic propagation in bimetallic welds

    International Nuclear Information System (INIS)

    Gardahaut, A.

    2013-01-01

    This study fits into the field of ultrasonic non-destructive evaluation. It consists in the development of a dynamic ray tracing model to simulate the ultrasonic propagation in bimetallic welds. The approach has been organised in three steps. First of all, an image processing technique has been developed and applied on the macro-graphs of the weld in order to obtain a smooth cartography of the crystallographic orientation. These images are used as input data for a dynamic ray tracing model adapted to the study of anisotropic and inhomogeneous media such as bimetallic welds. Based on a kinematic and a dynamic ray tracing model, usually used in geophysics, it allows the evaluation of ray trajectories between a source point and an observation point, and the computation of the ultrasonic amplitude through the geometrical spreading of an elementary ray tube. This model has been validated in 2D by comparison of the results with a hybrid semi-analytical/finite elements code, then in 3D thanks to experimental results made on the mock-ups of the studied bimetallic welds. (author) [fr

  18. Degradation of Bimetallic Model Electrocatalysts ___ an in situ XAS Study

    Energy Technology Data Exchange (ETDEWEB)

    Friebel, Daniel

    2011-06-22

    One of the major challenges in the development of clean energy fuel cells is the performance degradation of the electrocatalyst, which, apart from poisoning effects, can suffer from corrosion due to its exposure to a harsh environment under high potentials. In this communication, we demonstrate how interactions of Pt with a transition metal support affect not only, as commonly intended, the catalytic activity, but also the reactivity of Pt towards oxide formation or dissolution. We use two well-defined single-crystal model systems, Pt/Rh(111) and Pt/Au(111) and a unique x-ray spectroscopy technique with enhanced energy resolution to monitor the potential-dependent oxidation state of Pt, and find two markedly different oxidation mechanisms on the two different substrates. This information can be of great significance for future design of more active and more stable catalysts. We have studied the potential-induced degradation of Pt monolayer model electrocatalysts on Rh(111) and Au(111) single-crystal substrates. The anodic formation of Pt oxides was monitored using in situ high energy resolution fluorescence detection x-ray absorption spectroscopy (HERFD XAS). Although Pt was deposited on both substrates in a three-dimensional island growth mode, we observed remarkable differences during oxide formation that can only be understood in terms of strong Pt-substrate interactions throughout the Pt islands. Anodic polarization of Pt/Rh(111) up to +1.6 V vs. RHE (reversible hydrogen electrode) leads to formation an incompletely oxidized passive layer, whereas formation of PtO2 and partial Pt dissolution is observed for Pt/Au(111).

  19. Two 3D structured Co-Ni bimetallic oxides as cathode catalysts for high-performance alkaline direct methanol fuel cells

    Science.gov (United States)

    Liu, Yan; Shu, Chengyong; Fang, Yuan; Chen, Yuanzhen; Liu, Yongning

    2017-09-01

    Two NiCo2O4 bimetallic oxides were synthesized via a facile hydrothermal method. SEM and TEM observations show that these materials have three-dimensional (3D) dandelion-like (DL) and flower-like (FL) morphologies. Their large specific surface areas (90.68 and 19.8 m2·g-1) and porous structures provide many active sites and effective transport pathways for the oxygen reduction reaction (ORR). Electrochemical measurements with a rotating ring-disc electrode (RRDE) indicate that the electron transfer numbers of the NiCo2O4-DL and NiCo2O4-FL catalysts for ORR in an alkaline solution are 3.97 and 3.91, respectively. Fuel cells were assembled with the bimetallic oxides, PtRu/C and a polymer fiber membrane (PFM) as cathode catalysts, anode catalyst and electrolyte film, respectively. For NiCo2O4-DL, the peak power density reaches up to 73.5 mW·cm-2 at 26 °C, which is the highest room-temperature value reported to date. The high catalytic activity of NiCo2O4 is mainly attributed to the presence of many Co3+ cations that directly donate electrons to O2 to reduce it via a more efficient and effective route. Furthermore, the catalytic performance of NiCo2O4-DL is superior to that of NiCo2O4-FL because it has a higher specific surface area and is less crystalline.

  20. 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

  1. Minimizing Freshwater Consumption in the Wash-Off Step in Textile Reactive Dyeing by Catalytic Ozonation with Carbon Aerogel Hosted Bimetallic Catalyst

    Directory of Open Access Journals (Sweden)

    Enling Hu

    2018-02-01

    Full Text Available In textile reactive dyeing, dyed fabrics have to be rinsed in the wash-off step several times to improve colorfastness. Thus, the multiple rinsing processes drastically increase the freshwater consumption and meanwhile generate massive waste rinsing effluents. This paper addresses an innovative alternative to recycle the waste effluents to minimize freshwater consumption in the wash-off step. Accordingly, catalytic ozonation with a highly effective catalyst has been applied to remedy the waste rinsing effluents for recycling. The carbon aerogel (CA hosted bimetallic hybrid material (Ag–Fe2O3@CA was fabricated and used as the catalyst in the degradation of residual dyes in the waste rinsing effluents by ozonation treatments. The results indicate the participation of Ag–Fe2O3@CA had strikingly enhanced the removal percentage of chemical oxidation demand by 30%. In addition, it has been validated that waste effluents had been successfully reclaimed after catalytic ozonation with Ag–Fe2O3@CA. They could be additionally reused to reduce freshwater consumption in the wash-off step, but without sacrificing the color quality of corresponding fabrics in terms of color difference and colorfastness. This study may be the first to report the feasibility of catalytic ozonation in minimization of freshwater consumption in the wash-off step in textile reactive dyeing.

  2. In Situ Industrial Bimetallic Catalyst Characterization using Scanning Transmission Electron Microscopy and X-ray Absorption Spectroscopy at One Atmosphere and Elevated Temperature.

    Science.gov (United States)

    Prestat, Eric; Kulzick, Matthew A; Dietrich, Paul J; Smith, Mr Matthew; Tien, Mr Eu-Pin; Burke, M Grace; Haigh, Sarah J; Zaluzec, Nestor J

    2017-08-18

    We have developed a new experimental platform for in situ scanning transmission electron microscope (STEM) energy dispersive X-ray spectroscopy (EDS) which allows real time, nanoscale, elemental and structural changes to be studied at elevated temperature (up to 1000 °C) and pressure (up to 1 atm). Here we demonstrate the first application of this approach to understand complex structural changes occurring during reduction of a bimetallic catalyst, PdCu supported on TiO 2 , synthesized by wet impregnation. We reveal a heterogeneous evolution of nanoparticle size, distribution, and composition with large differences in reduction behavior for the two metals. We show that the data obtained is complementary to in situ STEM electron energy loss spectroscopy (EELS) and when combined with in situ X-ray absorption spectroscopy (XAS) allows correlation of bulk chemical state with nanoscale changes in elemental distribution during reduction, facilitating new understanding of the catalytic behavior for this important class of materials. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  3. Decomposition of methane over alumina supported Fe and Ni–Fe bimetallic catalyst: Effect of preparation procedure and calcination temperature

    Directory of Open Access Journals (Sweden)

    A.S. Al-Fatesh

    2018-02-01

    Full Text Available Catalytic decomposition of methane has been studied extensively as the production of hydrogen and formation of carbon nanotube is proven crucial from the scientific and technological point of view. In that context, variation of catalyst preparation procedure, calcination temperature and use of promoters could significantly alter the methane conversion, hydrogen yield and morphology of carbon nanotubes formed after the reaction. In this work, Ni promoted and unpromoted Fe/Al2O3 catalysts have been prepared by impregnation, sol–gel and co-precipitation method with calcination at two different temperatures. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption, temperature programmed reduction (TPR and thermogravimetric analysis (TGA techniques. The catalytic activity was tested for methane decomposition reaction. The catalytic activity was high when calcined at 500 °C temperature irrespective of the preparation method. However while calcined at high temperature the catalyst prepared by impregnation method showed a high activity. It is found from XRD and TPR characterization that disordered iron oxides supported on alumina play an important role for dissociative chemisorptions of methane generating molecular hydrogen. The transmission electron microscope technique results of the spent catalysts showed the formation of carbon nanotube which is having length of 32–34 nm. The Fe nanoparticles are present on the tip of the carbon nanotube and nanotube grows by contraction–elongation mechanism. Among three different methodologies impregnation method was more effective to generate adequate active sites in the catalyst surface. The Ni promotion enhances the reducibility of Fe/Al2O3 oxides showing a higher catalytic activity. The catalyst is stable up to six hours on stream as observed in the activity results.

  4. Catalytic activity of bimetallic Zn/TiO2 catalyst for degradation of herbicide paraquat: synthesis and characterization

    Science.gov (United States)

    Sakee, Uthai; Wanchanthuek, Ratchaneekorn

    2017-11-01

    The preparation and characterization of Zn/TiO2 catalysts were performed and the photocatalytic properties of the resulting catalysts were tested using the paraquat degradation reaction under UV and solar light irradiation. The effect of the preparation method, amount of Zn loading, the calcination temperature and the thermal annealing during the autoclave aging were studied as well as the light irradiation during the testing reaction. The initial concentration of paraquat was 400 ppm, the pH during the catalytic testing was seven and the reaction temperature was 30 °C. The characterization information were obtained from XRD, XPS, UV-vis diffuse reflectance, FTIR, TEM and BET techniques. They were used to explain the expressed catalytic activity of Zn/TiO2. The results showed that the Zn/TiO2 catalyst from the hydrothermal method could remove about 80% of the paraquat from the solution (using 4 g l-1 of catalyst). The characterization data showed that the surface area, porous structure and dispersion of Zn species could affect the ability of the paraquat removal rather than the crystallnity of the TiO2 in the catalyst. The XPS spectra suggested that the preparation method, between the sol gel and hydrothermal, could not affect the state of the Zn and Ti, which presented in the Zn2+ and Ti4+ forms. This primary result will lead us to further study to elucidate the main active site by the XPS technique. Moreover, it clearly showed that the lowering of the band gap energy in the Zn/TiO2 was achieved (compared to bare TiO2), and this phenomena was one of the factors that gave the higher photocatalytic activity of the Zn/TiO2 catalyst.

  5. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper

    Science.gov (United States)

    Han, Zhiping; Li, Shuirong; Jiang, Feng; Wang, Tuo; Ma, Xinbin; Gong, Jinlong

    2014-08-01

    This paper describes an investigation of the promotional effect of Cu on the catalytic performance of Pt/Al2O3 catalysts for propane dehydrogenation. We have shown that Pt/Al2O3 catalysts possess higher propylene selectivity and lower deactivation rate as well as enhanced anti-coking ability upon Cu addition. The optimized loading content of Cu is 0.5 wt%, which increases the propylene selectivity to 90.8% with a propylene yield of 36.5%. The origin of the enhanced catalytic performance and anti-coking ability of the Pt-Cu/Al2O3 catalyst is ascribed to the intimate interaction between Pt and Cu, which is confirmed by the change of particle morphology and atomic electronic environment of the catalyst. The Pt-Cu interaction inhibits propylene adsorption and elevates the energy barrier of C-C bond rupture. The inhibited propylene adsorption diminishes the possibility of coke formation and suppresses the cracking reaction towards the formation of lighter hydrocarbons on Pt-Cu/Al2O3, while a higher energy barrier for C-C bond cleavage suppresses the methane formation.

  6. 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

    2015-09-07

    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.

  7. Structure and size of bimetallic palladium - platinum clusters in an hydro-treatment catalyst; Structure et taille de particules bimetalliques palladium - platine dans un catalyseur d'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Bazin, D. [Paris-11 Univ., 91 - Orsay (France). Lab. de Physique des Solides; Guillaume, D.; Uzio, D.; Lopez, S. [Institut Francais du Petrole, Catalysis and Separation Div., 69 - Vernaison (France); Pichon, Ch. [Institut Francais du Petrole, Physics and Analysis Div., 69 - Vernaison (France)

    2005-07-01

    Highly dispersed supported bimetallic PdPt catalysts were prepared by incipient wetness co-impregnation of alumina with platinum bis-acetylacetonate Pt(Acac){sub 2} and palladium bis-acetylacetonate Pd(Acac){sub 2}. The resulting Pt{sub 4}Pd/Al{sub 2}O{sub 3} and Pt{sub 6}Pd/Al{sub 2}O{sub 3} catalytic systems dedicated to hydro-de-aromatization in presence of sulfur were characterized by X-ray absorption spectroscopy, transmission electron microscopy and volumetric H{sub 2}-O{sub 2} titration. Direct structural evidence is given of the presence of nanometer bimetallic particles. Moreover, the complete set of results indicates a 'cherry-like' structure for the bimetallic clusters with a preferential distribution of palladium atoms at the cluster surface. Catalytic results shows that the optimum composition leading to the appropriate surface structure must be adjusted as a function of the size of the clusters. (authors)

  8. 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...

  9. Enhanced Electroreductive Removal of Bromate by a Supported Pd-In Bimetallic Catalyst: Kinetics and Mechanism Investigation.

    Science.gov (United States)

    Lan, Huachun; Mao, Ran; Tong, Yating; Liu, Yanzhen; Liu, Huijuan; An, Xiaoqiang; Liu, Ruiping

    2016-11-01

    In this work, the electroreductive removal of bromate by a Pd 1 -In 4 /Al 2 O 3 catalyst in a three-dimensional electrochemical reactor was investigated. A total of 96.4% of bromate could be efficiently reduced and completely converted into bromide within 30 min under optimized conditions. On the basis of the characterization results and kinetics analysis, a synergistic effect of Pd and In was observed, and Pd 1 -In 4 /Al 2 O 3 had the highest reaction rate constant of 0.1275 min -1 (vs 0.0413, 0.0328, and 0.0253 min -1 for In/Al 2 O 3 , Pd/Al 2 O 3 , and Al 2 O 3 ). The results of electron spin resonance and scavenger experiments confirmed that both direct electron transfer and indirect reduction by atomic H* were involved in the bromate removal process, while the direct reduction played a more important role. Moreover, the introduction of In could increase the zeta potential of Pd 1 -In 4 /Al 2 O 3 , facilitating bromate adsorption and its subsequent reduction on the catalyst. Finally, a reaction mechanism for bromate reduction by Pd 1 -In 4 /Al 2 O 3 was proposed based on all the experimental results.

  10. Kinetics on NiZn Bimetallic Catalysts for Hydrogen Evolution via Selective Dehydrogenation of Methylcyclohexane to Toluene

    KAUST Repository

    Shaikh Ali, Anaam

    2017-01-18

    Liquid organic chemical hydrides are effective hydrogen storage media for easy and safe transport. The chemical couple of methylcyclohexane (MCH) and toluene (TOL) has been considered one of the feasible cycles for a hydrogen carrier, but the selective dehydrogenation of MCH to TOL has been reported using only Pt-based noble metal catalysts. This study reports MCH dehydrogenation to TOL using supported NiZn as a selective, non-noble-metal catalyst. A combined experimental and computational study was conducted to provide insight into the site requirements and reaction mechanism for MCH dehydrogenation to TOL, which were compared with those for cyclohexane (CH) dehydrogenation to benzene (BZ). The kinetic measurements carried out at 300-360°C showed an almost zero order with respect to MCH pressure in the high-pressure region (≥10 kPa) and nearly a positive half order with respective to H pressure (≤40 kPa). These kinetic data for the dehydrogenation reaction paradoxically indicate that hydrogenation of a strongly chemisorbed intermediate originating from TOL is the rate-determining step. Density functional theory (DFT) calculation confirms that the dehydrogenated TOL species at the aliphatic (methyl) position group (CHCH) were strongly adsorbed on the surface, which must be hydrogenated to desorb as TOL. This hydrogen-assisted desorption mechanism explains the essential role of excess H present in the feed in maintaining the activity of the metallic surface for hydrogenation. The rate of the CH to BZ reaction was less sensitive to H pressure than that of MCH to TOL, which can be explained by the absence of a methyl group in the structure, which in turn reduces the binding energy of the adsorbed species. DFT suggests that the improved TOL selectivity by adding Zn to Ni was due to Zn atoms preferentially occupying low-coordination sites on the surface (the corner and edge sites), which are likely the unselective sites responsible for the C-C dissociation of the

  11. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October 1995--December 1995

    Energy Technology Data Exchange (ETDEWEB)

    Song, C.; Cooke, W.S.; Schmidt, E.; Schobert, H.H.

    1996-02-01

    Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. Here in this quarterly, we report on the catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds in the reactions of dibenzothiophene (DBT) with hydrogen under conditions related to coal liquefaction. The catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds have been examined in the hydrogenation and hydrodesulfurization reactions of dibenzothiophene (DBT) under conditions related to coal liquefaction. The metal compounds are candidate catalyst precursors for direct coal liquefaction. The reactions were carried out in batch microautoclave reactors at 400{degrees}C for 30 minutes with 6.9 MPa (cold) hydrogen pressure, and tridecane solvent. A metal loading of 0.5 mol% resulted in low conversion and only hydrogenation. Addition of sulfur in 4:1 molar ratio led only to a minor increase in conversion and hydrodesulfurization. The use of a higher boiling solvent (octadecane vs. tridecane) was beneficial in providing increased conversion, hydrodesulfurization, and hydrogenation. An increase in metal compound loading to 36.2 mol% led to a dramatic increase in conversion, hydrodesulfurization, and hydrocracking. Molybdenum hexacarbonyl at 36 mol% loading, with added sulfur at 6:1 ratio and octadecane solvent, gave 100% conversion of dibenzothiophene to other products with 100% hydrodesulfurization. Ammonium tetrathiomolybdate and molybdenum(III) chloride are less active under similar conditions. A cobalt-molybdenum thiocubane complex gave unexpectedly low conversions. Iron and cobalt carbonyls also provided very low conversions, even with added sulfur.

  12. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    Data.gov (United States)

    U.S. Environmental Protection Agency — A bimetallic catalyst, AgPd@g-C3N4, synthesized by reducing silver and palladium salts over graphitic carbon nitride (g-C3N4), enables the concerted reductive...

  13. Disorder effect on heat capacity, self-diffusion coefficient, and choosing best potential model for melting temperature, in gold–copper bimetallic nanocluster with 55 atoms

    International Nuclear Information System (INIS)

    Taherkhani, Farid; Akbarzadeh, Hamed; Feyzi, Mostafa; Rafiee, Hamid Reza

    2015-01-01

    Molecular dynamics simulation has been implemented for doping effect on melting temperature, heat capacity, self-diffusion coefficient of gold–copper bimetallic nanostructure with 55 total gold and copper atom numbers and its bulk alloy. Trend of melting temperature for gold–copper bimetallic nanocluster is not same as melting temperature copper–gold bulk alloy. Molecular dynamics simulation of our result regarding bulk melting temperature is consistence with available experimental data. Molecular dynamics simulation shows that melting temperature of gold–copper bimetallic nanocluster increases with copper atom fraction. Semi-empirical potential model and quantum Sutton–Chen potential models do not change melting temperature trend with copper doping of gold–copper bimetallic nanocluster. Self-diffusion coefficient of copper atom is greater than gold atom in gold–copper bimetallic nanocluster. Semi-empirical potential within the tight-binding second moment approximation as new application potential model for melting temperature of gold–copper bulk structure shows better result in comparison with EAM, Sutton–Chen potential, and quantum Sutton–Chen potential models

  14. Hydrogen production using Ag-Pd/TiO2 bimetallic catalysts: is there a combined effect of surface plasmon resonance with the Schottky mechanism on the photo-catalytic activity?(Conference Presentation)

    Science.gov (United States)

    Nadeem, Muhammad Amtiaz; Idriss, Hicham; Al-Oufi, Maher; Ahmed, Khaja Wahab; Anjum, Dalaver H.

    2016-10-01

    A series of Ag-Pd/TiO2 catalysts have been prepared, characterized and tested for H2 production activities from water in the presence of organic sacrificial agents. The synergistic effect of metallic properties (plasmonic and Schottky mechanisms) was investigated. XPS results indicated that silver is present in the form of its oxides (Ag2O and AgO) at 0.2-0.4 wt. % loading while palladium is present as PdO and Pd metal at similar loading. However, metallic character for silver particles increases while that of palladium metal particles decreases with increasing their % in the investigated range (0-1 wt. %). HRTEM results coupled with EDX analyses indicated the presence of two types of Ag containing particles (large ones with about 4-6 nm and smaller ones with ca. 1nm in size). Palladium was only found forming Ag-Pd alloy/composite with a wide size distribution range between 10-60 nm. Both particles are composed of silver and palladium, however. Optimal photocatalytic H2 production rates were obtained for catalysts with a palladium to silver ratios between 4 and 1.5 in the case of bimetallic catalysts. In addition, H2 production rates showed linear dependency on plasmonic response of Ag. The study demonstrates that increased H2 production rates can be achieved from an understanding of plasmonic and Schottky properties of metals loaded on top of the semiconductor.

  15. Hydroconversion of n-hexane using Pt/H-MOR and Pt/H-BEA catalysts with various Pt contents and bimetallic PtPd/H-MOR, PtPd/H-BEA, PtIr/H-MOR and PtIr/H-BEA catalysts with various secondary metal contents

    Energy Technology Data Exchange (ETDEWEB)

    Aboul-Gheit, A.K.; Abdel-Hamid, S.M.; Awadallah, A.E. [Process Development Div., Egyptian Petroleum Research Inst., Nasr City, Cairo (Egypt)

    2004-03-01

    Monometallic catalysts containing 0.35 up to 0.50 wt%Pt on H-MOR or H-BEA zeolites, as well as bimetallic catalysts containing Pd or Ir of 0.05 up to 0.20-0.25 wt% combined with a fixed Pt content of 0.35 wt% also supported on H-MOR or H-BEA were prepared and tested for n-hexane hydroconversion in a hydrogen flow using pulsed reactor system. The reaction products were gas chromatographically analysed and the catalysts were characterised for acid sites strength distribution via ammonia temperature programmed desorption (TPD) and for metal(s) dispersion in the support via pulsed hydrogen chemisorption. Increased Pt content in either zeolites decreased its dispersion. The addition of Pd to Pt increased the metals dispersion in both zeolites up to a certain content, whereas Ir addition, principally, decreased dispersion. Maximum isohexanes production behaved parallel to the metals dispersion in the PtPd containing catalysts (structure sensitive). Hydrocracking was more active on the H-MOR supported catalysts, compared to those supported on H-BEA due to higher acid sites number and strength in the former zeolite. Benzene production via dehydrocyclisation of n-hexane was relatively more active on the H-BEA containing catalysts than on those containing H-MOR, due to the less effective diffusion resistance in the BEA channels. (orig.)

  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. 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. Mesoporous silica supported Pd/Ag bimetallic nanoparticles as a ...

    Indian Academy of Sciences (India)

    Priyanka Verma

    2017-09-19

    Sep 19, 2017 ... bUnit of Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto 615-8520,. Japan. cJST, PRESTO, 4-1-8 Honcho, Kawaguchi, ... Silver-based bimetallic Pd/Ag plasmonic catalysts supported on mesoporous silica catalyze the chemoselective reduction of nitrostyrene (NS) to ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-10-20

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

  20. Dispersion enhanced metal/zeolite catalysts

    Science.gov (United States)

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  1. A photoactive bimetallic framework for direct aminoformylation ...

    Science.gov (United States)

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditions. The entwined AgPd@g-C3N4 catalyst was very effective in exploiting formic acid as a source of hydrogen and acting as a formylating agent under photochemical conditions. Prepared for submission to Royal Society of Chemistry (RSC) journal, Green Chemistry

  2. Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study

    KAUST Repository

    Della Monica, Francesco

    2016-08-25

    A series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis and characterization of bimetallic Pd-Ni catalysts in a CeO2 matrix for the generation of H2 by the reforming reaction of methanol

    International Nuclear Information System (INIS)

    Contreras C, R.

    2016-01-01

    The hydrothermal method was used for the synthesis of CeO 2 nano rods using Ce(NO 3 ) 3 ·6H 2 O and NH 4 OH. The catalytic support was calcined at 700 degrees Celsius. The synthesis of CeO 2 nano rods were impregnated with an aqueous solution of Ni(NO 3 ) 2 ·6H 2 O by an incipient wetness impregnation method at an appropriate concentration to yield 5 and 15% of Ni in the catalysts. Then 0.5% of Pd was impregnated using PdCl 2 . The samples obtained were calcined at 400 and reduced at 450 degrees Celsius. The catalytic materials were characterized by: temperature programmed reduction (TPR), Scanning Electron Microscopy (Sem) , surface area and X-ray diffraction (XRD) . Sem results showed that the CeO 2 is formed by nano rods and in lesser proportion semi spherical particles. Bet surface area of the catalysts decreases with Ni loading onto the CeO 2 nano rods. Pd O and Ni O were reduced at low and high temperature as was observed by TPR. The CeO 2 one-dimensional nano rods showed a highly crystalline structure with sharp diffraction peaks, with a typical fluorite structure (cubic structure of the CeO 2 ) and characteristic peaks corresponding to metallic Ni. No diffraction peaks of Pd were found. This is due to the low concentration of this metal in the catalyst. These catalysts showed high activity and selectivity to H 2 at maximum reaction temperature. According to the results of activity and selectivity, the catalysts with Pd-Ni are an alternative for the H 2 production in auto thermal reforming reaction of methanol. (Author)

  4. H2 INTERACTION WITH BIMETALLIC DIMERS SUPPORTED ON THE MgO(100) SURFACE: A DFT CLUSTER MODEL STUDY

    OpenAIRE

    PIOTR MATCZAK

    2012-01-01

    The interaction between the H2 molecule and the PdAg, PdAu, PtAg and PtAu bimetallic dimers deposited on the MgO(100) surface is investigated using density functional theory (DFT). The bimetallic dimers, whose molecular axes are considered to be perpendicular to the support surface, are adsorbed on top of an oxygen atom. Within this adsorption mode, the dimers prefer the orientation in which their Pd or Pt end is closer to the oxygen atom. The Ag and Au ends of the MgO-supported dimers captur...

  5. Formation of C2 oxygenates and ethanol from syngas on an Fe-decorated Cu-based catalyst: insight into the role of Fe as a promoter.

    Science.gov (United States)

    Ling, Lixia; Wang, Qiang; Zhang, Riguang; Li, Debao; Wang, Baojun

    2017-11-22

    In this study, the formation mechanism of C 2 oxygenates and ethanol from syngas on Fe-decorated Cu bimetallic catalyst was investigated using density functional theory (DFT) calculations together with microkinetic modeling. The results showed that CH 2 was the most favored monomer among all the CH x (x = 1-3) species over the FeCu bimetallic catalyst, which was more favorable than CH 3 OH formation. Namely, the FeCu catalyst exhibited a good selectivity toward CH 2 formation instead of CH 3 OH formation in syngas conversion. Starting from the CH 2 monomer, CH 2 CO and CH 3 CO via CO insertion into CH 2 and CH 2 CO hydrogenation were the major products instead of C 2 hydrocarbons or methane, CH 3 CO was successively hydrogenated to ethanol via CH 3 CHO and CH 3 CH 2 O intermediates. Moreover, the microkinetic modeling showed that the FeCu bimetallic catalyst had a high selectivity toward ethanol rather than methanol and methane. Further, the addition of Fe into the Cu catalyst promoted CH x formation by accelerating C-O bond cleavage, suppressed methanol formation, and facilitated C 2 oxygenate formation rather than methane formation, suggesting that the synergetic effect between Fe and Cu played an important role in the formation of C 2 oxygenates and ethanol. In addition, it is believed that the insights derived from this study can provide clues for the catalyst design of oxygenate synthesis and other bimetallic catalytic systems.

  6. 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.

  7. MODELING STYRENE HYDROGENATION KINETICS USING PALLADIUM CATALYSTS

    Directory of Open Access Journals (Sweden)

    G. T. Justino

    Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.

  8. Hydroxylation of Benzene via CH Activation Using Bimetallic ...

    Science.gov (United States)

    A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light. Prepared for submission to American Chemical Society (ACS) journal, ACS Sustainable Chemistry & Engineering.

  9. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    Science.gov (United States)

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditi...

  10. Synthesis and characterization of bimetallic nanocatalysts and their ...

    Indian Academy of Sciences (India)

    group and also paves the way for selective activation of C=O bond. Keywords. Bimetallic nanocatalysts; TiO2-supported; ... transition metals of group VIII of the periodic table. However, the selectivity of these metals with ... replica was performed by ultrasonically dispersing the catalyst powder and depositing a drop of the ...

  11. Effect of local metal microstructure on adsorption on bimetallic surfaces: Atomic nitrogen on Ni/Pt(111)

    Science.gov (United States)

    Guo, Wei; Vlachos, Dionisios G.

    2013-05-01

    The adsorption of atomic nitrogen on Ni/Pt(111) surface bimetallics has been investigated as a function of the local microstructure of Ni and Pt atoms via density functional theory (DFT) calculations. Microstructures include surface and subsurface Ni atoms on Pt(111) as limiting cases, and also small clusters of Ni in the first and/or second layer of Pt. It is shown that the binding energy of N can be approximated as a perturbation from that on the host metal (Pt) with a linear short-ranged correction from the guest metal (Ni) that accounts for the coordination environment of nitrogen up to the 3rd nearest Ni neighbor. This model is rationalized with the d-band center theory. Coverage effects are also included. The model can be parameterized with a limited number of DFT calculations and applied to other bimetallic catalysts to estimate the coverage dependent binding energy on complex metal microstructures.

  12. Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

    Science.gov (United States)

    Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

    2018-05-01

    In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

  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. Facile Synthesis of Highly Active and Robust Ni-Mo Bimetallic Electrocatalyst for Hydrocarbon Oxidation in Solid Oxide Fuel Cells

    NARCIS (Netherlands)

    Hua, B.; Li, M.; Zhang, Y.-Q.; Chen, J.; Sun, Y.-F.; Yan, N.; Li, J.; Luo, J.L.

    2016-01-01

    We report a novel Ni–Mo bimetallic alloy decorated with multimicrocrystals as an efficient anode catalyst for hydrocarbon-fueled solid oxide fuel cells (SOFCs). We show that these Ni–Mo bimetallic alloys are highly active, thermally stable, and sulfur/coke tolerant electrocatalysts for hydrocarbon

  15. 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.

  16. H2 Interaction with Bimetallic Dimers Supported on the MgO(100) Surface: a DFT Cluster Model Study

    Science.gov (United States)

    Matczak, Piotr

    2012-08-01

    The interaction between the H2 molecule and the PdAg, PdAu, PtAg and PtAu bimetallic dimers deposited on the MgO(100) surface is investigated using density functional theory (DFT). The bimetallic dimers, whose molecular axes are considered to be perpendicular to the support surface, are adsorbed on top of an oxygen atom. Within this adsorption mode, the dimers prefer the orientation in which their Pd or Pt end is closer to the oxygen atom. The Ag and Au ends of the MgO-supported dimers capture the H2 molecule with small exoenergetic effects. The spontaneous dissociation of H2 on these ends does not occur. Thus, the MgO support decreases the ability of the dimers to adsorb and dissociate the H2 molecule. From a catalytic viewpoint, it means that the activity of small bimetallic clusters toward the dissociative adsorption of H2 is reduced when they are arranged on MgO. On the other hand, the results of our calculations show that the presence of the MgO support strengthens the binding of H atoms inside the PdAu, PtAg and PtAu dimers.

  17. Preparation of bimetallic nanoparticles using a facile green synthesis method and their application.

    Science.gov (United States)

    Xia, Bihua; He, Fang; Li, Lidong

    2013-04-16

    A straightforward, economically viable, and green approach for the synthesis of well-stabilized Au/Ag bimetallic nanoparticles is described; this method uses nontoxic and renewable degraded pueraria starch (DPS) as a matrix and mild reaction conditions. The DPS acted as both a reducing agent and a capping agent for the bimetallic nanoparticles. Au/Ag bimetallic nanoparticles were successfully grown within the DPS matrixes, and the bimetallic structures were characterized using various methods, including high-resolution transmission electron microscopy, energy-dispersive X-ray, and X-ray diffraction. Moreover, it was shown that these DPS-capped Au/Ag bimetallic nanoparticles could function as catalysts for the reduction of 4-nitrophenol in the presence of NaBH4 and were more effective than Au or Ag monometallic nanoparticles.

  18. Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes

    Directory of Open Access Journals (Sweden)

    Trung Dang-Bao

    2017-07-01

    Full Text Available Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer. This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst life-time. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

  19. Bimetallic Schiff base complexes: models for conjugated shape-persistent metallopolymers.

    Science.gov (United States)

    Leung, Alfred C W; Hui, Joseph K-H; Chong, Jonathan H; MacLachlan, Mark J

    2009-07-14

    New Schiff base ligands with two metal binding sites have been prepared. Copper and zinc complexes of the ligands, which serve as models for rigid, conjugated metallopolymers, were synthesized and characterized. The copper complexes display only weak intramolecular antiferromagnetic interactions, suggesting that the polymer structure is not useful for developing magnetic materials. Preliminary investigations of the novel polymers, including the preparation of a conjugated zinc-containing polymer, are reported.

  20. Screening of Catalysts for Hydrodeoxygenation of Phenol as Model Compound for Bio-oil

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

    2013-01-01

    Four groups of catalysts have been tested for hydrodeoxygenation (HDO) of phenol as a model compound of bio-oil, including: oxide catalysts, methanol synthesis catalysts, reduced noble metal catalysts, and reduced non-noble metal catalysts. In total 23 different catalysts were tested at 100 bar H2...... and 275 °C in a batch reactor. The experiments showed that none of the tested oxides and methanol synthesis catalysts had any significant activity for phenol HDO at the given conditions, which were linked to their inability to hydrogenate the phenol. HDO of phenol over reduced metal catalysts could...

  1. Biosupported Bimetallic Pd Au Nanocatalysts for Dechlorination of Environmental Contaminants

    Energy Technology Data Exchange (ETDEWEB)

    De Corte, S.; Fitts, J.; Hennebel, T.; Sabbe, T.; Bliznuk, V.; Verschuere, S.; van der Lelie, D.; Verstraete, W.; Boon, N.

    2011-08-30

    Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichloroethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L{sup -1} and reduced simultaneously by Shewanella oneidensis in the presence of H{sub 2}, the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.

  2. Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol

    Science.gov (United States)

    Transfer hydrogenation and hydrodeoxygenation of model bio-oil compounds (p-cresol and furfural) and bio-oils derived from biomass via traditional pyrolysis and tail-gas reactive pyrolysis (TGRP) were conducted. Mild batch reaction conditions were employed, using isopropanol as a hydrogen donor over...

  3. Low platinum catalyst and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Di-Jia; Chong, Lina

    2017-11-21

    A low platinum catalyst and method for making same. The catalyst comprises platinum-transition metal bimetallic alloy microcrystallites over a transition metal-nitrogen-carbon composite. A method of making a catalyst comprises preparation of transition metal organic frameworks, infusion of platinum, thermal treatment, and reduction to form the microcrystallites and composite.

  4. Bimetallic redox synergy in oxidative palladium catalysis.

    Science.gov (United States)

    Powers, David C; Ritter, Tobias

    2012-06-19

    (II/IV) catalysis has guided the successful development of many reactions. Herein we discuss differences between monometallic Pd(IV) and bimetallic Pd(III) redox catalysis. We address whether appreciation of the relevance of bimetallic Pd(III) redox catalysis is of academic interest exclusively, serving to provide a more nuanced description of catalysis, or if the new insight regarding bimetallic Pd(III) chemistry can be a platform to enable future reaction development. To this end, we describe an example in which the hypothesis of bimetallic redox chemistry guided reaction development, leading to the discovery of reactivity distinct from monometallic catalysts.

  5. Mechanistic insights on ethanol dehydrogenation on Pd-Au model catalysts: a combined experimental and DFT study.

    Science.gov (United States)

    Evans, E J; Li, H; Yu, Wen-Yueh; Mullen, G M; Henkelman, G; Mullins, C Buddie

    2017-11-22

    In this study, we have combined ultra-high vacuum (UHV) experiments and density functional theory (DFT) calculations to investigate ethanol (EtOH) dehydrogenation on Pd-Au model catalysts. Using EtOH reactive molecular beam scattering (RMBS), EtOH temperature-programmed desorption (TPD), and DFT calculations, we show how different Pd ensemble sizes on Au(111) can affect the mechanism for EtOH dehydrogenation and H 2 production. The Au(111) surface with an initial coverage of 2 monolayers of Pd (2 ML Pd-Au) had the highest H 2 yield. However, the 1 ML Pd-Au catalyst showed the highest selectivity and stability, yielding appreciable amounts of only H 2 and acetaldehyde. Arrhenius plots of H 2 production confirm that the mechanisms for EtOH dehydrogenation differed between 1 and 2 ML Pd-Au, supporting the perceived difference in selectivity between the two surfaces. DFT calculations support this difference in mechanism, showing a dependence of the initial dehydrogenation selectivity of EtOH on the size of Pd ensemble. DFT binding energies and EtOH TPD confirm that EtOH has increasing surface affinity with increasing Pd ensemble size and Pd coverage, indicating that surfaces with more Pd are more likely to induce an EtOH reaction instead of desorb. Our theoretical results show that the synergistic influence of atomic ensemble and electronic effects on Pd/Au(111) can lead to different H 2 association energies and EtOH dehydrogenation capacities at different Pd ensembles. These results provide mechanistic insights into ethanol's dehydrogenation interactions with different sites on the Pd-Au surface and can potentially aid in bimetallic catalyst design for applications such as fuel cells.

  6. Electrocatalytic oxidation of ethylene glycol at palladium-bimetallic nanocatalysts (PdSn and PdNi) supported on sulfonate-functionalised multi-walled carbon nanotubes

    CSIR Research Space (South Africa)

    Ramulifho, T

    2013-04-01

    Full Text Available Electrocatalytic oxidation of ethylene glycol (EG) in alkaline medium using nano-scaled palladium-based bimetallic catalysts (PdM, where M = Ni and Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) is compared. The bimetallic...

  7. Bimetallic Nanoparticles: Synthesis, Characterization, and Applications in Catalysis

    OpenAIRE

    Landry, Alexandra Marcela

    2016-01-01

    Bimetallic nanoparticles can lead to catalysts with improved turnover rates and selectivities, but many synthetic protocols, such as impregnation or precipitation, typically form particles of non-uniform size and composition. Colloidal methods may be able to improve their uniformity, but often require reagents that poison catalytic surfaces (ex. S, B, P). Such compositional non-uniformity and ubiquitous impurities have prevented rigorous conclusions about the consequences of alloying on react...

  8. Surface Structures of Model Metal Catalysts in Reactant Gases.

    Science.gov (United States)

    Tao, Franklin Feng; Ralston, Walter T; Liu, Huimin; Somorjai, Gabor A

    2018-01-18

    Atomic scale knowledge of the surface structure of a metal catalyst is essential for fundamentally understanding the catalytic reactions performed on it. A correlation between the true atomic surface structure of a metal catalyst under reaction conditions and the corresponding catalytic performance is the key in pursuing mechanistic insight at a molecular level. Here the surface structures of model, metal catalysts in both ultrahigh vacuum (UHV) and gaseous environments of CO at a wide range of pressures are discussed. The complexity of observed surface structures in CO is illustrated, driving the necessity for visualization of the catalytic metals under realistic reaction conditions. Technical barriers for visualization of metal surfaces in situ at high temperature and high pressure are discussed.

  9. Kinetic modeling of ethylbenzene dehydrogenation over hydrotalcite catalysts

    KAUST Repository

    Atanda, Luqman

    2011-07-01

    Kinetics of ethylbenzene dehydrogenation to styrene was investigated over a series of quaternary mixed oxides of Mg3Fe0.25Me0.25Al0.5 (Me=Co, Mn and Ni) catalysts prepared by calcination of hydrotalcite-like compounds and compared with commercial catalyst. The study was carried out in the absence of steam using a riser simulator at 400, 450, 500 and 550°C for reaction times of 5, 10, 15 and 20s. Mg3Fe0.25Mn0.25Al0.5 afforded the highest ethylbenzene conversion of 19.7% at 550°C. Kinetic parameters for the dehydrogenation process were determined using the catalyst deactivation function based on reactant conversion model. The apparent activation energies for styrene production were found to decrease as follows: E1-Ni>E1-Co>E1-Mn. © 2011 Elsevier B.V.

  10. Estimation of Kinetic Parameters in an Automotive SCR Catalyst Model

    DEFF Research Database (Denmark)

    Åberg, Andreas; Widd, Anders; Abildskov, Jens

    2016-01-01

    A challenge during the development of models for simulation of the automotive Selective Catalytic Reduction catalyst is the parameter estimation of the kinetic parameters, which can be time consuming and problematic. The parameter estimation is often carried out on small-scale reactor tests...

  11. Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

    DEFF Research Database (Denmark)

    Bjørgum, Erlend; Chen, De; Bakken, Mari G.

    2005-01-01

    precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

  12. Sulfur Resistance of Pt-W Catalysts

    Directory of Open Access Journals (Sweden)

    Carolina P. Betti

    2013-01-01

    Full Text Available The sulfur resistance of low-loaded monometallic Pt catalysts and bimetallic Pt-W catalysts during the partial selective hydrogenation of styrene, a model compound of Pygas streams, was studied. The effect of metal impregnation sequence on the activity and selectivity was also evaluated. Catalysts were characterized by ICP, TPR, XRD, and XPS techniques. Catalytic tests with sulfur-free and sulfur-doped feeds were performed. All catalysts showed high selectivities (>98% to ethylbenzene. Activity differences between the catalysts were mainly attributed to electronic effects due to the presence of different electron-rich species of Pt0 and electron-deficient species of Ptδ+. Pt0 promotes the cleavage of H2 while Ptδ+ the adsorption of styrene. The catalyst successively impregnated with W and Pt (WPt/Al was more active and sulfur resistant than the catalyst prepared with an inverse impregnation order (PtW/Al. The higher poison resistance of WPt/Al was attributed to both steric and electronic effects.

  13. Progress, Challenge, and Perspective of Bimetallic TiO2-Based Photocatalysts

    Directory of Open Access Journals (Sweden)

    Anna Zielińska-Jurek

    2014-01-01

    Full Text Available Bimetallic TiO2-based photocatalysts have attracted considerable attention in recent years as a class of highly active catalysts and photocatalysts under both UV and Vis light irradiation. Bimetallic noble metal structures deposited on TiO2 possess the ability to absorb visible light, in a wide wavelength range (broad LSPR peak, and therefore reveal the highest level of activity as a result of utilization of a large amount of incident photons. On the other hand they can enhance the rate of trapping photoexcited electrons and inhibit the recombination process due to the capability of the storage of photoexcited electrons. Based on literature two groups of bimetallic photocatalysts were distinguished. The first group includes bimetallic TiO2 photocatalysts (BMOX, highly active under UV and Vis light irradiation in a variety of oxidation reactions, and the second group presents bimetallic photocatalysts (BMRED exceptionally active in hydrogenation reactions. This review summarizes recent advances in the preparation and environmental application of bimetallic TiO2-based photocatalysts. Moreover, the effects of various parameters such as particle shape, size, amount of metals, and calcination on the photocatalytic activity of bimetallic TiO2-based photocatalysts are also discussed.

  14. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  15. Fabrication of bimetallic nanostructures via aerosol-assisted electroless silver deposition for catalytic CO conversion.

    Science.gov (United States)

    Byeon, Jeong Hoon; Kim, Jang-Woo

    2014-03-12

    Bimetallic nanostructures were fabricated via aerosol-assisted electroless silver deposition for catalytic CO conversion. An ambient spark discharge was employed to produce nanocatalysts, and the particles were directly deposited on a polytetrafluoroethylene substrate for initiating silver deposition to form Pd-Ag, Pt-Ag, Au-Ag bimetallic nanostructures as well as a pure Ag nanostructure. Kinetics and morphological evolutions in the silver deposition with different nanocatalysts were comparatively studied. The Pt catalyst displayed the highest catalytic activity for electroless silver deposition, followed by the order Pd > Au > Ag. Another catalytic activity of the fabricated bimetallic structures in the carbon monoxide conversion was further evaluated at low-temperature conditions. The bimetallic systems showed significantly higher catalytic activity than that from a pure Ag system.

  16. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    The title of my PhD thesis is “Design of Heterogeneous Catalysts”. Three reactions have been investigated: the methanation reaction, the Fischer-Tropsch reaction, and the NH3-based selective catalytic reduction (SCR) of NO. The experimental work performed in connection with the methanation reaction...... hydrogenation. For both systems a maximum in catalytic activity was found for some of the bimetallic catalysts being superior to the monometallic catalysts. This resulted in volcano curves for all investigated systems. In the Fischer-Tropsch reaction promotion of cobalt catalysts with manganese was studied...... 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 vanadium-based catalyst...

  17. Highly Stable and Active Catalyst for Sabatier Reactions

    Science.gov (United States)

    Hu, Jianli; Brooks, Kriston P.

    2012-01-01

    Highly active Ru/TiO2 catalysts for Sabatier reaction have been developed. The catalysts have shown to be stable under repeated shutting down/startup conditions. When the Ru/TiO2 catalyst is coated on the engineered substrate Fe-CrAlY felt, activity enhancement is more than doubled when compared with an identically prepared engineered catalyst made from commercial Degussa catalyst. Also, bimetallic Ru-Rh/TiO2 catalysts show high activity at high throughput.

  18. Synthesis of Supported Bimetal Catalysts using Galvanic Deposition Method.

    Science.gov (United States)

    Mahara, Yuji; Ohyama, Junya; Sawabe, Kyoichi; Satsuma, Atsushi

    2018-02-22

    Supported bimetallic catalysts have been studied because of their enhanced catalytic properties due to metal-metal interactions compared with monometallic catalysts. We focused on galvanic deposition (GD) as a bimetallization method, which achieves well-defined metal-metal interfaces by exchanging heterogeneous metals with different ionisation tendencies. We have developed Ni@Ag/SiO 2 catalysts for CO oxidation, Co@Ru/Al 2 O 3 catalysts for automotive three-way reactions and Pd-Co/Al 2 O 3 catalysts for methane combustion by using the GD method. In all cases, the catalysts prepared by the GD method showed higher catalytic activity than the corresponding monometallic and bimetallic catalysts prepared by the conventional co-impregnation method. The GD method provides contact between noble and base metals to improve the electronic state, surface structure and reducibility of noble metals. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Synergistic effect in the oxidation of benzyl alcohol using citrate-stabilized gold bimetallic nanoparticles supported on alumina

    Science.gov (United States)

    Gómez-Villarraga, Fernando; Radnik, Jörg; Martin, Andreas; Köckritz, Angela

    2016-06-01

    Bimetallic nanoparticles (NPs) containing gold and various second metals ( M = Pd, Pt, Cu, and Ag) supported on alumina (AuM/Alumina) were prepared using sodium citrate as stabilizer. In addition, supported monometallic Au/Alumina and Pd/Alumina were synthesized and tested to reveal synergistic effects in the catalytic evaluation of the bimetallic catalysts. The monometallic and bimetallic NPs revealed average sizes below 10 nm. The oxidation of benzyl alcohol with molecular oxygen as oxidant at mild conditions in liquid phase in the absence and presence (toluene or NaOH aqueous solution, 0.2 M) of a solvent was selected as test reaction to evaluate the catalytic properties of the above-mentioned solids. AuPd/Alumina exhibited the best catalytic activity among all bimetallic catalysts using toluene as solvent and under solvent-free conditions, respectively. In comparison to the monometallic catalysts, a synergistic effect with AuPd/Alumina was only evident in the solvent-free reaction. The AuPd/Alumina catalyst was able to oxidize benzyl alcohol selectively depending on the reaction medium into benzaldehyde (toluene or solvent-free) or benzoic acid (NaOH aqueous solution, 0.2 M). However, the catalyst deactivated due to particle growth of the bimetallic AuPd NPs by Ostwald ripening and leaching was not observed in the oxidation using toluene as solvent. The size of the catalytically active NPs, the metal composition of the particles, and the reaction conditions greatly influenced the catalytic oxidation results.

  20. Study of carbon-supported bimetallic PtCu nanoparticles by ASAXS

    International Nuclear Information System (INIS)

    Bulat, N.V.; Avakyan, L.A; Pryadchenko, V.V.; Srabionyan, V.V.; Belenov, S.V.; Bugaev, L.A.

    2017-01-01

    Bimetallic platinum-copper nanoparticles on carbon support are studied as a perspective electrochemical catalyst by anomalous small-angle X-ray scattering near the Pt absorption L 3 -edge. The simultaneous fitting of several diffraction patterns measured at different photon energies lead to a satisfactory agreement between experimental and model curves in the assumption of core-shell structure of the particles with Pt-rich shell and Cu-rich core. It is shown that the average size of as prepared nanoparticles is about 6 nm with distribution spread of about ±2 nm and with thickness of Pt-rich shell approximately 1.6 nm. After annealing at 350o C the average size of the particles increased by two times with additional enlargement of the Pt-rich shell thickness. (paper)

  1. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.

    1991-10-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  2. Dendritic Pt–Cu bimetallic nanocrystals with a high electrocatalytic activity toward methanol oxidation

    International Nuclear Information System (INIS)

    Zhang Jintao; Ma Jizhen; Wan Yong; Jiang Jianwen; Zhao, X.S.

    2012-01-01

    Highlights: ► Dendritic Pt–Cu bimetallic nanocrystals were synthesized by one-step aqueous-phase reduction. ► The formation process of dendritic Pt–Cu bimetallic nanocrystals can be carried out under mild conditions. ► The dendritic Pt–Cu bimetallic nanocrystals exhibited a higher catalytic activity toward the electro-oxidation of methanol than commercial Pt/C catalysts. ► 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 2 PtCl 6 and CuCl 2 at a mild temperature (60 °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.

  3. 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.

  4. Sulfur Deactivation of NOx Storage Catalysts: A Multiscale Modeling Approach

    Directory of Open Access Journals (Sweden)

    Rankovic N.

    2013-09-01

    Full Text Available Lean NOx Trap (LNT catalysts, a promising solution for reducing the noxious nitrogen oxide emissions from the lean burn and Diesel engines, are technologically limited by the presence of sulfur in the exhaust gas stream. Sulfur stemming from both fuels and lubricating oils is oxidized during the combustion event and mainly exists as SOx (SO2 and SO3 in the exhaust. Sulfur oxides interact strongly with the NOx trapping material of a LNT to form thermodynamically favored sulfate species, consequently leading to the blockage of NOx sorption sites and altering the catalyst operation. Molecular and kinetic modeling represent a valuable tool for predicting system behavior and evaluating catalytic performances. The present paper demonstrates how fundamental ab initio calculations can be used as a valuable source for designing kinetic models developed in the IFP Exhaust library, intended for vehicle simulations. The concrete example we chose to illustrate our approach was SO3 adsorption on the model NOx storage material, BaO. SO3 adsorption was described for various sites (terraces, surface steps and kinks and bulk for a closer description of a real storage material. Additional rate and sensitivity analyses provided a deeper understanding of the poisoning phenomena.

  5. On the degradation of fuel cell catalyst. From model systems to high surface area catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Arenz, M. [Copenhagen Univ. (Denmark). Dept. of Chemistry

    2010-07-01

    In the presented work, as an alternative accelerated degradation tests in the form of half-cell measurements combined with identical location transmission electron microscopy (IL-TEM){sup 10,} {sup 11} are presented. It is demonstrated that for different catalysts the degradation mechanism can be scrutinized in detail. Thus this approach enables the systematic investigation of fuel cell catalyst degradation in a reduced period of time. (orig.)

  6. Bond Energies in Models of the Schrock Metathesis Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J.; Dixon, David A.

    2011-06-23

    Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR)(OH)₂ (M = Cr, Mo, W; CRR = CH₂, CHF, CF₂) and MO₂(OH)₂ compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH₂)(OH) ₂ transition metal complexes are predicted using high level CCSD(T) calculations. The metallacycle intermediates formed by reaction of C₂H4 with M(NH)-(CH₂)(OH)2 and MO₂(OH)₂ are investigated at the same level of theory. Additional corrections were added to the complete basis set limit to obtain near chemical accuracy ((1 kcal/mol). A comparison between adiabatic and diabatic BDEs is made and provides an explanation of trends in the BDEs. Electronegative groups bonded on the carbenic carbon lead to less stable Schrock-type complexes as the adiabatic BDEs ofMdCF₂ andMdCHF bonds are much lower than theMdCH₂ bonds. The Cr compounds have smaller BDEs than theWorMo complexes and should be less stable. Different M(NH)(OH)₂(C₃H₆) and MO(OH)₂(OC₂H4) metallacycle intermediates are investigated, and the lowest-energy metallacycles have a square pyramidal geometry. The results show that consideration of the singlet_triplet splitting in the carbene in the initial catalyst as well as in the metal product formed by the retro [2+2] cycloaddition is a critical component in the design of an effective olefin metathesis catalyst in terms of the parent catalyst and the groups being transferred.

  7. Model studies of methanol synthesis on copper catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, J.; Nakamura, I.; Uchijima, T. [Univ. of Tsukuba, Ibaraki (Japan); Watanabe, T. [Research Inst. of Innovative Technology for Earth, Kyoto (Japan); Fujitani, T. [National Inst. for Resources and Environment, Ibaraki (Japan)

    1996-12-31

    The synthesis of methanol by the hydrogenation of CO{sub 2} over Zn-deposited and Zn-free copper surfaces has been studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). It was shown that the Zn deposited on Cu(111) and poly-Cu acted as a promoter for methanol synthesis, while the Zn on Cu(110) and Cu(100) had no such a promotional effect. The turnover frequency (TOF) for Zn/Cu(111) linearly increased with Zn coverage below {Theta}Zn--0.19, and then decreased above {Theta}Zn=0.20. The optimum TOF obtained at {Theta}Zn--0-19 was thirteen-fold larger than TOF for the Zn-free Cu(111) surface. On the other hand, no promotional effect of Zn was observed for the reverse water-gas shift reaction on all the surfaces. The results indicate the formation of special sites for methanol synthesis on Zn/Cu(111). The Zn-deposited Cu(111) can be regarded as a model of Cu/ZnO catalysts because the TOF and the activation energy for methanol formation over the Zn-deposited Cu(111) were in fairly good agreement with those for the Cu/ZnO powder catalysts. The post-reaction surface analysis by XPS showed the formation of formate species (HCOOa). The formate coverage was proportional to the activity for methanol formation below {Theta}Zn=0.20, suggesting that the hydrogenation of the formate species is the rate-determining step of methanol formation. The formate species was stabilized by Zn species on Cu(111) in the absence of ZnO species. STM results on the Zn-deposited Cu(111) suggested the formation of a Cu-Zn surface alloy. The presence of special sites for methanol synthesis was also indicated in the results of powder catalysts.

  8. A Numerical Model for Thermal Effects in a Microwave Irradiated Catalyst Bed

    OpenAIRE

    Lanz, Jason E.

    1998-01-01

    Electromagnetic and heat transfer analysis is used to determine possibility of selective heating of nanometer-sized, metallic catalyst particles attached to a ceramic support through microwave irradiation. This analysis is incorporated into a macroscopic heat transfer model of a packed and fluidized catalyst bed heated by a microwave field to predict thermal effects associated with selective heating of the catalyst sites. The model shows a dependence on particle size and microwave frequency...

  9. 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.

  10. Multiscale modeling for materials design: Molecular square catalysts

    Science.gov (United States)

    Majumder, Debarshi

    In a wide variety of materials, including a number of heterogeneous catalysts, the properties manifested at the process scale are a consequence of phenomena that occur at different time and length scales. Recent experimental developments allow materials to be designed precisely at the nanometer scale. However, the optimum design of such materials requires capabilities to predict the properties at the process scale based on the phenomena occurring at the relevant scales. The thesis research reported here addresses this need to develop multiscale modeling strategies for the design of new materials. As a model system, a new system of materials called molecular squares was studied in this research. Both serial and parallel multiscale strategies and their components were developed as parts of this work. As a serial component, a parameter estimation tool was developed that uses a hierarchical protocol and consists of two different search elements: a global search method implemented using a genetic algorithm that is capable of exploring large parametric space, and a local search method using gradient search techniques that accurately finds the optimum in a localized space. As an essential component of parallel multiscale modeling, different standard as well as specialized computational fluid dynamics (CFD) techniques were explored and developed in order to identify a technique that is best suited to solve a membrane reactor model employing layered films of molecular squares as the heterogeneous catalyst. The coupled set of non-linear partial differential equations (PDEs) representing the continuum model was solved numerically using three different classes of methods: a split-step method using finite difference (FD); domain decomposition in two different forms, one involving three overlapping subdomains and the other involving a gap-tooth scheme; and the multiple-timestep method that was developed in this research. The parallel multiscale approach coupled continuum

  11. 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.

  12. Adhesive forces at bimetallic interfaces

    International Nuclear Information System (INIS)

    Das, M.P.; Nafari, N.; Ziesche, P.; Kaschner, H.R.

    1987-03-01

    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

  13. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    Directory of Open Access Journals (Sweden)

    I. V. Derevich

    2017-01-01

    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  14. 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.

  15. Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

    Science.gov (United States)

    Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

    2017-02-01

    In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

  16. A generic model for photocatalytic activity as a function of catalyst thickness

    DEFF Research Database (Denmark)

    Nielsen, Morten G.; In, Su-Il; Vesborg, Peter C.K.

    2012-01-01

    value for increasing catalyst film thickness. Conversely, having opposing directions of illumination and incident gas, there exists an optimal catalyst film thickness with respect to activity. In the present work, we demonstrate, quantify and model this effect using methane photooxidation over PVD TiO2...

  17. Hydroxylation of Benzene via C-H Activation Using Bimetallic CuAg@g-C3N4

    Science.gov (United States)

    A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light.

  18. Synthesis and characterization of bimetallic Cu-Ni/ZrO{sub 2} nanocatalysts: H{sub 2} production by oxidative steam reforming of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Hernandez, R.; Mondragon Galicia, G.; Mendoza Anaya, D.; Palacios, J. [Instituto Nacional de Investigaciones Nucleares; Carretera Mexico-Toluca S/N La Marquesa, Ocoyoacac, Estado de Mexico C.P. 52750 (Mexico); Angeles-Chavez, C. [Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas, No. 152, C.P. 07730, Mexico D.F. (Mexico); Arenas-Alatorre, J. [Instituto de Fisica-UNAM, Apartado Postal 20-364, C.P. 01000, Mexico D.F. (Mexico)

    2008-09-15

    Cu/ZrO{sub 2}, Ni/ZrO{sub 2} and bimetallic Cu-Ni/ZrO{sub 2} catalysts were prepared by deposition-precipitation method to produce hydrogen by oxidative steam reforming of methanol (OSRM) reaction in the range of 250-360 C. TPR analysis of the Cu-Ni/ZrO{sub 2} catalyst showed that the presence of Cu facilitates the reduction of the Ni at lower temperatures. In addition, this sample showed two reduction peaks, the former peak was attributed to the reduction of the adjacent Cu and Ni atoms which could be forming a bimetallic Cu-rich phase, and the second was assigned to the remaining Ni atoms forming bimetallic Ni-rich nanoparticles. Transmission Electron Microscopy revealed Cu or Ni nanoparticles on the monometallic samples, while bimetallic nanoparticles were identified on the Cu-Ni/ZrO{sub 2} catalyst. On the other hand, Cu-Ni/ZrO{sub 2} catalyst exhibited better catalytic activity than the monometallic samples. The difference between them was related to the Cu-Ni nanoparticles present on the former catalyst, as well as the bifunctional role of the bimetallic phase and the support that improve the catalytic activity. All the catalysts showed the same selectivity toward H{sub 2} at the maximum reaction temperature and it was {proportional_to}60%. The high selectivity toward CO is associated to the presence of the bimetallic Ni-rich nanoparticles, as evidenced by TEM-EDX analysis, since this behavior is similar to the one showed by the monometallic Ni-catalyst. (author)

  19. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction. Quarterly summary, June 1, 1991--August 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.

    1991-10-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  20. Bimetallic structure fabricated by laser interference lithography for tuning surface plasmon resonance.

    Science.gov (United States)

    Liu, C H; Hong, M H; Cheung, H W; Zhang, F; Huang, Z Q; Tan, L S; Hor, T S A

    2008-07-07

    Tuning of surface plasmon resonance by gold and silver bimetallic thin film and bimetallic dot array is investigated. Laser interference lithography is applied to fabricate the nanostructures. A bimetallic dot structure is obtained by a lift-off procedure after gold and silver thin film deposition by an electron beam evaporator. Surface plasmon behaviors of these films and nanostructures are studied using UV-Vis spectroscopy. It is observed that for gold thin film on quartz substrate, the optical spectral peak is blue shifted when a silver thin film is coated over it. Compared to the plasmon band in single metal gold dot array, the bimetallic nanodot array shows a similar blue shift in its spectral peak. These shifts are both attributed to the interaction between gold and silver atoms. Electromagnetic interaction between gold and silver nanostructures is discussed using a simplified spring model.

  1. Structure and chemistry of model catalysts in ultrahigh vacuum

    Science.gov (United States)

    Walker, Joshua D.

    The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of

  2. Oxide-supported metal clusters: models for heterogeneous catalysts

    International Nuclear Information System (INIS)

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  3. Bisphenol A Synthesis - Modeling of Industrial Reactor and Catalyst Deactivation

    Czech Academy of Sciences Publication Activity Database

    Prokop, Zdeněk; Hanková, Libuše; Jeřábek, Karel

    2004-01-01

    Roč. 60, - (2004), s. 77-83 Sp/Iss/ SI ISSN 1381-5148. [Asia-Pacific Congress on Catalysis /3./. Dalian, 12.10.2003-15.10.2003] R&D Projects: GA ČR GA104/02/1104 Institutional research plan: CEZ:AV0Z4072921 Keywords : bisphenol A * catalyst deactivation * ion exchanger catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.582, year: 2004

  4. Synergistic effect in the oxidation of benzyl alcohol using citrate-stabilized gold bimetallic nanoparticles supported on alumina

    Energy Technology Data Exchange (ETDEWEB)

    Gómez-Villarraga, Fernando, E-mail: ferchogomezv@gmail.com; Radnik, Jörg; Martin, Andreas; Köckritz, Angela [Leibniz-Institut für Katalyse e.V. an der Universität Rostock (Germany)

    2016-06-15

    Bimetallic nanoparticles (NPs) containing gold and various second metals (M = Pd, Pt, Cu, and Ag) supported on alumina (AuM/Alumina) were prepared using sodium citrate as stabilizer. In addition, supported monometallic Au/Alumina and Pd/Alumina were synthesized and tested to reveal synergistic effects in the catalytic evaluation of the bimetallic catalysts. The monometallic and bimetallic NPs revealed average sizes below 10 nm. The oxidation of benzyl alcohol with molecular oxygen as oxidant at mild conditions in liquid phase in the absence and presence (toluene or NaOH aqueous solution, 0.2 M) of a solvent was selected as test reaction to evaluate the catalytic properties of the above-mentioned solids. AuPd/Alumina exhibited the best catalytic activity among all bimetallic catalysts using toluene as solvent and under solvent-free conditions, respectively. In comparison to the monometallic catalysts, a synergistic effect with AuPd/Alumina was only evident in the solvent-free reaction. The AuPd/Alumina catalyst was able to oxidize benzyl alcohol selectively depending on the reaction medium into benzaldehyde (toluene or solvent-free) or benzoic acid (NaOH aqueous solution, 0.2 M). However, the catalyst deactivated due to particle growth of the bimetallic AuPd NPs by Ostwald ripening and leaching was not observed in the oxidation using toluene as solvent. The size of the catalytically active NPs, the metal composition of the particles, and the reaction conditions greatly influenced the catalytic oxidation results.Graphical Abstract.

  5. Hydrogen Production on Ag-Pd/TiO2 Bimetallic Catalysts: Is there a Combined Effect of Surface Plasmon Resonance with Schottky Mechanism on the Photo-Catalytic Activity?

    KAUST Repository

    Nadeem, Muhammad A.

    2017-03-28

    Despite many observations that plasmonics can enhance photocatalytic reactions, their relative role in the overall reaction rate is not thoroughly investigated. Here we report that silver nanoparticles contribution in the reaction rate by its plasmonic effect is negligible when compared to that of Pd (Schottky effect). To conduct the study a series of Ag−Pd/TiO2 catalysts have been prepared, characterized and tested for H2 production from water in the presence of an organic sacrificial agent. Pd was chosen as a standard high work function metal needed for the Schottky junction to pump away electrons from the conduction band of the semiconductor and Ag (whose work function is ca. 1 eV lower than that of Pd) for its high plasmonic resonance response at the edge of the bandgap of TiO2. While H2 production rates showed linear dependency on plasmonic response of Ag in the Pd−Ag series, the system performed less than that of pure Pd. In other words, the plasmonic contribution of Ag in the Ag−Pd/TiO2 catalyst for hydrogen production, while confirmed using different excitation energies, is small. Therefore, the “possible” synergistic effect of plasmonic (in the case of Ag) and Schottky-mechanism (in the case of Pd) is minor when compared to that of Schottky-effect alone.

  6. 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.

  7. Statistical modeling for Toluene Diisocyanate and Polypropylene Glycol Polymerization with Ferric Acetylacetonate as Catalyst

    International Nuclear Information System (INIS)

    Semsarzadeh, M. A.; Salehi, H.

    2001-01-01

    Polyurethane elastomer was synthesized with propylene glycol and toluene diisocyanate with ferric acetylacetonate catalyst. This polymerization was modeled using the kinetic equations. The number and weight average degrees of polymerization (DP w and DP n ), the number and weight average molecular weights (M w and M n ) and the polydispersity index parameters were found and tested as function of time and conversion and they were finally compared with GPC laboratory and experimental results. The effect of concentration of the catalyst and the addition sequence of starting materials and catalyst on M n , M w , DPI and M z /M n are reported and discussed

  8. A mathematical model and optimization of the cathode catalyst layer structure in PEM fuel cells

    International Nuclear Information System (INIS)

    Wang Qianpu; Song Datong; Navessin, Titichai; Holdcroft, Steven; Liu Zhongsheng

    2004-01-01

    A spherical flooded-agglomerate model for the cathode catalyst layer of a proton exchange membrane fuel cell, which includes the kinetics of oxygen reduction, at the catalyst vertical bar electrolyte interface, proton transport through the polymer electrolyte network, the oxygen diffusion through gas pore, and the dissolved oxygen diffusion through electrolyte, is considered. Analytical and numerical solutions are obtained in various control regimes. These are the limits of (i) oxygen diffusion control (ii) proton conductivity control, and (iii) mixture control. The structure and material parameters, such as porosity, agglomerate size, catalyst layer thickness and proton conductivity, on the performance are investigated under these limits. The model could help to characterize the system properties and operation modes, and to optimize catalyst layer design

  9. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M

    2002-01-01

    ) and Differential Scanning Calorimetry (DSC). Fundamental thermodynamic data like temperatures and molar heats of solid-solid transition and fusion, phase diagrams, heat capacities of solids and liquids, heat of mixing and heats of complex formation have been obtained and the results are discussed in relation...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  10. Ordered mesoporous materials as model supports to study catalyst preparation

    NARCIS (Netherlands)

    Sietsma, J.R.A.

    2007-01-01

    Catalysts are indispensable to modern-day society because of their prominent role in petroleum refining, chemical processing, and the reduction of environmental pollution. The catalytically active component often consists of small metal (oxide) particles that are supported on a carrier such as

  11. Copper Affects the Location of Zinc in Bimetallic Ion-Exchanged Mordenite.

    Science.gov (United States)

    Reule, Allen A C; Shen, Jing; Semagina, Natalia

    2018-03-25

    Bimetallic ion exchange on a zeolite often impacts its catalytic properties compared to its monometallic counterparts. Here, we address the synergistic effect of simultaneous copper and zinc ion exchange on mordenite (MOR), as found earlier for dimethyl ether (DME) carbonylation. Samples with various Cu/Zn ratios were characterized by diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS) in the 3600 and 720 cm -1 regions, pore distribution analysis through Ar physisorption, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and transmission electron microscopy (TEM). When ion-exchanged alone, copper preferentially occupies 12-membered rings, whereas zinc occupies 8-membered rings. In bimetallic combinations, the zinc addition was found to prevent the copper from sintering into nanoparticles and to increase its coordination strength to the zeolite. At a Cu/Zn ratio of 0.25 (for MOR with Si/Al=6.5), copper promotes zinc ion exchange into 12-membered rings, more specifically, into T4 sites that are known for the formation of the coke precursor in DME carbonylation on a MOR. The sites became blocked during the bimetallic ion exchange, leading to suppressed catalyst deactivation. The study contributes to the understanding of mutual ion effects in bimetallic exchanged zeolites and highlights the major role of copper as a governing factor in determining the location of co-exchanged zinc on a MOR. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kuila, Debasish [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States); Ilias, Shamsuddin [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Ana C.; Goncalves, A.P.; Gasche, T. Almeida [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Ferraria, A.M.; Rego, A.M. Botelho do [Universidade Tecnica de Lisboa, IST, Centro de Quimica-Fisica Molecular and IN, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, M.R.; Bola, A. Margarida [I3N-Universidade de Aveiro, Department Fisica, Aveiro (Portugal); Branco, J.B., E-mail: jbranco@itn.p [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2010-05-14

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi{sub 2} (An = Th, U) and ThCu{sub 2} were used as precursors and the products (2NiO.UO{sub 3}, 2NiO.ThO{sub 2} and 2CuO.ThO{sub 2}) 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 H{sub 2} and CO and stable for a period of time of {approx}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/Al{sub 2}O{sub 3}. 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 H{sub 2}-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  14. Modeling of Ultrathin Catalyst Layers in Polymer Electrolyte Fuel Cells: Proton Transport and Water Management

    OpenAIRE

    Chan, Karen Ka Wing

    2013-01-01

    Ultrathin catalyst layers (UTCLs) are emerging as a promising alternative to conventional catalyst layers in polymer electrolyte fuel cells. In comparison, UTCLs have dramatically reduced Pt loading and thicknesses and are ionomer–free. We explore two open questions in the theory of UTCLs (1) the proton transport mechanism within the ionomer–free layer and (2) water management in membrane electrode assemblies (MEAs) with UTCLs. To investigate (1), we present a UTCL model, which assumes the pr...

  15. Catalysts and process for liquid hydrocarbon fuel production

    Science.gov (United States)

    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.

  16. Modeling Deactivation of Catalysts for Selective Catalytic Reduction of NOx by KCl Aerosols

    DEFF Research Database (Denmark)

    Olsen, Brian Kjærgaard; Castellino, Francesco; Jensen, Anker Degn

    2017-01-01

    A detailed model for the deactivation of a V2O5–WO3/TiO2-based SCR monolith catalyst by potassium poisoning has been developed and validated. The model accounts for deposition of KCl aerosol particles present in the flue gas on the external catalyst surface, the reaction of the deposited particles...... with the catalyst at the surface of the monolith wall, the transport and accumulation of potassium, bound to Brønsted acid sites, throughout the catalyst wall, and the resulting loss in SCR activity. Using an experimentally measured KCl aerosol size distribution as input, the model can replicate the observed...... deactivation rate of a 3 wt % V2O5-7 wt % WO3/TiO2 monolith catalyst, exposed to a KCl aerosol at 350 °C for about 1000 h, as well as the resulting potassium-to-vanadium molar ratios in the catalyst wall. Simulations show that the particle deposition rate, as well as the deactivation rate, decreases...

  17. 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.

  18. Effect of nanoscale flows on the surface structure of nanoporous catalysts.

    Science.gov (United States)

    Montemore, Matthew M; Montessori, Andrea; Succi, Sauro; Barroo, Cédric; Falcucci, Giacomo; Bell, David C; Kaxiras, Efthimios

    2017-06-07

    The surface structure and composition of a multi-component catalyst are critical factors in determining its catalytic performance. The surface composition can depend on the local pressure of the reacting species, leading to the possibility that the flow through a nanoporous catalyst can affect its structure and reactivity. Here, we explore this possibility for oxidation reactions on nanoporous gold, an AgAu bimetallic catalyst. We use microscopy and digital reconstruction to obtain the morphology of a two-dimensional slice of a nanoporous gold sample. Using lattice Boltzmann fluid dynamics simulations along with thermodynamic models based on first-principles total-energy calculations, we show that some sections of this sample have low local O 2 partial pressures when exposed to reaction conditions, which leads to a pure Au surface in these regions, instead of the active bimetallic AgAu phase. We also explore the effect of temperature on the surface structure and find that moderate temperatures (≈300-450 K) should result in the highest intrinsic catalytic performance, in apparent agreement with experimental results.

  19. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  20. Mono and bimetallic nanoparticles of gold, silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

    International Nuclear Information System (INIS)

    Santhanalakshmi, J.; Venkatesan, P.

    2011-01-01

    Mono metallic (Au, Ag, Pd) and bimetallic (Au–Ag, Ag–Pd, Au–Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au–Ag = 9.2, Ag–Pd = 9.6, Au–Pd = 9.4 nm) are characterized by UV–Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.Graphical Abstract

  1. Mono and bimetallic nanoparticles of gold, silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

    Science.gov (United States)

    Santhanalakshmi, J.; Venkatesan, P.

    2011-02-01

    Mono metallic (Au, Ag, Pd) and bimetallic (Au-Ag, Ag-Pd, Au-Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au-Ag = 9.2, Ag-Pd = 9.6, Au-Pd = 9.4 nm) are characterized by UV-Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.

  2. An introduction to catalyst

    International Nuclear Information System (INIS)

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  3. 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)

  4. Parameter estimation and analysis of an automotive heavy-duty SCR catalyst model

    DEFF Research Database (Denmark)

    Åberg, Andreas; Widd, Anders; Abildskov, Jens

    2017-01-01

    A single channel model for a heavy-duty SCR catalyst was derived based on first principles. The model considered heat and mass transfer between the channel gas phase and the wash coat phase. The parameters of the kinetic model were estimated using bench-scale monolith isothermal data. Validation ...

  5. Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials.

    Science.gov (United States)

    Bedford, Nicholas M; Showalter, Allison R; Woehl, Taylor J; Hughes, Zak E; Lee, Sungsik; Reinhart, Benjamin; Ertem, S Piril; Coughlin, E Bryan; Ren, Yang; Walsh, Tiffany R; Bunker, Bruce A

    2016-09-27

    Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when two different metallic species are mixed at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesized with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy, and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods was then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence dependence in both surface structure and surface composition. Replica exchange with solute tempering molecular dynamics simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged

  6. Synthesis and hydrogenation application of Pt-Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer

    Science.gov (United States)

    Jin, Zhijun; Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong

    2017-12-01

    Different generations of poly(propylene imine) (Gn-PPI) terminated with N-containing 15-membered triolefinic macrocycle (GnM) (n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts GnM-(Ptx/Pd10-x) (x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between GnM and the complexes of Pt(PPh3)4 and Pd(PPh3)4. The structure and catalytic properties of GnM-(Ptx/Pd10-x) were characterized via Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd-Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd-Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations (n) of GnM-(Pt3/Pd7) (n = 2, 3, 4, 5).

  7. 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%.

  8. Novel dynamic effects in electrocatalysis of methanol oxidation on supported nanoporous TiO2 bimetallic nanocatalysts

    International Nuclear Information System (INIS)

    Hepel, Maria; Dela, Indeewari; Hepel, Tadeusz; Luo, Jin; Zhong, C.J.

    2007-01-01

    New dynamic aspects of the catalysis of methanol oxidation reaction (MOR) have been studied using quantum mechanical calculations applied to the support-catalyst cluster interactions and surface diffusivity of adsorbed intermediates. For very small catalyst-support clusters, we have found a strong enhancement of the ligand effect for bimetallic catalysts of the type Pt n M m attributed to the decreased local density of states near the Fermi level of Pt atoms neighboring the additive metal atom M. This enhancement results in a decreased barrier for surface diffusion of adsorbed CO ad through the cooperative diffusion mechanism, based on structural relaxation of the catalyst-support cluster, proposed in this work. The strong ligand effect dominates over the Schwoebel potential and trapping well effects, being responsible for accumulation of poisoning intermediates at step sites on the catalyst surface and gradual decrease of catalytic activity with decreasing size of catalyst nanoparticles. The lattice relaxation and strong ligand effects in small catalyst-support clusters lead to lower adsorption energy for CO ad and thus, to higher reactivity and mobility of reactants and intermediates. The experimental investigations included submonolayer films of bi-functional catalysts (PtRu, PtFe) deposited on novel nanostructured supporting materials, designed with the goal of achieving high variability of their electronic and chemical properties to influence the catalytic activity of sub-monolayer catalyst. The mesoscopic TiO 2 supporting film formation was investigated using EQCN, pulse voltammetric and AFM techniques. The conditions for the formation of monodispersed TiO 2 nanoparticles with regular nanopores (nanotubes), 20-80 nm in diameter, were described. It follows from EQCN and voltammetric measurements and AFM image analysis that the nanopores are formed by a dissolution-precipitation mechanism. The catalysts, Pt and PtRu, deposited on supporting nanoporous TiO 2-x

  9. Optimization of alkali catalyst for transesterification of jatropha curcus using adaptive neuro-fuzzy modeling

    Directory of Open Access Journals (Sweden)

    Vipan K Sohpal

    2014-06-01

    Full Text Available Transesterification of Jatropha curcus for biodiesel production is a kinetic control process, which is complex in nature and controlled by temperature, the molar ratio, mixing intensity and catalyst process parameters. A precise choice of catalyst is required to improve the rate of transesterification and to simulate the kinetic study in a batch reactor. The present paper uses an Adaptive Neuro-Fuzzy Inference System (ANFIS approach to model and simulate the butyl ester production using alkaline catalyst (NaOH. The amounts of catalyst and time for reaction have been used as the model’s input parameters. The model is a combination of fuzzy inference and artificial neural network, including a set of fuzzy rules which have been developed directly from experimental data. The proposed modeling approach has been verified by comparing the expected results with the practical results which were observed and obtained through a batch reactor operation. The application of the ANFIS test shows which amount of catalyst predicted by the proposed model is suitable and in compliance with the experimental values at 0.5% level of significance.

  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. Kinetic modelling of the isomerization of N-Hexane using bifunctional Pt-Ni-MOR catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Brito, K.D.; Sousa, B.V.; Rodrigues, M.G.F.; Alves, J.J.N. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], E-mail: jailson@deq.ufcg.edu.br

    2008-01-15

    The objective of the present work is to realize the kinetic modelling regarding deactivation of Pt-Ni catalysts present in mordenite zeolite and monitor the isomerization reaction of n-hexane. The catalysts have been prepared with different metal ratios for comparison in terms of ion exchange and characterization by the XRD technique, in order to correlate the catalytic behavior of the material with its properties. The catalysts were also evaluated during the isomerization reaction of n-hexane. According to the XRD analyses it was observed that the incorporation of the metals Pt and Ni in the structure of the mordenite zeolite did not change the X-Ray diffractograms after the ionic exchange process and calcination of the catalysts. Based on the results of the catalytic investigation, a kinetic model was proposed to deactivate the catalysts. By means of two correlations, the deactivation parameters were determined, allowing establishing the profile of the activity at any time, when the composition of one of the metals is known. According to the results of this work, there might be the possibility that the proposed model of deactivation is a result of coke formation. (author)

  12. Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Hui [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); Huang, Yunpeng; Shen, Mingwu; Guo, Rui; Cao, Xueyan [College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); Shi, Xiangyang, E-mail: xshi@dhu.edu.cn [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); CQM - Centro de Quimica da Madeira, Universidade da Madeira, Campus da Penteada, 9000-390 Funchal (Portugal)

    2012-04-15

    Fe/Pd bimetallic nanoparticles (NPs) have held great promise for treating trichloroethylene (TCE)-contaminated groundwater, without the accumulation of chlorinated intermediates. However, the conventionally used colloidal Fe/Pd NPs usually aggregate rapidly, resulting in a reduced reactivity. To reduce the particle aggregation, we employed electrospun polyacrylic acid (PAA)/polyvinyl alcohol (PVA) polymer nanofibers as a nanoreactor to immobilize Fe/Pd bimetallic NPs. In the study, the water-stable PAA/PVA nanofibrous mats were complexed with Fe (III) ions via the binding with the free carboxyl groups of PAA for subsequent formation and immobilization of zero-valent iron (ZVI) NPs. Fe/Pd bimetallic NPs were then formed by the partial reduction of Pd(II) ions with ZVI NPs. The formed electrospun nanofibrous mats containing Fe/Pd bimetallic NPs with a diameter of 2.8 nm were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy. The Fe/Pd NP-containing electrospun PAA/PVA nanofibrous mats exhibited higher reactivity than that of the ZVI NP-containing mats or colloidal Fe/Pd NPs in the dechlorination of trichloroethylene (TCE), which was used as a model contaminant. With the high surface area to volume ratio, high porosity, and great reusability of the fibrous mats immobilized with the bimetallic NPs, the composite nanofibrous mats should be amenable for applications in remediation of various environmental contaminants.

  13. Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles

    International Nuclear Information System (INIS)

    Ma, Hui; Huang, Yunpeng; Shen, Mingwu; Guo, Rui; Cao, Xueyan; Shi, Xiangyang

    2012-01-01

    Fe/Pd bimetallic nanoparticles (NPs) have held great promise for treating trichloroethylene (TCE)-contaminated groundwater, without the accumulation of chlorinated intermediates. However, the conventionally used colloidal Fe/Pd NPs usually aggregate rapidly, resulting in a reduced reactivity. To reduce the particle aggregation, we employed electrospun polyacrylic acid (PAA)/polyvinyl alcohol (PVA) polymer nanofibers as a nanoreactor to immobilize Fe/Pd bimetallic NPs. In the study, the water-stable PAA/PVA nanofibrous mats were complexed with Fe (III) ions via the binding with the free carboxyl groups of PAA for subsequent formation and immobilization of zero-valent iron (ZVI) NPs. Fe/Pd bimetallic NPs were then formed by the partial reduction of Pd(II) ions with ZVI NPs. The formed electrospun nanofibrous mats containing Fe/Pd bimetallic NPs with a diameter of 2.8 nm were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy. The Fe/Pd NP-containing electrospun PAA/PVA nanofibrous mats exhibited higher reactivity than that of the ZVI NP-containing mats or colloidal Fe/Pd NPs in the dechlorination of trichloroethylene (TCE), which was used as a model contaminant. With the high surface area to volume ratio, high porosity, and great reusability of the fibrous mats immobilized with the bimetallic NPs, the composite nanofibrous mats should be amenable for applications in remediation of various environmental contaminants.

  14. A proposed agglomerate model for oxygen reduction in the catalyst layer of proton exchange membrane fuel cells

    International Nuclear Information System (INIS)

    Zhang, Xiaoxian; Gao, Yuan; Ostadi, Hossein; Jiang, Kyle; Chen, Rui

    2014-01-01

    Highlights: • We developed a new agglomerate model to describe oxygen reduction reaction. • We showed how to calculate the model parameters from catalyst layer structure. • We verified the agglomerate model. - Abstract: Oxygen diffusion and reduction in the catalyst layer of PEM fuel cell is an important process in fuel cell modelling, but models able to link the reduction rate to catalyst-layer structure are lack; this paper makes such an effort. We first link the average reduction rate over the agglomerate within a catalyst layer to a probability that an oxygen molecule, which is initially on the agglomerate surface, will enter and remain in the agglomerate at any time in the absence of any electrochemical reaction. We then propose a method to directly calculate distribution function of this probability and apply it to two catalyst layers with contrasting structures. A formula is proposed to describe these calculated distribution functions, from which the agglomerate model is derived. The model has two parameters and both can be independently calculated from catalyst layer structures. We verify the model by first showing that it is an improvement and able to reproduce what the spherical model describes, and then testing it against the average oxygen reductions directly calculated from pore-scale simulations of oxygen diffusion and reaction in the two catalyst layers. The proposed model is simple, but significant as it links the average oxygen reduction to catalyst layer structures, and its two parameters can be directly calculated rather than by calibration

  15. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst

    Directory of Open Access Journals (Sweden)

    M. Toghyani

    2015-07-01

    Full Text Available The Pt/γ-Al2O3 catalyst life time was limited by the formation of coke on the external and internal surfaces of catalyst in dehydrogenation reactors. The kinetics of decoking of dehydrogenation catalyst was studied in a pilot scale fixed bed reactor experimentally. The effects of temperature, oxygen concentration and other operating conditions on decoking process were investigated. A kinetic model was deve-loped to describe the decoking of mentioned catalyst. An objective function was defined as the sum of squares of the deviations among the calculated and plant data. Accordingly the appropriate values were found in order to minimize this function. It was concluded that there was a good agreement between simulation results and experimental data.  © 2015 BCREC UNDIP. All rights reservedReceived: 18th September 2014; Revised: 28th February 2015; Accepted: 9th March 2015How to Cite: Toghyani, M., Rahimi, A., Mamanpoush, M., Kazemian, R., Harandizadeh, A.H. (2015. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 155-161. (doi:10.9767/bcrec.10.2.7357.155-161 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7357.155-161  

  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. Determination of concentration distribution and velocity of a catalyst in a model of a fluidized bed reactor using nuclear techniques

    International Nuclear Information System (INIS)

    Santos, V.A. dos.

    1981-09-01

    A simplified model of a cracking unit was construct. The gaseous phase consisted of air, the solid phase (zeolite catalyst cracking) and both the phases circulate at the ambiente temperature in the steady state with 500 g of catalyst and air flow of 1600 1/h. Measurements for the circulation time of the solid phase (catalyst), concentration and radial distribution of catalyst have been carried out. The reduced experimental model of the cracking reactor (FCC) was used and radioctive tracer and attenuation of γ-radiation techniques were employed. (E.G.) [pt

  18. Theoretical and Experimental Analysis of Formability of Explosive Welded Mg/Al Bimetallic Bars

    Directory of Open Access Journals (Sweden)

    Mróz S.

    2017-06-01

    Full Text Available The paper has presented the results of theoretical studies and experimental tests of the plastic deformation of Mg/Al bimetallic specimens. Theoretical studies were carried out using the Forge2011® computer program. Physical modeling, on the other hand, was performed using the Gleeble3800 simulator. Bimetallic bars of an outer diameter of 22.5 mm and a cladding layer thickness of 1.7 mm were obtained by the explosive welding method. Samples for formability tests, characterized by a diameter-to-length ratio of 1, were taken from the bars. The theoretical studies and experimental tests were carried out for the temperature range from 300 to 400°C and for different strain rates. Based on the obtained investigation results it has been found that the main parameters influencing the formability of Mg/Al bimetallic bars are strain rate than the process temperature.

  19. Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.; Colby, Robert J.; Kabius, Bernd C.; Rob van Veen, J. A.; Jentys, Andreas; Lercher, Johannes A.

    2013-08-01

    The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, which was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.

  20. Hydrodeoxygenation of waste fat for diesel production: Study on model feed with Pt/alumina catalyst

    DEFF Research Database (Denmark)

    Madsen, Anders Theilgaard; Ahmed, El Hadi; Christensen, Claus H.

    2011-01-01

    Hydrodeoxygenation of waste fats and oils is a viable method for producing renewable diesel oil. In this study a model feed consisting of oleic acid and tripalmitin in molar ratio 1:3 was hydrotreated at 325°C with 20bars H2 in a stirred batch autoclave with a 5wt% Pt/γ-Al2O3 catalyst, and samples...

  1. Monolayer Iron Carbide Films on Au(111) as a Fischer–Tropsch Model Catalyst

    DEFF Research Database (Denmark)

    Mannie, Gilbère; Lammich, Lutz; Li, Yong-Wang

    2014-01-01

    Using scanning tunneling microscopy (STM), we characterize the atomic-scale details of ultrathin films of iron carbide (FexCy) on Au(111) synthesized as a potential model system for the active iron carbide phase in iron Fischer–Tropsch synthesis (FTS) catalysts. The experiments show that room...

  2. Surface science approach to Pt/carbon model catalysts: XPS, STM and microreactor studies

    Science.gov (United States)

    Motin, Abdul Md.; Haunold, Thomas; Bukhtiyarov, Andrey V.; Bera, Abhijit; Rameshan, Christoph; Rupprechter, Günther

    2018-05-01

    Pt nanoparticles supported on carbon are an important technological catalyst. A corresponding model catalyst was prepared by physical vapor deposition (PVD) of Pt on sputtered HOPG (highly oriented pyrolytic graphite). The carbon substrate before and after sputtering as well as the Pt/HOPG system before and after Pt deposition and annealing were examined by XPS and STM. This yielded information on the surface density of defects, which serve as nucleation centres for Pt, and on the size distribution (mean size/height) of the Pt nanoparticles. Two different model catalysts were prepared with mean sizes of 2.0 and 3.6 nm, both turned out to be stable upon UHV-annealing to 300 °C. After transfer into a UHV-compatible flow microreactor and subsequent cleaning in UHV and under mbar pressure, the catalytic activity of the Pt/HOPG model system for ethylene hydrogenation was examined under atmospheric pressure flow conditions. This enabled to determine temperature-dependent conversion rates, turnover frequencies (TOFs) and activation energies. The catalytic results obtained are in line with the characteristics of technological Pt/C, demonstrating the validity of the current surface science based model catalyst approach.

  3. Strategies for Probing Nanometer-Scale Electrocatalysts: From Single Particles to Catalyst-Membrane Architectures

    Energy Technology Data Exchange (ETDEWEB)

    Korzeniewski, Carol [Texas Tech Univ., Lubbock, TX (United States). Department of Chemistry & Biochemistry

    2014-01-20

    The project primary objectives are to prepare and elucidate the promoting properties of materials that possess high activity for the conversion of hydrogen and related small molecules (water, oxygen, carbon monoxide and methanol) in polymer electrolyte fuel cells. One area of research has focused on the study of catalyst materials. Protocols were developed for probing the structure and benchmarking the activity of Pt and Pt bimetallic nanometer-scale catalyst against Pt single crystal electrode standards. A second area has targeted fuel cell membrane and the advancement of simple methods mainly based on vibrational spectroscopy that can be applied broadly in the study of membrane structure and transport properties. Infrared and Raman methods combined with least-squares data modeling were applied to investigate and assist the design of robust, proton conductive membranes, which resist reactant crossover.

  4. Fresh tar (from biomass gasification) destruction with downstream catalysts: comparison of their intrinsic activity with a realistic kinetic model

    Energy Technology Data Exchange (ETDEWEB)

    Corella, J.; Narvaez, I.; Orio, A. [Complutense Univ. of Madrid (Spain). Dept. of Chemical Engineering

    1996-12-31

    A model for fresh tar destruction over catalysts placed downstream a biomass gasifier is presented. It includes the stoichio-metry and the calculation of the kinetic constants for the tar destruction. Catalysts studied include commercial Ni steam reforming catalysts and calcinated dolomites. Kinetic constants for tar destruction are calculated for several particle sizes, times- on-stream and temperatures of the catalyst and equivalence ratios in the gasifier. Such intrinsic kinetic constants allow a rigorous or scientific comparison of solids and conditions to be used in an advanced gasification process. (orig.) 4 refs.

  5. Knowledge Based Catalyst Design by High Throughput Screening of Model Reactions and Statistical Modelling Conception de catalyseur par criblage à haut débit de réactions modèles et modélisation statistique

    Directory of Open Access Journals (Sweden)

    Morra G.

    2013-08-01

    Full Text Available Material design and synthesis are key steps in the development of catalysts. They are usually based on an empiric and/or theoretical approach. The recently developed high-throughput experimentation can accelerate optimisation of new catalytic formulations by systematic screening in a predefined study domain. This work aims at developing a QSAR (Quantitative Structure Activity Relationship method based on kinetic and mechanistic descriptors for metal and acid catalysis. Physico-chemicalfeatures of approximately sixty bimetallic catalysts have been measured according to their performance in two model reactions: xylene hydrogenation for catalysis on metallic sites and isomerisation of 3,3-dimethyl-l-butene for catalysis on acid sites. These descriptors were finally used to model the performances of around twenty catalysts for a more complex reaction: n-decane dehydrogenation. La définition et la préparation de matériaux sont des étapes clés dans le développement de catalyseurs. Celles-ci peuvent être effectuées de façon empirique et/ou à partir de bases théoriques. Par ailleurs, l’expérimentation à haut débit, technologie récente, permet d’accélérer l’optimisation de formulations catalytiques par exemple par criblage systématique d’un espace d’étude prédéfini. Cet article a pour objet de développer une méthode QSAR (Quantitative Structure Activity Relationship basée sur la recherche de descripteurs cinétiques et mécanistiques, dans le domaine de la catalyse acide et métallique supportée. Des caractéristiques physico-chimiques (descripteurs d’une soixantaine de catalyseurs bimétalliques ont été mesurées suivant leur performance dans deux réactions modèles : l’hydrogénation de ro-xylène pour rendre compte de la catalyse par le métal et l’isomérisation du diméthyl-3,3butène-1 pour la catalyse par les sites acides. Ces descripteurs ont été ensuite mis à profit pour modéliser les performances

  6. Mathematical model of Fischer-Tropsch catalyst pellet with pointed centers of synthesis

    Science.gov (United States)

    Derevich, I. V.; Fokina, A. Yu

    2017-11-01

    The productivity of Fischer-Tropsch reactors is determined by the efficiency of heat and mass transfer processes inside the catalyst pellets. To reduce the diffusion resistance, the pellet base is made porous. The porous structure of the granules causes a discrete arrangement of cobalt metallic microparticles whose size can reach tens of microns. The distance between these active centres significantly exceeds their characteristic size and the homogeneous catalyst model is incorrect. A mathematical model of heat and mass transfer processes inside a porous spherical pellet with localised active centres is proposed. The heat of the exothermic synthesis reaction is removed from the surface of the granule to the synthesis gas stream washing the catalyst pellet by heat transfer. The components of the synthesis gas enter the granule surface as a result of mass transfer. On the basis of the self-consistent field method, the values of the temperature and concentration of the synthesis gas components at the active centres were determined. It is shown that there is a critical temperature of the synthesis gas washing the granule, exceeding critical temperature leads to a substantial overheating of the active centres. In this case, the surface of the catalyst pellet is superheated slightly. The principal difference between the homogeneous and heterogeneous models in catalytic reactions is discussed.

  7. Preparation of Pt–Ru bimetallic catalyst supported on carbon

    Indian Academy of Sciences (India)

    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 ...

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

    Indian Academy of Sciences (India)

    Unknown

    of carbon nanotube (Iijima 1991) was first based on the carbon-arc method, though the carbon nanotube prepared by this method are more graphitic, the low yield and rela- tively small length (< 1 m) make the production cost very high. The template synthesis method (Martin 1994) and catalytic production methods (Jose et ...

  9. Preparation of Pt–Ru bimetallic catalyst supported on carbon ...

    Indian Academy of Sciences (India)

    2016-08-26

    Aug 26, 2016 ... 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 ...

  10. Efficient utilization of bimetallic catalyst in low environment syngas ...

    Indian Academy of Sciences (India)

    Sonal

    2017-10-26

    Oct 26, 2017 ... environment syngas for liquid fuel production. SONAL, KAMAL K PANT. ∗ and SREEDEVI UPADHYAYULA. Department of Chemical Engineering, Indian Institute of Technology, Delhi 110 016, India. E-mail: kkpant@chemical.iitd.ac.in. MS received 27 May 2017; revised 21 August 2017; accepted 31 ...

  11. Bimetallic Pt-Au nanocatalysts electrochemically deposited on graphene and their electrocatalytic characteristics towards oxygen reduction and methanol oxidation.

    Science.gov (United States)

    Hu, Yaojuan; Zhang, Hua; Wu, Ping; Zhang, Hui; Zhou, Bo; Cai, Chenxin

    2011-03-07

    The burgeoning demand for clean and energy-efficient fuel cell system requires electrocatalysts to deliver greater activity and selectivity. Bimetallic catalysts have proven superior to single metal catalysts in this respect. This work reports the preparation, characterization, and electrocatalytic characteristics of a new bimetallic nanocatalyst. The catalyst, Pt-Au-graphene, was synthesized by electrodeposition of Pt-Au nanostructures on the surface of graphene sheets, and characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), and voltammetry. The morphology and composition of the nanocatalyst can be easily controlled by adjusting the molar ratio between Pt and Au precursors. The electrocatalytic characteristics of the nanocatalysts for the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) were systematically investigated by cyclic voltammetry. The Pt-Au-graphene catalysts exhibits higher catalytic activity than Au-graphene and Pt-graphene catalysts for both the ORR and the MOR, and the highest activity is obtained at a Pt/Au molar ratio of 2:1. Moreover, graphene can significantly enhance the long-term stability of the nanocatalyst toward the MOR by effectively removing the accumulated carbonaceous species formed in the oxidation of methanol from the surface of the catalyst. Therefore, this work has demonstrated that a higher performance of ORR and the MOR could be realized at the Pt-Au-graphene electrocatalyst while Pt utilization also could be greatly diminished. This method may open a general approach for the morphology-controlled synthesis of bimetallic Pt-M nanocatalysts, which can be expected to have promising applications in fuel cells.

  12. 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

  13. Synthesis of Pd–Ni/C bimetallic materials and their application in non-enzymatic hydrogen peroxide detection

    Directory of Open Access Journals (Sweden)

    Kazici Hilal Celik

    2017-10-01

    Full Text Available In this study, carbon based bimetallic materials (Pd-Ni/C were synthesized by polyol method in order to increase the hydrogen peroxide reduction catalytic activity of Pd using Ni metal. Hydrogen peroxide reduction and sensing properties of the prepared catalysts were measured by electrochemical methods. As a result, we have established that the addition of Ni at different ratios to Pd has a considerable electrocatalytic effect on H2O2 reduction. This work provides a simple route for preparation of Pd-Ni catalysts to create a very active and sensible electrochemical sensor for H2O2 sensing.

  14. Bimetallic Carbides-Based Nanocomposite as Superior Electrocatalyst for Oxygen Evolution Reaction.

    Science.gov (United States)

    Tang, Yu-Jia; Liu, Chun-Hui; Huang, Wei; Wang, Xiao-Li; Dong, Long-Zhang; Li, Shun-Li; Lan, Ya-Qian

    2017-05-24

    The development of highly efficient and low-cost oxygen evolution electrocatalysts is extremely imperative for the new energy technology. Transition metal carbides have been investigated as remarkable hydrogen evolution reaction (HER) electrocatalysts but undesired oxygen evolution reaction (OER) electrocatalysts and need further study. Here, a cobalt-molybdenum-based bimetallic carbide coated by N-doped porous carbon and anchored on N-doped reduced graphene oxide film (Co 6 Mo 6 C 2 /NCRGO) is synthesized by directly carbonizing the Co-doped polyoxometalate/conductive polymer/graphene oxide (Co-PCG) precursors. The precise control of the Co/Mo molar ratio in the Co-PCG precursor is of critical importance to synthesize pure phase bimetallic carbide of Co 6 Mo 6 C 2 . As the highly active and robust OER electrocatalyst, the Co 6 Mo 6 C 2 /NCRGO composite exhibits excellent activity in alkaline solution, affording a low overpotential of 260 mV versus RHE at 10 mA cm -2 , a small Tafel slope of 50 mV dec -1 , as well as long-term stability. The superior OER performances are strongly associated with the active Co 6 Mo 6 C 2 particles, polypyrrole (PPy)-derived N-doped porous carbon, and the conductive RGO films. Remarkably, it is the first evidence that the bimetallic carbides were used as the OER catalysts with such high OER activity.

  15. 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.

  16. Biomimetic Catalysts for Oxidation of Veratryl Alcohol, a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Marcelino Maneiro

    2013-03-01

    Full Text Available Kraft pulp has to be bleached to eliminate the chromophoric structures, which cause a darkening of the pulp. In Nature, an equivalent role is assumed by ligninolytic enzymes such as lignin peroxidases, manganese peroxidases and laccases. The development of low molecular weight manganese peroxidase mimics may achieve environmentally-safe bleaching catalysts for the industry. Herein we report the synthesis and characterization of six manganese(III complexes 1–6, incorporating dianionic hexadentate Schiff base ligands (H2L1-H2L4 and different anions. Complex 4, Mn2L22(H2O2(DCA2 was crystallographically characterized. Complexes 1–4 behave as more efficient mimics of peroxidase in contrast to 5–6. We have studied the use of these complexes as catalysts for the degradation of the lignin model compound veratryl alcohol. The biomimetic catalysts were used in conjunction with chlorine-free inexpensive co-oxidants as dioxygen or hydrogen peroxide. Yields up to 30% of veratryl alcohol conversion to veratraldehyde have been achieved at room temperature in presence of air flow using 0.5% of catalyst.

  17. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  18. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  19. A novel dynamic kinetic model of oxygen isotopic exchange on a supported metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Galdikas, Arvaidas; Duprez, Daniel; Descorme, Claude

    2004-09-15

    A time-resolved kinetic analysis has been developed for modeling experimental results of {sup 18}O/{sup 16}O isotopic exchange over oxide-supported metal catalysts. Model is based on two very important points: (1) the parallel calculation of surface and bulk diffusion and (2) the implication of certain O species such as superoxides. The model includes adsorption-desorption processes on metal clusters and oxygen spillover from the metal to the surface of support and vice versa. Different mechanisms of exchange were also taken into account via mononuclear (O atoms, O{sup -}, OH) or binuclear (superoxides) oxygen species. A refined model taking into account surface diffusion, direct exchange on surface of support by binuclear oxygen species and bulk diffusion was also developed. Kinetic (reaction rates and diffusion coefficients) as well as thermodynamic parameters (activation energies) were derived by fitting theoretical and experimental curves of {sup 18}O{sub 2}, {sup 18}O{sup 16}O and {sup 16}O{sub 2} gas phase concentrations versus time. The experimental results of Pt/CeZrO{sub 2} catalyst samples obtained in the 200-450 deg. C range of temperatures are examined. The refined model provides a very good fitting of the kinetic curves recorded with ceria-zirconia-supported catalysts. Moreover, values of diffusion coefficients and activation energies are in good agreement with already published values found by other methods. For a better understanding of all the steps of exchange, the kinetics of {sup 18}O and {sup 16}O distribution on the surface of metal clusters and on the surface of support are calculated and analyzed. On the basis of this model, a computer code is developed for analysis and calculations of kinetic and thermodynamic parameters of automotive catalysts.

  20. Optical properties and sensing applications of stellated and bimetallic nanoparticles

    Science.gov (United States)

    Smith, Alison F.

    This dissertation focuses on developing guidelines to aid in the design of new bimetallic platforms for sensing applications. Stellated metal nanostructures are a class of plasmonic colloids in which large electric field enhancements can occur at sharp features, making them excellent candidates for surface enhanced Raman spectroscopy (SERS) and surface enhanced infrared spectroscopy (SE-IRS) platforms. Shape-dependent rules for convex polyhedra such as cubes or octahedra exist, which describe far-field scattering and near-field enhancements. However, such rules are lacking for their concave (stellated) counterparts. This dissertation presents the optical response of stellated Au nanocrystals with Oh, D4h, D3h, C2v, and T d symmetry, which were modeled to systematically investigate the role of symmetry, branching, and particle orientation with respect to excitation source using finite difference time domain (FDTD) calculations. Expanding on stellated nanostructures, bimetallic compositions introduce an interplay between overall architecture and composition to provide tunable optical properties and the potential of new functionality. However, decoupling the complex compositional and structural contributions to the localized surface plasmon resonance (LSPR) remains a challenge, especially when the monometallic counterparts are not synthetically accessible for comparison and the theoretical tools for capturing gradient compositions are lacking. This dissertation explores a stellated Au-Pd nanocrystal model system with Oh symmetry to decouple structural and complex compositional effects on LSPR. (Abstract shortened by ProQuest.).

  1. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin [Univ. of California, Berkeley, CA (United States)

    2004-05-01

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al2O3) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum

  2. Modeling Low-Platinum-Loading Effects in Fuel-Cell Catalyst Layers

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Wonseok; Weber, Adam Z.

    2011-01-01

    The cathode catalyst layer within a proton-exchange-membrane fuel cell is the most complex and critical, yet least understood, layer within the cell. The exact method and equations for modeling this layer are still being revised and will be discussed in this paper, including a 0.8 reaction order, existence of Pt oxides, possible non-isopotential agglomerates, and the impact of a film resistance towards oxygen transport. While the former assumptions are relatively straightforward to understand and implement, the latter film resistance is shown to be critically important in explaining increased mass-transport limitations with low Pt-loading catalyst layers. Model results demonstrate agreement with experimental data that the increased oxygen flux and/or diffusion pathway through the film can substantially decrease performance. Also, some scale-up concepts from the agglomerate scale to the more macroscopic porous-electrode scale are discussed and the resulting optimization scenarios investigated.

  3. A Systematic Modelling Framework for Phase Transfer Catalyst Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Sales-Cruz, Mauricio; Hyung Kim, Sun

    2016-01-01

    equilibria, as well as kinetic mechanisms and rates. This paper presents a modelling framework for design and analysis of PTC systems that requires a minimum amount of experimental data to develop and employ the necessary thermodynamic and reaction models and embeds them into a reactor model for simulation...... in an aqueous phase. These reacting systems are receiving increased attention as novel organic synthesis options due to their flexible operation, higher product yields, and ability to avoid hazardous or expensive solvents. Major considerations in the design and analysis of PTC systems are physical and chemical....... The application of the framework is made to two cases in order to highlight the performance and issues of activity coefficient models for predicting design and operation and the effects when different organic solvents are employed....

  4. Development of Cu and Ni catalysts supported on ZrO2 for the generation of H2 by means of the reaction of reformed methanol in atmosphere oxidizer

    International Nuclear Information System (INIS)

    Lopez C, P.

    2012-01-01

    ZrO 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 3 CO 2 ) 2 ·H 2 O or NiNO 3 ·6H 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 2 oxide showed differences as a function of the metal addition. Between them, the Cu/ZrO 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 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)

  5. From Colloidal Monodisperse Nickel Nanoparticles to Well-Defined Ni/Al2O3Model Catalysts.

    Science.gov (United States)

    Zacharaki, Eirini; Beato, Pablo; Tiruvalam, Ramchandra R; Andersson, Klas J; Fjellvåg, Helmer; Sjåstad, Anja O

    2017-09-26

    In the past few decades, advances in colloidal nanoparticle synthesis have created new possibilities for the preparation of supported model catalysts. However, effective removal of surfactants is a prerequisite to evaluate the catalytic properties of these catalysts in any reaction of interest. Here we report on the colloidal preparation of surfactant-free Ni/Al 2 O 3 model catalysts. Monodisperse Ni nanoparticles (NPs) with mean particle size ranging from 4 to 9 nm were synthesized via thermal decomposition of a zerovalent precursor in the presence of oleic acid. Five weight percent Ni/Al 2 O 3 catalysts were produced by direct deposition of the presynthesized NPs on an alumina support, followed by thermal activation (oxidation-reduction cycle) for complete surfactant removal and surface cleaning. Structural and morphological characteristics of the nanoscale catalysts are described in detail following the propagation of the bulk and surface Ni species at the different treatment stages. Powder X-ray diffraction, electron microscopy, and temperature-programmed reduction experiments as well as infrared spectroscopy of CO adsorption and magnetic measurements were conducted. The applied thermal treatments are proven to be fully adequate for complete surfactant removal while preserving the metal particle size and the size distribution at the level attained by the colloidal synthesis. Compared with standard impregnated Ni/Al 2 O 3 catalysts, the current model materials display narrowed Ni particle size distributions and increased reducibility with a higher fraction of the metallic nickel atoms exposed at the catalyst surface.

  6. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tewell, Craig Richmond [Univ. of California, Berkeley, CA (United States)

    2002-01-01

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl4 and a Al(Et)3 co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl2 and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl4 in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl2 by TiCl4 resulting in a thin film of MgCl2/TiClx, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl2/TiClx on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to ~1 Torr of Al(Et)3.

  7. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst

    KAUST Repository

    Hossain, Mohammad M.

    2012-10-01

    The kinetics of ethylbenzene (EB) dehydrogenation over a FeO x-meso-Al 2O 3 catalyst is studied. The models were developed based on physicochemical characterization and a CREC fluidized Riser Simulator data. N 2 adsorption shows that the synthesized FeO x-meso-Al 2O 3 catalyst is mesoporous with pore size between 9 and 35nm. TPR profile indicates that iron on meso-Al 2O 3 forms easily reducible nanostructured crystals which is confirmed by TEM image. NH 3- and CO-TPD analysis, respectively reveals the availability of both acidic and basic sites. The dehydrogenation of ethylbenzene on FeO x-meso-Al 2O 3 catalyst mainly gives styrene (∼99%) while a small amount of benzene, toluene and coke are also detected. Based on the experimental observations two Langmuir-Hinshelwood type kinetics models are formulated. The possible catalyst deactivation is expressed as function of EB conversion. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one type site Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the physical constraints. The activation energy for the formation of styrene (80kJ/mol) found to be significantly lower than that of the undesired products benzene (144kJ/mol) and toluene (164kJ/mol). The estimated heat of adsorptions of EB and ST are found to be 55kJ/mol and 19kJ/mol, respectively. © 2012 Elsevier B.V.

  8. Modeling of ethylbenzene dehydrogenation kinetics process taking into account deactivation of catalyst bed of the reactor

    Directory of Open Access Journals (Sweden)

    V. K. Bityukov

    2017-01-01

    Full Text Available Styrene synthesis process occurring in a two-stage continuous adiabatic reactor is a complex chemical engineering system. It is characterized by indeterminacy, nonstationarity and occurs in permanent uncontrolled disturbances. Therefore, the task of developing the predictive control system of the main product concentration of the dehydrogenation reaction - styrene to maintain this value within a predetermined range throughout the period of operation is important. This solution is impossible without the development of the process model on the basis of the kinetic revised scheme, taking into account the drop of the reactor catalytic bed activity due to coke formation on the surface. The article justifies and proposes: the drop changes dependence of catalyst bed activity as a time of reactor block operation function and improved model of chemical reactions kinetics. The synthesized mathematical model of the process is a system of ordinary differential equations and allows you: to calculate the concentration profiles of reaction mixture components during the passage of the charge through the adiabatic reactor stage, to determine the contact gas composition at the outlet of the reactor stages throughout the cycle of catalytic system, taking into account temperature changes and drop of the catalyst bed activity. The compensation of the decreased catalyst bed activity is carried out by raising the temperature in the reactor block for the duration of the operation. The estimation of the values of chemical reactions rate constants, as well as the calculation and analysis of the main and by-products concentrations of dehydrogenation reactions at the outlet of the reactor plant is curried out. Simulation results show that the change of temperature of the reactor, carried out by the exponential law considering deactivation of the catalyst bed allows the yield in a given range of technological regulations throughout the operation cycle of the reactor block.

  9. Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: A spectroscopic study

    KAUST Repository

    Gallo, Alessandro

    2013-01-01

    Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir 4(CO)10(SnCl3)2] and NEt 4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9) 4 onto pre-formed Ir metal particles. These solids possess promising properties, in terms of selectivity, as catalysts for propane dehydrogenation to propene. Detailed CO-adsorption DRIFTS, XANES and EXAFS characterization studies have been performed on these systems in order to compare the structural and electronic evolution of systems in relation to the nature of the Ir-Sn bonds present in the precursor compounds and to propose a structural model of the Ir-Sn species present at the silica surface of the final catalyst. © 2013 The Royal Society of Chemistry.

  10. Modelling of the kinetics of deactivation of monofunctional catalysts with an acid strength distribution in their nonhomogeneous surface. Application to the deactivation of commercial catalysts in the fcc process

    Energy Technology Data Exchange (ETDEWEB)

    Corella, J.; Menendez, M.

    1986-01-01

    A model for the kinetics of the deactivation of monofunctional catalysts with a heterogeneous or non-uniform active surface is presented. This model is based on previous work by Butt et al. (1978, Chem. Engng Sci. 33, 1321) and starts from the consideration of a function of strength distribution for the active sites. Four types of strength distribution are considered. In the model time-on-stream is used as the independent variable. The influence of the values of the parameters of the catalyst surface on the activity-time curves and the parametric sensitivity of the model are analyzed. With the consideration of the non-uniformity of the catalyst surface developed in this model one can adjust perfectly well the data of deactivation of commercial catalysts in the cracking of gas oils and the empirical correlation of a general character proposed by Pacheco and Petersen (1984a, J. Catalysis 86, 75) for a large variety of processes and catalysts.

  11. Modeling the Kinetics of Deactivation of Catalysts during the Upgrading of Bio-Oil

    Energy Technology Data Exchange (ETDEWEB)

    Weber, Robert S.; Olarte, Mariefel V.; Wang, Huamin

    2015-01-25

    The fouling of catalysts for the upgrading of bio-oils appears to be very different from the fouling of catalysts for the hydroprocessing of petroleum-derived streams. There are two reasons for the differences: a) bio-oil contains polarizable components and phases that can stabilize reaction intermediates exhibiting charge separation and b) bio-oil components contain functional groups that contain O, notably carbonyls (>C=O). Aldol condensation of carbonyls affords very different pathways for the production of oligomeric, refractory deposits than does dehydrogenation/polymerization of petroleum-derived hydrocarbons. Colloquially, we refer to the bio-oil derived deposits as “gunk” to discriminate them from coke, the carbonaceous deposits encountered in petroleum refining. Classical gelation, appears to be a suitable model for the “gunking” reaction. Our work has helped explain the temperature range at which bio-oil should be pre-processed (“stabilized”) to confer longer lifetimes on the catalysts used for more severe processing. Stochastic modeling (kinetic Monte Carlo simulations) appears suitable to capture the rates of oligomerization of bio-oil. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  12. Origin of synergistic effect over Ni-based bimetallic surfaces: A density functional theory study

    Science.gov (United States)

    Fan, Chen; Zhu, Yi-An; Xu, Yue; Zhou, Yan; Zhou, Xing-Gui; Chen, De

    2012-07-01

    Density functional theory calculations have been conducted to explore the physical origin of the synergistic effect over Ni-based surface alloys using methane dissociation as a probe reaction. Some late transition metal atoms (M = Cu, Ru, Rh, Pd, Ag, Pt, and Au) are substituted for surface Ni atoms to examine the variation in electronic structure and adsorption property of Ni(111). Two types of threefold hollow sites, namely, the Ni2M and Ni3 sites, are taken into account. The calculated results indicate that the variation in the CHx adsorption energy at the Ni2M and Ni3 sites is dominated by the ensemble and ligand effect, respectively, and the other factors such as surface and adsorbate distortion and electrostatic interaction affect the catalytic properties of the bimetallic surfaces to a smaller extent. Both the Brønsted-Evans-Polanyi relationship and the scaling correlation hold true on the Ni-based bimetallic surfaces. With the combination of these two linear energy relations, the corrected binding energy of atomic C is found to be a good descriptor for representing the catalytic activity of the alloyed surfaces. Considering the compromise between the catalytic activity and catalyst stability, we suggest that the Rh/Ni catalyst is a good candidate for methane dissociation.

  13. 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.

  14. A Bimetallic Aluminium(Salphen) Complex for the Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide.

    Science.gov (United States)

    Wu, Xiao; North, Michael

    2017-01-10

    A bimetallic aluminium(salphen) complex is reported as a sustainable, efficient and inexpensive catalyst for the synthesis of cyclic carbonates from epoxides and carbon dioxide. In the presence of this complex and tetrabutylammonium bromide, terminal and internal epoxides reacted at 50 °C and 10 bar carbon dioxide pressure to afford their corresponding cyclic carbonates in yields of 50-94 % and 30-71 % for terminal and internal cyclic carbonates, respectively. Mechanistic studies using deuterated epoxides and an analogous monometallic aluminium(salphen) chloride complex support a mechanism for catalysis by the bimetallic complex, which involves intramolecular cooperative catalysis between the two aluminium centres. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  16. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

    2006-05-20

    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  17. First-Principles Approach to Heat and Mass Transfer Effects in Model Catalyst Studies

    OpenAIRE

    Matera, Sebastian; Reuter, Karsten

    2009-01-01

    We assess heat and mass transfer limitations in in situ studies of model catalysts with a first-principles based multiscale modeling approach that integrates a detailed description of the surface reaction chemistry and the macro-scale flow structures. Using the CO oxidation at RuO2(110) as a prototypical example we demonstrate that factors like a suppressed heat conduction at the backside of the thin single-crystal, and the build-up of a product boundary layer above the flat-faced surface pla...

  18. Ammonia synthesis and decomposition on a Ru-based catalyst modeled by first-principles

    DEFF Research Database (Denmark)

    Hellman, A.; Honkala, Johanna Karoliina; Remediakis, Ioannis

    2009-01-01

    A recently published first-principles model for the ammonia synthesis on an unpromoted Ru-based catalyst is extended to also describe ammonia decomposition. In addition, further analysis concerning trends in ammonia productivity, surface conditions during the reaction, and macro......-properties, such as apparent activation energies and reaction orders are provided. All observed trends in activity are captured by the model and the absolute value of ammonia synthesis/decomposition productivity is predicted to within a factor of 1-100 depending on the experimental conditions. Moreover it is shown: (i...

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

    International Nuclear Information System (INIS)

    Wang, Qiliang; Jeong, Seung-Woo; Choi, Heechul

    2012-01-01

    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.

  20. Atomic structure of graphene supported heterogeneous model catalysts

    International Nuclear Information System (INIS)

    Franz, Dirk

    2017-04-01

    Graphene on Ir(111) forms a moire structure with well defined nucleation centres. Therefore it can be utilized to create hexagonal metal cluster lattices with outstanding structural quality. At diffraction experiments these 2D surface lattices cause a coherent superposition of the moire cell structure factor, so that the measured signal intensity scales with the square of coherently scattering unit cells. This artificial signal enhancement enables the opportunity for X-ray diffraction to determine the atomic structure of small nano-objects, which are hardly accessible with any experimental technique. The uniform environment of every metal cluster makes the described metal cluster lattices on graphene/Ir(111) an attractive model system for the investigation of catalytic, magnetic and quantum size properties of ultra-small nano-objects. In this context the use of x-rays provides a maximum of flexibility concerning the possible sample environments (vacuum, selected gases, liquids, sample temperature) and allows in-situ/operando measurements. In the framework of the present thesis the structure of different metal clusters grown by physical vapor deposition in an UHV environment and after gas exposure have been investigated. On the one hand the obtained results will explore many aspects of the atomic structure of these small metal clusters and on the other hand the presented results will proof the capabilities of the described technique (SXRD on cluster lattices). For iridium, platinum, iridium/palladium and platinum/rhodium the growth on graphene/Ir(111) of epitaxial, crystalline clusters with an ordered hexagonal lattice arrangement has been confirmed using SXRD. The clusters nucleate at the hcp sites of the moire cell and bind via rehybridization of the carbon atoms (sp 2 → sp 3 ) to the Ir(111) substrate. This causes small displacements of the substrate atoms, which is revealed by the diffraction experiments. All metal clusters exhibit a fcc structure, whereupon

  1. Atomic structure of graphene supported heterogeneous model catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Franz, Dirk

    2017-04-15

    Graphene on Ir(111) forms a moire structure with well defined nucleation centres. Therefore it can be utilized to create hexagonal metal cluster lattices with outstanding structural quality. At diffraction experiments these 2D surface lattices cause a coherent superposition of the moire cell structure factor, so that the measured signal intensity scales with the square of coherently scattering unit cells. This artificial signal enhancement enables the opportunity for X-ray diffraction to determine the atomic structure of small nano-objects, which are hardly accessible with any experimental technique. The uniform environment of every metal cluster makes the described metal cluster lattices on graphene/Ir(111) an attractive model system for the investigation of catalytic, magnetic and quantum size properties of ultra-small nano-objects. In this context the use of x-rays provides a maximum of flexibility concerning the possible sample environments (vacuum, selected gases, liquids, sample temperature) and allows in-situ/operando measurements. In the framework of the present thesis the structure of different metal clusters grown by physical vapor deposition in an UHV environment and after gas exposure have been investigated. On the one hand the obtained results will explore many aspects of the atomic structure of these small metal clusters and on the other hand the presented results will proof the capabilities of the described technique (SXRD on cluster lattices). For iridium, platinum, iridium/palladium and platinum/rhodium the growth on graphene/Ir(111) of epitaxial, crystalline clusters with an ordered hexagonal lattice arrangement has been confirmed using SXRD. The clusters nucleate at the hcp sites of the moire cell and bind via rehybridization of the carbon atoms (sp{sup 2} → sp{sup 3}) to the Ir(111) substrate. This causes small displacements of the substrate atoms, which is revealed by the diffraction experiments. All metal clusters exhibit a fcc structure

  2. Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

    Science.gov (United States)

    Zhang, Lei; Wen, Xin; Lei, Zhang; Gao, Long; Sha, Xiangling; Ma, Zhenhua; He, Huibin; Wang, Yusu; Jia, Yang; Li, Yonghui

    2018-04-01

    Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction) was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction), SEM (scanning electron microscope), BET test and transient test. The experiments show that: * The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. * The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. * The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

  3. Model studies of secondary hydrogenation in Fischer-Tropsch synthesis studied by cobalt catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Aaserud, Christian

    2003-07-01

    Mass transfer effects are very important in Fischer-Tropsch (FT) synthesis. In order to study the FT synthesis without the influence of any transport limitations, cobalt foils have been used as model catalysts. The effect of pretreatment (number of calcinations and different reduction times) for cobalt foil catalysts at 220 {sup o}C, 1 bar and H{sub 2}/CO = 3 has been studied in a microreactor. The foils were examined by Scanning electron microscopy (SEM). It was found that the catalytic activity of the cobalt foil increases with the number of pretreatments possibly due to an increase in the surface area of the cobalt foil. The SEM results support the assumption that the surface area of the cobalt foil increases with the number of pretreatments. The reduction time was also found to influence the catalytic activity of the cobalt foil. Highest activity was obtained using a reduction time of only five min (compared to one and thirty min). The decrease in activity after reduction for thirty min compared to five min was suggested to be due to restructuring of the surface of the cobalt foil and a reduction time of only 1 min was not enough to reduce the cobalt foil sufficiently. Time of reduction did also influence the product distribution. Increased reduction time resulted in a lower selectivity to light products and increased selectivity to heavier components. The paraffin/olefin ratio increased with increasing CO-conversion also for cobalt foils. The paraffin/olefin ratio also increased when the reduction period of the cobalt foil was increased at a given CO-conversion. Hydrogenation of propene to propane has been studied as a model reaction for secondary hydrogenation of olefins in the FT synthesis. The study has involved promoted and unpromoted cobalt FT catalysts supported on different types of supports and also unsupported cobalt. Hydrogenation of propene was carried out at 120 {sup o}C, 1.8 bar and H{sub 2}/C{sub 3}H{sub 6} 6 in a fixed bed microreactor. The rate

  4. Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

    Science.gov (United States)

    Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

    2018-04-01

    A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

  5. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  6. Dendrimer-templated Ag-Pd bimetallic nanoparticles.

    Science.gov (United States)

    Chung, Young-Min; Rhee, Hyun-Ku

    2004-03-01

    Ultrafine dendrimer-templated Ag-Pd bimetallic nanoparticles with various metal compositions have been prepared successfully using silver(I)-bis(oxalato)palladate(II) complex. The use of an oxalate complex, in which two metal ions exist in one complex, is found to be effective in preventing unfavorable silver halide formation and thus suitable for the formation of Ag-Pd bimetallic nanoparticles.

  7. 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).

  8. Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: reaction and separation.

    Science.gov (United States)

    Shu, Qing; Nawaz, Zeeshan; Gao, Jixian; Liao, Yuhui; Zhang, Qiang; Wang, Dezheng; Wang, Jinfu

    2010-07-01

    A solid acid catalyst that can keep high activity and stability is necessary when low cost feedstocks are utilized for biodiesel synthesis because the reaction medium contains a large amount of water. Three solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. The structure of these catalysts was characterized by a variety of techniques. A new process that used the coupling of the reaction and separation was employed, which greatly improved the conversion of cottonseed oil (triglyceride) and free fatty acids (FFA) when a model waste oil feedstock was used. The vegetable oil asphalt-based catalyst showed the highest catalytic activity. This was due to the high density and stability of its acid sites, its loose irregular network, its hydrophobicity that prevented the hydration of -OH species, and large pores that provided more acid sites for the reactants. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  9. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  10. Direct Measurement of the Surface Energy of Bimetallic Nanoparticles: Evidence of Vegard's Rulelike Dependence

    Science.gov (United States)

    Chmielewski, Adrian; Nelayah, Jaysen; Amara, Hakim; Creuze, Jérôme; Alloyeau, Damien; Wang, Guillaume; Ricolleau, Christian

    2018-01-01

    We use in situ transmission electron microscopy to monitor in real time the evaporation of gold, copper, and bimetallic copper-gold nanoparticles at high temperature. Besides, we extend the Kelvin equation to two-component systems to predict the evaporation rates of spherical liquid mono- and bimetallic nanoparticles. By linking this macroscopic model to experimental TEM data, we determine the surface energies of pure gold, pure copper, Cu50 Au50 , and Cu25 Au75 nanoparticles in the liquid state. Our model suggests that the surface energy varies linearly with the composition in the liquid Cu-Au nanoalloy; i.e., it follows a Vegard's rulelike dependence. To get atomic-scale insights into the thermodynamic properties of Cu-Au alloys on the whole composition range, we perform Monte Carlo simulations employing N -body interatomic potentials. These simulations at a microscopic level confirm the Vegard's rulelike behavior of the surface energy obtained from experiments combined with macroscopic modeling.

  11. Catalyst based processes at back end of nuclear fuel cycle

    International Nuclear Information System (INIS)

    Vincent, T.

    2013-01-01

    Heterogeneous catalysts occupy a pivotal position in chemical industry. Their advanced preparation technology allows us to employ these catalysts for wide range of application. But the deployment of catalyst based radiochemical technology has to address the particular features like aggressive nitric acid media and intensive radiation fields. This put forward the rigid requirements to a choice of catalysts: high chemical and radiation stability of the catalyst and support, mechanical durability, catalytic activity and simplicity of preparation. Hydrogenation process with Pt/SiO 2 has been adopted industrially for making uranous nitrate (U 4+ ) from uranyl nitrate (U 6+ ) in PUREX process at commercial reprocessing plants. Bimetallic catalysts are being explored for the destruction of nitrates generated during nuclear fuel cycle operations

  12. MECHANISTIC KINETIC MODELS FOR STEAM REFORMING OF CONCENTRATED CRUDE ETHANOL ON NI/AL2O3 CATALYST

    Directory of Open Access Journals (Sweden)

    O. A. OLAFADEHAN

    2015-05-01

    Full Text Available Mechanistic kinetic models were postulated for the catalytic steam reforming of concentrated crude ethanol on a Ni-based commercial catalyst at atmosphere pressure in the temperature range of 673-863 K, and at different catalyst weight to the crude ethanol molar flow rate ratio (in the range 0.9645-9.6451 kg catalyst h/kg mole crude ethanol in a stainless steel packed bed tubular microreactor. The models were based on Langmuir-Hinshelwood-Hougen-Watson (LHHW and Eley-Rideal (ER mechanisms. The optimization routine of Nelder-Mead simplex algorithm was used to estimate the inherent kinetic parameters in the proposed models. The selection of the best kinetic model amongst the rival kinetic models was based on physicochemical, statistical and thermodynamic scrutinies. The rate determining step for the steam reforming of concentrated crude ethanol on Ni/Al2O3 catalyst was found to be surface reaction between chemisorbed CH3O and O when hydrogen and oxygen were adsorbed as monomolecular species on the catalyst surface. Excellent agreement was obtained between the experimental rate of reaction and conversion of crude ethanol, and the simulated results, with ADD% being ±0.46.

  13. Ammonia synthesis and decomposition on a Ru-based catalyst modeled by first-principles

    Science.gov (United States)

    Hellman, A.; Honkala, K.; Remediakis, I. N.; Logadóttir, Á.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Nørskov, J. K.

    2009-06-01

    A recently published first-principles model for the ammonia synthesis on an unpromoted Ru-based catalyst is extended to also describe ammonia decomposition. In addition, further analysis concerning trends in ammonia productivity, surface conditions during the reaction, and macro-properties, such as apparent activation energies and reaction orders are provided. All observed trends in activity are captured by the model and the absolute value of ammonia synthesis/decomposition productivity is predicted to within a factor of 1-100 depending on the experimental conditions. Moreover it is shown: (i) that small changes in the relative adsorption potential energies are sufficient to get a quantitative agreement between theory and experiment ( Appendix A) and (ii) that it is possible to reproduce results from the first-principles model by a simple micro-kinetic model ( Appendix B).

  14. Disproportionation of rosin on an industrial Pd/C catalyst: reaction pathway and kinetic model discrimination.

    Science.gov (United States)

    Souto, Juan Carlos; Yustos, Pedro; Ladero, Miguel; Garcia-Ochoa, Felix

    2011-02-01

    In this work, a phenomenological study of the isomerisation and disproportionation of rosin acids using an industrial 5% Pd on charcoal catalyst from 200 to 240°C is carried out. Medium composition is determined by elemental microanalysis, GC-MS and GC-FID. Dehydrogenated and hydrogenated acid species molar amounts in the final product show that dehydrogenation is the main reaction. Moreover, both hydrogen and non-hydrogen concentration considering kinetic models are fitted to experimental data using a multivariable non-linear technique. Statistical discrimination among the proposed kinetic models lead to the conclusion hydrogen considering models fit much better to experimental results. The final kinetic model involves first-order isomerisation reactions of neoabietic and palustric acids to abietic acid, first-order dehydrogenation and hydrogenation of this latter acid, and hydrogenation of pimaric acids. Hydrogenation reactions are partial first-order regarding the acid and hydrogen. Copyright © 2010 Elsevier Ltd. All rights reserved.

  15. A comprehensive model for the supported vanadium oxide catalyst: The umbrella model

    NARCIS (Netherlands)

    Lingen, J.N.J. van

    2006-01-01

    Supported vanadium oxide catalysts are widely used in industry. However, the molecular structure of the active species, responsible for the actual catalysis, is for a large part still unknown. This thesis describes four years study on the elucidation of this molecular structure. It mainly focuses on

  16. Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

    NARCIS (Netherlands)

    Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP

    2000-01-01

    The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and

  17. Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

    Science.gov (United States)

    Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

    2017-04-18

    interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell

  18. Selective hydrodechlorination of 1,2-dichloroethane catalyzed by trace Pd decorated Ag/Al2O3 catalysts prepared by galvanic replacement

    Science.gov (United States)

    Sun, Jingya; Han, Yuxiang; Fu, Heyun; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

    2018-01-01

    Ag catalysts decorated by trace Pd supported on γ-Al2O3 with different structure and chemical properties were prepared using a combined impregnation and galvanic replacement method. For comparison, monometallic Ag/γ-Al2O3 and Pd/γ-Al2O3 catalysts were prepared using the impregnation method. Gas-phase catalytic hydrodechlorination of 1,2-dichloroethane to ethylene was investigated on those catalysts. The structures and chemical compositions of bimetallic Pd-Ag particles in the catalysts were controlled by adjusting Pd replacement amount. The as-prepared catalysts were characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and in-situ FTIR spectroscopy of CO adsorption. The results demonstrated that contiguous Pd sites dominated in the monometallic Pd/γ-Al2O3 catalyst, while Pd atoms were separately decorated on the surface of Ag particles in the bimetallic Pd-Ag/γ-Al2O3 catalysts when Pd replacement amount was below 0.30 wt.%. At Pd replacement amount of 0.30 wt.%, Pd ensembles with contiguous Pd sites developed in the bimetallic catalyst. Thus, monometallic Pd/γ-Al2O3 catalyst displayed negligible ethylene selectivity toward the catalytic hydrodechlorination of 1,2-dichloroethane, while bimetallic Pd-Ag/γ-Al2O3 catalyst with a Pd replacement amount of 0.13 wt.% exhibited 94.6% of ethylene selectivity. Furthermore, selectivity to incompletely dechlorinated byproduct chloroethylene decreased with Pd replacement amount, due to the enhanced decoration effect of Pd on large Ag ensembles. Findings in this work provide a promising bimetallic catalyst prepared by galvanic replacement for the selective catalytic hydrodechlorination of 1,2-dichloroethane.

  19. Steam reforming of biomass gasification tar using benzene as a model compound over various Ni supported metal oxide catalysts.

    Science.gov (United States)

    Park, Hyun Ju; Park, Sung Hoon; Sohn, Jung Min; Park, Junhong; Jeon, Jong-Ki; Kim, Seung-Soo; Park, Young-Kwon

    2010-01-01

    The steam reforming of benzene as a model compound of biomass gasification tar was carried out over various Ni/metal oxide catalysts. The effects of the support, temperature, Ni-precursor, Ni loading and reaction time were examined, and their catalytic performance was compared with that of a commercial Ni catalyst. Among the Ni/metal oxide catalysts used, 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) showed the highest catalytic performance owing to its greater redox characteristics and increased surface area, irrespective of the reaction temperature. The catalytic activity of 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) was higher than that of the commercial Ni catalyst. Moreover, the catalyst activity was retained due to its excellent resistance to coke deposition even after 5h. The Ni-precursor played a critical role in the catalytic activity. With the exception of nickel nitrate, all the Ni-precursors (chloride and sulfate) caused deactivation of the catalyst.

  20. Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

    KAUST Repository

    Al-Shareef, Reem A.

    2017-11-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx bimetallic catalysts is also prepared by ion-exchange (IE). According to the results of STEM, XAS and H2 chemisorption, all bimetallic nanoparticles, prepared using neither SOMC nor IE, produce discrete formation of monometallic species (either Pt or Pd). Most catalysts exhibit a narrow particle size distribution with an average diameter ranging from 1 to 3 nm for samples prepared by IE and from 2 to 5 nm for the ones synthesized by SOMC. For all catalysts investigated in the present work, iso-butane reaction with hydrogen under differential conditions (conversions below 5%) leads to the formation of methane and propane (hydrogenolysis), n-butane (isomerization), and traces of iso-butylene (dehydrogenation). The total rate of reaction decreases with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate (expressed as moles converted per total surface metal per second) of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the results suggest a selective coverage of Pt (100) surface by a Pd layer, followed by a buildup of Pd overcoat onto a Pd layer assuming that each metal keeps its intrinsic catalytic properties. There is no mutual electronic charge transfer between the two metals (DFT). For the PtPd catalysts prepared by IE, the catalytic behavior cannot simply be explained by a surface coverage of highly active Pt metal by less active Pd (not observed), suggesting there is formation of a surface alloy between Pt and Pd collaborated by EXAFS and DFT. The catalytic results are explained by a simple structure activity relationship based on the previously proposed mechanism of C-H bond and C-C Bond activation and cleavage for iso-butane hydrogenolysis

  1. Formation of bimetallic Ag-Pd nanoclusters via the reaction between Ag nanoclusters and Pd2+ ions.

    Science.gov (United States)

    Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Wang, Guo-Rung; Chen, Jiun-Ming; Shih, Shou-Chu; Tang, Mau-Tsu; Liu, Ding-Goa; Lee, Jyh-Fu; Chen, Jing-Ming; Hwang, Bing-Joe

    2006-06-01

    We have investigated systematically the mechanistic aspects of the Ag-Pd bimetallic cluster formation within sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles by using in-situ X-ray absorption spectroscopy (XAS). A two-step sequential reduction method is employed for the synthesis of Ag-Pd bimetallic clusters. The first step involves preparation of Ag nanoclusters, by mixing the Ag+ ions containing the AOT microemulsion system with a reducing agent hydrazine (N2H4) containing the AOT microemulsion system. In the second step, the addition of Pd2+ ions to Ag nanoclusters led to the formation of Ag-Pd bimetallic clusters via the reaction between Ag nanoclusters and Pd2+ ions in AOT reverse micelles. The reduction of silver ions and the formation of corresponding Ag nanoclusters are monitored as a function of the dosage of the reducing agent, hydrazine. In-situ XAS allowed probing of the reaction between Ag nanoclusters and Pd2+ ions during the formation of Ag-Pd bimetallic clusters. Analysis of Ag and Pd K-edge XAS spectra reveals that in the final stage Ag-Pd clusters, in which "Ag" atoms prefer to be surrounded by "Pd" and "Pd" atoms prefer to be surrounded by "Pd", were formed. On the basis of XAS results presented here, we are able to propose a structural model for each step so that this work provides a detailed insight into the mechanism of nucleation and growth of Ag-Pd bimetallic clusters. We also discussed the atomic distribution of Ag and Pd atoms in Ag-Pd bimetallic clusters based on the calculated XAS structural parameters.

  2. Part I: A Comparative Thermal Aging Study on the Regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as Model Catalysts for Automotive Three Way Catalysts

    Directory of Open Access Journals (Sweden)

    Qinghe Zheng

    2015-10-01

    Full Text Available The rhodium (Rh component in automotive three way catalysts (TWC experiences severe thermal deactivation during fuel shutoff, an engine mode (e.g., at downhill coasting used for enhancing fuel economy. In a subsequent switch to a slightly fuel rich condition, in situ catalyst regeneration is accomplished by reduction with H2 generated through steam reforming catalyzed by Rh0 sites. The present work reports the effects of the two processes on the activity and properties of 0.5% Rh/Al2O3 and 0.5% Rh/CexOy-ZrO2 (CZO as model catalysts for Rh-TWC. A very brief introduction of three way catalysts and system considerations is also given. During simulated fuel shutoff, catalyst deactivation is accelerated with increasing aging temperature from 800 °C to 1050 °C. Rh on a CZO support experiences less deactivation and faster regeneration than Rh on Al2O3. Catalyst characterization techniques including BET surface area, CO chemisorption, TPR, and XPS measurements were applied to examine the roles of metal-support interactions in each catalyst system. For Rh/Al2O3, strong metal-support interactions with the formation of stable rhodium aluminate (Rh(AlO2y complex dominates in fuel shutoff, leading to more difficult catalyst regeneration. For Rh/CZO, Rh sites were partially oxidized to Rh2O3 and were relatively easy to be reduced to active Rh0 during regeneration.

  3. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient

  4. 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.

  5. Ni-Based Catalysts for the Hydrotreatment of Fast Pyrolysis Oil

    NARCIS (Netherlands)

    Ardiyanti, A. R.; Bykova, M. V.; Khromova, S. A.; Yin, W.; Venderbosch, R. H.; Yakovlev, V. A.; Heeres, Hero

    Catalytic hydrotreatment is an attractive technology to convert fast pyrolysis oil to stabilized oil products for co processing in conventional crude oil refinery units. We report here the use of novel bimetallic NiCu- and NiPd-based (Picula) catalysts characterized by a high Ni content (29-58 wt %)

  6. Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst

    Science.gov (United States)

    Lee, Heejin; Kim, Hannah; Yu, Mi Jin; Ko, Chang Hyun; Jeon, Jong-Ki; Jae, Jungho; Park, Sung Hoon; Jung, Sang-Chul; Park, Young-Kwon

    2016-06-01

    The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst.

  7. Two-phase model of hydrogen transport to optimize nanoparticle catalyst loading for hydrogen evolution reaction

    DEFF Research Database (Denmark)

    Kemppainen, Erno; Halme, Janne; Hansen, Ole

    2016-01-01

    With electrocatalysts it is important to be able to distinguish between the effects of mass transport and reaction kinetics on the performance of the catalyst. When the hydrogen evolution reaction (HER) is considered, an additional and often neglected detail of mass transport in liquid...... is the evolution and transport of gaseous H2, since HER leads to the continuous formation of H2 bubbles near the electrode. We present a numerical model that includes the transport of both gaseous and dissolved H2, as well as mass exchange between them, and combine it with a kinetic model of HER at platinum (Pt......) nanoparticle electrodes. We study the effect of the diffusion layer thickness and H2 dissolution rate constant on the importance of gaseous transport, and the effect of equilibrium hydrogen coverage and Pt loading on the kinetic and mass transport overpotentials. Gaseous transport becomes significant when...

  8. Modelling the aqueous and nonaqueous interfaces for CO2 electro-reduction over Sn catalysts

    Science.gov (United States)

    Sheng, Tian; Sun, Shi-Gang

    2018-01-01

    In CO2 electroreduction, Sn catalysts with a high overpotential for hydrogen evolution reaction and a high selectivity towards formic acid formation are very attractive. Many efforts have been made for improving the catalytic performance and for understanding the mechanisms. In electrochemistry, the role of solvents for surface reactions was deserved to be investigated, in particular for some nonaqueous solvents. Here, we have modeled the aqueous (water) and nonaqueous (acetonitrile and dichloromethane) for investigation of CO2 electroreduction on Sn surface, by constrained ab initio molecular dynamics simulations and thermodynamic integrations, including a number of explicit solvent molecules in computational models. It was found that CO2 reduction is initiated from formate formation and solvents, in particular, water can effectively facilitate the reaction.

  9. Catalytic activity of bimetallic AuPd alloys supported MgO and MnO2 nanostructures and their role in selective aerobic oxidation of alcohols

    Directory of Open Access Journals (Sweden)

    Hamed Alshammari

    2017-10-01

    Full Text Available The use of metal oxides as supports for gold and palladium (Au-Pd nano alloys constitutes new horizons to improve catalysts materials for very important reactions. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance. In this study, nanostructures of magnesium oxide (MgO and manganese dioxide (MnO₂ were synthesised and utilized as supports for Au-Pd nanoparticle catalysts. Gold and palladium were deposited on these supports using sol-immobilisation method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol and 1-octanol, respectively. These catalysts were found to be more selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The effect of base supports on the disproportionation reaction during the oxidation process was investigated. The results show that MgO stopped the disproportionation reaction for both aromatic and aliphatic alcohols while MnO₂ stopped it in the case of benzyl alcohol only. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

  10. Application of a Coated Film Catalyst Layer Model to a High Temperature Polymer Electrolyte Membrane Fuel Cell with Low Catalyst Loading Produced by Reactive Spray Deposition Technology

    Directory of Open Access Journals (Sweden)

    Timothy D. Myles

    2015-10-01

    Full Text Available In this study, a semi-empirical model is presented that correlates to previously obtained experimental overpotential data for a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC. The goal is to reinforce the understanding of the performance of the cell from a modeling perspective. The HT-PEMFC membrane electrode assemblies (MEAs were constructed utilizing an 85 wt. % phosphoric acid doped Advent TPS® membranes for the electrolyte and gas diffusion electrodes (GDEs manufactured by Reactive Spray Deposition Technology (RSDT. MEAs with varying ratios of PTFE binder to carbon support material (I/C ratio were manufactured and their performance at various operating temperatures was recorded. The semi-empirical model derivation was based on the coated film catalyst layer approach and was calibrated to the experimental data by a least squares method. The behavior of important physical parameters as a function of I/C ratio and operating temperature were explored.

  11. Dry (CO2) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

    International Nuclear Information System (INIS)

    Niu, Juntian; Du, Xuesen; Ran, Jingyu; Wang, Ruirui

    2016-01-01

    Graphical abstract: - Highlights: • CH appears to be the most abundant species on Pt(1 1 1) surface in CH 4 dissociation. • CO 2 * + H* → COOH* + * → CO* + OH* is the dominant reaction pathway in CO 2 activation. • Major reaction pathway in CH oxidation: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. • C* + OH* → COH* + * → CO* + H* is the dominant reaction pathway in C oxidation. - Abstract: Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H 2 /CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO 2 and CH 4 . In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH 4 direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH 4 dehydrogenation on Pt(1 1 1) surface. In the process of CO 2 activation, three possible reaction pathways are considered to contribute to the CO 2 decomposition: (I) CO 2 * + * → CO* + O*; (II) CO 2 * + H* → COOH* + * → CO* + OH*; (III) CO 2 * + H* → mono-HCOO* + * → bi-HCOO* + * [CO 2 * + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In addition, the kinetic results also indicate this process is not easy

  12. α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Meifen; Xin, Hui; Guo, Zhi; Guo, Dapeng; Wang, Yan; Zhao, Peng; Li, Jingyi, E-mail: lijingyicn@163.com

    2017-01-01

    Highlights: • The catalysts were prepared by reduction method at room temperature. • α-Alkylation of ketones and primary alcohols occurred on Au-Pd/CeO{sub 2} in visible light. • Superior catalytic activities were shown on bimetallic Au-Pd/CeO{sub 2} catalysts. • The catalyst can be reused for 4 times. • The mechanism of the synthesis for ketones was proposed. - Abstract: The direct α-alkylation of ketones with primary alcohols to obtain the corresponding saturated coupled ketones was achieved with bimetallic gold(Au)-palladium(Pd) nanoparticles(NPs) supported on a transition metal oxide (such as CeO{sub 2}). This system demonstrated a higher catalytic property than Au/CeO{sub 2} and Pd/CeO{sub 2} under visible light irradiation at 40 ± 3 °C in an Ar atmosphere. Such phenomenon was caused by the synergistic effect between Au and Pd. Isopropyl alcohol was used as the solvent and CH{sub 3}ONa as the base. The effect of the bimetallic Au-Pd mass ratio and the two different transition metal oxide supports (such as CeO{sub 2} or ZrO{sub 2}) during the reaction process was studied. The highest catalytic activity of those examined happened with the 1.5 wt% Au-1.5 wt% Pd (Au and Pd mass ratio 1:1)/CeO{sub 2} photo-catalyst. The intensity and wavelength of the visible light had a strong influence on the system. The catalyst can be reused for four times. A reaction mechanism was proposed for the α-alkylation of ketones with primary alcohols.

  13. α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide

    International Nuclear Information System (INIS)

    Bai, Meifen; Xin, Hui; Guo, Zhi; Guo, Dapeng; Wang, Yan; Zhao, Peng; Li, Jingyi

    2017-01-01

    Highlights: • The catalysts were prepared by reduction method at room temperature. • α-Alkylation of ketones and primary alcohols occurred on Au-Pd/CeO 2 in visible light. • Superior catalytic activities were shown on bimetallic Au-Pd/CeO 2 catalysts. • The catalyst can be reused for 4 times. • The mechanism of the synthesis for ketones was proposed. - Abstract: The direct α-alkylation of ketones with primary alcohols to obtain the corresponding saturated coupled ketones was achieved with bimetallic gold(Au)-palladium(Pd) nanoparticles(NPs) supported on a transition metal oxide (such as CeO 2 ). This system demonstrated a higher catalytic property than Au/CeO 2 and Pd/CeO 2 under visible light irradiation at 40 ± 3 °C in an Ar atmosphere. Such phenomenon was caused by the synergistic effect between Au and Pd. Isopropyl alcohol was used as the solvent and CH 3 ONa as the base. The effect of the bimetallic Au-Pd mass ratio and the two different transition metal oxide supports (such as CeO 2 or ZrO 2 ) during the reaction process was studied. The highest catalytic activity of those examined happened with the 1.5 wt% Au-1.5 wt% Pd (Au and Pd mass ratio 1:1)/CeO 2 photo-catalyst. The intensity and wavelength of the visible light had a strong influence on the system. The catalyst can be reused for four times. A reaction mechanism was proposed for the α-alkylation of ketones with primary alcohols.

  14. Jacobsen Catalyst as a Cytochrome P450 Biomimetic Model for the Metabolism of Monensin A

    Directory of Open Access Journals (Sweden)

    Bruno Alves Rocha

    2014-01-01

    Full Text Available Monensin A is a commercially important natural product isolated from Streptomyces cinnamonensins that is primarily employed to treat coccidiosis. Monensin A selectively complexes and transports sodium cations across lipid membranes and displays a variety of biological properties. In this study, we evaluated the Jacobsen catalyst as a cytochrome P450 biomimetic model to investigate the oxidation of monensin A. Mass spectrometry analysis of the products from these model systems revealed the formation of two products: 3-O-demethyl monensin A and 12-hydroxy monensin A, which are the same ones found in in vivo models. Monensin A and products obtained in biomimetic model were tested in a mitochondrial toxicity model assessment and an antimicrobial bioassay against Staphylococcus aureus, S. aureus methicillin-resistant, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Escherichia coli. Our results demonstrated the toxicological effects of monensin A in isolated rat liver mitochondria but not its products, showing that the metabolism of monensin A is a detoxification metabolism. In addition, the antimicrobial bioassay showed that monensin A and its products possessed activity against Gram-positive microorganisms but not for Gram-negative microorganisms. The results revealed the potential of application of this biomimetic chemical model in the synthesis of drug metabolites, providing metabolites for biological tests and other purposes.

  15. Hybrid plasma-catalytic steam reforming of toluene as a biomass tar model compound over Ni/Al₂O₃ catalysts

    OpenAIRE

    Liu, SY; Mei, DH; Nahil, MA; Gadkari, S; Gu, S; Williams, PT; Tu, X

    2017-01-01

    In this study, plasma-catalytic steam reforming of toluene as a biomass tar model compound was carried out in a coaxial dielectric barrier discharge (DBD) plasma reactor. The effect of Ni/Al2O3 catalysts with different nickel loadings (5–20 wt%) on the plasma-catalytic gas cleaning process was evaluated in terms of toluene conversion, gas yield, by-products formation and energy efficiency of the plasma-catalytic process. Compared to the plasma reaction without a catalyst, the combination of D...

  16. Half-sandwich group 4 metal siloxy and silsesquioxane complexes : Soluble model systems for silica-grafted olefin polymerization catalysts

    NARCIS (Netherlands)

    Duchateau, R; Cremer, U; Harmsen, RJ; Mohamud, SI; Abbenhuis, HCL; van Santen, RA; Meetsma, A; Thiele, SKH; van Tol, MFH; Kranenburg, M

    1999-01-01

    The cuboctameric hydroxysilsesquioxane (c-C5H9)(7)Si8O12(OH) (2), obtained after hydrolysis of (c-C5H9)(7)Si8O12Cl (1), and triphenylsilanol have been applied as model supports for silica-grafted olefin polymerization catalysts. The ligands were introduced on group 4 metals by either chloride

  17. Catalytic Partial Oxidation of Cyclohexane by Bimetallic Ag/Pd Nanoparticles on Magnesium Oxide.

    Science.gov (United States)

    Liu, Xi; Conte, Marco; He, Qian; Knight, David W; Murphy, Damien M; Taylor, Stuart H; Whiston, Keith; Kiely, Christopher J; Hutchings, Graham J

    2017-09-04

    The liquid-phase oxidation of cyclohexane to cyclohexanol and cyclohexanone was investigated by synthesizing and testing an array of heterogeneous catalysts comprising: monometallic Ag/MgO, monometallic Pd/MgO and a set of bimetallic AgPd/MgO catalysts. Interestingly, Ag/MgO was capable of a conversion comparable to current industrial routes of approximately 5 %, and with a high selectivity (up to 60 %) to cyclohexanol, thus making Ag/MgO an attractive system for the synthesis of intermediates for the manufacture of nylon fibres. Furthermore, following the doping of Ag nanoparticles with Pd, the conversion increased up to 10 % whilst simultaneously preserving a high selectivity to the alcohol. Scanning transmission electron microscopy and energy dispersive spectroscopy of the catalysts showed a systematic particle-size-composition variation with the smaller Ag-Pd nanoparticles being statistically richer in Pd. Analysis of the reaction mixture by electron paramagnetic resonance (EPR) spectroscopy coupled with the spin-trapping technique showed the presence of large amounts of alkoxy radicals, thus providing insights for a possible reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Modeling the kinetics of cobalt Fischer-Tropsch catalyst deactivation trends through an innovative modified Weibull distribution.

    Science.gov (United States)

    Khorashadizadeh, Mahdi; Atashi, Hossein

    2017-07-26

    Since the increase in clean energy demand is driven by environmental concerns, energy management is an ever-lasting issue globally. Among the different scenarios for energy manufacturing, the catalytic route through the famous process named Fischer-Tropsch Synthesis provides beneficial consequences including pollution reduction and economic efficiency, among others. In this regard, catalyst stability must be taken into account as a crucial performance parameter, especially in the expensive cobalt-catalyzed CO hydrogenation processes. As catalyst deactivation seems to be inevitable in catalytic processes, deactivation issues such as the extent, failure rate, or reactivation significantly influence the exploration, development, design, and operation of commercial processes. Accordingly, the deactivation trend of a cobalt-based catalyst was modeled via an innovative Weibull distribution base, which presents a significant advance over the existing macroscopic deactivation models. Being employed to obtain informative equations, the model parameters provide valuable information about the catalyst lifetime, which can be used as a useful predictive tool for industrial control purposes.

  19. The use of mechanical alloying for the preparation of palladized magnesium bimetallic particles for the remediation of PCBs.

    Science.gov (United States)

    Coutts, Janelle L; Devor, Robert W; Aitken, Brian; Hampton, Michael D; Quinn, Jacqueline W; Clausen, Christian A; Geiger, Cherie L

    2011-09-15

    The kinetic rate of dechlorination of a polychlorinated biphenyl (PCB-151) by mechanically alloyed Mg/Pd was studied for optimization of the bimetallic system. Bimetal production was first carried out in a small-scale environment using a SPEX 8000M high-energy ball mill with 4-μm-magnesium and palladium impregnated on graphite, with optimized parameters including milling time and Pd-loading. A 5.57-g sample of bimetal containing 0.1257% Pd and ball milled for 3 min resulted in a degradation rate of 0.00176 min(-1)g(-1) catalyst as the most reactive bimetal. The process was then scaled-up, using a Red Devil 5400 Twin-Arm Paint Shaker, fitted with custom plates to hold milling canisters. Optimization parameters tested included milling time, number of ball bearings used, Pd-loading, and total bimetal mass milled. An 85-g sample of bimetal containing 0.1059% Pd and ball-milled for 23 min with 16 ball bearings yielded the most reactive bimetal with a degradation rate of 0.00122 min(-1)g(-1) catalyst. Further testing showed adsorption did not hinder extraction efficiency and that dechlorination products were only seen when using the bimetallic system, as opposed to any of its single components. The bimetallic system was also tested for its ability to degrade a second PCB congener, PCB-45, and a PCB mixture (Arochlor 1254); both contaminants were seen to degrade successfully. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. 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.

  1. 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

    2016-04-25

    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.

  2. Modeling intraparticle transports during propylene polymerizations using supported metallocene and dual function metallocene as catalysts: Single particle model

    Directory of Open Access Journals (Sweden)

    Li Hua-Rong

    2014-01-01

    Full Text Available Two improved multigrain models (MGMs for preparing homopolypropylene and long chain branched polypropylene via propylene polymerization using silica-supported metallocene or dual function metallocene as catalysts are presented in this paper. The presented models are used to predict the intraparticle flow fields involved in the polymerizations. The simulation results show that the flow field distributions involve dare basically identical. The results also show that both the two polymerization processes have an initiation stage and the controlling step for them is reaction-diffusion-reaction with the polymerization proceeding. Furthermore, the simulation results show that the intra particle mass transfer resistance has significant effect on the polymerization but the heat transfer resistance can be ignored.

  3. Use of Cold Gas Dynamic Spraying of bi-metallic powder mixtures as alternative to classic powder metallurgy route for producing intermetallic materials

    Directory of Open Access Journals (Sweden)

    Vit Jan

    2016-06-01

    Full Text Available The paper presents cold gas dynamic spraying (or Cold Spray as a novel surface treatment technology capable not only of surface modifications but also being used as bulk creating technology. This is demonstrated on numerous samples where bi-metallic powder feedstock is deposited into bulk, self-standing pieces of material that does not need the support of substrate. Mixtures from the group of Fe, Al, Ti, Ni, Cu were used for the initial bi-metallic mixtures. The deposited samples were then subjected to annealing at temperatures ranging from 300 to 1100°C in protective atmosphere and resulting morphologies and microstructures were analysed. Generally materials with high proportion of intermetallic phase content were obtained. These are discussed as potential scaffolds for metal or polymer matrix composites or as hi temperature resistive supports for catalysts with filter functions.

  4. A review on kinetic modeling of deactivation of SAPO-34 catalyst during Methanol to Olefins (MTO) process

    OpenAIRE

    Mohammad Ali Ahmadi, Seyed; Askari, Sima; Halladj, Rouein

    2013-01-01

    The major cause of deactivation in the MTO reaction over SAPO-34 is coke deposition that influences both activity and selectivity. This review describes different kinetic modeling of deactivation  of SAPO-34 during MTO process. It also presents different deactivation functions for the methanol conversion and the yields of olefins, which are hyperbolic and exponential respectively. A modified Voorhies model that estimates the average coke selectivity and catalyst capacity for olefin formation ...

  5. In situ hydrogenation of model compounds and raw bio-oil over Raney Ni catalyst

    International Nuclear Information System (INIS)

    Xu, Ying; Long, Jinxing; Liu, Qiying; Li, Yanbin; Wang, Chenguang; Zhang, Qi; Lv, Wei; Zhang, Xinghua; Qiu, Songbai; Wang, Tiejun; Ma, Longlong

    2015-01-01

    Graphical abstract: Over Raney Ni catalyst, the aqueous phase reforming (APR) of methanol could couple with the hydrogenation of the model compounds of bio-oil and the raw bio-oil. The hydrogen product from the APR of methanol could offer hydrogen source for the upgrading of the raw bio-oil. The main products of acetone and phenol were isopropanol and cyclohexanol. At 220 °C and 3 MPa, the conversion of acetone and phenol reached the highest point with 55.76% and 64.65% and the bio-oil was improved not only on the appearance but also on the composition significantly. The contents of ketone/aldehyde and organic acids decreased from 30.36% and 39.89% to 9.32% and 30.25% respectively. The contents of alcohols and esters increased from 8.89% and 4.9% to 16.33% and 20.53%. During the in situ hydrogenation process, hydrogenation and esterification were the main reactions in the bio-oil. - Highlights: • We proposed a novel hydrogenation method in mild condition without adding external hydrogen. • The methanol APR and hydrogenation of model compounds and the raw bio-oil could couple with each other. • The hydrogen generated in situ by the APR of methanol could be used for the hydrogenation of the raw bio oil. • After in situ hydrogenation, the appearance and composition of the bio oil was improved significantly. - Abstract: The conversion of renewable energy is one of the most important research fields. A novel upgrading method of bio-oil produced from fast pyrolysis of biomass was reported in the paper. Methanol, as hydrogenation liquid donor, was used in the hydrogenation process instead of hydrogen gas. The effects on the aqueous phase reforming (APR) of methanol and the in situ hydrogenation of model compounds (acetone and phenol) and bio-oil were investigated. The results showed that over Raney Ni catalyst, the in situ hydrogenation could couple with the APR of methanol. The conversions of acetone and phenol reached the highest point with 55.76% and 64

  6. Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

    Energy Technology Data Exchange (ETDEWEB)

    Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei; Ball, Madelyn; Huber, George W.; Zanchet, Daniela; Dumesic, James A.

    2018-03-01

    FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. The catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H2O activation on FeOx species at or near the Pt surface, mostly in the (II) oxidation state.

  7. Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

    Science.gov (United States)

    Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

    2018-03-01

    Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

  8. Interaction of NO2 with model NSR catalysts: metal-oxide interaction controls initial NOx storage mechanism.

    Science.gov (United States)

    Desikusumastuti, Aine; Staudt, Thorsten; Qin, Zhihui; Happel, Markus; Laurin, Mathias; Lykhach, Yaroslava; Shaikhutdinov, Shamil; Rohr, Friedemann; Libuda, Jörg

    2008-10-24

    Using scanning tunneling microscopy (STM), molecular-beam (MB) methods and time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we investigate the mechanism of initial NO(x) uptake on a model nitrogen storage and reduction (NSR) catalyst. The model system is prepared by co-deposition of Pd metal particles and Ba-containing oxide particles onto an ordered alumina film on NiAl(110). We show that the metal-oxide interaction between the active noble metal particles and the NO(x) storage compound in NSR model catalysts plays an important role in the reaction mechanism. We suggest that strong interaction facilitates reverse spillover of activated oxygen species from the NO(x) storage compound to the metal. This process leads to partial oxidation of the metal nanoparticles and simultaneous stabilization of the surface nitrite intermediate.

  9. 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

  10. Jacobsen Catalyst as a Cytochrome P450 Biomimetic Model for the Metabolism of Monensin A

    Czech Academy of Sciences Publication Activity Database

    Rocha, B. A.; de Oliveira, A. M.; Pazin, M.; Dorta, D.J.; Rodrigues, A.P.N.; Berretta, A.A.; Peti, A. P. F.; de Moraes, L.A.B.; Lopes, N. P.; Pospíšil, Stanislav; Gates, P. J.; Assis, M. D.

    2014-01-01

    Roč. 2014, č. 2014 (2014), s. 1-8 ISSN 2314-6133 Institutional support: RVO:61388971 Keywords : Monensin A * Jacobsen Catalyst Subject RIV: EE - Microbiology, Virology Impact factor: 1.579, year: 2014

  11. Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

    KAUST Repository

    Isimjan, Tayirjan T.

    2013-04-01

    The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

  12. Transient Model of Heat,Mass,and Charge transfer as well as Electrochemistry in the Cathode Catalyst Layer of a PEMFC

    OpenAIRE

    Genevey, Daniel Bruno

    2001-01-01

    A transient model of the cathode catalyst layer of a proton exchange membrane fuel cell is presented. The catalyst layer structure can be described as a superposition of the polymer membrane, the backing layer, and some additional platinum particles. The model, which incorporates some of the features of the pseudo-homogeneous models currently present in the literature, considers the kinetics of the electrochemical reaction taking place at the platinum surface, the proton transport through the...

  13. Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

    KAUST Repository

    Zwaschka, Gregor

    2018-01-22

    The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

  14. Theoretical modeling of structure and function of cathode catalyst layers in PEMFC

    International Nuclear Information System (INIS)

    Wang, Q.; Eikerling, M.; Song, D.; Liu, Z.

    2004-01-01

    'Full text:' In this work, we first investigate transport and reaction kinetics in single agglomerates of cathode catalyst layers in proton exchange fuel cells. Two types of spherical agglomerates are evaluated, which represent limiting structures that can be obtained by distinct synthetic procedures. One type consists of a mixture of carbon/catalyst particles and proton conducting perfluorosulfonated ionomer (PFSI). The other type consists of carbon/catalyst particles and water-filled pores. Performance of the former type is rationalized on the basis of the well-known Thiele-modulus. Characteristics of the latter type are studied using Nernst-Planck and Poisson equations. Aspects of current conversion, reactant and current distributions, and catalyst utilization are explored. In general, the PFSI-filled agglomerates exhibit more homogeneous distributions of reaction rates. Effectiveness factors for them are close to one. However, it was found that proton penetration depths in waterflooded agglomerates could be quite significant as well under certain conditions, resulting in unexpectedly high catalyst utilization. The effects of agglomerate radius and of boundary conditions at the agglomerate surface are studied. Moreover, using the same approach, we evaluate the performance of a flat PFSI-free catalyst layer with water-filled pore space. Compared with conventional composite catalyst layers impregnated with PFSI, the PFSI-free layer exhibits better performance and high Pt utilization for thicknesses less than 0.1 μm. The significance of these results for the optimization catalyst layers in view of operation conditions and synthesis methods is discussed. (author)

  15. Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.

    Science.gov (United States)

    Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias

    2013-03-14

    A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.

  16. In-Situ TEM Study of a Nanoporous Ni–Co Catalyst Used for the Dry Reforming of Methane

    Directory of Open Access Journals (Sweden)

    Takeshi Fujita

    2017-10-01

    Full Text Available We performed in-situ transmission electron microscopy (TEM on a dealloyed nanoporous NiCo catalyst used for the dry reforming of methane (DRM to investigate the origin of the catalytic activity and structural durability. The in-situ observations and local chemical analysis indicated that the DRM induced chemical demixing of Ni and Co accompanied by grain refinement, implying possible “synergic effects” in a general bimetallic NiCo catalyst when used for the DRM.

  17. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  18. Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Matera, S.; Blomberg, S.; Hoffmann, M. J.; Zetterberg, J.; Gustafson, J.; Lundgren, E.; Reuter, K.

    2015-06-17

    We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

  19. 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.

  20. Synthesis of Pd-Au bimetallic nanocrystals via controlled overgrowth.

    Science.gov (United States)

    Lim, Byungkwon; Kobayashi, Hirokazu; Yu, Taekyung; Wang, Jinguo; Kim, Moon J; Li, Zhi-Yuan; Rycenga, Matthew; Xia, Younan

    2010-03-03

    This paper describes the synthesis of Pd-Au bimetallic nanocrystals with controlled morphologies via a one-step seeded-growth method. Two different reducing agents, namely, L-ascorbic acid and citric acid, were utilized for the reduction of HAuCl(4) in an aqueous solution to control the overgrowth of Au on cubic Pd seeds. When L-ascorbic acid was used as the reducing agent, conformal overgrowth of Au on the Pd nanocubes led to the formation of Pd-Au nanocrystals with a core-shell structure. On the contrary, localized overgrowth of Au was observed when citric acid was used as the reducing agent, producing Pd-Au bimetallic dimers. Through this morphological control, we were able to tune the localized surface plasmon resonance peaks of Pd-Au bimetallic nanostructures in the visible region.

  1. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    KAUST Repository

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

  2. 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.)

  3. Combined high-pressure cell-ultrahigh vacuum system for fast testing of model metal alloy catalysts using scanning mass spectrometry

    DEFF Research Database (Denmark)

    Johansson, Martin; Jørgensen, Jan Hoffmann; Chorkendorff, Ib

    2004-01-01

    An apparatus for fabrication, surface analysis in ultrahigh vacuum, and testing of the catalytic activity of model metal alloy catalysts is described. Arrays of model catalysts are produced by electron-beam deposition of up to four metals simultaneously onto a substrate. The surface analysis...... be studied on a substrate 10 mm in diameter. A high pressure cell with an all-metal sealed ultrahigh vacuum lock is also described as part of the work. ©2004 American Institute of Physics....

  4. Modeling of Diffusion Process in the Isotopic Oxygen Exchange Experiments of CexZr(1-xO2 Catalysts

    Directory of Open Access Journals (Sweden)

    Arvaidas GALDIKAS

    2013-03-01

    Full Text Available The oxygen mobility processes during the temperature programmed oxygen isotopic exchange is considered by proposed kinetic model. Model includes simple and complex heteroexchange reactions and bulk diffusion processes. The model is applied to fit experimental curves of CexZr(1-xO2 catalysts with different composition in order to calculate reaction rates and diffusion coefficients, and activation energies of those processes.DOI: http://dx.doi.org/10.5755/j01.ms.19.1.1630

  5. Synthesis and evaluation of novel biochar-based and metal oxide-based catalysts for removal of model tar (toluene), ammonia, and hydrogen sulfide from simulated producer gas

    Science.gov (United States)

    Bhandari, Pushpak

    Gasification is a thermochemical conversion process in which carbonaceous feedstock is gasified in a controlled atmosphere to generate producer gas. The producer gas is used for production of heat, power, fuels and chemicals. Various contaminants such as tars, NH3, and H2S in producer gas possess many problems due to their corrosive nature and their ability to clog and deactivate catalysts. In this study, several catalysts were synthesized, characterized, and tested for removal of three contaminants (toluene (model tar), NH3, and H2S) from the biomass-generated producer gas. Biochar, a catalyst, was generated from gasification of switchgrass. Activated carbon and acidic surface activated carbon were synthesized using ultrasonication method from biochar. Acidic surface was synthesized by coating activated carbon with dilute acid. Mixed metal oxide catalysts were synthesized from hydrotalcite precursors using novel synthesis technique using microwave and ultrasonication. Surface area of activated carbon (˜900 m2/g) was significantly higher than that of its precursor biochar (˜60 m2/g). Surface area of metal oxide catalyst was approximately 180 m2/g after calcination. Biochar, activated carbon, and acidic surface activated carbon showed toluene removal efficiencies of approximately 78, 88, and 88 %, respectively, when the catalysts were tested individually with toluene in the presence of producer gas at 800 °C. The toluene removal efficiencies increased to 86, 91, and 97 % using biochar, activated carbon and acidic surface activated carbon, respectively in the presence of NH3 and H2S in the producer gas. Increase in toluene removal efficiencies in presence of NH3 and H2S indicates that NH3 and H 2S play a role in toluene reforming reactions during simultaneous removal of contaminants. Toluene removal efficiency for mixed metal oxide was approximately 83%. Ammonia adsorption capacities were 0.008 g NH3/g catalyst for biochar and 0.03g NH3/g catalyst for activated

  6. Characterization measurements of Ti-SS bimetallic transition joint samples

    International Nuclear Information System (INIS)

    Budagov, Yu.; Sabirov, B.; Sisakyan, A.

    2008-01-01

    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

  7. Directly observing catalytic intermediates of methane dry reforming (MDR) on model Ni(111) catalyst via in operando surface techniques

    Science.gov (United States)

    Yuan, Kaidi

    In this work, near ambient pressure x-ray photoelectron spectroscopy was used to trace the in operando catalytic intermediates of methane dry reforming on model Ni(111) catalyst. The following reactive carbon intermediates have been characterized from dissociation of CH4: *CH, *C1 (Ni3C), *Cn (n≥2) and clock-reconstructed Ni2C. They can develop into inert graphene, and the conditions for this transition have been explored. One the other hand, the oxygen intermediates from CO2 dissociation were also studied, which play an important role on restraining graphene growth. Their dynamic coverage decreases with increasing temperature, which is suggested the fundamental mechanism of regional carbon overspill and causes irreversible graphene formation. Therefore, solutions based on Ni-O stabilization were proposed in developing coking resisting catalysts.

  8. Kinetics and mechanism of NH3 synthesis over Fe(100 and K/Fe(100 model catalysts

    Directory of Open Access Journals (Sweden)

    A. Z. Moshfegh

    2004-06-01

    Full Text Available   In this investigation kinetics and mechanism of NH3 synthesis over Fe(100 and K/Fe(100 model catalysts have been studied. In this context, adsorption kinetics of both N2/Fe (100 and H2/Fe (100systems is initially investigated. By using statistical mechanic approach, we have determined the adsorption coefficient for N2 and H2 molecules as well as transition probability of different states of adsorption and dissociation of the reactants molecules. The effect of surface catalyst temperature on the reaction rate (TOF is studied under different reactant partial pressures. The mechanism of NH3 synthesis is suggested based on LH surface reactions model. According to the obtained results, activation energy for the reaction over Fe (100 and K/Fe(100 (for θk=0.1ML was determined 19.6 and 11.1 kcal/mole, respectively. The order of reaction on both catalysts with respect to PN2 and PH2 was unity and negative, respectively. Based on our data analysis, the NH3 synthesis obeys Temkin isotherm.

  9. Electrical performances of pyroelectric bimetallic strip heat engines describing a Stirling cycle

    Science.gov (United States)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2015-12-01

    This paper deals with the analytical modeling of pyroelectric bimetallic strip heat engines. These devices are designed to exploit the snap-through of a thermo-mechanically bistable membrane to transform a part of the heat flowing through the membrane into mechanical energy and to convert it into electric energy by means of a piezoelectric layer deposited on the surface of the bistable membrane. In this paper, we describe the properties of these heat engines in the case when they complete a Stirling cycle, and we evaluate the performances (available energy, Carnot efficiency...) of these harvesters at the macro- and micro-scale.

  10. 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

    2016-02-03

    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.

  11. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2006-03-03

    rate-determining steps. In the coming year, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on Fe catalysts with/without K and Pt promoters and at various levels of Al{sub 2}O{sub 3} support, providing a database for understanding (1) effects of promoter and support on elementary kinetic parameters and (2) for validation of computational models that incorporate effects of surface structure and promoters. Kinetic parameters will be incorporated into a microkinetics model, enabling prediction of rate without invoking assumptions, e.g. of a rate-determining step or a most-abundant surface intermediate. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on two model surfaces: (1) Fe(110) with 1/4 ML subsurface carbon, and (2) Fe(110) with 1/4 ML Pt adatoms. Reaction networks for FTS on these systems were characterized in full detail by evaluating the thermodynamics and kinetics of each elementary step. We discovered that subsurface C stabilizes all the reactive intermediates, in contrast to Pt, which destabilizes most of them. A comparative study of the reactivities of the modified-Fe surfaces against pure Fe is expected to yield a more comprehensive understanding of promotion mechanisms for FTS on Fe.

  12. Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

    KAUST Repository

    Samantaray, Manoja

    2017-02-10

    Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.

  13. Au@Pd Bimetallic Nanocatalyst for Carbon-Halogen Bond Cleavage: An Old Story with New Insight into How the Activity of Pd is Influenced by Au.

    Science.gov (United States)

    Liu, Rui; Chen, Hui-Min; Fang, Li-Ping; Xu, Cuihong; He, Zuoliang; Lai, Yujian; Zhao, Huachao; Bekana, Deribachew; Liu, Jing-Fu

    2018-03-21

    AuPd bimetallic nanocatalysts exhibit superior catalytic performance in the cleavage of carbon-halogen bonds (C-X) in the hazardous halogenated pollutants. A better understanding of how Au atoms promote the reactivity of Pd sites rather than vaguely interpreting as bimetallic effect and determining which type of Pd sites are necessary for these reactions are crucial factors for the design of atomically precise nanocatalysts that make full use of both the Pd and Au atoms. Herein, we systematically manipulated the coordination number of Pd-Pd, d-orbital occupation state, and the Au-Pd interface of the Pd reactive centers and studied the structure-activity relationship of Au-Pd in the catalyzed cleavage of C-X bonds. It is revealed that Au enhanced the activity of Pd atoms primarily by increasing the occupation state of Pd d-orbitals. Meanwhile, among the Pd sites formed on the Au surface, five to seven contiguous Pd atoms, three or four adjacent Pd atoms, and isolated Pd atoms were found to be the most active in the cleavage of C-Cl, C-Br, and C-I bonds, respectively. Besides, neighboring Au atoms directly contribute to the weakening of the C-Br/C-I bond. This work provides new insight into the rational design of bimetallic metal catalysts with specific catalytic properties.

  14. Oxidative-reforming of model biogas over NiO/Al2O3 catalysts: The influence of the variation of support synthesis conditions

    International Nuclear Information System (INIS)

    Asencios, Yvan J.O.; Elias, Kariny F.M.; Assaf, Elisabete M.

    2014-01-01

    obtained at neutral pH conditions was the best support for nickel catalysts in the oxidative-reforming of model biogas

  15. Oxidative-reforming of model biogas over NiO/Al{sub 2}O{sub 3} catalysts: The influence of the variation of support synthesis conditions

    Energy Technology Data Exchange (ETDEWEB)

    Asencios, Yvan J.O., E-mail: yvan.jesus@unifesp.br [Departamento de Ciências do Mar, Universidade Federal de São Paulo, Av. Alm. Saldanha da Gama, 89, Ponta da Praia, CEP: 11030-400, Santos-SP (Brazil); Elias, Kariny F.M. [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil); Assaf, Elisabete M., E-mail: eassaf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil)

    2014-10-30

    high coke formation which affected the course of the reaction. The γ-Al{sub 2}O{sub 3} synthesized from bayerite obtained at neutral pH conditions was the best support for nickel catalysts in the oxidative-reforming of model biogas.

  16. Dynamic Modelling of Glucose Oxidation with Palladium Catalyst Deactivation in Multifunctional CSTR; Benefits of Periodic Operation

    Czech Academy of Sciences Publication Activity Database

    Gogová, Zuzana; Hanika, Jiří

    2009-01-01

    Roč. 150, č. 1 (2009), s. 223-230 ISSN 1385-8947 R&D Projects: GA ČR(CZ) GD203/08/H032 Institutional research plan: CEZ:AV0Z40720504 Keywords : glucose oxidation * palladium catalyst * periodic operation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.816, year: 2009

  17. 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

  18. Development of Coke-tolerant Transition Metal Catalysts for Dry Reforming of Methane

    KAUST Repository

    Al-Sabban, Bedour E.

    2016-11-07

    Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested

  19. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Fang; Yang, Die; Chen, Zuliang, E-mail: zuliang.chen@newcastle.edu.au; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    Highlights: • Green synthesis of bimetallic Fe/Pd NPs was firstly reported using the one-step method. • 98.0% of Orange II was removed by Fe/Pd NPs, but only 16.0% by Fe NPs. • Fe/Pd NPs with a diameter ranging from 10 to 100 nm were observed. • Removing Orange II using Fe/Pd NPs involved both adsorption and catalytic degradation. - Abstract: To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12 h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe{sup 2+} and Pd{sup 2+}, had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography–Mass Spectrum (HPLC–MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation.

  20. Modeling to study the role of catalyst in the formation of graphitic shells during carbon nanofiber growth subjected to reactive plasma

    Science.gov (United States)

    Gupta, Ravi; Gupta, Neha; Sharma, Suresh C.

    2018-04-01

    An analytical model to study the role of a metal catalyst nanofilm in the nucleation, growth, and resulting structure of carbon nanofibers (CNFs) in low-temperature hydrogen diluted acetylene plasma has been developed. The model incorporates the nanostructuring of thin catalyst films, growth of CNF, restructuring of catalyst nanoparticles during growth, and its repercussion on the resulting structure (alignment of rolled graphene sheets around catalyst nanoparticles) by taking into account the plasma sheath formalization, kinetics of neutrals and positively charged species in the reactive plasma, flux of plasma species onto the catalyst front surface, and numerous surface reactions for carbon generation. In order to examine the influence of the catalyst film on the growth of CNFs, the numerical solutions of the model equations have been obtained for experimentally determined initial conditions and glow discharge plasma parameters. From the solutions obtained, we found that nanostructuring of thin films leads to the formation of small nanoparticles with high surface number density. The CNF nucleates over these small-sized nanoparticles grow faster and attain early saturation because of the quick poisoning of small-sized catalyst particles, and contain only a few graphitic shells. However, thick nanofilms result in shorter CNFs with large diameters composed of many graphitic shells. Moreover, we found that the inclination of graphitic shells also depends on the extent up to which the catalyst can reconstruct itself during the growth. The small nanoparticles show much greater elongation along the growth axis and also show a very small difference between their tip and base diameter during the growth due to which graphitic shells align at very small angles as compared to the larger nanoparticles. The present study is useful to synthesize the thin and more extended CNFs/CNTs having a smaller opening angle (inclination angle of graphene layers) as the opening angle has a

  1. Bi-metallic nanoparticles as cathode electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jun; Amine, Khalil; Wang, Xiaoping; Luo, Xiangyi; Myers, Deborah J.

    2018-03-27

    A lithium-air battery cathode catalyst includes core-shell nanoparticles on a carbon support, wherein: a core of the core-shell nanoparticles is platinum metal; and a shell of the core-shell nanoparticles is copper metal; wherein: the core-shell nanoparticles have a weight ratio of the copper metal to the platinum metal from about 4% to about 6% copper to from about 2% to about 12% platinum, with a remaining percentage being the carbon support.

  2. Facile growth of Ag@Pt bimetallic nanorods on electrochemically ...

    Indian Academy of Sciences (India)

    Abstract. 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 elec- trode using galvanic displacement method for the electrooxidation of hydrazine. Initially, one dimensional.

  3. A bimetallic nanocomposite electrode for direct and rapid ...

    Indian Academy of Sciences (India)

    A new label-free electrochemical DNA biosensor is presented based on carbon paste electrode (CPE) modified with gold (Au) and platinum (Pt) nanoparticles to prepare the bimetallic nanocomposite electrode. The proposed sensor was made by immobilization of 15-mer single stranded oligonucleotide probe related to ...

  4. Multiphase catalysts for selective reduction of NOx with hydrocarbons

    International Nuclear Information System (INIS)

    Maisuls, S.E.

    2000-01-01

    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

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

    International Nuclear Information System (INIS)

    Carballo, Luis M; Zea, Hugo R

    1999-01-01

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

  6. DFT simulations and microkinetic modelling of 1-pentyne hydrogenation on Cu20 model catalysts.

    Science.gov (United States)

    Ma, Li; Melander, Marko; Weckman, Timo; Lipasti, Saana; Laasonen, Kari; Akola, Jaakko

    2016-04-01

    Adsorption and dissociation of H2 and hydrogenation of 1-pentyne on neutral and anionic Cu20 clusters have been investigated using the density functional theory and microkinetic modelling. Molecular adsorption of H2 is found to occur strictly at atop sites. The H2 dimer is activated upon adsorption, and the dissociation occurs with moderate energy barriers. The dissociated H atoms reside preferentially on 3-fold face and 2-fold edge sites. Based on these results, the reaction paths leading to the partial and total hydrogenation of 1-pentyne have been studied step-by-step. The results suggest that copper clusters can display selective activity on the hydrogenation of alkyne and alkene molecules. The hydrogenated products are more stable than the corresponding initial reactants following an energetic staircase with the number of added H atoms. Stable semi-hydrogenated intermediates are formed before the partial (1-pentene) and total (pentane) hydrogenation stages of 1-pentyne. The microkinetic model analysis shows that C5H10 is the dominant product. Increasing the reactants (C5H8/H2) ratio enhances the formation of products (C5H10 and C5H12). Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Cu/ZnO aggregates in siliceous mesoporous matrices : development of a new model methanol synthesis catalyst

    OpenAIRE

    Berg, Maurits W. E. van den; Polarz, Sebastian; Tkachenko, Olga P.; Klementiev, Konstantin V.; Bandyopadhyay, Mahuya; Khodeir, Lamma; Gies, Hermann; Muhler, Martin; Grünert, Wolfgang

    2006-01-01

    Copper and zinc were introduced into mesoporous siliceous matrices with the goal of obtaining model methanol synthesis catalysts with intense interaction between copper and the ZnO promoter. The preparation methods included various aqueous routes starting from acetate solutions (into MCM-48) and a route involving an organometallic step thermolysis of a liquid heterocubane of Zn4O4 type ([CH3ZnOCH2CH2OCH3]4) in a wormhole-type silica of 5 nm average pore size followed by aqueous Cu (nitrate) i...

  8. Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

    Science.gov (United States)

    Herz, Richard K.

    1989-01-01

    The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

  9. Preparation, characterization and electrocatalytic activity for oxygen reduction reaction in PEMFCs of bimetallic PdNi nanoalloy

    Directory of Open Access Journals (Sweden)

    E. F. Abo Zeid

    2017-09-01

    Full Text Available Abstract The modified polyol reduction method was used to prepare a carbon-supported bimetallic PdNi nanoalloys (BMNAs. The prepared catalyst was characterized using X-ray diffraction and transmission electron microscopy. The obtained data indicated that, the average particle size of the alloys in the range ≈ 20–50 nm. The morphology structure shows uniformly distributed particles on the supported carbon surface. The catalytic activity of the compounds for oxygen reduction reaction was investigated by cyclic voltammetry and electrochemical polarization measurements in rotating disk electrodes. As a function of time and calcination temperature, the improved activity and stability were obtained at 300 °C for 3 h.

  10. 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.

  11. FeRu/TiO2 and Fe/TiO2 catalysts after reduction and Fischer-Tropsch synthesis studied by Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Kraan, A.M. van der; Nonnekens, R.C.H.; Niemantsverdriet, J.W.

    1986-01-01

    A series of TiO 2 -supported bimetallic FeRu catalysts with different Fe:Ru ratios (infinity; 10:1; 3:1; 1:1; 1:3) has been studied by means of in situ Moessbauer spectroscopy. The influence of reduction and Fischer-Tropsch synthesis on the state of iron in the FeRu/TiO 2 catalysts is derived. (Auth.)

  12. Study of Ag induced bimetallic (Au-Ag) nanowires on silicon (5 5 12) surfaces: Experiment and theoretical aspects

    Science.gov (United States)

    Bhukta, Anjan; Bagarti, Trilochan; Guha, Puspendu; Ravulapalli, Sathyavathi; Satpati, Biswarup; Rakshit, Bipul; Maiti, Paramita; Parlapalli, Venkata Satyam

    2017-10-01

    The reconstructed vicinal (high index) silicon surfaces, such as, Si (5 5 12) composes row-like structures that can be used as templates for growing aligned nanowires. By using a sub-monolayers of Ag, prior to Au deposition on reconstructed Si (5 512) surface, intermixing of Au and Ag, enhancement of aspect ratio of bimetallic Au-Ag nanowires with tunable morphology is reported. This is attributed to a combined effect of pre-grown Ag strips as nucleation centers for incoming Au ad-atoms and anisotropic Au-Ag intermixing. To achieve optimum conditions for the growth of larger aspect ratio Au-Ag nanostructures, the growth kinetics have been studied by varying growth and annealing temperatures. At ≈400 °C, the Ag diffused into silicon substrate and the inter-diffusion found to inhibit the formation of Au-Ag bimetallic nanostructures. Controlled experiments under ultra-high vacuum condition in a molecular beam epitaxy system and in-situ scanning tunneling microscopy measurements along with ex-situ scanning transmission and secondary electron microscopy measurements have been carried out to understand the bimetallic nanostructure growth. Kinetic Monte Carlo (KMC) simulations based on kinematics of ad-atoms on an anisotropic template with a solid on solid model in which the relative ratios of binding energies (that are obtained from the Density Functional Theory) have been used and the KMC simulations results agree with the experimental observations. Advantage of having bimetallic structures as effective substrates for Surface enhanced Raman spectroscopy application is demonstrated by detecting Rhodamine 6 G (R6G) molecule at the concentration of 10-7M.

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

    International Nuclear Information System (INIS)

    Daud, M.; Khan, Z.; Ashgar, A.; Danish, M. I.; Qazi, I. A.

    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 X-ray florescence techniques were utilized for characterization of bimetallic Fe/Pt nanoparticles. Optimum dose, ph, temperature, and contact time were determined for removal through batch tests, both for metal based nanoparticles and anionic exchange resin. Adsorption data fitted well the Langmuir isotherm and conformed to the pseudo first-order kinetic model. Results indicated 97% reduction in nitrate by 0.25 mg/L of Fe/Pt nanoparticles at ph 7 and 83% reduction in nitrate was observed using 0.50 mg/L anionic exchange resins at ph 4 and contact time of one hour. Overall, Fe/Pt bimetallic nanoparticles demonstrated greater removal efficiency due to the small particle size, extremely large surface area (627 m 2 /g), and high adsorption capacity.

  14. Design of bimetal catalysts Pt-Ni/CeO2-1D for generation of H2 by the reforming reaction of methanol

    International Nuclear Information System (INIS)

    Sarmiento F, I.

    2016-01-01

    CeO 2 nano rods were synthesized by hydrothermal method and were used as support for preparing catalysts bimetallic Pt Ni / CeO 2 -1D. The catalysts were prepared by classical impregnation by the conventional wet method. The prepared catalysts are Pt (0.5 %) - Ni (5 %) / CeO 2 and Pt (0.5 %) - Ni (15 %) / CeO 2 , which were characterized by different physico-chemical techniques: Bet, Sem, TPR and XRD, that were evaluated in the Auto thermal Steam reforming of Methanol for H 2 production. The Bet surface area results, show that the surface area of the catalysts decreases as the nominal load of Ni in the catalyst, increases. Sem shows, that the catalyst support (CeO 2 -1D) and the bimetallic catalysts are conformed by nano rods. By XRD were identified the crystalline phases present, in the catalytic material: cerianite distinctive phase of cerium oxide and metallic Ni; however it was not possible to observe diffraction peaks of Platinum using this technique. The temperature-programmed reduction (TPR) analysis allowed to obtain the reduction profiles, of the different species present on the catalysts. The catalytic activity tests carried out, showed that the catalysts total 100% methanol conversion is achieved at 300 degrees Celsius, making them excellent, to be used in reactions at low temperature conditions. Selectivity towards H 2 , is very similar in both catalysts, and it reaches a 50% yield per mole of methanol fed stoichiometrically. (Author)

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

    International Nuclear Information System (INIS)

    Banerjee, Madhuchanda; Dey, Binita; Talukdar, Jayanta; Chandra Kalita, Mohan

    2014-01-01

    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

  16. Catalysts preparing

    International Nuclear Information System (INIS)

    Normatov, I.Sh.; Mirsaidov, U.M.

    2003-01-01

    One of the base area of zeolites industry using is catalysis. The catalytic properties of zeolites use in the carbonated reactions in the petrochemistry. Last years zeolite catalysts use in oxidative-reduction processes

  17. Lunar CATALYST

    Data.gov (United States)

    National Aeronautics and Space Administration — Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) is a NASA initiative to encourage the development of U.S. private-sector robotic lunar...

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

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

    2016-01-04

    The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

  19. 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...

  20. Challenges in bimetallic multilayer structure formation: Pt growth on Cu monolayers on Ru(0001).

    Science.gov (United States)

    Mancera, Luis A; Engstfeld, Albert K; Bensch, Andreas; Behm, R Jürgen; Groß, Axel

    2017-09-13

    In a joint experimental and theoretical study, we investigated the formation and morphology of PtCu/Ru(0001) bimetallic surfaces grown at room and higher temperatures under UHV conditions. We obtained the PtCu/Ru(0001) surfaces by deposition of Pt atoms on a previously created Cu/Ru(0001) structure which includes only one Cu monolayer. Bimetallic surfaces prepared at different Pt coverages are investigated using STM imaging, revealing the existence of reconstruction lines and Cu islands. Although primarily created Cu islands continue growing in size by increasing Pt coverage, a continuous formation of new Cu islands is observed. This leads to an atypical exponential increase of the island density as well as to an atypical behavior of the average number of atoms per island for low Pt coverages. Although coalescence of the islands is observed for high Pt coverages, the island density remains almost constant in that regime. In order to understand the trends observed in the experiments, we study the stability of these surfaces, atom adsorption, and adatom diffusion using periodic density functional theory calculations. On the basis of the experimental observations and the first-principles calculations, we suggest a model that includes exchange of Pt adatoms with Cu surface atoms, Pt and Cu adatom diffusion, and attractive (repulsive) interactions between Cu (Pt) adatoms with substitutional Pt surface atoms, which explains the main trends in island formation and growth observed in the experiment.

  1. Catalytic Steam Reforming of Toluene as a Model Compound of Biomass Gasification Tar Using Ni-CeO2/SBA-15 Catalysts

    Directory of Open Access Journals (Sweden)

    Erik Dahlquist

    2013-07-01

    Full Text Available Nickel supported on SBA-15 doped with CeO2 catalysts (Ni-CeO2/SBA-15 was prepared, and used for steam reforming of toluene which was selected as a model compound of biomass gasification tar. A fixed-bed lab-scale set was designed and employed to evaluate the catalytic performances of the Ni-CeO2/SBA-15 catalysts. Experiments were performed to reveal the effects of several factors on the toluene conversion and product gas composition, including the reaction temperature, steam/carbon (S/C ratio, and CeO2 loading content. Moreover, the catalysts were subjected to analysis of their carbon contents after the steam reforming experiments, as well as to test the catalytic stability over a long experimental period. The results indicated that the Ni-CeO2/SBA-15 catalysts exhibited promising capabilities on the toluene conversion, anti-coke deposition and catalytic stability. The toluene conversion reached as high as 98.9% at steam reforming temperature of 850 °C and S/C ratio of 3 using the Ni-CeO2(3wt%/SBA-15 catalyst. Negligible coke formation was detected on the used catalyst. The gaseous products mainly consisted of H2 and CO, together with a little CO2 and CH4.

  2. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

    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.

  3. Kinetic modeling of hydrocracking reaction in a trickle-bed reactor with Pt/Y-zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lee, BalSang; Park, Myung-June; Kim, Young-A; Park, Eun Duck [Ajou University, Suwon (Korea, Republic of); Han, Jeongsik [Agency for Defense Development, Daejeon (Korea, Republic of); Jeong, Kwang-Eun; Kim, Chul-Ung; Jeong, Soon-Yong [Korea Research Institute of Chemical Technology (KRICT), Daejeon (Korea, Republic of)

    2014-03-15

    A kinetic model is developed to predict the entire distribution of hydrocarbon products for the hydrocracking reaction with Pt/Y-zeolite catalysts in a trickle-bed reactor. Operating conditions, such as temperature, pressure, and wax and H{sub 2} flow rates were varied to evaluate their effects on conversion and distribution, and kinetic parameters were estimated using the experimental data that covers the window of operating conditions. The comparison between experimental data and simulated results corroborated the validity of the developed model, and the quantitative prediction of the reactor performance was clearly demonstrated. To make evident the usefulness of the model, an optimization method, genetic algorithm (GA), was applied, and the optimal condition for the maximum production of C{sub 10}-C{sub 17} was successfully calculated.

  4. Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction

    DEFF Research Database (Denmark)

    Hernandez-Fernandez, Patricia; Masini, Federico; McCarthy, David Norman

    2014-01-01

    Low-temperature fuel cells are limited by the oxygen reduction reaction, and their widespread implementation in automotive vehicles is hindered by the cost of platinum, currently the best-known catalyst for reducing oxygen in terms of both activity and stability. One solution is to decrease...... the amount of platinum required, for example by alloying, but without detrimentally affecting its properties. The alloy PtxY is known to be active and stable, but its synthesis in nanoparticulate form has proved challenging, which limits its further study. Herein we demonstrate the synthesis...

  5. PLASTIC WASTE CONVERSION TO LIQUID FUELS OVER MODIFIED-RESIDUAL CATALYTIC CRACKING CATALYSTS: MODELING AND OPTIMIZATION USING HYBRID ARTIFICIAL NEURAL NETWORK – GENETIC ALGORITHM

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2012-04-01

    Full Text Available The plastic waste utilization can be addressed toward different valuable products. A promising technology for the utilization is by converting it to fuels. Simultaneous modeling and optimization representing effect of reactor temperature, catalyst calcinations temperature, and plastic/catalyst weight ratio toward performance of liquid fuel production was studied over modified catalyst waste. The optimization was performed to find optimal operating conditions (reactor temperature, catalyst calcination temperature, and plastic/catalyst weight ratio that maximize the liquid fuel product. A Hybrid Artificial Neural Network-Genetic Algorithm (ANN-GA method was used for the modeling and optimization, respectively. The variable interaction between the reactor temperature, catalyst calcination temperature, as well as plastic/catalyst ratio is presented in surface plots. From the GC-MS characterization, the liquid fuels product was mainly composed of C4 to C13 hydrocarbons.KONVERSI LIMBAH PLASTIK MENJADI BAHAN BAKAR CAIR DENGAN METODE PERENGKAHAN KATALITIK MENGGUNAKAN KATALIS BEKAS YANG TERMODIFIKASI: PEMODELAN DAN OPTIMASI MENGGUNAKAN GABUNGAN METODE ARTIFICIAL NEURAL NETWORK DAN GENETIC ALGORITHM. Pemanfaatan limbah plastik dapat dilakukan untuk menghasilkan produk yang lebih bernilai tinggi. Salah satu teknologi yang menjanjikan adalah dengan mengkonversikannya menjadi bahan bakar. Permodelan, simulasi dan optimisasi simultan yang menggambarkan efek dari suhu reaktor, suhu kalsinasi katalis, dan rasio berat plastik/katalis terhadap kinerja produksi bahan bakar cair telah dipelajari menggunakan katalis bekas termodifikasi Optimisasi ini ditujukan untuk mencari kondisi operasi optimum (suhu reaktor, suhu kalsinasi katalis, dan rasio berat plastik/katalis yang memaksimalkan produk bahan bakar cair. Metode Hybrid Artificial Neural Network-Genetic Algorithm (ANN-GA telah digunakan untuk permodelan dan optimisasi simultan tersebut. Inetraksi antar variabel

  6. Bimetallic spacer means for a nuclear fuel assembly

    International Nuclear Information System (INIS)

    Anthony, A.J.

    1981-01-01

    A bimetallic spacer means designed to be cooperatively associated with a nuclear fuel assembly and operative to resist the occurrence of in-reactor bowing of the nuclear fuel assembly. The subject bimetallic spacer means in accord with one embodiment of the invention includes a member formed, at least principally, of Zircaloy to which are attached a plurality of stainless steel strips. The latter stainless steel strips are located on the external surface of the Zircaloy member and with the major axis of each of the plurality of stainless steel strips extending substantially perpendicular to the major axis of the Zircaloy member. In accord with another embodiment of the invention, the subject bimetallic spacer means includes a member formed at least principally of Zircaloy to which a plurality of stainless steel strips are attached so as to be positioned thereon externally thereof and with the major axis of each of the plurality of stainless steel strips extending substantially parallel to the major axis of the Zircaloy member. In accord with a further embodiment of the invention, the stainless steel strips are attached to preselected members, each embodying at least a cladding of Zircaloy, which are located in the rows of fuel rods that define the perimeter of the fuel matrix of the nuclear fuel assembly. In each of the embodiments, the stainless steel strips during power production expand outwardly to a greater extent than do the members to which the stainless steel strips are attached, thereby forming stiff springs which abut against like bimetallic spacer means with which the other nuclear fuel assemblies are provided in a given nuclear reactor core to thus prevent the occurrence of in-reactor bowing of the nuclear fuel assemblies. Namely, the stainless steel strips expand laterally relative to the fuel assembly and thereby occupy the space adjacent to the external surface of the fuel assembly

  7. Synthesis by Microwaves of Bimetallic Nano-Rhodium-Palladium

    Directory of Open Access Journals (Sweden)

    M. Ugalde

    2013-01-01

    Full Text Available An improved acrylamide sol-gel technique using a microwave oven in order to synthesize bimetallic Rh-Pd particles is reported and discussed. The synthesis of Pd and Rh nanoparticles was carried out separately. The polymerization to form the gel of both Rh and Pd was carried out at 80°C under constant agitations. The method chosen to prepare the Rh and Pd xerogels involved the decomposition of both gels. The process begins by steadily increasing the temperature of the gel inside a microwave oven (from 80°C to 170°C. In order to eliminate the by-products generated during the sol-gel reaction, a heat treatment at a temperature of 1000°C for 2 h in inert atmosphere was carried out. After the heat treatment, the particle size increased from 50 nm to 200 nm, producing the bimetallic Rh-Pd clusters. It can be concluded that the reported microwave-assisted, sol-gel method was able to obtain nano-bimetallic Rh-Pd particles with an average size of 75 nm.

  8. Facile synthesis of bimetallic nanoparticles by femtosecond laser irradiation method

    Directory of Open Access Journals (Sweden)

    Joseph Lik Hang Chau

    2017-02-01

    Full Text Available Bimetallic Pt–Au and Fe–Pt nanoparticles are successfully fabricated by high-intensity laser irradiation of aqueous solution without any chemical reducing agent. The mechanism of the formation of bimetallic nanoalloys by laser irradiation of the solution without using any reducing agent was mainly attributed to the optically induced decomposition of water molecule. When an intense femtosecond laser field is focused in an aqueous solution containing metal ions, the free electrons will be produced by the dissociation of water molecules, these free electrons and hydrogen radicals contained in the plasma might be caught by H+ or OH− ions to form the bubbles of H2 and O2 gases or they can be trapped by metal ions, resulting in the formation of metal atoms during the femtosecond laser irradiation process. The average size of the bimetallic nanoparticles increases with irradiation time. This technique is simple and ‘green’ process without using any chemicals except for metal salt and dispersing agent.

  9. Structural and morphological evaluation of Ru–Pd bimetallic nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Xianfeng [Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing, MI 48824 (United States); Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Lin, Rui; Ofoli, Robert Y. [Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing, MI 48824 (United States); Mei, Zhi, E-mail: zmei@chem.wayne.edu [Department of Chemistry, Wayne State University, Detroit, MI 48202 (United States); Jackson, James E., E-mail: jackson@chemistry.msu.edu [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States)

    2016-04-15

    Ru–Pd bimetallic nanocrystals are successfully synthesized via a facile polyol co-reduction method. The resulting nanocrystals show spheres, triangular nanoplates, decahedra, nanorods, and irregular shapes. A combination of Pd{sup II} and Ru{sup III} precursors tends to yield Ru–Pd bimetallic nanocrystals of higher shape monodispersity than those from Pd{sup II} and Ru{sup II} precursors. The mole ratio between Ru and Pd components in the precursor solution also plays a key role in determining the size/shape distribution of the nanocrystals, with higher Pd/Ru ratios generating products of more uniform size. Elemental analyses and electron microscopy studies suggest that the obtained nanocrystals have alloyed structures over the full composition space and that they form through either monomer addition or coalescence mechanisms. - Highlights: • 1. Polyol reduction method generates well-controlled Ru–Pd alloy nanocrystals. • Ru precursor types play a significant role in tuning particle morphology and structures. • Pd to Ru precursor molar ratio controls final particle size and composition. • Ru–Pd bimetallic nanocrystals display alloyed structures over full composition space.

  10. Highly dispersed metal catalyst

    Science.gov (United States)

    Xiao, Xin; West, William L.; Rhodes, William D.

    2016-11-08

    A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

  11. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  12. The utilization of hydroxyapatite-supported CaO-CeO2 catalyst for biodiesel production

    International Nuclear Information System (INIS)

    Yan, Beibei; Zhang, Ying; Chen, Guanyi; Shan, Rui; Ma, Wenchao; Liu, Changye

    2016-01-01

    Highlights: • Hydroxyapatite derived from waste animal bones was served as the support for bimetallic CaO-CeO 2 catalyst. • The 30%CaO-CeO 2 /HAP-650 catalyst exhibited excellent performance on biodiesel production. • The yield of FAME was 84.4 % after eight cycles. • Minor leaching concentrations of cerium and calcium species were detected in the product. - Abstract: The study investigated the effect of a bimetallic supported catalyst in biodiesel production. Calcined waste bone derived hydroxyapatite (HAP), a solid waste from animal, was served as the support for CaO-CeO 2 catalyst. Various characterization techniques such as FT-IR, BET, SEM-EDS, CO 2 -TPD and XRD analysis were used to analyse the activity of this heterogeneous catalyst. The effect of main parameters in preparation process such as calcination temperature and active component loading on catalyst performance were discussed to obtain the optimal preparation conditions. Under the optimal reaction conditions (11 wt.% dosage of 30%CaO-CeO 2 /HAP-650 catalyst and 9:1 methanol to oil molar ratio at 65 °C for 3 h) the highest biodiesel yield of 91.84% was obtained. Stability test indicated that the yield (84.4%) of fatty acid methyl ester was produced after 8 re-used cycles due to the low leaching of catalyst components. The experimental results showed that biodiesel production cost might be lowered while producing relatively high yield at the present of long life-span catalyst.

  13. Bimetal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ng, K. Y. Simon; Salley, Steve O.; Wang, Huali

    2017-10-03

    A catalyst comprises a carbide or nitride of a metal and a promoter element. The metal is selected from the group consisting of Mo, W, Co, Fe, Rh or Mn, and the promoter element is selected from the group consisting of Ni, Co, Al, Si, S or P, provided that the metal and the promoter element are different. The catalyst also comprises a mesoporous support having a surface area of at least about 170 m.sup.2 g.sup.-1, wherein the carbide or nitride of the metal and the promoter element is supported by the mesoporous support, and is in a non-sulfided form and in an amorphous form.

  14. 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 development...

  15. Tryptophan-Assisted Synthesis Reduces Bimetallic Gold/Silver Nanoparticle Cytotoxicity and Improves Biological Activity

    Directory of Open Access Journals (Sweden)

    Igor O. Shmarakov

    2014-10-01

    Full Text Available Aiming to reduce the potential in vivo hepato-and nephrotoxicity of Ag/Au bimetallic nanoparticles (NPs stabilized by sodium dodecyl sulphate (SDS, an approach involving a simultaneous reduction of silver nitrate and tetrachlorauratic acid using tryptophan (Trp as a reducing/stabilizing agent was applied during NP synthesis. The obtained Ag/Au/Trp NPs (5–15 nm sized were able to form stable aggregates with an average size of 370–450 nm and were potentially less toxic than Ag/Au/SDS in relation to a mouse model system based on clinical biochemical parameters and oxidative damage product estimation. Ag/Au/Trp NPs were shown to exhibit anticancer activity in relation to a Lewis lung carcinoma model. The data generated from the present study support the fact that the use of tryptophan in NP synthesis is effective in attenuating the potential hepatotoxicity and nephrotoxicity of NPs during their in vivo application.

  16. One-step synthesis of gold bimetallic nanoparticles with various metal-compositions

    International Nuclear Information System (INIS)

    Bratescu, Maria Antoaneta; Takai, Osamu; Saito, Nagahiro

    2013-01-01

    Highlights: ► Synthesis of bimetallic nanoparticles in an aqueous solution discharge. ► Alloying gold with divalent sp metals, trivalent sp metals, 3d or 4d metals. ► Formation mechanism of bimetallic nanoparticles by metal reduction and gold erosion. ► Blue and red shift of surface plasmon resonance. -- Abstract: A rapid, one-step process for the synthesis of bimetallic nanoparticles by simultaneous metal reduction and gold erosion in an aqueous solution discharge was investigated. Gold bimetallic nanoparticles were obtained by alloying gold with various types of metals belonging to one of the following categories: divalent sp metals, trivalent sp metals, 3d or 4d metals. The composition of the various gold bimetallic nanoparticles obtained depends on electrochemical factors, charge transfer between gold and other metal, and initial concentration of metal in solution. Transmission electron microscopy and energy dispersive spectroscopy show that the gold bimetallic nanoparticles were of mixed pattern, with sizes of between 5 and 20 nm. A red-shift of the surface plasmon resonance band in the case of the bimetallic nanoparticles Au–Fe, Au–Ga, and Au–In, and a blue-shift of the plasmon band of the Au–Ag nanoparticles was observed. In addition, the interaction of gold bimetallic nanoparticles with unpaired electrons, provided by a stable free radical molecule, was highest for those NPs obtained by alloying gold with a 3d metal

  17. Dry (CO{sub 2}) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Juntian [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Du, Xuesen, E-mail: xuesendu@cqu.edu.cn [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Ran, Jingyu, E-mail: jyran@189.cn [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Wang, Ruirui [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China)

    2016-07-15

    Graphical abstract: - Highlights: • CH appears to be the most abundant species on Pt(1 1 1) surface in CH{sub 4} dissociation. • CO{sub 2}* + H* → COOH* + * → CO* + OH* is the dominant reaction pathway in CO{sub 2} activation. • Major reaction pathway in CH oxidation: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. • C* + OH* → COH* + * → CO* + H* is the dominant reaction pathway in C oxidation. - Abstract: Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H{sub 2}/CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO{sub 2} and CH{sub 4}. In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH{sub 4} direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH{sub 4} dehydrogenation on Pt(1 1 1) surface. In the process of CO{sub 2} activation, three possible reaction pathways are considered to contribute to the CO{sub 2} decomposition: (I) CO{sub 2}* + * → CO* + O*; (II) CO{sub 2}* + H* → COOH* + * → CO* + OH*; (III) CO{sub 2}* + H* → mono-HCOO* + * → bi-HCOO* + * [CO{sub 2}* + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In

  18. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  19. Catalytic Hydrodeoxygenation of Biomass Pyrolysis Vapor Model Compounds over Molybdenum Sulfide Catalysts: Influence of Support, H2S and Water

    DEFF Research Database (Denmark)

    Arndal, Trine Marie Hartmann; Høj, Martin; Pintos, Delfina Garcia

    Conventional fast pyrolysis of biomass produces a high yield of bio-oil through well-established technologies1. The produced bio-oil must be further processed in order to decrease the content of oxygen(from 15-30 wt% down to heating...... value,acidity and stability1-2. Upgrading of condensed pyrolysis oil is challenged by severe polymerization andcoking upon heating. Instead, it is proposed to perform pyrolysis in the presence of hydrogen and an HDOcatalyst for immediate stabilization and upgrading of reactive pyrolysis products...... is to provide a proof-ofconceptfor the continuous conversion of solid biomass to low oxygen, fuel-grade bio-oil.In this contribution, a combined experimental, characterization and theoretical study of catalytic hydrodeoxygenationof biomass pyrolysis vapor model compounds over molybdenum sulfide catalysts...

  20. Disproportionation phenema of wistite phase in the model iron catalysts for ammonia synthesis studied by Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Pattek-Janczyk, A.; Miczko, B.

    1990-01-01

    A model iron catalysts for ammonia synthesis containing a large amount of wustite (35 wt%) has been studied during the annealing in an inert atmosphere in the temperature range of 573-773 K. Changes in magnetite and wustite phases were followed by Muessbauer spectroscopy (MS). Before starting the thermal treatment, two kinds of wustite of different structures have been found by MS and X-ray diffraction. The behaviour of both kinds of wustite during the annealing was different. One of them, closer to the stoichiometric compound, disproportionated at once into magnetite and iron; its content decreased systematically without changes in the Muessbauer parameters. In the second wustite, only qualitatieve changes were observed at first (its nonstoichiometry decreases without changes in content and, next, this phase started to disproportionate too. (auhtor). 31 refs.; 6 figs.; 2 tabs

  1. Modeling the RNA 2'OH activation: possible roles of metal ion and nucleobase as catalysts in self-cleaving ribozymes.

    Science.gov (United States)

    Chval, Zdeněk; Chvalová, Daniela; Leclerc, Fabrice

    2011-09-22

    The RNA 2'OH activation as taking place in the first chemical step of self-cleaving ribozymes is studied theoretically by DFT and MP2 methods using a continuum solvation model (CPCM). The reaction of proton transfer is studied in the presence of two kinds of catalysts: a fully hydrated metal ion (Mg(2+)) or partially hydrated nucleobase (guanine), taken separately or together leading to three different modes of activation. The metal ion is either directly bound (inner-sphere) or indirectly bound (outer-sphere) to the 2'OH group and a hydroxide ion acts as a general or specific base; the nucleobase is taken in anionic or in neutral enol-tautomeric forms playing itself the role of general base. The presence of a close metal ion (outer-sphere) lowers the pK(a) value of the 2'OH group by several log units in both metal-ion and nuleobase catalysis. The direct metal coordination to the 2'OH group (inner-sphere) further stabilizes the developing negative charge on the nucleophile. The switching from the inner-sphere to the outer-sphere coordination appears to be driven by the energy cost for reorganizing the first coordination shell rather than by the electrostatic repulsion between the ligands. The metal-ion catalysis is more effective with a specific base in the dianionic mechanism. On the other hand, the nucleobase catalysis is more effective in the monoanionic mechanism and in the presence of a metal ion acting as a cofactor through nonspecific electrostatic interactions. The results establish a baseline to study the possible roles of metal and nucleobase catalysts and their environment in more realistic models for self-cleaving ribozymes.

  2. Thermal Stability of Au/NbOx/Nb and Au/Nb2O5/W Model Catalysts Studied by Angle-resolved X-ray Photoelectron Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Lykhach, Yaroslava; Plšek, Jan; Spirovová, Ilona; Bastl, Zdeněk

    2003-01-01

    Roč. 68, č. 10 (2003), s. 1791-1804 ISSN 0010-0765 R&D Projects: GA ČR GA104/02/0664 Institutional research plan: CEZ:AV0Z4040901 Keywords : model metal catalysts * angle resolved photoemission * depth profiles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.041, year: 2003

  3. In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

    KAUST Repository

    Al-Sabban, Bedour

    2017-05-02

    Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests

  4. Coal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kroenig, W.

    1944-02-11

    Some considerations in the selection of a catalyst for the liquid phase of coal hydrogenation are discussed. Some of the previous history of such selections is mentioned. At one stage of the development, the principal catalyst had been iron sulfate (FeSO/sub 4/.7H/sub 2/O). Later, for reasons of cost and availability of large supplies, selections had turned to mixtures of iron sulfate and one or another of some iron oxide- and aluminum oxide-containing byproducts of aluminum manufacture, namely Bayermasse, Luxamsse, or Lautamasse. Much of the discussion centered on optimal proportions for such mixtures, particularly as related to pH values of resulting coal pastes. Upper Silesian coal was more alkaline than Ruhr coal, and Bayermasse, etc., were quite alkaline. Thus, since the iron sulfate served as a partial neutralizer for the coal as well as a catalyst, it seemed necessary to increase the proportions of iron sulfate in the catalyst mixture when processing coal of greater alkalinity. A further reason for a greater proportion of iron sulfate seemed to be that most of the catalytic activity of the iron came from the ferrous iron of iron sulfate rather than from the ferric iron of the other materials. Ferrous-ferric ratios also seemed to indicate that Luxmasse or Lautamasse might be better catalyst components than Bayermasse but their water content sometimes caused handling problems, so Bayermasse had been more widely used. Formation of deposits in the preheater was more likely due to the Bayermasse than to the iron sulfate; sodium sulfide could help to prevent them.

  5. Influence of relative rolling reduction and thickness layers bimetallic plate at the non-uniformity of the strain after rolling process

    Science.gov (United States)

    Rydz, D.; Stradomski, G.; Dyja, H.

    2017-02-01

    In the article were made numerical and laboratory tests of two-layers rolling process sheet composed of Al99,8 + M1E. Laboratory tests made with use of 150 mm diameter working rolls mill. To the modeling of the bimetallic plate rolling were taken the FEM Forge 2D software based on the theory of plasticity and MathCad program (in which to the rolling process modeling were used the mathematical model developed in the work [5] based on the theory of viscoelasticity). The aim of study was to determine the influence of layer thickness HT0/HM0 and relative deformation ε on the uneven distribution of steel sheet deformation after rolling process. Calculations based on the theory of viscoelasticity allowed additionally take into account the impact of the delayed effects of the variation of viscoelastic deformation of layers of the bimetallic plate rolling process.

  6. 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 particular in situ and ex situ X-ray diffraction, in situ X-ray absorption spectroscopy, transmission electron microscopy combined with electron energy loss spectroscopy and X-ray fluorescence, we have studied the formation of intermetallic Ni–Ga catalysts of two compositions: NiGa and Ni5Ga3. These methods...... demonstrate that the catalysts with the desired intermetallic phase and composition are formed upon reduction in hydrogen and enable us to propose a mechanism of the Ni–Ga nanoparticles formation. By studying the effect of calcination prior to catalyst reduction, we show that the reactivity depends...

  7. Stability of the Shallow Axisymmetric Parabolic-Conic Bimetallic Shell by Nonlinear Theory

    Directory of Open Access Journals (Sweden)

    M. Jakomin

    2011-01-01

    Full Text Available In this contribution, we discuss the stress, deformation, and snap-through conditions of thin, axi-symmetric, shallow bimetallic shells of so-called parabolic-conic and plate-parabolic type shells loaded by thermal loading. According to the theory of the third order that takes into account the balance of forces on a deformed body, we present a model with a mathematical description of the system geometry, displacements, stress, and thermoelastic deformations. The equations are based on the large displacements theory. We numerically calculate the deformation curve and the snap-through temperature using the fourth-order Runge-Kutta method and a nonlinear shooting method. We show how the temperature of both snap-through depends on the point where one type of the rotational curve transforms into another.

  8. Effects of Irregular Bimetallic Nanostructures on the Optical Properties of Photosystem I from Thermosynechococcus elongatus

    Directory of Open Access Journals (Sweden)

    Imran Ashraf

    2015-07-01

    Full Text Available The fluorescence of photosystem I (PSI trimers in proximity to bimetallic plasmonic nanostructures have been explored by single-molecule spectroscopy (SMS at cryogenic temperature (1.6 K. PSI serves as a model for biological multichromophore-coupled systems with high potential for biotechnological applications. Plasmonic nanostructures are fabricated by thermal annealing of thin metallic films. The fluorescence of PSI has been intensified due to the coupling with plasmonic nanostructures. Enhancement factors up to 22.9 and 5.1 are observed for individual PSI complexes coupled to Au/Au and Ag/Au samples, respectively. Additionally, a wavelength dependence of fluorescence enhancement is observed, which can be explained by the multichromophoric composition of PSI.

  9. Bactericidal and catalytic performance of green nanocomposite based-on chitosan/carbon black fiber supported monometallic and bimetallic nanoparticles.

    Science.gov (United States)

    Ali, Fayaz; Khan, Sher Bahadar; Kamal, Tahseen; Anwar, Yasir; Alamry, Khalid A; Asiri, Abdullah M

    2017-12-01

    Nanoparticles were synthesized on the surface of green nanocomposite based on carbon black dispersed in chitosan (CB-CS) fibres. The nanoparticles were monometallic Co, Ag and Cu and bimetallic Co + Cu and Co + Ag. The CB-CS fibres were prepared and introduced into separate metal salt solutions containing Co 2+ , Ag + and Cu 2+ and mixed Co 2+ +Cu 2+ and Co 2+ +Ag + ions. The metal ions immobilized on the surface of CB-CS were reduced using sodium borohydride (NaBH 4 ) as reducing agent to synthesize the corresponding zero-valent metal nanoparticles-loaded CB-CS fibres. All the nanoparticles-loaded CB-CS samples were characterized using field emission-scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction techniques. When tested as catalysts, the nanoparticles-loaded CB-CS showed excellent catalytic ability for the reduction of toxic and environmentally unwanted pollutants of para-nitrophenol, congo red and methyl orange dyes. Afterwards, the antimicrobial activities of virgin and metal-loaded CB-CS fibres were tested and the metal-loaded CB-CS fibres were found to be effective against Escherichia coli. In addition, the catalyst can be recovered easily by simply removing the fibres from the reaction mixture and can be recycled several times while maintaining high catalytic efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Electrochemically reduced graphene-oxide supported bimetallic nanoparticles highly efficient for oxygen reduction reaction with excellent methanol tolerance

    Science.gov (United States)

    Yasmin, Sabina; Cho, Sung; Jeon, Seungwon

    2018-03-01

    We report a simple and facile method for the fabrication of bimetallic nanoparticles on electrochemically reduced graphene oxide (ErGO) for electrocatalytic oxygen reduction reaction (ORR) in alkaline media. First, reduced graphene oxide supported palladium and manganese oxide nanoparticle (rGO/Pd-Mn2O3) catalyst was synthesized via a simple chemical method at room temperature; then, it was electrochemically reduced for oxidation reduction reaction (ORR) in alkaline media. The chemical composition and morphological properties of ErGO/Pd-Mn2O3 was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The TEM images reveals that, nano-sized Pd and Mn2O3 particles were disperse on the ErGO sheet without aggregation. The as-prepared ErGO/Pd-Mn2O3 was employed for ORR in alkaline media which shows higher ORR activity with more positive onset and half-wave potential, respectively. Remarkably, ErGO/Pd-Mn2O3 reduced oxygen via four-electron transfer pathway with negligible amount of intermediate peroxide species (HO2-). Furthermore, the higher stability and excellent methanol tolerance of the ErGO/Pd-Mn2O3 compared to commercial Pt/C (20 wt%) catalyst, indicating its suitability for fuel cells.

  11. Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle-Size Effects.

    Science.gov (United States)

    O'Brien, Casey P; Dostert, Karl-Heinz; Schauermann, Swetlana; Freund, Hans-Joachim

    2016-10-24

    The selectivity in the hydrogenation of acrolein over Fe 3 O 4 -supported Pd nanoparticles has been investigated as a function of nanoparticle size in the 220-270 K temperature range. While Pd(111) shows nearly 100 % selectivity towards the desired hydrogenation of the C=O bond to produce propenol, Pd nanoparticles were found to be much less selective towards this product. In situ detection of surface species by using IR-reflection absorption spectroscopy shows that the selectivity towards propenol critically depends on the formation of an oxopropyl spectator species. While an overlayer of oxopropyl species is effectively formed on Pd(111) turning the surface highly selective for propenol formation, this process is strongly hindered on Pd nanoparticles by acrolein decomposition resulting in CO formation. We show that the extent of acrolein decomposition can be tuned by varying the particle size and the reaction temperature. As a result, significant production of propenol is observed over 12 nm Pd nanoparticles at 250 K, while smaller (4 and 7 nm) nanoparticles did not produce propenol at any of the temperatures investigated. The possible origin of particle-size dependence of propenol formation is discussed. This work demonstrates that the selectivity in the hydrogenation of acrolein is controlled by the relative rates of acrolein partial hydrogenation to oxopropyl surface species and of acrolein decomposition, which has significant implications for rational catalyst design. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Chong, Lina [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Engineering Research Center of Light Alloy Net Forming and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai P.R. China; Goenaga, Gabriel A. [Chemical and Biomolecular Engineering Department, University of Tennessee, Knoxville, TN 37996 USA; Williams, Kia [University of South Florida, Tampa FL 33620 USA; Barkholtz, Heather M. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Grabstanowicz, Lauren R. [Alcoa Technical Center, New Kensington PA 15068 USA; Brooksbank, Jeremy A. [Chemical and Biomolecular Engineering Department, University of Tennessee, Knoxville, TN 37996 USA; Papandrew, Alex B. [Chemical and Biomolecular Engineering Department, University of Tennessee, Knoxville, TN 37996 USA; Elzein, Radwan [University of South Florida, Tampa FL 33620 USA; Schlaf, Rudiger [University of South Florida, Tampa FL 33620 USA; Zawodzinski, Thomas A. [Chemical and Biomolecular Engineering Department, University of Tennessee, Knoxville, TN 37996 USA; Zou, Jianxin [Engineering Research Center of Light Alloy Net Forming and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai P.R. China; Ma, Shengqian [University of South Florida, Tampa FL 33620 USA; Liu, Di-Jia [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA

    2016-05-31

    We demonstrated that the oxygen reduction reaction (ORR) activity over the catalysts derived from pyrolyzed cobalt zeolitic imidazolate frameworks depends strongly on the imidazole ligand structure and cobalt content. The activity and durability of these catalysts were tested in the proton exchange membrane fuel cell for the first time. The membrane electrode assembly containing a catalyst derived from Co/Zn bimetallic ZIF at cathode achieved an open circuit voltage of 0.93 V, a current density of 28 mA cm-2 at 0.8 ViR-free and a peak power density of 374 mW cm-2.

  13. Modeling and optimization of Fischer-Tropsch synthesis over Co-Mn-Ce/SiO2 catalyst using hybrid RSM/LHHW approaches

    International Nuclear Information System (INIS)

    Zohdi-Fasaei, Hossein; Atashi, Hossein; Farshchi Tabrizi, Farshad; Mirzaei, Ali Akbar

    2017-01-01

    Operating conditions considerably affect the energy required for Fischer-Tropsch synthesis, depending on the catalyst composition and reactor type (catalyst system). This paper reports the use of cobalt-manganese-cerium supported on silica as a novel CO hydrogenation catalyst, to produce hydrocarbons in a fixed bed micro-reactor. Response surface methodology (RSM) was applied to study the effects of temperature, pressure, feed ratio and their interactions on CO consumption rate, and the selectivity of light olefins (light olefinity), methane and C 5+ hydrocarbons. Quadratic mathematical models adequately described the responses in this catalyst system. According to Langmuir Hinshelwood Hougen Watson (LHHW) approach, kinetic mechanism of the reaction was found to be an associative adsorption of H 2 and CO. Statistical analysis demonstrated that pressure and feed ratio were the most important factors for the production of C 5+ and light alkenes, respectively. Model graphs indicated that minimum methane selectivity was achieved at 523.15 k and 2 bar. The maximum amounts of light olefins and heavier hydrocarbons were obtained at H 2 /CO = 1 and H 2 /CO = 2, respectively. Characterization of precursor and calcined catalyst (before and after the reaction) was carried out using SEM and BET techniques. - Highlights: • The performance of a new catalytic system was studied using RSM as a research plan. • Interactions between significant factors were investigated using mathematical models. • Based on LHHW approach, kinetic mechanism was molecular adsorptions of H 2 and CO. • RSM rate expression was in consistent with the LHHW kinetic model. • Hybrid RSM/LHHW is promising for optimization, mechanism and selectivity studies.

  14. 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.

  15. Catalyst Architecture

    DEFF Research Database (Denmark)

    Catalyst Architecture’ takes its point of departure in a broadened understanding of the role of architecture in relation to developmental problems in large cities. Architectural projects frame particular functions and via their form language, they can provide the user with an aesthetic experience....... The broadened understanding of architecture consists in that an architectural project, by virtue of its placement in the context and of its composition of programs, can have a mediating role in a positive or cultural development of the district in question. In this sense, we talk about architecture as catalyst...... cities on the planet have growing pains and social cohesiveness is under pressure from an increased difference between rich and poor, social segregation, ghettoes, immigration of guest workers and refugees, commercial mass tourism etc. In this context, it is important to ask which role architecture...

  16. Synthesis of ultrasmall, homogeneously alloyed, bimetallic nanoparticles on silica supports

    Science.gov (United States)

    Wong, A.; Liu, Q.; Griffin, S.; Nicholls, A.; Regalbuto, J. R.

    2017-12-01

    Supported nanoparticles containing more than one metal have a variety of applications in sensing, catalysis, and biomedicine. Common synthesis techniques for this type of material often result in large, unalloyed nanoparticles that lack the interactions between the two metals that give the particles their desired characteristics. We demonstrate a relatively simple, effective, generalizable method to produce highly dispersed, well-alloyed bimetallic nanoparticles. Ten permutations of noble and base metals (platinum, palladium, copper, nickel, and cobalt) were synthesized with average particle sizes from 0.9 to 1.4 nanometers, with tight size distributions. High-resolution imaging and x-ray analysis confirmed the homogeneity of alloying in these ultrasmall nanoparticles.

  17. Electrocatalysis in alkaline media: Mechanistic studies of fuel cell reactions on well-defined model catalysts

    Science.gov (United States)

    Spendelow, Jacob S.

    Scanning tunneling microscopy and electrochemical techniques have been used to study several electrocatalytic reactions occurring on Pt(111) and Pt(111)/Ru surfaces in alkaline media. The reactions chosen, CO oxidation, methanol oxidation, and oxygen reduction, are relevant to direct methanol fuel cells (DMFCs). Each is relatively slow, and therefore requires high loading of precious metal catalysts to achieve sufficient fuel cell power density. The focus of these studies has been on determining mechanisms and limiting factors in each reaction. Special attention has been given to the role of adsorbed Ru and the role of Pt defects in enhancing catalytic activity. All defects were found to be more active than terraces for CO oxidation on Pt(111) in alkaline media at DMFC-relevant potentials. Step-typed defects enhance methanol dehydrogenation, but kink-type defects are inactive for this reaction. All defects are inactive for oxygen reduction. These observations can be explained in terms of the local geometric and electronic structure at defects. Adsorbate-adsorbate repulsions, with resultant effects on activation barriers, control the rates of CO oxidation, as well as methanol oxidation. In the case of CO, coverage-dependent CO-CO repulsions and OH-OH repulsions on defects both enhance kinetics. In the case of methanol, repulsive interactions with CO decrease the rate of methanol dehydrogenation, thus giving rise to the CO poisoning effect. Ru was found to promote both methanol dehydrogenation and CO oxidation on adjacent Pt sites. Ru enhances methanol dehydrogenation through two distinct ligand effects: it increases the intrinsic dehydrogenation activity of adjacent Pt sites, and it causes CO to diffuse away from these active sites, decreasing the CO poisoning effect. A Ru ligand effect also enhances CO oxidation by weakening the Pt-CO bond. Ru supplies adsorbed OH for bifunctional CO oxidation, but since Pt defects can also supply OH in alkaline media, the Ru

  18. Catalytic and peroxidase-like activity of carbon based-AuPd bimetallic nanocomposite produced using carbon dots as the reductant

    International Nuclear Information System (INIS)

    Yang, Liuqing; Liu, Xiaoying; Lu, Qiujun; Huang, Na; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

    2016-01-01

    In this report, carbon-based AuPd bimetallic nanocomposite (AuPd/C NC) was synthesized using carbon dots (C-dots) as the reducing agent and stabilizer by a simple green sequential reduction strategy, without adding other agents. The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like property. The structure and morphology of these nanoparticles were clearly characterized by UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The AuPd/C NC catalyst exhibits noticeably higher catalytic activity than Pd and Au nanoparticles in catalysis reduction of 4-nitrophenol (4-NP). Moreover, based on the high peroxidase-like property of AuPd/C NC, a new colorimetric detection method for hydrogen peroxide (H 2 O 2 ) has been designed using 3,3′,5,5′-tetramethyl-benzidine (TMB) as the substrate, which provides a simple and sensitive means to detect H 2 O 2 in wide linear range of 5 μM–500 μM and 500 μM–4 mM with low detection limit of 1.6 μM (S/N = 3). Therefore, the facile synthesis strategy for bimetallic nanoparticles by the mild reductant of carbon dot will provide some new thoughts for preparing of carbon-based metal nanomaterials and expand their application in catalysis and analytical chemistry areas. - Highlights: • Carbon-based AuPd bimetallic nanocomposite was synthesized using carbon dots. • The green sequential reduction strategy synthesis method is simple, green, convenient and effective. • The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like activity. • The AuPd/C NC exhibits noticeably higher catalytic activity in reduction of 4-nitrophenol. • A new colorimetric detection method for hydrogen peroxide based on AuPd/C NC was proposed.

  19. New catalysts for coal processing: Metal carbides and nitrides

    Energy Technology Data Exchange (ETDEWEB)

    S. Ted Oyama; David F. Cox

    1999-12-03

    The subject of this research project was to investigate the catalytic properties of a new class of materials, transition metal carbides and nitrides, for treatment of coal liquid and petroleum feedstocks. The main objectives were: (1) preparation of catalysts in unsupported and supported form; (2) characterization of the materials; (3) evaluation of their catalytic properties in HDS and HDN; (4) measurement of the surface properties; and (5) observation of adsorbed species. All of the objectives were substantially carried out and the results will be described in detail below. The catalysts were transition metal carbides and nitrides spanning Groups 4--6 in the Periodic Table. They were chosen for study because initial work had shown they were promising materials for hydrotreating. The basic strategy was first to prepare the materials in unsupported form to identify the most promising catalyst, and then to synthesize a supported form of the material. Already work had been carried out on the synthesis of the Group VI compounds Mo{sub 2}C, Mo{sub 2}N, and WC, and new methods were developed for the Group V compounds VC and NbC. All the catalysts were then evaluated in a hydrotreating test at realistic conditions. It was found that the most active catalyst was Mo{sub 2}C, and further investigations of the material were carried out in supported form. A new technique was employed for the study of the bulk and surface properties of the catalysts, near edge x-ray absorption spectroscopy (NEXAFS), that fingerprinted the electronic structure of the materials. Finally, two new research direction were explored. Bimetallic alloys formed between two transition metals were prepared, resulting in catalysts having even higher activity than Mo{sub 2}C. The performance of the catalysts in hydrodechloration was also investigated.

  20. 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)

  1. CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

    Science.gov (United States)

    Gao, Doudou; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

    2018-01-01

    The catalysts containing Cu, Ni bi-metallic nanoparticles were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts into the highly porous and hydrothermally stable metal-organic framework MIL-101 via a simple liquid impregnation method. When the total amount of loading metal is 3 × 10-4 mol, Cu2Ni1@MIL-101 catalyst shows higher catalytic activity comparing to CuxNiy@MIL-101 with different molar ratio of Cu and Ni (x, y = 0, 0.5, 1.5, 2, 2.5, 3). Cu2Ni1@MIL-101 catalyst has the highest catalytic activity comparing to mono-metallic Cu and Ni counterparts and pure bi-metallic CuNi nanoparticles in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. Additionally, in the hydrolysis reaction, the Cu2Ni1@MIL- 101 catalyst possesses excellent catalytic performances, which exhibit highly catalytic activity with turn over frequency (TOF) value of 20.9 mol H2 min-1 Cu mol-1 and a very low activation energy value of 32.2 kJ mol-1. The excellent catalytic activity has been successfully achieved thanks to the strong bi-metallic synergistic effects, uniform distribution of nanoparticles and the bi-functional effects between CuNi nanoparticles and the host of MIL-101. Moreover, the catalyst also displays satisfied durable stability after five cycles for the hydrolytically releasing H2 from AB. The non-noble metal catalysts have broad prospects for commercial applications in the field of hydrogen-stored materials due to the low prices and excellent catalytic activity.

  2. Oxidation of glycerol to biobased chemicals using supported mono- and bimetallic noble metal catalysts

    NARCIS (Netherlands)

    Pazhavelikkakath Purushothaman, Rajeesh

    2014-01-01

    Het gebruik van fossiele bronnen staat onder druk. Dit wordt mede veroorzaakt door het besef dat ze eindig zijn en dat de bijkomende CO2 emissies bijdragen aan wereldwijde klimaat veranderingen. Biomassa wordt gezien als een aantrekkelijk alternatief voor de productie van koolstof gebaseerde

  3. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard

    2018-01-01

    significantly when using Fe-Ni/ZrO2 instead of Fe/ZrO2 alone. Moreover, the ZrO2 support contributed to improve the yield as a phase transition of ZrO2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO2 , resulting in a higher catalytic activity...... of the material. Interestingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce H2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N2 instead of H2. Fe-Ni/ZrO2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl...

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

    NARCIS (Netherlands)

    Westsson, E.E.; Koper, G.J.M.

    2014-01-01

    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

  5. Copper Modified Magnetic Bimetallic Nano-catalysts Ligand Regulated Catalytic Activity

    Science.gov (United States)

    Postsynthetic modification of magnetic nano ferrites (Fe3O4) has been accomplished by anchoring glutathione and dopamine on the surface. The Cu nano particles immobilized over these surfaces were investigated for the coupling and cyclo addition reactions. The Fe3O4-DOPA-Cu (na...

  6. Mono(NCN-pincer palladium)-metalloporphyrin catalysts: evidence for supramolecular bimetallic catalysis

    NARCIS (Netherlands)

    Suijkerbuijk, B.M.J.M.; Schamhart, D. J.; Kooijman, H.; Spek, A.L.; van Koten, G.; Klein Gebbink, R.J.M.

    2010-01-01

    The synthesis and catalytic properties of ditopic mono-pincer-mono-porphyrin complexes were investigated. The statistical Adler condensation reaction of 3,5-bis(methoxymethyl)-4-bromo-benzaldehyde, p-tolylaldehyde, and pyrrole, furnished an AB3-type tetraphenylporphyrin, containing three

  7. Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

    Directory of Open Access Journals (Sweden)

    Claudia Espro

    2017-03-01

    Full Text Available This review provides an overview of heterogeneous bimetallic Pd-Fe catalysts in the C–C and C–O cleavage of platform molecules such as C2–C6 polyols, furfural, phenol derivatives and aromatic ethers that are all easily obtainable from renewable cellulose, hemicellulose and lignin (the major components of lignocellulosic biomasses. The interaction between palladium and iron affords bimetallic Pd-Fe sites (ensemble or alloy that were found to be very active in several sustainable reactions including hydrogenolysis, catalytic transfer hydrogenolysis (CTH and aqueous phase reforming (APR that will be highlighted. This contribution concentrates also on the different synthetic strategies (incipient wetness impregnation, deposition-precipitaion, co-precipitaion adopted for the preparation of heterogeneous Pd-Fe systems as well as on the main characterization techniques used (XRD, TEM, H2-TPR, XPS and EXAFS in order to elucidate the key factors that influence the unique catalytic performances observed.

  8. Transformation of sodium bicarbonate and CO2 into sodium formate over NiPd nanoparticle catalyst

    Science.gov (United States)

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-01-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability. PMID:24790945

  9. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    Science.gov (United States)

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-09-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  10. Transformation of sodium bicarbonate and CO2 into sodium formate over NiPd nanoparticle catalyst.

    Science.gov (United States)

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-01-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  11. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    Directory of Open Access Journals (Sweden)

    Mengnan eWang

    2013-09-01

    Full Text Available The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs. Ni NPs and eight NiM (M stands for a second metal NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  12. A Tunable Bimetallic MOF-74 for Adsorption Chiller Applications: A Tunable Bimetallic MOF-74 for Adsorption Chiller Applications

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jian [Pacific Northwest National Laboratory, 99352 Richland WA USA; Zheng, Jian [Pacific Northwest National Laboratory, 99352 Richland WA USA; Barpaga, Dushyant [Pacific Northwest National Laboratory, 99352 Richland WA USA; Sabale, Sandip [Pacific Northwest National Laboratory, 99352 Richland WA USA; P.G. Department of Chemistry, Jaysingpur College, 416101 Jaysingpur Maharashtra India; Arey, Bruce [Environmental Molecular Sciences Laboratory (EMSL), Pacific Northwest National Laboratory, 99352 Richland WA USA; Derewinski, Miroslaw A. [Pacific Northwest National Laboratory, 99352 Richland WA USA; McGrail, B. Peter [Pacific Northwest National Laboratory, 99352 Richland WA USA; Motkuri, Radha Kishan [Pacific Northwest National Laboratory, 99352 Richland WA USA

    2018-02-12

    A mixed metal strategy, in which two different metal nodes coexist in one MOF framework, was examined using MOF-74. The Ni salt precursor for the MOF-74(Ni) analogue was partially replaced during synthesis with relatively inexpensive Zn salt. These bimetallic MOFs were developed and examined for water sorption for potential use in adsorption cooling/chiller applications. Varying concentration ratios of Ni:Zn in MOF-74 achieved using this mixed metal strategy were shown to provide unique impacts on H2O uptake while significantly mitigating the costs of synthesis

  13. Effects of Pt and ionomer ratios on the structure of catalyst layer: A theoretical model for polymer electrolyte fuel cells

    Science.gov (United States)

    Ishikawa, H.; Sugawara, Y.; Inoue, G.; Kawase, M.

    2018-01-01

    The 3D structure of the catalyst layer (CL) in the polymer electrolyte fuel cell (PEFC) is modeled with a Pt/carbon (Pt/C) ratio of 0.4-2.3 and ionomer/carbon (i/C) ratio of 0.5-1.5, and the structural properties are evaluated by numerical simulation. The models are constructed by mimicking the actual shapes of Pt particles and carbon aggregates, as well as the ionomer adhesion in real CLs. CLs with different compositions are characterized by structural properties such as Pt inter-particle distance, ionomer coating thickness, pore size distribution, tortuosity, and ionomer coverage on Pt. The results for Pt/C = 1.0, i/C = 1.0 with Pt loading of 0.3 mg cm-2 and 50% porosity are validated against measured data for CLs with the same composition. With increasing i/C ratio, the smaller pores disappear and the number of isolated pores increases; while the ionomer connection and its coverage on Pt are significantly enhanced at i/C ∼1.0. With increasing Pt/C ratio, the Pt inter-particle distance decreases as the particles connect with each other. The tortuosity of the pores and the ionomer exhibits a trade-off relation depending on the ionomer volume. Further CL design concepts to optimize both O2 diffusion and H+ conduction are discussed.

  14. 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.

  15. Versatile Optimization of Chemical Ordering in Bimetallic Nanoparticles

    KAUST Repository

    Kovács, Gábor

    2017-01-05

    Chemical ordering in bimetallic nanocrystallites can now be efficiently determined by density-functional calculations with the help of topological energy expressions. Herein, we deal with extending the usage of that computational scheme. We show that it enables one to structurally characterize bimetallic nanoparticles of less regular shapes than previously studied magic-type particles. In fcc Pd–Au particles of different shapes (cuboctahedral Pd58Au58, C3v Pd61Au61, cubic Pd68Au67, and truncated octahedral Pd70Au70), we identify the surface segregation of gold as the driving force to the lowest-energy chemical ordering. We applied the calculated descriptor values quantifying the segregation propensity of Au and energies of Pd–Au bonds in these ∼1.5 nm large particles to optimize and analyze the chemical ordering in 3.7–6 nm large Pd–Au particles. We also discuss how to predict the chemical ordering in nanoalloys at elevated temperatures. The present study paves the way to advanced structural investigations of nanoalloys to substantially accelerate their knowledge-driven engineering and manufacturing.

  16. 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 meta...... dependence on the initial metal composition. Our results suggest that not only the ORR activity, but also the corrosion resistance of the synthesized NPs, are dependent on the structural disorder resulting from the de-alloying process.......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...... nanoparticles almost completely de-alloy during acid leaching, i.e. under reaction conditions in a fuel cell. To scrutinize the resulting particle structure after de-alloying we used pair distribution function (PDF) analysis and X-ray diffraction (XRD) gaining insight into the structural disorder and its...

  17. CO2 activation on bimetallic CuNi nanoparticles

    Directory of Open Access Journals (Sweden)

    Natalie Austin

    2016-10-01

    Full Text Available Density functional theory calculations have been performed to investigate the structural, electronic, and CO2 adsorption properties of 55-atom bimetallic CuNi nanoparticles (NPs in core-shell and decorated architectures, as well as of their monometallic counterparts. Our results revealed that with respect to the monometallic Cu55 and Ni55 parents, the formation of decorated Cu12Ni43 and core-shell Cu42Ni13 are energetically favorable. We found that CO2 chemisorbs on monometallic Ni55, core-shell Cu13Ni42, and decorated Cu12Ni43 and Cu43Ni12, whereas, it physisorbs on monometallic Cu55 and core-shell Cu42Ni13. The presence of surface Ni on the NPs is key in strongly adsorbing and activating the CO2 molecule (linear to bent transition and elongation of C˭O bonds. This activation occurs through a charge transfer from the NPs to the CO2 molecule, where the local metal d-orbital density localization on surface Ni plays a pivotal role. This work identifies insightful structure-property relationships for CO2 activation and highlights the importance of keeping a balance between NP stability and CO2 adsorption behavior in designing catalytic bimetallic NPs that activate CO2.

  18. Probing the interaction of Rh, Co and bimetallic Rh-Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation.

    Science.gov (United States)

    Varga, E; Pusztai, P; Óvári, L; Oszkó, A; Erdőhelyi, A; Papp, C; Steinrück, H-P; Kónya, Z; Kiss, J

    2015-10-28

    The interaction of CeO2-supported Rh, Co and bimetallic Rh-Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1-5%), Rh forms 2-8 nm particles. Between 473-673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt.

  19. A genetically optimized kinetic model for ethanol electro-oxidation on Pt-based binary catalysts used in direct ethanol fuel cells

    Science.gov (United States)

    Sánchez-Monreal, Juan; García-Salaberri, Pablo A.; Vera, Marcos

    2017-09-01

    A one-dimensional model is proposed for the anode of a liquid-feed direct ethanol fuel cell. The complex kinetics of the ethanol electro-oxidation reaction is described using a multi-step reaction mechanism that considers free and adsorbed intermediate species on Pt-based binary catalysts. The adsorbed species are modeled using coverage factors to account for the blockage of the active reaction sites on the catalyst surface. The reaction rates are described by Butler-Volmer equations that are coupled to a one-dimensional mass transport model, which incorporates the effect of ethanol and acetaldehyde crossover. The proposed kinetic model circumvents the acetaldehyde bottleneck effect observed in previous studies by incorporating CH3CHOHads among the adsorbed intermediates. A multi-objetive genetic algorithm is used to determine the reaction constants using anode polarization and product selectivity data obtained from the literature. By adjusting the reaction constants using the methodology developed here, different catalyst layers could be modeled and their selectivities could be successfully reproduced.

  20. Recent Advances in Supported Metal Catalysts for Syngas Production from Methane

    Directory of Open Access Journals (Sweden)

    Mohanned Mohamedali

    2018-03-01

    Full Text Available Over the past few years, great attention is paid to syngas production processes from different resources especially from abundant sources, such as methane. This review of the literature is intended for syngas production from methane through the dry reforming (DRM and the steam reforming of methane (SRM. The catalyst development for DRM and SRM represents the key factor to realize a commercial application through the utilization of more efficient catalytic systems. Due to the enormous amount of published literature in this field, the current work is mainly dedicated to the most recent achievements in the metal-oxide catalyst development for DRM and SRM in the past five years. Ni-based supported catalysts are considered the most widely used catalysts for DRM and SRM, which are commercially available; hence, this review has focused on the recent advancements achieved in Ni catalysts with special focus on the various attempts to address the catalyst deactivation challenge in both DRM and SRM applications. Furthermore, other catalytic systems, including Co-based catalysts, noble metals (Pt, Rh, Ru, and Ir, and bimetallic systems have been included in this literature review to understand the observed improvements in the catalytic activities and coke suppression property of these catalysts.

  1. Application of New Electrolyte Model to Phase Transfer Catalyst (PTC) Systems

    DEFF Research Database (Denmark)

    Hyung Kim, Sun; Anantpinijwatna, Amata; Kang, Jeong Won

    2015-01-01

    behaviours of all components including water, organic solvents, inorganic salts, and the PTC. In this work, a new electrolyte model based on the KT-UNIFAC group contribution approach has been developed by adding the Debye-Hückel theory and a second virial coefficient-type term into the KT-UNIFAC model....... The temperature-dependent parameters of the new model are introduced to improve the description of phase equilibria in temperature ranges between 273.15 and 373.15 K. The proposed model has been successfully applied to the predictions of phase behaviours of alkali halide aqueous solutions that are usually found...

  2. Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

    International Nuclear Information System (INIS)

    Jeena, S. E.; Gnanaprakasam, P.; Selvaraju, T.

    2017-01-01

    A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt 40 /C or Pt 20 /C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

  3. Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jeena, S. E.; Gnanaprakasam, P. [Karunya University, Department of Chemistry (India); Selvaraju, T., E-mail: veluselvaraju@gmail.com [Bharathiar University, Department of Chemistry (India)

    2017-01-15

    A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt{sub 40}/C or Pt{sub 20}/C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

  4. Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

    Science.gov (United States)

    Jeena, S. E.; Gnanaprakasam, P.; Selvaraju, T.

    2017-01-01

    A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt40/C or Pt20/C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

  5. Next Generation Catalyst Engineering via Support Modification

    Science.gov (United States)

    2016-01-21

    performance of AT-treated MEAs is related to an improved interface between the catalyst and Nafion ionomer . Among potential explanations, this...Gennett, Ryan O’Hayre. Effect of Halide-Modified Model Carbon Supports on Catalyst Stability, ACS Applied Materials & Interfaces , (12 2012): 0...model carbon supports on catalyst stability”, ACS Appl. Mater. Interfaces , 4 (12), 6728-6734 (2012) 4) Demonstration of Improved Durability Using a

  6. Sonochemically preparation and characterization of bimetallic Ni-Co/Al2O3-ZrO2 nanocatalyst: Effects of ultrasound irradiation time and power on catalytic properties and activity in dry reforming of CH4.

    Science.gov (United States)

    Mahboob, Salar; Haghighi, Mohammad; Rahmani, Farhad

    2017-09-01

    The catalytic performance of nanostructured Ni-Co/Al 2 O 3 -ZrO 2 catalysts, prepared by ultrasound-assisted impregnation method was examined in the dry reforming of methane. The effect of irradiation power and irradiation time have been studied by changing time (0, 20, 80min) and power of the sonication (30, 60, 90W) during the synthesis which resulted in different physiochemical properties of the nanocatalyst. The nanocatalysts were characterized by XRD, FESEM, PSD, EDX, TEM, TPR-H 2 , BET, FTIR and TG analyses. Based on the characterization results, ultrasound treatment endowed the sample with more uniform and smaller nanoparticles; higher surface area, stronger metal-support interaction and more homogenous dispersion. Moreover, the analyses exhibited smaller particles with higher surface area and less population of particle aggregates at longer and highly irradiated nanocatalysts. The nanocatalyst irradiated at 90W for 80min (the longest irradiation time and the most intense power) showed a uniform morphology and a very narrow particles size distribution. More than 65% of particles of this nanocatalyst were in the range of 10-30nm. Activity tests demonstrated that employing ultrasound irradiation during impregnation improves feed conversion and products yield, reaching values close to equilibrium. Among sonicated nanocatalysts, with increasing power and time of irradiation, the nanocatalyst represents higher activity. The superior performance amongst the various bimetallic catalysts tested was observed over the catalyst with 90W and 80min ultrasonic irradiation which is stable in 24h time on stream test. The excellent anti-coking performance of this bimetallic catalyst, confirmed by TG and FESEM analyses of spent catalyst, is closely related to the promoting effect of sonication on the metal-support interaction, Ni dispersion and particle size; and probably, the synergy between metallic species. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Automotive Catalyst State Diagnosis Using Microwaves

    Directory of Open Access Journals (Sweden)

    Moos Ralf

    2015-01-01

    Full Text Available The state of catalysts plays a key role in automotive exhaust gas aftertreatment. The soot or ash loading of Diesel particulate filters, the oxygen loading degree in three-way catalysts, the amount of stored ammonia in SCR catalysts, or the NOx loading degree in NOx storage catalysts are important parameters that are today determined indirectly and in a model-based manner with gas sensors installed upstream and/or downstream of the catalysts. This contribution gives an overview on a novel approach to determine the catalyst state directly by a microwave-based technique. The method exploits the fact that the catalyst housing acts as a microwave cavity resonator. As “sensing” elements, one or two simple antennas are mounted inside the catalyst canning. The electrical properties of the catalyst device (ceramic honeycomb plus coating and storage material can be measured. Preferably, the resonance characteristics, e.g., the resonance frequencies, of selected cavity modes are observed. The information on the catalyst interior obtained in such a contactless manner is very well correlated with the catalyst state as will be demonstrated for different exhaust gas aftertreatment systems.

  8. Government As Innovation Catalyst: Lessons From The Early Center For Medicare And Medicaid Innovation Models.

    Science.gov (United States)

    Perla, Rocco J; Pham, Hoangmai; Gilfillan, Richard; Berwick, Donald M; Baron, Richard J; Lee, Peter; McCannon, C Joseph; Progar, Kevin; Shrank, William H

    2018-02-01

    Congress established the Center for Medicare and Medicaid Innovation (CMMI) to design, test, and spread innovative payment and service delivery models that either reduce spending without reducing the quality of care or improve the quality of care without increasing spending. CMMI sought to leverage these models to foster market innovation and accelerate the transformation of payment and care delivery to achieve the Triple Aim of better health, better care, and lower cost. This article provides a perspective on the design and execution of CMMI's five initial models, the resulting outcomes and lessons, and how their core concepts evolved within and spread beyond CMMI. This experience yields three key insights that could inform future efforts by CMMI and public and private payers, including model designs and policy decisions. These insights center on the need for iterative testing and learning guided by market feedback, more realistic time frames to demonstrate impact on cost and quality, and greater integration of models.

  9. Catalytic reforming of toluene as tar model compound: effect of Ce and Ce-Mg promoter using Ni/olivine catalyst.

    Science.gov (United States)

    Zhang, Ruiqin; Wang, Huajian; Hou, Xiaoxue

    2014-02-01

    Tar produced by biomass gasification as a route of renewable energy must be removed before the gas can be used. This study was undertaken using toluene as a model tar compound for evaluating its steam reforming conversion with three Ni-based catalysts, Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. Effects of Ce and Mg promoters on the reaction activity and coke deposition were studied. Overall the performance of Ce and Mg promoted Ni/olivine catalysts is better than that of only Ce promoter and Ni/olivine alone. The experimental results indicate that Ni-Ce-Mg/olivine catalysts could improve the resistance to carbon deposition, enhance energy gases yield and resist 10ppm H2S poison at 100mLmin(-1) for up to 400min. Furthermore, the activity of catalysts was related to the steam/carbon (S/C) ratios; at S/C ratio=5, T=790°C, space velocity=782h(-1) and t=2h, the Ni-Ce-Mg/olivine system yielded 89% toluene conversion, 5.6Lh(-1) product gas rate, 62.6mol% H2 content and 10% (mol useful gas mol(-1) toluene) energy yield. Moreover, at low S/C ratio, it had higher reaction activity and better ability to prevent coking. There is a small amount of carbon deposition in the form of amorphous carbon after 7h. Various characterization techniques such as XRD, FTIR and thermogravimetric were performed to investigate the coke deposition of Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. It is suggested that 3% Ni-1% Ce-1% Mg/olivine was the most promising catalyst due to its minimum coke amount and the lower activation energy of coke burning. Copyright © 2014. Published by Elsevier Ltd.

  10. Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al2O3 catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR

    International Nuclear Information System (INIS)

    Grilc, M.; Likozar, B.; Levec, J.

    2014-01-01

    Raw residual wood biomass, containing cellulose, hemicellulose and lignin, was liquefied at low temperature by ultrasound-assisted solvolysis and acidolysis by glycerol, diethylene glycol and p-toluenesulfonic acid. Liquefied biomass was consequently upgraded by hydrotreatment utilizing heterogeneous catalysis over NiMo/Al 2 O 3 bifunctional catalyst. Effects of temperature (200−350 °C), heating rate (2.5–10.0 K min −1 ), hydrogen/nitrogen pressure (2−8 MPa), mixing (250−1000 min −1 ), hydrogen donor solvent (tetralin) and catalyst contents on deoxygenation were established. Reactions of liquefaction products, such as levulinic acid, were quantified based on their functional groups by Fourier transform infrared spectroscopy, whereas catalyst was examined by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction analysis (XRD). Chemical kinetics of hydrodeoxygenation (HDO), decarbonylation and decarboxylation were determined by originally developed lumped model, based on reaction mechanisms and pathways, while the external mass transfer resistance proved to be negligible under the applied hydrodynamic conditions. The presence of hydrocracking reactions was confirmed by a decrease in product viscosity, and the upgrade for energetic or fuel applications by measurements of calorific value. - Highlights: • Liquefaction of waste lignocellulosic biomass with glycerol at low temperature. • Hydrotreatment, hydrocracking and hydrodeoxygenation of liquefied waste biomass. • Deoxygenation using heterogeneous catalysis over NiMo/Al 2 O 3 bifunctional catalyst. • Proposal of reaction mechanism; chemical kinetics and mass transfer considerations. • Effect of temperature, heating rate, pressure, mixing, solvent and catalyst content

  11. Catalyst Deactivation and Regeneration Processes in Biogas Tri-Reforming Process. The Effect of Hydrogen Sulfide Addition

    Directory of Open Access Journals (Sweden)

    Urko Izquierdo

    2018-01-01

    Full Text Available This work studies Ni-based catalyst deactivation and regeneration processes in the presence of H2S under a biogas tri-reforming process for hydrogen production, which is an energy vector of great interest. 25 ppm of hydrogen sulfide were continuously added to the system in order to provoke an observable catalyst deactivation, and once fully deactivated two different regeneration processes were studied: a self-regeneration and a regeneration by low temperature oxidation. For that purpose, several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on alumina modified with CeO2 and ZrO2 were used as well as a commercial Katalco 57-5 for comparison purposes. Ni/Ce-Al2O3 and Ni/Ce-Zr-Al2O3 catalysts almost recovered their initial activity. For these catalysts, after the regeneration under oxidative conditions at low temperature, the CO2 conversions achieved—79.5% and 86.9%, respectively—were significantly higher than the ones obtained before sulfur poisoning—66.7% and 45.2%, respectively. This effect could be attributed to the support modification with CeO2 and the higher selectivity achieved for the Reverse Water-Gas-Shift (rWGS reaction after catalysts deactivation. As expected, the bimetallic Rh-Ni/Ce-Al2O3 catalyst showed higher resistance to deactivation and its sulfur poisoning seems to be reversible. In the case of the commercial and Ni/Zr-Al2O3 catalysts, they did not recover their activity.

  12. Modeling and simulation of graphene/palladium catalyst reformer for hydrogen generation from waste of IC engine

    Science.gov (United States)

    Rahman, A.; Aung, K. M.

    2018-01-01

    A small amount of hydrogen made by on-board reformer is added to the normal intake air and gasoline mixture in the vehicle’s engine could improves overall combustion quality by allowing nearly twice as much air for a given amount of fuel introduced into the combustion chamber. This can be justified based on the calorific value of Hydrogen (H2) 141.9 MJ/kg while the gasoline (C6.4H11.8) is 47MJ/kg. Different weight % of Pd and GO uses for the reformer model and has conducted simulation by COMSOL software. The best result found for the composition of catalyst (palladium 30% and graphene 70%). The study shows that reformer yield hydrogen 23% for the exhaust temperature of 600-900°C and 20% for 80-90°C. Pumping hydrogen may boost the fuel atomization and vaporization at engine idle condition, which could enhances the fuel combustion efficiency. Thus, this innovative technology would be able to save fuel about 12% and reduce the emission about 35%.

  13. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division

    2014-09-01

    Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.

  14. The Women's Health Care Empowerment Model as a Catalyst for Change in Developing Countries.

    Science.gov (United States)

    Mitroi, Lavinia R; Sahak, Medina; Sherzai, Ayesha Z; Sherzai, Dean

    2016-01-01

    Women's empowerment has been attempted through a number of different fields including the realms of politics, finance, and education, yet none of these domains are as promising as health care. Here we review preliminary work in this domain and introduce a model for women's empowerment through involvement in health care, titled the "women's health care empowerment model." Principles upon which our model is built include: acknowledging the appropriate definition of empowerment within the cultural context, creating a women's network for communication, integrating local culture and tradition into training women, and increasing the capability of women to care for their children and other women.

  15. 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....... by impregnation, showing similar catalytic performance as the atomic layer deposition-prepared catalyst, yielding single-walled carbon nanotubes with a similar narrow chirality distribution.......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...

  16. Predictive Modelling of Phase-Transfer Catalyst Systems for Improved and Innovative Design

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Hyung Kim, Sun; Sales-Cruz, Mauricio

    2016-01-01

    increasing attention as a novel organic synthesis option due to its flexible and easier operation, higher production yield, and ability to eliminate expensive solvents, although, not eliminating the use of solvents. New mathematical models of the PTC system, which includes physical and chemical equilibrium......, reaction mechanism and unit operation has been developed. In the developed model, the PTC system is divided into four sub-systems of aqueous-organic solvent partition, inorganic salt in aqueous phase, PTC in aqueous phase, and PTC in aqueous phase. Each subsystem requires an appropriate thermodynamic model...... significantly widened, making it feasible to identify new and innovative biphasic reaction options. In this paper, the predictive qualities of the new model together with the improvements in the predicted design and operation of reaction with PTC systems are highlighted. Also, applications of problem...

  17. Principles and Methods for the Rational Design of Core-Shell Nanoparticle Catalysts with Ultralow Noble Metal Loadings.

    Science.gov (United States)

    Hunt, Sean T; Román-Leshkov, Yuriy

    2018-03-06

    Conspecuts Commercial and emerging renewable energy technologies are underpinned by precious metal catalysts, which enable the transformation of reactants into useful products. However, the noble metals (NMs) comprise the least abundant elements in the lithosphere, making them prohibitively scarce and expensive for future global-scale technologies. As such, intense research efforts have been devoted to eliminating or substantially reducing the loadings of NMs in various catalytic applications. These efforts have resulted in a plethora of heterogeneous NM catalyst morphologies beyond the traditional supported spherical nanoparticle. In many of these new architectures, such as shaped, high index, and bimetallic particles, less than 20% of the loaded NMs are available to perform catalytic turnovers. The majority of NM atoms are subsurface, providing only a secondary catalytic role through geometric and ligand effects with the active surface NM atoms. A handful of architectures can approach 100% NM utilization, but severe drawbacks limit general applicability. For example, in addition to problems with stability and leaching, single atom and ultrasmall cluster catalysts have extreme metal-support interactions, discretized d-bands, and a lack of adjacent NM surface sites. While monolayer thin films do not possess these features, they exhibit such low surface areas that they are not commercially relevant, serving predominantly as model catalysts. This Account champions core-shell nanoparticles (CS NPs) as a vehicle to design highly active, stable, and low-cost materials with high NM utilization for both thermo- and electrocatalysis. The unique benefits of the many emerging NM architectures could be preserved while their fundamental limitations could be overcome through reformulation via a core-shell morphology. However, the commercial realization of CS NPs remains challenging, requiring concerted advances in theory and manufacturing. We begin by formulating seven

  18. 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.

  19. Reactive Nano-Layered Bimetallics for Non-Destructive Debonding of Munition Components

    National Research Council Canada - National Science Library

    Minnicino, Michael A; Sands, James M; Hirvonen, James K; Demaree, J. D

    2004-01-01

    The U.S. Army Research Laboratory (ARL) has demonstrated that a bonded bimetallic stratified nanocomposite structure can, with a small electrical or thermal initiation, completely and quickly (<10 ms...

  20. 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

  1. Chemistry of Bimetallic Linked Cyclopentadienyl Complexes: Progress Report, 1 December 1986 --30 November 1989

    Science.gov (United States)

    Schrock, R. R.

    1989-01-01

    Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. (CBS)

  2. An analytic model of formation of carbon nanotubes by the vapor-liquid-drop mechanism and the possibility of optimizing catalysts of nanotube growth on the basis of this model

    Science.gov (United States)

    Alekseev, N. I.; Afanas'ev, D. V.; Charykov, N. A.

    2007-07-01

    A model of the growth of carbon nanotubes of various types from nanodrops of metallic catalysts supersaturated with carbon was developed. The model was used to calculate cocatalysts minimizing the work of critical nucleus formation. Among pure substances, atoms of iron family metals characterized by the lowest van der Waals interaction energy with graphene islands and a certain energy of chemical bonds with carbon are optimum. More effective catalysts can be prepared by selecting components in a certain ratio. The most effective combinations found empirically were nickel-yttrium and cobalt-molybdenum.

  3. 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)

  4. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    New Pei Yee

    2008-04-01

    Full Text Available A one-dimensional mathematical model was developed to simulate the performance of catalytic fixed bedreactor for carbon dioxide reforming of methane over Rh/Al2O3 catalyst at atmospheric pressure. The reactionsinvolved in the system are carbon dioxide reforming of methane (CORM and reverse water gas shiftreaction (RWGS. The profiles of CH4 and CO2 conversions, CO and H2 yields, molar flow rate and molefraction of all species as well as reactor temperature along the axial bed of catalyst were simulated. In addition,the effects of different reactor temperature on the reactor performance were also studied. The modelscan also be applied to analyze the performances of lab-scale micro reactor as well as pilot-plant scale reactorwith certain modifications and model verification with experimental data. © 2008 BCREC UNDIP. All rights reserved.[Received: 20 August 2008; Accepted: 25 September 2008][How to Cite: N.A.S. Amin, I. Istadi, N.P. Yee. (2008. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering and Catalysis, 3 (1-3: 21-29. doi:10.9767/bcrec.3.1-3.19.21-29

  5. High Sensitive and Selective Sensing of Hydrogen Peroxide Released from Pheochromocytoma Cells Based on Pt-Au Bimetallic Nanoparticles Electrodeposited on Reduced Graphene Sheets

    Directory of Open Access Journals (Sweden)

    Guangxia Yu

    2015-01-01

    Full Text Available In this study, a high sensitive and selective hydrogen peroxide (H2O2 sensor was successfully constructed with Pt-Au bimetallic nanoparticles (Pt-Au NPs/reduced graphene sheets (rGSs hybrid films. Various molar ratios of Au to Pt and different electrodeposition conditions were evaluated to control the morphology and electrocatalytic activity of the Pt-Au bimetallic nanoparticles. Upon optimal conditions, wide linear ranges from 1 µM to 1.78 mM and 1.78 mM to 16.8 mM were obtained, with a detection limit as low as 0.31 µM. Besides, due to the synergetic effects of the bimetallic NPs and rGSs, the amperometric H2O2 sensor could operate at a low potential of 0 V. Under this potential, not only common anodic interferences induced from ascorbic acid, uric acid and dopamine, but also the cathodic interference induced from endogenous O2 could be effectively avoided. Furthermore, with rat pheochromocytoma cells (PC 12 as model, the proposed sensor had been successfully used in the detection of H2O2 released from the cancer cells. This method with wide linear ranges and excellent selectivity can provide a promising alternative for H2O2 monitoring in vivo in the fields of physiology, pathology and diagnosis.

  6. Bimetallic low thermal-expansion panels of Co-base and silicide-coated Nb-base alloys for high-temperature structural applications

    International Nuclear Information System (INIS)

    Rhein, R.K.; Novak, M.D.; Levi, C.G.; Pollock, T.M.

    2011-01-01

    Research highlights: → Low net thermal expansion bimetallic structural lattice constructed. → Temperatures on the order of 1000 deg. C reached. → Improved silicide coating for niobium alloy developed. - Abstract: The fabrication and high temperature performance of low thermal expansion bimetallic lattices composed of Co-base and Nb-base alloys have been investigated. A 2D sheet lattice with a coefficient of thermal expansion (CTE) lower than the constituent materials of construction was designed for thermal cycling to 1000 deg. C with the use of elastic-plastic finite element analyses. The low CTE lattice consisted of a continuous network of the Nb-base alloy C-103 with inserts of high CTE Co-base alloy Haynes 188. A new coating approach wherein submicron alumina particles were incorporated into (Nb, Cr, Fe) silicide coatings was employed for oxidation protection of the Nb-base alloy. Thermal gravimetric analysis results indicate that the addition of submicron alumina particles reduced the oxidative mass gain by a factor of four during thermal cycling, increasing lifetime. Bimetallic cells with net expansion of 6 x 10 -6 /deg. C and 1 x 10 -6 /deg. C at 1000 deg. C were demonstrated and their measured thermal expansion characteristics were consistent with analytical models and finite element analysis predictions.

  7. Thin film metallization for micro-bimetallic actuators

    Science.gov (United States)

    Gorrell, Jonathan Frank

    In this study, eleven different thin film metallization systems were evaluated for use in micro-bimetallic actuators for microelectromechanical structures. These films were evaporated or sputtered onto silicon wafers. The film stress and stress relaxation were determined by measuring changes in the wafer curvature. The phases and micro-structure of these films were evaluated with, scanning electron microscopy, transmission electron microscopy, Auger electron spectroscopy, electron probe micro-analysis, X-ray diffraction and line shape analysis, and atomic force microscopy. Bimetallic actuator may be operated to generate either force or displacement. The displacement mode is dominated by the coefficient of thermal expansion while the force mode is a function of both Young's modulus and coefficient of thermal expansion of the active layer material. In both modes the maximum displacement or force is determined by the material's yield strength. A figure of merit was developed to aid in material selection. The 5052 aluminum alloy films showed that solid solution strengthening can double the yield strength of a thin film. The T201 aluminum alloy films showed that precipitates can increase yield strength by 2.5 times. The 2090 alloy film oxidized during the first heating. Based on isothermal stress relaxation data and changes in the micro-structure of the 5052 and T201 alloy thin films, two mechanisms involving logarithmic creep have been postulated to cause stress relaxation. One mechanism is movement of dislocations in slip systems that terminate at the surface while the other is dislocations moving in slip systems that terminate at grain boundaries. Copper gold intermetallics films oxidized and plastically deformed before the order-disorder transformation occurred, but showed that ordered intermetallics have a lower stress relaxation rate than the solid solution phase. The Alsb3Ti films showed no stress relaxation at 450sp°C, plastically deformed only above 500sp

  8. Ostwald ripening in a Pt/SiO2 model catalyst studied by in situ TEM

    DEFF Research Database (Denmark)

    Simonsen, Søren Bredmose; Chorkendorff, Ib; Dahl, Søren

    2011-01-01

    by the Ostwald ripening mechanism. The in situ TEM images also provide information about the temporal evolution of the Pt particle size distribution and of the growth or decay of the individual nanoparticles. The observed Pt nanoparticle changes compare well with predictions made by mean-field kinetic models...... for ripening, but deviations are revealed for the time-evolution for the individual nanoparticles. A better description of the individual nanoparticle ripening is obtained by kinetic models that include local correlations between neighboring nanoparticles in the atom-exchange process....

  9. Effect of phase interaction on catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Chai, Shujing [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); The Institute of Seawater Desalination and Miltipurpose Utilization, State Oceanic Administration, Tianjin 300192 (China); Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); Xian, Hui [Tianjin Polytechnic University, School of Computer Science & Software Engineering, Tianjin 300387 (China); Mi, Wenbo [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparation Technology, Faculty of Science, Tianjin University, Tianjin 300354 (China); Li, Xingang, E-mail: xingang_li@tju.edu.cn [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China)

    2017-04-30

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO{sub 2} and Al{sub 2}O{sub 3}. • Interaction between SnO{sub 2} and Al{sub 2}O{sub 3} phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn{sup 4+} cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalysts. Our results show that interaction between the Al{sub 2}O{sub 3} and SnO{sub 2} phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO{sub 2}/Al{sub 2}O{sub 3} catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO{sub 2}, which probably results from the change of electron concentration on the interface of the SnO{sub 2} and Al{sub 2}O{sub 3} phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn{sup 4+} cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO{sub 2}-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  10. 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.

  11. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    Science.gov (United States)

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  12. Generator Approach to Evolutionary Optimization of Catalysts and its Integration with Surrogate Modeling

    Czech Academy of Sciences Publication Activity Database

    Holeňa, Martin; Linke, D.; Rodemerck, U.

    2011-01-01

    Roč. 159, č. 1 (2011), s. 84-95 ISSN 0920-5861 R&D Projects: GA ČR GA201/08/0802 Institutional research plan: CEZ:AV0Z10300504 Keywords : optimization of catalytic materials * evolutionary optimization * surrogate modeling * artificial neural networks * multilayer perceptron * regression boosting Subject RIV: IN - Informatics, Computer Science Impact factor: 3.407, year: 2011

  13. Surface analysis of model systems: From a metal-graphite interface to an intermetallic catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kwolek, Emma J. [Iowa State Univ., Ames, IA (United States)

    2016-10-25

    This thesis summarizes research completed on two different model systems. In the first system, we investigate the deposition of the elemental metal dysprosium on highly-oriented pyrolytic graphite (HOPG) and its resulting nucleation and growth. The goal of this research is to better understand the metal-carbon interactions that occur on HOPG and to apply those to an array of other carbon surfaces. This insight may prove beneficial to developing and using new materials for electronic applications, magnetic applications and catalysis.

  14. Reaction mechanism of coal liquefaction: hydrogenolysis of model compound using synthetic pyrite as catalysts. 7. Property change of synthetic pyrite catalyst with the time after production; Sekitan ekika hanno kiko (model kagobutsu no hanno). 7. Gosei ryukatetsu shokubai no keiji henka ni tsuite

    Energy Technology Data Exchange (ETDEWEB)

    Ito, H.; Meno, H.; Uemaki, O.; Shibata, T.; Tsuji, T. [Hokkaido University, Sapporo (Japan)

    1996-10-28

    Reactions of various model compounds were investigated using synthetic pyrites for coal liquefaction. In this study, successive changes of the catalysts were investigated from the reactions of model compounds by using three different synthetic pyrites with the lapse of time after production. Benzyl phenyl ether, dibenzyl, and n-octylbenzene were used as model compounds. Reactions were conducted in an autoclave, into which sample, catalyst, decalin as solvent, and initial hydrogen pressure 10 MPa were charged. The autoclave was held at 450 or 475{degree}C of reaction temperature for 1 hour. The catalyst with a shorter lapse of time after production acted to hydrogen transfer, and inhibited the formation of condensation products due to the stabilization of decomposed fragment. It also acted to isomerization of materials by cutting alkyl side chains. When adding sulfur to the catalyst with longer lapse of time after production under these reaction conditions, it inhibited the formation of condensation products for the reaction of benzyl phenyl ether. However, it did not provide the effect for the reaction of n-octylbenzene. 5 refs., 3 figs.

  15. Dehydrogenation Kinetics and Modeling Studies of MgH2 Enhanced by Transition Metal Oxide Catalysts Using Constant Pressure Thermodynamic Driving Forces

    Directory of Open Access Journals (Sweden)

    Saidi Temitope Sabitu

    2012-06-01

    Full Text Available The influence of transition metal oxide catalysts (ZrO2, CeO2, Fe3O4 and Nb2O5 on the hydrogen desorption kinetics of MgH2 was investigated using constant pressure thermodynamic driving forces in which the ratio of the equilibrium plateau pressure (pm to the opposing plateau (pop was the same in all the reactions studied. The results showed Nb2O5 to be vastly superior to other catalysts for improving the thermodynamics and kinetics of MgH2. The modeling studies showed reaction at the phase boundary to be likely process controlling the reaction rates of all the systems studied.

  16. [NiFe] hydrogenase structural and functional models: new bio-inspired catalysts for hydrogen evolution

    International Nuclear Information System (INIS)

    Oudart, Y.

    2006-09-01

    Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)

  17. Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts

    International Nuclear Information System (INIS)

    Mayr, Lukas; Klötzer, Bernhard; Penner, Simon; Rameshan, Raffael; Rameshan, Christoph

    2014-01-01

    An ultra-high vacuum (UHV) setup for “real” and “inverse” model catalyst preparation, depth-resolved near-surface spectroscopic characterization, and quantification of catalytic activity and selectivity under technologically relevant conditions is described. Due to the all-quartz reactor attached directly to the UHV-chamber, transfer of the catalyst for in situ testing without intermediate contact to the ambient is possible. The design of the UHV-compatible re-circulating batch reactor setup allows the study of reaction kinetics under close to technically relevant catalytic conditions up to 1273 K without contact to metallic surfaces except those of the catalyst itself. With the attached differentially pumped exchangeable evaporators and the quartz-microbalance thickness monitoring equipment, a reproducible, versatile, and standardised sample preparation is possible. For three-dimensional near-surface sample characterization, the system is equipped with a hemispherical analyser for X-ray photoelectron spectroscopy (XPS), electron-beam or X-ray-excited Auger-electron spectroscopy, and low-energy ion scattering measurements. Due the dedicated geometry of the X-ray gun (54.7°, “magic angle”) and the rotatable sample holder, depth analysis by angle-resolved XPS measurements can be performed. Thus, by the combination of characterisation methods with different information depths, a detailed three-dimensional picture of the electronic and geometric structure of the model catalyst can be obtained. To demonstrate the capability of the described system, comparative results for depth-resolved sample characterization and catalytic testing in methanol steam reforming on PdGa and PdZn near-surface intermetallic phases are shown

  18. 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.

  19. Iron-57 and iridium-193 Moessbauer spectroscopic studies of supported iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1988-01-01

    57 Fe and 193 Ir Moessbauer spectroscopy shows that silica- and alumina-supported iron-iridium catalysts formed by calcination in air contain mixtures of small particle iron(III) oxide and iridium(IV) oxide. The iridium dioxide in both supported catalysts is reduced in hydrogen to metallic iridium. The α-Fe 2 O 3 in the silica supported materials is predominantly reduced in hydrogen to an iron-iridium alloy whilst in the alumina-supported catalyst the iron is stabilised by treatment in hydrogen as iron(II). Treatment of a hydrogen-reduced silica-supported iron catalyst in hydrogen and carbon monoxide is accompanied by the formation of iron carbides. Carbide formation is not observed when the iron-iridium catalysts are treated in similar atmospheres. The results from the bimetallic catalysts are discussed in terms of the hydrogenation of associatively adsorbed carbon monoxide and the selectivity of supported iron-iridium catalysts to methanol formation. (orig.)

  20. Engineering catalyst microenvironments for metal-catalyzed hydrogenation of biologically derived platform chemicals.

    Science.gov (United States)

    Schwartz, Thomas J; Johnson, Robert L; Cardenas, Javier; Okerlund, Adam; Da Silva, Nancy A; Schmidt-Rohr, Klaus; Dumesic, James A

    2014-11-17

    It is shown that microenvironments formed around catalytically active sites mitigate catalyst deactivation by biogenic impurities that are present during the production of biorenewable chemicals from biologically derived species. Palladium and ruthenium catalysts are inhibited by the presence of sulfur-containing amino acids; however, these supported metal catalysts are stabilized by overcoating with poly(vinyl alcohol) (PVA), which creates a microenvironment unfavorable for biogenic impurities. Moreover, deactivation of Pd catalysts by carbon deposition from the decomposition of highly reactive species is suppressed by the formation of bimetallic PdAu nanoparticles. Thus, a PVA-overcoated PdAu catalyst was an order of magnitude more stable than a simple Pd catalyst in the hydrogenation of triacetic acid lactone, which is the first step in the production of biobased sorbic acid. A PVA-overcoated Ru catalyst showed a similar improvement in stability during lactic acid hydrogenation to propylene glycol in the presence of methionine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Electrocatalytic Reduction-oxidation of Chlorinated Phenols using a Nanostructured Pd-Fe Modified Graphene Catalyst

    International Nuclear Information System (INIS)

    Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong

    2015-01-01

    A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O 2 to H 2 O 2 , which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O 2 to H 2 O 2 .

  2. Trimetallic (Aurod-Pdshell-Ptcluster Catalyst Used as Amperometric Hydrogen Peroxide Sensor

    Directory of Open Access Journals (Sweden)

    Shou-I Cheng

    2014-11-01

    Full Text Available Bimetallic nanostructured core-shell structures are commonly used as catalysts in a wide variety of reactions. We surmised that the addition of an additional metal would potentially allow catalytic tailoring with the possibility of an increase in activity. Here a tri-metallic catalytic structure, consisting of clustered catalytic Pt on the surface of a Pd shell supported on a rod shaped Au core was fabricated. The significance of the additional metallic component is shown by comparative electrochemically active surface area (ECSA analysis results for the trimetallic Aurod-Pdshell-Ptcluster, bimetallic Aurod-Ptcluster and monometallic JM-Pt (used as a reference, which have respective ECSA values (cm2/mgPt of 1883.0, 1371.7 and 879. The potential utility of the trimetallic catalysts was shown in a hydrogen peroxide sensing protocol, which showed the catalyst to have a sensitivity of 604 ìA/mMcm2 within a linear range of 0.0013–6.191 mM.

  3. Morphological and Compositional Design of Pd-Cu Bimetallic Nanocatalysts with Controllable Product Selectivity toward CO2 Electroreduction.

    Science.gov (United States)

    Zhu, Wenjin; Zhang, Lei; Yang, Piaoping; Chang, Xiaoxia; Dong, Hao; Li, Ang; Hu, Congling; Huang, Zhiqi; Zhao, Zhi-Jian; Gong, Jinlong

    2018-02-01

    Electrochemical conversion of carbon dioxide (electrochemical reduction of carbon dioxide) to value-added products is a promising way to solve CO 2 emission problems. This paper describes a facile one-pot approach to synthesize palladium-copper (Pd-Cu) bimetallic catalysts with different structures. Highly efficient performance and tunable product distributions are achieved due to a coordinative function of both enriched low-coordinated sites and composition effects. The concave rhombic dodecahedral Cu 3 Pd (CRD-Cu 3 Pd) decreases the onset potential for methane (CH 4 ) by 200 mV and shows a sevenfold CH 4 current density at -1.2 V (vs reversible hydrogen electrode) compared to Cu foil. The flower-like Pd 3 Cu (FL-Pd 3 Cu) exhibits high faradaic efficiency toward CO in a wide potential range from -0.7 to -1.3 V, and reaches a fourfold CO current density at -1.3 V compared to commercial Pd black. Tafel plots and density functional theory calculations suggest that both the introduction of high-index facets and alloying contribute to the enhanced CH 4 current of CRD-Cu 3 Pd, while the alloy effect is responsible for high CO selectivity of FL-Pd 3 Cu. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Kinetics and mechanism of the heterogeneous catalyzed oxidative decolorization of Acid-Blue 92 using bimetallic metal-organic frameworks.

    Science.gov (United States)

    El-sharkawy, Rehab G; El-din, Ahmed S Badr; El-din H Etaiw, Safaa

    2011-09-01

    The kinetics study of the oxidative decolorization of Acid-Blue 92 has been investigated by hydrogen peroxide catalyzed with bimetallic metal-organic frameworks. The used metal-organic frameworks (MOF) are [Ph3SnCu(CN)2·L] where L=pyrazine (pyz) 1, methylpyrazine (mepyz) 2, 4,4'-bipyridine (bpy) 3, trans-1,2-bis(4-pyridyl)ethene (tbpe) 4 or 1,2-bis(4-pyridyl)ethane (bpe) 5. The reaction was followed by conventional UV-Vis spectrophotometer at λmax=571 nm. The reaction exhibited first-order kinetics with respect to [dye] and [H2O2]. The reactivity of the catalysts depends on the type of the medium and thereafter decreases in strong alkaline media. Addition of NaCl enhances the reaction rate. Also, the irradiation of the reaction with UV-light enhanced the rate of AB-92 mineralization by about 86.9%. The reaction was entropy-controlled as confirmed by the isokinetic relationship. A reaction mechanism was proposed with the formation of free radicals as an oxidant. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. EFFECTS OF CATALYST MORPHOLOGY ON HYDROTREATING REACTIONS

    Directory of Open Access Journals (Sweden)

    TYE CHING THIAN

    2008-08-01

    Full Text Available Due to the new environmental regulations for fuel quality, refineries need to process cleaner fuel. This requires an improvement in performance of hydrotreating catalysts. Improvements in catalyst activity require knowledge of the relationships between catalyst morphology and activity. Molybdenum sulfide, the generally agreed catalysts that give the best performance in hydrocracking and hydrotreating was investigated for its morphology effects on hydrotreating reactions. Three types of MoS2 catalysts with different morphology were studied. They are crystalline MoS2, exfoliated MoS2 and MoS2 derived from a precursor, molybdenum naphthenate. Exfoliated MoS2 with minimal long range order, with much higher rim edges has shown relative higher hydrogenation activity. Generally, results of MoS2 catalyst activities in hydrogenation, hydrodesulfurization, hydrodenitrogenation and hydrideoxy¬gena¬tion are in agreement with the rim-edge model.

  6. Modeling the selective catalytic reduction of NOx by ammonia over a Vanadia-based catalyst from heavy duty diesel exhaust gases

    International Nuclear Information System (INIS)

    Yun, Byoung Kyu; Kim, Man Young

    2013-01-01

    A numerical simulation for prediction of NO X conversion over a commercial V 2 O 5 catalyst with NH 3 as a reductant was performed for a heavy duty diesel engine applications. The chemical behaviors of the SCR reactor are described by using the global NO X kinetics including standard, fast, and NH 3 oxidation reactions with the Langmuir–Hinshelwood (LH) mechanism incorporated into the commercial Boost code. After introducing mathematical models for the SCR reaction with specific reaction parameters, the effects of various parameters such as space velocities, the O 2 , H 2 O, NO 2 , and NH 3 concentrations on the NOx conversion are thoroughly studied and validated by comparing with the experimental data available in the literature. It is found that NO X conversion increases with decreasing space velocity, H 2 O concentration, and NH 3 /NO X ratio, and increasing O 2 concentration and NO 2 /NO X ratio. The study shows that not only is the present approach adopted is flexible in treating performance of the commercial V 2 O 5 based SCR catalyst, it is also accurate and efficient for the prediction of NO X conversion in diesel exhaust environments. - Highlights: ► To find the reaction parameters for LH mechanism over a commercial V2O5 catalyst. ► To investigate the effects of various parameters on the SCR NO X conversion. ► To present benchmark solutions on SCR behavior with diesel exhaust environments.

  7. Theoretical investigations of olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cundari, T.R.; Gordon, M.S. [North Dakota State Univ., Fargo, ND (United States)

    1992-01-01

    An ab initio analysis of the electronic structure of high-valent, transition-metal alkylidenes as models for olefin metathesis catalysts is presented. The catalyst models studied fall into three categories: {open_quotes}new{close_quotes} metathesis catalyst models-tetrahedral M(OH){sup 2}(XH)(CH{sub 2}) complexes; {open_quotes}old{close_quotes} metathesis catalyst models-tetrahedral MCl{sub 2}(Y)(CH{sub 2}) complexes and alkylidene-substituted Mo metathesis catalysts, Mo(OH){sub 2}(NH)(=C(H)Z). The effect on the bonding caused by modification of either the metal, ligands, or alkylidene substitutents is considered. 21 refs., 2 figs., 5 tabs.

  8. Modeling Geometric Arrangements of TiO2-Based Catalyst Substrates and Isotropic Light Sources to Enhance the Efficiency of a Photocatalystic Oxidation (PCO) Reactor

    Science.gov (United States)

    Richards, Jeffrey T.; Levine, Lanfang H.; Husk, Geoffrey K.

    2011-01-01

    The closed confined environments of the ISS, as well as in future spacecraft for exploration beyond LEO, provide many challenges to crew health. One such challenge is the availability of a robust, energy efficient, and re-generable air revitalization system that controls trace volatile organic contaminants (VOCs) to levels below a specified spacecraft maximum allowable concentration (SMAC). Photocatalytic oxidation (PCO), which is capable of mineralizing VOCs at room temperature and of accommodating a high volumetric flow, is being evaluated as an alternative trace contaminant control technology. In an architecture of a combined air and water management system, placing a PCO unit before a condensing heat exchanger for humidity control will greatly reduce the organic load into the humidity condensate loop ofthe water processing assembly (WPA) thereby enhancing the life cycle economics ofthe WPA. This targeted application dictates a single pass efficiency of greater than 90% for polar VOCs. Although this target was met in laboratory bench-scaled reactors, no commercial or SBIR-developed prototype PCO units examined to date have achieved this goal. Furthermore, the formation of partial oxidation products (e.g., acetaldehyde) was not eliminated. It is known that single pass efficiency and partial oxidation are strongly dependent upon the contact time and catalyst illumination, hence the requirement for an efficient reactor design. The objective of this study is to maximize the apparent contact time and illuminated catalyst surface area at a given reactor volume and volumetric flow. In this study, a Ti02-based photocatalyst is assumed to be immobilized on porous substrate panels and illumination derived from linear isotropic light sources. Mathematical modeling using computational fluid dynamics (CFD) analyses were performed to investigate the effect of: 1) the geometry and configuration of catalyst-coated substrate panels, 2) porosity of the supporting substrate, and 3

  9. Pilot‐scale investigation and CFD modeling of particle deposition in low‐dust monolithic SCR DeNOx catalysts

    DEFF Research Database (Denmark)

    Heiredal, Michael Lykke; Jensen, Anker Degn; Thøgersen, Joakim Reimer

    2013-01-01

    Deposition of particles in selective catalytic reduction DeNOx monolithic catalysts was studied by low‐dust pilot‐scale experiments. The experiments showed a total deposition efficiency of about 30%, and the deposition pattern was similar to that observed in full‐scale low‐dust applications. On e...

  10. Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

    NARCIS (Netherlands)

    Mahfud, F. H.; Ghijsen, F.; Heeres, H. J.

    2007-01-01

    The use of homogeneous ruthenium catalysts to hydrogenate the water-soluble fraction of pyrolysis oil is reported. Pyrolysis oil, which is obtained by fast pyrolysis of lignocellulosic biomass at 450-600 degrees C, contains significant amounts of aldehydes and ketones (e.g. 1-hydroxy-2-propanone (1)

  11. 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

    The activity and stability of Pt5Gd for the oxygen reduction reaction (ORR) have been studied, using a combination of electrochemical measurements, angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and density functional theory calculations. Sputter-cleaned, polycrystalline Pt5Gd shows a ...... 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....

  12. Optimization of the reaction parameters of heavy naphtha reforming process using Pt-Re/Al2O3 catalyst system

    Directory of Open Access Journals (Sweden)

    Hussien A. Elsayed

    2017-12-01

    Full Text Available One of the most significant procedures in oil refineries is naphtha catalytic reforming unit in which high octane gasoline is gained. Normally, in oil refineries, flow instability in the composition of feedstock can affect the product quality. The aim of the present work was focused on modifications of the final product flow rate and product’s octane number with respect to the modifications of the feedstock composition. The main three reforming reactions investigated, namely; dehydrogenation, dehydrocyclization, and hydrocracking were conducted employing silica supported bimetallic (Pt-Re patented catalyst. Optimization of the catalytic process reaction conditions, i.e.; temperature, hydrogen pressure and liquid hourly space velocity (LHSV was carried out with regard to conversion and selectivity. The optimization results indicated that heavy naphtha component conversion (paraffin’s and naphthenes increases with an increasing in reaction temperature and pressure while decreases with an increase in LHSV. The kinetic study of catalytic reforming reactions reported helped establishing the reaction model explicitly.

  13. Tryptophan-Assisted Synthesis Reduces Bimetallic Gold/Silver Nanoparticle Cytotoxicity and Improves Biological Activity

    Directory of Open Access Journals (Sweden)

    Igor O. Shmarakov

    2014-10-01

    Full Text Available Aiming to reduce the potential in vivo hepato-and neph‐ rotoxicity of Ag/Au bimetallic nanoparticles (NPs stabi‐ lized by sodium dodecyl sulphate (SDS, an approach involving a simultaneous reduction of silver nitrate and tetrachlorauratic acid using tryptophan (Trp as a reduc‐ ing/stabilizing agent was applied during NP synthesis. The obtained Ag/Au/Trp NPs (5-15 nm sized were able to form stable aggregates with an average size of 370-450 nm and were potentially less toxic than Ag/Au/SDS in relation to a mouse model system based on clinical biochemical param‐ eters and oxidative damage product estimation. Ag/Au/Trp NPs were shown to exhibit anticancer activity in relation to a Lewis lung carcinoma model. The data generated from the present study support the fact that the use of tryptophan in NP synthesis is effective in attenuating the potential hepatotoxicity and nephrotoxicity of NPs during their in vivo application.

  14. 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

  15. Sn interaction with the CeO.sub.2./sub.(111) system: bimetallic bonding and ceria reduction

    Czech Academy of Sciences Publication Activity Database

    Škoda, M.; Cabala, M.; Cháb, Vladimír; Prince, K. C.; Sedláček, L.; Skála, T.; Šutara, F.; Matolín, V.

    2008-01-01

    Roč. 254, č. 14 (2008), 4375-4379 ISSN 0169-4332 R&D Projects: GA MŠk(CZ) LC06058 Institutional research plan: CEZ:AV0Z10100521 Keywords : resonant photoemission * RPES * XPS * LEED * ceria * tin * reduction * bimetallic interaction * bimetallic bonding Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.576, year: 2008

  16. Cr(VI) reduction in wastewater using a bimetallic galvanic reactor

    International Nuclear Information System (INIS)

    Lugo-Lugo, Violeta; Barrera-Diaz, Carlos; Bilyeu, Bryan; Balderas-Hernandez, Patricia; Urena-Nunez, Fernando; Sanchez-Mendieta, Victor

    2010-01-01

    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.

  17. Melting phenomena: effect of composition for 55-atom Ag-Pd bimetallic clusters.

    Science.gov (United States)

    Cheng, Daojian; Wang, Wenchuan; Huang, Shiping

    2008-05-14

    Understanding the composition effect on the melting processes of bimetallic clusters is important for their applications. Here, we report the relationship between the melting point and the metal composition for the 55-atom icosahedral Ag-Pd bimetallic clusters by canonical Monte Carlo simulations, using the second-moment approximation of the tight-binding potentials (TB-SMA) for the metal-metal interactions. Abnormal melting phenomena for the systems of interest are found. Our simulation results reveal that the dependence of the melting point on the composition is not a monotonic change, but experiences three different stages. The melting temperatures of the Ag-Pd bimetallic clusters increase monotonically with the concentration of the Ag atoms first. Then, they reach a plateau presenting almost a constant value. Finally, they decrease sharply at a specific composition. The main reason for this change can be explained in terms of the relative stability of the Ag-Pd bimetallic clusters at different compositions. The results suggest that the more stable the cluster, the higher the melting point for the 55-atom icosahedral Ag-Pd bimetallic clusters at different compositions.

  18. A sequential vesicle pool model with a single release sensor and a ca(2+)-dependent priming catalyst effectively explains ca(2+)-dependent properties of neurosecretion

    DEFF Research Database (Denmark)

    Walter, Alexander M; da Silva Pinheiro, Paulo César; Verhage, Matthijs

    2013-01-01

    identified. We here propose a Sequential Pool Model (SPM), assuming a novel Ca(2+)-dependent action: a Ca(2+)-dependent catalyst that accelerates both forward and reverse priming reactions. While both models account for fast fusion from the Readily-Releasable Pool (RRP) under control of synaptotagmin-1...... - synaptotagmin-1 - slower Ca(2+)-dependent release components persist. These findings have provoked working models involving parallel releasable vesicle pools (Parallel Pool Models, PPM) driven by alternative Ca(2+) sensors for release, but no slow release sensor acting on a parallel vesicle pool has been......, the origins of slow release differ. In the SPM the slow release component is attributed to the Ca(2+)-dependent refilling of the RRP from a Non-Releasable upstream Pool (NRP), whereas the PPM attributes slow release to a separate slowly-releasable vesicle pool. Using numerical integration we compared model...

  19. Determination of the catalyst velocity profile along the riser of a fluidized bed reactor model by nuclear techniques

    International Nuclear Information System (INIS)

    Santos, V.A. dos; Dantas, C.C.

    1982-01-01

    A method adequated to industrial applications of flow measurements in fuidized bed reactor was developed. To measure the medium velocity of a catalyst, where the velocity is low, a radioactive tracer was used, 59 Fe and, to measure density by gamma attenuation, a standard source of 241 Am was used. The signals produced in NaI (Tl) scintilators detectors, were sent simultaneously to an electronic clock, to register the transit time, in the medium velocity measure of the catalyst whose reproductibility was 0.4%. The total estimated error for the method was a maximum of 4%. Important simplifications and pratical advantages are presented, if the method is compared to conventional measures with tracers. (E.G.) [pt

  20. Novel micro-reactor flow cell for investigation of model catalysts using in situ grazing-incidence X-ray scattering

    DEFF Research Database (Denmark)

    Kehres, Jan; Pedersen, Thomas; Masini, Federico

    2016-01-01

    -incidence small-angle X-ray scattering (GISAXS) in transmission through 10 µm-thick entrance and exit windows by using micro-focused beams. An additional thinning of the Pyrex glass reactor lid allows simultaneous acquisition of the grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ experiments......The design, fabrication and performance of a novel and highly sensitive micro-reactor device for performing in situ grazing-incidence X-ray scattering experiments of model catalyst systems is presented. The design of the reaction chamber, etched in silicon on insulator (SIO), permits grazing...