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Sample records for catalytic reactions experiments

  1. Forced thermal cycling of catalytic reactions: experiments and modelling

    DEFF Research Database (Denmark)

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune;

    2007-01-01

    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...... by dynamic thermal limitations of the reactor. (c) 2007 Elsevier B.V. All rights reserved....

  2. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-12-31

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  3. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-09-30

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  4. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Vivek V Ranade

    2014-03-01

    Catalytic reactions are ubiquitous in chemical and allied industries. A homogeneous or heterogeneous catalyst which provides an alternative route of reaction with lower activation energy and better control on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach.

  5. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System.

    Science.gov (United States)

    Buonomo, Joseph A; Aldrich, Courtney C

    2015-10-26

    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

  6. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  7. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  8. Determination of Catalytic Coefficient for a First-Order Reaction

    Science.gov (United States)

    Fraga, E. R.; And Others

    1975-01-01

    Describes an undergraduate physical chemistry experiment in which the acid catalyzed hydrolysis of sucrose is used to determine the catalytic coefficient of the hydronium ion, the catalyst in this reaction. (MLH)

  9. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  10. The Catalytic Asymmetric Intramolecular Stetter Reaction.

    Science.gov (United States)

    de Alaniz, Javier Read; Rovis, Tomislav

    2009-05-01

    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  11. Catalytic Radical Domino Reactions in Organic Synthesis

    Science.gov (United States)

    Sebren, Leanne J.; Devery, James J.; Stephenson, Corey R.J.

    2014-01-01

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes. PMID:24587964

  12. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen

    2007-01-01

    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...... understanding of the nature of the electrochemical promotion is also presented....

  13. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG XiaoMing

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  14. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  15. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  16. Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations

    Science.gov (United States)

    Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

    2017-01-01

    High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.

  17. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)

    2005-05-15

    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  18. Heterogeneous catalytic hydrogenation reactions in continuous-flow reactors.

    Science.gov (United States)

    Irfan, Muhammad; Glasnov, Toma N; Kappe, C Oliver

    2011-03-21

    Microreactor technology and continuous flow processing in general are key features in making organic synthesis both more economical and environmentally friendly. Heterogeneous catalytic hydrogenation reactions under continuous flow conditions offer significant benefits compared to batch processes which are related to the unique gas-liquid-solid triphasic reaction conditions present in these transformations. In this review article recent developments in continuous flow heterogeneous catalytic hydrogenation reactions using molecular hydrogen are summarized. Available flow hydrogenation techniques, reactors, commonly used catalysts and examples of synthetic applications with an emphasis on laboratory-scale flow hydrogenation reactions are presented.

  19. Catalytic Hydrogenation Reaction of Naringin-Chalcone. Study of the Electrochemical Reaction

    Directory of Open Access Journals (Sweden)

    B. A. López de Mishima

    2000-03-01

    Full Text Available The electrocatalytic hydrogenation reaction of naringin derivated chalcone is studied. The reaction is carried out with different catalysts in order to compare with the classic catalytic hydrogenation.

  20. Raman Nanospectroscopy of a Photo-Catalytic Reaction

    NARCIS (Netherlands)

    van Schrojenstein Lantman, E.M.

    2014-01-01

    A chemical reaction between molecules requires a certain amount of energy to occur. A catalyst can lower this activation energy, resulting in a faster, greener and more sustainable chemical process. Ideally, one would like to follow a reaction over a single catalytic nanoparticle, to fully understan

  1. Catalytic Reactions in Heavy-ion Collisions

    CERN Document Server

    Kolomeitsev, E E

    2011-01-01

    We discuss a new type of reactions of a phi meson production on hyperons, pi Y--> phi Y and anti-kaons bar-K N --> phi Y. These reactions are not suppressed according to Okubo-Zweig-Iizuka rule and can be a new efficient source of phi mesons in a nucleus-nucleus collision. We discuss how these reactions can affect the centrality dependence and the rapidity distributions of the phi yield.

  2. Catalytic reactions in heavy-ion collisions

    Science.gov (United States)

    Kolomeitsev, E. E.; Tomášik, B.

    2012-06-01

    We discuss a new type of reactions of a ϕ-meson production on hyperons, πY → ϕY and antikaons -KN → ϕY. These reactions are not suppressed according to Okubo-Zweig-Iizuka rule and can be a new efficient source of ϕ mesons in a nucleus-nucleus collision. We discuss how these reactions can affect the centrality dependence and the rapidity distributions of the ϕ yield.

  3. Electrochemistry as a Tool for Study, Delvelopment and Promotion of Catalytic Reactions

    DEFF Research Database (Denmark)

    Petrushina, Irina

    The first two chapters of the dissertation are dedicated to definition of the peculiarities of electrochemical processes and also common features and differences between heterogeneous redox and catalytic reactions and electrochemical reactions. The main common characteristic of heterogeneous...... catalytic reactions and electrochemical reactions is defined. It is the Fermi level of the catalyst, which is also the electrochemical potential of the electrode. According to the Newns-Anderson theory, Fermi level of catalysts affects (or even define) their activity. The electrochemical potential can...... be measured and changed by polarization in electrochemical experiment. In Chapter 3 the nature of the electrochemical heterogeneous catalytic reactions is dicussed, including the new theory of electrochemical promotion. This theory is based on electrochemical change of the Fermi level of the catalyst. It also...

  4. [Lipases in catalytic reactions of organic chemistry].

    Science.gov (United States)

    Bezborodov, A M; Zagustina, N A

    2014-01-01

    Aspects of enzymatic catalysis in lipase-catalyzed reactions of organic synthesis are discussed in the review. The data on modern methods of protein engineering and enzyme modification allowing a broader range of used substrates are briefly summarized. The application of lipase in the preparation of pharmaceuticals and agrochemicals containing no inactive enantiomers and in the synthesis of secondary alcohol enantiomers and optically active amides is demonstrated. The subject of lipase involvement in the C-C bond formation in the Michael reaction is discussed. Data on the enzymatic synthesis of construction materials--polyesters, siloxanes, etc.--are presented. Examples demonstrating the application of lipase enzymatic catalysis in industry are given.

  5. Identifying systematic DFT errors in catalytic reactions

    DEFF Research Database (Denmark)

    Christensen, Rune; Hansen, Heine Anton; Vegge, Tejs

    2015-01-01

    Using CO2 reduction reactions as examples, we present a widely applicable method for identifying the main source of errors in density functional theory (DFT) calculations. The method has broad applications for error correction in DFT calculations in general, as it relies on the dependence...

  6. Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

    Directory of Open Access Journals (Sweden)

    Xiaoqing Zhang

    2013-01-01

    Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

  7. Modular, Catalytic Enantioselective Construction of Quaternary Carbon Stereocenters by Sequential Cross-Coupling Reactions.

    Science.gov (United States)

    Potter, Bowman; Edelstein, Emma K; Morken, James P

    2016-07-01

    The catalytic Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates in the presence of RuPhos ligand occurs with high regioselectivity and enantiospecificity, furnishing nonracemic compounds with quaternary centers. Mechanistic experiments suggest that the reaction occurs by transmetalation with allyl migration, followed by rapid reductive elimination.

  8. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  9. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    Science.gov (United States)

    Tsotsis, T. T.; Sane, R. C.

    1987-04-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  10. Acid-base bifunctional catalytic surfaces for nucleophilic addition reactions.

    Science.gov (United States)

    Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-09-01

    This article illustrates the modification of oxide surfaces with organic amine functional groups to create acid-base bifunctional catalysts, summarizing our previous reports and also presenting new data. Immobilization of organic amines as bases on inorganic solid-acid surfaces afforded highly active acid-base bifunctional catalysts, which enabled various organic transformations including C--C coupling reactions, though these reactions did not proceed with either the homogeneous amine precursors or the acidic supports alone. Spectroscopic characterization, such as by solid-state MAS NMR and FTIR, revealed not only the interactions between acidic and basic sites but also bifunctional catalytic reaction mechanisms.

  11. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

    Villalobos, Luis Francisco

    2016-02-29

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane\\'s ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Polymer and Membrane Design for Low Temperature Catalytic Reactions.

    Science.gov (United States)

    Villalobos, Luis Francisco; Xie, Yihui; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2016-04-01

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed.

  13. Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions**

    OpenAIRE

    Yu, Zhiyong; Ely, Robert J.; Morken, James P.

    2014-01-01

    The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides a forum for the inspiration of new reaction development. In this manuscript, we present a synthesis of discodermolide that employs a previously undisclosed stereoselective catalytic diene hydroboration a...

  14. Synthesis and Catalytic Asymmetric Reaction of Chiral Pyridine Prolinol Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; ZHANG Yong-Xin; DU Da-Ming; HUA Wen-Ting

    2003-01-01

    @@ The enantioselective reduction of prochiral ketones with borane in the presence of a chiral ligand leading to enantiomerically pure secondary alcohols has received considerable attention in recent years. [1] Enantiomerically pure secondary alcohols are important intermediates for the synthesis of various other organic compounds such as halides, esters, ethers, ketones and amines. To the best of our knowledge, the use of pyridine prolinol derivatives in the reduction of ketones has not been reported so far. Thus, it should be of interest to investigate the catalytic a bility of such ligands. We have an ongoing project in the synthesis and application of chiral pyridine derivatives in chiral molecular recognition[2] and we want to evaluate the effect resulting from the introduction of a pyridinyl moiety onto the catalysts. We expect that the cooperation of pyridine unit and chiral prolinol unit in new ligands may result in unique properties for catalytic reaction.

  15. Thermodynamics behind carbon nanotube growth via endothermic catalytic decomposition reaction.

    Science.gov (United States)

    Harutyunyan, Avetik R; Kuznetsov, Oleg A; Brooks, Christopher J; Mora, Elena; Chen, Gugang

    2009-02-24

    Carbon filaments can be grown using hydrocarbons with either exothermic or endothermic catalytic decomposition enthalpies. By in situ monitoring the evolution of the reaction enthalpy during nanotube synthesis via methane gas, we found that although the decomposition reaction of methane is endothermic an exothermic process is superimposed which accompanies the nanotube growth. Analysis shows that the main contributor in this liberated heat is the radiative heat transfer from the surroundings, along with dehydrogenation reaction of in situ formed secondary hydrocarbons on the catalyst surface and the carbon hydrogenation/oxidation processes. This finding implies that nanotube growth process enthalpy is exothermic, and particularly, it extends the commonly accepted temperature gradient driven growth mechanism to the growth via hydrocarbons with endothermic decomposition enthalpy.

  16. Synthesis of (+)-discodermolide by catalytic stereoselective borylation reactions.

    Science.gov (United States)

    Yu, Zhiyong; Ely, Robert J; Morken, James P

    2014-09-01

    The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for the alkylation of chiral enolates. Furthermore, this synthesis of discodermolide provides the first examples of the asymmetric 1,4-diboration of dienes and borylative diene-aldehyde couplings in complex-molecule synthesis.

  17. Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions**

    Science.gov (United States)

    Yu, Zhiyong; Ely, Robert J.

    2014-01-01

    The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides a forum for the inspiration of new reaction development. In this manuscript, we present a synthesis of discodermolide that employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for chiral enolate alkylation. In addition, this synthesis of discodermolide provides the first examples of diene 1,4-diboration and borylative diene-aldehyde couplings in complex molecule synthesis. PMID:25045037

  18. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG XuMu

    2001-01-01

    @@ Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals

  19. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

    Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals  ……

  20. Hydrogen production from methane through catalytic partial oxidation reactions

    Science.gov (United States)

    Freni, S.; Calogero, G.; Cavallaro, S.

    This paper reviews recent developments in syn-gas production processes used for partial methane oxidation with and/or without steam. In particular, we examined different process charts (fixed bed, fluidised bed, membrane, etc.), kinds of catalysts (powders, foams, monoliths, etc.) and catalytically active phases (Ni, Pt, Rh, etc.). The explanation of the various suggested technical solutions accounted for the reaction mechanism that may selectively lead to calibrated mixtures of CO and H 2 or to the unwanted formation of products of total oxidation (CO 2 and H 2O) and pyrolysis (coke). Moreover, the new classes of catalysts allow the use of small reactors to treat large amounts of methane (monoliths) or separate hydrogen in situ from the other reaction products (membrane). This leads to higher conversions and selectivity than could have been expected thermodynamically. Although catalysts based on Rh are extremely expensive, they can be used to minimise H 2O formation by maximising H 2 yield.

  1. Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

    Science.gov (United States)

    Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

    2016-01-01

    This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

  2. Catalytic Reaction Synthesis for the Partial Oxidation of Methane to Formaldehyde.

    Science.gov (United States)

    Cardenas-Galindo, Maria-Guadalupe

    Catalytic reaction synthesis for the partial oxidation of methane to formaldehyde has been studied by combining microkinetic analysis with molecular orbital calculations. This strategy is used to establish microscopic correlations between the structure and composition of the active site and the kinetic parameters of the reaction mechanism. Using atom clusters to represent the active site of transition metal oxide catalysts, the relationship was probed between coordination number, oxidation state, and ionization potential of the active cation and the reaction steps of methane activation and surface reactions leading to formaldehyde formation. The analysis suggests that in transition metal oxide catalysts, the d-band orbitals of the metal cation should be empty, since otherwise CO_2 formation from CO oxidation will be excessive. Furthermore, the transition metal oxide d-band must be located at sufficiently low energy that it may accept electrons during methane activation. Oxygen O- species, representing vacancies in the 2p cluster band, will favor methane activation. However, clusters with fully occupied 2p bands (O^ {2-}^ecies) will favor formaldehyde production. Such inferences illustrate how experimental and theoretical information already incorporated into an existing microkinetic model for the reaction over V _2O_5 and MoO _3 catalysts can be extended to describe the reaction over new materials in the search for more active and selective catalysts. Using parameters estimated from the molecular orbital calculations, microkinetic reaction simulations were also shown to be useful to identify reactor operating conditions that may favor the production of formaldehyde. The simulation can be used to identify key experiments necessary to test the performance of postulated catalytic materials. The economic evaluation of the process design sets important target goals for methane conversion and formaldehyde selectivity that a catalytic material must satisfy to create a new

  3. Thermodynamic Analysis of Catalytic Cracking Reactions as the First Stage in the Development of Mathematical Description

    OpenAIRE

    Nazarova, Galina Yurievna; Ivanchina, Emilia Dmitrievna; Ivashkina, Elena Nikolaevna; Kiseleva, Svetlana; Stebeneva, Valeria

    2015-01-01

    In this work thermodynamic analysis of catalytic cracking reaction involving the high molecular weight hydrocarbons was carried out using quantum chemical method of calculation realized in Gaussian software. The method of calculation is DFT (Density Functional Theory), theoretical approximation is B3LYP model, 3-21G basis. The list of catalytic cracking reactions for calculation was prepared on the basis of the theoretical data about catalytic cracking, laboratory and experimental data from t...

  4. Catalytic and Gas-Solid Reactions Involving HCN over Limestone

    DEFF Research Database (Denmark)

    Jensen, Anker; Johnsson, Jan Erik; Dam-Johansen, Kim

    1997-01-01

    In coal-fired combustion systems solid calcium species may be present as ash components or limestone added to the combustion chamber. In this study heterogeneous reactions involving HCN over seven different limestones were investigated in a laboratory fixed-bed quartz reactor at 873-1,173 K....... Calcined limestone is an effective catalyst for oxidation of HCN. Under conditions with complete conversion of HCN at O-2 concentrations above about 5,000 ppmv the selectivity for formation of NO and N2O is 50-70% and below 5%, respectively. Nitric oxide can be reduced by HCN to N-2 in the absence of O-2...... and to N-2 and N2O in the presence of O-2. At low O-2 concentrations or low temperatures. HCN may react with CaO, forming calcium cyanamide, CaCN2. The selectivities for formation of NO and N2O from oxidation of CaCN2 is 20-25% for both species. The catalytic activity of limestone for oxidation of HCN...

  5. A study on the photo catalytic decomposition reactions of organics dissolved in water (II)

    Energy Technology Data Exchange (ETDEWEB)

    Sung, K.W.; Na, J. W.; Cho, Y. H.; Chung, H. H

    2000-01-01

    Experiments on aqueous TiO{sub 2} photo catalytic reaction of nitrogen containing organic compounds such as ethylamine, phenylhydrazine, pyridine, urea and EDTA were carried out. Based on the values calculated for the distribution of ionic species and atomic charge, the characteristics of their photo catalytic decomposition were estimated. It was shown that the decomposition characteristics was linearly proportional to nitrogen atomic charge value. On the other hand, the effects of aqueous pH, oxygen content and concentration on the TiO{sub 2} photo catalytic characteristics of EDTA, EDTA-Cu(II) and EDTA-Fe(III) were experimentally investigated. All EDTA systems were decomposed better in the pH range of 2.5-3.0 and with more dissolved oxygen. These results could be applied to construction of a process for removal of organic impurities dissolved in a source of system water, or for treatment of EDTA-containing liquid waste produced by a chemical cleaning in the domestic NPPs. (author)

  6. Catalytic reactor for promoting a chemical reaction on a fluid passing therethrough

    Science.gov (United States)

    Roychoudhury, Subir (Inventor); Pfefferle, William C. (Inventor)

    2001-01-01

    A catalytic reactor with an auxiliary heating structure for raising the temperature of a fluid passing therethrough whereby the catalytic reaction is promoted. The invention is a apparatus employing multiple electrical heating elements electrically isolated from one another by insulators that are an integral part of the flow path. The invention provides step heating of a fluid as the fluid passes through the reactor.

  7. Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

    KAUST Repository

    Al-Khattaf, S.

    2012-01-10

    Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro/mesoporous material was used to understand the effect of the presence of mesopores on these reactions. Various characterisation techniques, that is, XRD, SEM, TGA, FT-IR and nitrogen sorption measurements were applied for complete characterisation of the catalysts. Catalytic tests using CREC riser simulator showed that the micro/mesoporous composite catalyst exhibited higher catalytic activity as compared with the conventional microporous ZSM-5 and HY zeolite for transformation of m-xylene and for the catalytic cracking of TIPB, respectively. The outstanding catalytic reactivity of m-xylene and TIPB molecules were mainly attributed to the easier access of active sites provided by the mesopores. Apparent activation energies for the disappearance of m-xylene and TIPB over all catalysts were found to decrease in the order: EBCM>EZSM-5 and EBCM>EHY, respectively. © 2012 Canadian Society for Chemical Engineering.

  8. (Gold core) at (ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light

    KAUST Repository

    Wang, Jianfang

    2014-08-26

    Driving catalytic reactions with sunlight is an excellent example of sustainable chemistry. A prerequisite of solar-driven catalytic reactions is the development of photocatalysts with high solar-harvesting efficiencies and catalytic activities. Herein, we describe a general approach for uniformly coating ceria on monometallic and bimetallic nanocrystals through heterogeneous nucleation and growth. The method allows for control of the shape, size, and type of the metal core as well as the thickness of the ceria shell. The plasmon shifts of the Au@CeO2 nanostructures resulting from the switching between Ce(IV) and Ce(III) are observed. The selective oxidation of benzyl alcohol to benzaldehyde, one of the fundamental reactions for organic synthesis, performed under both broad-band and monochromatic light, demonstrates the visible-light-driven catalytic activity and reveals the synergistic effect on the enhanced catalysis of the Au@CeO2 nanostructures. © 2014 American Chemical Society.

  9. Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling

    Science.gov (United States)

    García, Andrés; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.

    2016-05-01

    Statistical mechanical modeling is developed to describe a catalytic conversion reaction A →Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Furthermore, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A .

  10. The First Catalytic Asymmetric Morita-Baylis-Hillman Reaction of Acrolein with Aromatic Aldehydes

    Institute of Scientific and Technical Information of China (English)

    曾兴平; 刘运林; 计从斌; 周剑

    2012-01-01

    We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama's catalyst β-isocupreidine C4, in combination with 20 mol% of 2,6-dimethoxybenzoic acid, could catalyze the reaction to give the desired products in up to 81% ee.

  11. Revealing structural dynamics in catalytic reactions using ultrafast transient x-ray absorption spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L. X.; Liu, D.; Chemical Sciences and Engineering Division; Northwestern Univ.

    2009-03-02

    Progression of a typical heterogeneous catalytic process as a function of a reaction parameter such as temperature can often be segmented, according to Fig. 1. Reactants first bind to active sites to form reaction intermediates with increases in temperature and kinetic energy (Region I). Further temperature increase leads to a full 'light-off' of the catalytic conversion and the reaction is dominated by the intra-particulate diffusion (Region II). The characteristic 'light-off' temperature at the boundary of region I and II often defines the activity of the catalyst. At even higher temperature enters the bulk diffusion region (III), where the catalytic reaction is limited mainly by mass transport between different phases. Significant efforts in practical catalyst design involve improving catalytic activities in the kinetic region (I) and reducing the 'light-off' temperature. Reaction rates at the kinetic region are defined by potential saddle points on top of which a series of 'transitional state' complexes are formed between the active sites and the adsorbed reactants (Fig. 2). Capturing structures of the 'transition state complexes' from the active center's perspective will provide ultimate understanding of catalytic mechanisms and insight into new catalyst design. Experimentally, however, it is a very challenging proposition.

  12. Process of forming catalytic surfaces for wet oxidation reactions

    Science.gov (United States)

    Jagow, R. B. (Inventor)

    1977-01-01

    A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

  13. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  14. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi

    2014-10-16

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

  15. Self-organized criticality of a catalytic reaction network under flow.

    Science.gov (United States)

    Awazu, Akinori; Kaneko, Kunihiko

    2009-07-01

    Self-organized critical behavior in a catalytic reaction network system induced by smallness in the molecule number is reported. The system under a flow of chemicals is shown to undergo a transition from a stationary to an intermittent reaction phase when the flow rate is decreased. In the intermittent reaction phase, two temporal regimes with active and halted reactions alternate. The number frequency of reaction events at each active regime and its duration time are shown to obey a universal power law with the exponents 4/3 and 3/2, respectively, independently of the parameters and network structure. These power laws are explained by a one-dimensional random-walk representation of the number of catalytically active chemicals. Possible relevance of the result to reaction dynamics in artificial and biological cells is briefly discussed.

  16. Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones.

    Science.gov (United States)

    Zhang, Junmin; Xing, Chong; Tiwari, Bhoopendra; Chi, Yonggui Robin

    2013-06-05

    We disclose the first catalytic activation of carbohydrates as formaldehyde equivalents to generate acyl anions as one-carbon nucleophilic units for a Stetter reaction. The activation involves N-heterocyclic carbene (NHC)-catalyzed C-C bond cleavage of carbohydrates via a retro-benzoin-type process to generate the acyl anion intermediates. This Stetter reaction constitutes the first success in generating formal formaldehyde-derived acyl anions as one-carbon nucleophiles for non-self-benzoin processes. The renewable nature of carbohydrates, accessible from biomass, further highlights the practical potential of this fundamentally interesting catalytic activation.

  17. Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters.

    Science.gov (United States)

    Yamada, Akira; Miyajima, Ken; Mafuné, Fumitaka

    2012-03-28

    Gas phase catalytic reactions involving the reduction of N(2)O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rh(n) (n = 10-28), using mass spectrometry. Sequential oxygen transfer reactions, Rh(n)O(m-1) + N(2)O → Rh(n)O(m) + N(2) (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, Rh(n)O(m) + CO → Rh(n)O(m-1) + CO(2) (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N(2)O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around Rh(n)O(m) (m ≥ 4) than around bare Rh(n). Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalytic CO oxidation reaction on a rhodium surface.

  18. Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.

    Science.gov (United States)

    Catlow, C Richard A

    2016-08-01

    Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.

  19. Preparation of Pd-Diimine@SBA-15 and Its Catalytic Performance for the Suzuki Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Jiahuan Yu

    2016-11-01

    Full Text Available A highly efficient and stable Pd-diimine@SBA-15 catalyst was successfully prepared by immobilizing Pd onto diimine-functionalized mesoporous silica SBA-15. With the help of diimine functional groups grafted onto the SBA-15, Pd could be anchored on a support with high dispersion. Pd-diimine@SBA-15 catalyst exhibited excellent catalytic performance for the Suzuki coupling reaction of electronically diverse aryl halides and phenylboronic acid under mild conditions with an ultralow amount of Pd (0.05 mol % Pd. When the catalyst amount was increased, it could catalyze the coupling reaction of chlorinated aromatics with phenylboronic acid. Compared with the catalytic performances of Pd/SBA-15 and Pd-diimine@SiO2 catalysts, the Pd-diimine@SBA-15 catalyst exhibited higher hydrothermal stability and could be repeatedly used four times without a significant decrease of its catalytic activity.

  20. Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions

    Science.gov (United States)

    Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.

    2017-01-01

    Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.

  1. Long-time experience in catalytic flue gas cleaning and catalytic NO{sub x} reduction in biofueled boilers

    Energy Technology Data Exchange (ETDEWEB)

    Ahonen, M. [Tampella Power Inc., Tampere (Finland)

    1996-12-31

    NO emissions are reduced by primary or secondary methods. Primary methods are based on NO reduction in the combustion zone and secondary methods on flue gas cleaning. The most effective NO reduction method is selective catalytic reduction (SCR). It is based on NO reduction by ammonia on the surface of a catalyst. Reaction products are water and nitrogen. A titanium-dioxide-based catalyst is very durable and selective in coal-fired power plants. It is not poisoned by sulphur dioxide and side reactions with ammonia and sulphur dioxide hardly occur. The long time experience and suitability of a titanium-dioxide-based catalyst for NO reduction in biofuel-fired power plants was studied. The biofuels were: peat, wood and bark. It was noticed that deactivation varied very much due to the type of fuel and content of alkalinities in fuel ash. The deactivation in peat firing was moderate, close to the deactivation noticed in coal firing. Wood firing generally had a greater deactivation effect than peat firing. Fuel and fly ash were analyzed to get more information on the flue gas properties. The accumulation of alkali and alkaline earth metals and sulphates was examined together with changes in the physical composition of the catalysts. In the cases where the deactivation was the greatest, the amount of alkali and alkaline earth metals in fuels and fly ashes and their accumulation were very significant. (author) (3 refs.)

  2. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  3. Side reactions in the selective catalytic reduction of NO with NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Madia, G.; Koebel, M.; Elsener, M.; Wokaun, A.

    2002-03-01

    The main and the side reactions of the SCR reaction with ammonia over TiO{sub 2}-WO{sub 3}-V{sub 2}O{sub 5} catalysts have been investigated using synthetic gas mixtures matching the composition of diesel exhaust. At high temperatures the selective catalytic oxidation of ammonia (SCO) and the formation of nitrous oxide compete with the SCR reaction. Water strongly inhibits the SCO of ammonia and the formation of nitrous oxide thus increasing the selectivity of the SCR reaction. However, water also inhibits SCR activity, most pronounced at low temperatures. (author)

  4. Catalytic effect and reaction mechanism of Ti doped in NaAlH4: A review

    Institute of Scientific and Technical Information of China (English)

    WANG Qiang; CHEN YunGui; WU ChaoLing; TAO MingDa

    2008-01-01

    Catalytic effect and hydrogen reaction mechanism of Ti doped in NaAlH4 were elaborated in this paper, and current viewpoints about Ti active species in hydrogen reaction were discussed, in a further step, the possibility and practicality of the hydrogen reaction mechanism of Ti-doped NaAlH4 were elucidated. They could be summarized as follows: while the current theory about the hydrogen reaction mecha-nism of Ti-doped NaAlH4 should be further improved and modified, the research on Ti-doped NaAlH4 would be a recommendable pattern for the catalyst research in other metal complex hydrides.

  5. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions durin

  6. Process Intensification. Continuous Two-Phase Catalytic Reactions in a Table-Top Centrifugal Contact Separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Schuur, Boelo; van Zwol, Floris; Haak, Robert M.; Minnaard, Adriaan J.; Feringa, Ben L.; Heeres, Hero J.; de Vries, Johannes G.; Prunier, ML

    2009-01-01

    Production of fine chemicals is mostly performed in batch reactors. Use of continuous processes has many advantages which may reduce the cost of production. We have developed the use of centrifugal contact separators (CCSs) for continuous two-phase catalytic reactions. This equipment has previously

  7. Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor;

    2007-01-01

    The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt...

  8. In situ synchrotron-based IR microspectroscopy to study catalytic reactions in zeolite crystals

    NARCIS (Netherlands)

    Stavitski, Eli; Kox, Marianne H. F.; Swart, Ingmar; de Groot, Frank M. F.; Weckhuysen, Bert M.

    2008-01-01

    In recent years a number of in situ microspectroscopic techniques have been explored to investigate catalytic reactions taking place in heterogeneous catalysts in a timeand space-resolved manner.[1–8] These spectroscopic methods have proven to be very successful in elucidating valuable structure–fun

  9. Utilization of the Recycle Reactor in Determining Kinetics of Gas-Solid Catalytic Reactions.

    Science.gov (United States)

    Paspek, Stephen C.; And Others

    1980-01-01

    Describes a laboratory scale reactor that determines the kinetics of a gas-solid catalytic reaction. The external recycle reactor construction is detailed with accompanying diagrams. Experimental details, application of the reactor to CO oxidation kinetics, interphase gradients, and intraphase gradients are discussed. (CS)

  10. In-situ scanning transmission X-ray microscopy of catalytic materials under reaction conditions

    NARCIS (Netherlands)

    de Smit, E.; Creemer, J.F.; Zandbergen, H.W.; Weckhuysen, B.M.; de Groot, F.M.F.

    2009-01-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant

  11. The Self-catalytic Esterification Reaction of O-Phosphoryl Serine Derivative

    Institute of Scientific and Technical Information of China (English)

    Jin Tang DU; Yan Mei LI; Zhong Zhou CHEN; Shi Zhong LUO; Yu Fen ZHAO

    2005-01-01

    O-Phosphoryl serine derivative can perform self-catalytic esterification reaction in the mixture of CH3OH and CHCl3 at the room temperature. The phosphoryl group participation was the key step of the esterification. This type of reactions were proposed through an intermediate of mixed phosphoric-carboxylic anhydride that might provide a clue to the function of the phosphoryl group in the phosphorylated enzymes and in the prebiotic synthesis of protein.

  12. Study of catalytic effect of ammonium molybdate on the bisphthalonitrile resins curing reaction with aromatic amine

    Institute of Scientific and Technical Information of China (English)

    Wen Ting Li; Fang Zuo; Kun Jia; Xiao Bo Liu

    2009-01-01

    A kind of catalyst, ammonium molybdate was developed in this paper to promote the curing reaction of bisphthalonitrile resins with aromatic amine as curing agent, and the catalytic effect was studied by differential scanning calorimetry (DSC), rheometric measurements and thermogravimetric analysis (TGA). The results indicated that the catalyst could improve the curing rate and increase the curing degree, which could be regulated by the content of the catalyst used in the reaction.

  13. Electronic and catalytic properties of iron porphyrin complexes: Trends and reaction mechanisms.

    OpenAIRE

    Mala, Alhaji

    2015-01-01

    ABSTRACTThe University of Manchester,School of Chemical Engineering and Analytical ScienceABSTRACT OF THESIS submitted by Mala Alhaji Sainna for the degree of Doctor of Philosophy (PhD) and entitled “Electronic and catalytic properties of iron porphyrin complexes: Trends and reaction mechanisms” The cytochrome P450s belong to the superfamily of proteins containing a heme cofactor and, thus, are termed hemoproteins. They perform important oxidation reactions in the body, and are, for instance,...

  14. In-situ scanning transmission X-ray microscopy of catalytic materials under reaction conditions

    OpenAIRE

    E. Smit; Creemer, J.F.; Zandbergen, H. W.; Weckhuysen, B. M.; Groot, F.M.F. de

    2009-01-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the...

  15. Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides.

    Science.gov (United States)

    Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu

    2016-05-20

    Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asymmetric catalysis. This methodology is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts.

  16. Interactions Between Surface Reactions and Gas-phase Reactions in Catalytic Combustion and Their Influence on Ignition of HCCI Engine

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The catalytic combustion of methane in a microchannel whose surface was coated with platinum(Pt)catalyst was studied by numerical-simulation. The effects of gas-phase reactions on the whole catalytic combustion process were analyzed at a high inlet pressure. A sensitivity analysis of the detailed mechanisms of the surface reaction of methane on Pt revealed that the most sensitive reactions affecting the heterogeneous ignition are oxygen adsorption/desorption and methane adsorption, and the most sensitive reactions affecting the homogeneous ignition are OH and H2O adsorption/desorption. The combustion process of the homogeneous charge compression ignition(HCCI) engine whose piston face was coated with Pt catalyst was simulated. The effects of catalysis and the most sensitive reactions on the ignition timing and the concentration of the main intermediate species during the HCCI engine combustion are discussed. The results show that the ignition timing of the HCCI engine can be increased by catalysis, and the most sensitive reactions affecting the ignition timing of the HCCI engine are OH and H2O adsorption/desorption.

  17. High-spatial-resolution mapping of catalytic reactions on single particles

    Science.gov (United States)

    Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan; Bechtel, Hans A.; Martin, Michael C.; Toste, F. Dean; Gross, Elad

    2017-01-01

    The critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has been used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. These observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles—which contain metal atoms with low coordination numbers—are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.

  18. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    Science.gov (United States)

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

    2014-08-01

    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  19. Surface Acidity as Descriptor of Catalytic Activity for Oxygen Evolution Reaction in Li-O2 Battery.

    Science.gov (United States)

    Zhu, Jinzhen; Wang, Fan; Wang, Beizhou; Wang, Youwei; Liu, Jianjun; Zhang, Wenqing; Wen, Zhaoyin

    2015-10-28

    Unraveling the descriptor of catalytic activity, which is related to physical properties of catalysts, is a major objective of catalysis research. In the present study, the first-principles calculations based on interfacial model were performed to study the oxygen evolution reaction mechanism of Li2O2 supported on active surfaces of transition-metal compounds (TMC: oxides, carbides, and nitrides). Our studies indicate that the O2 evolution and Li(+) desorption energies show linear and volcano relationships with surface acidity of catalysts, respectively. Therefore, the charging voltage and desorption energies of Li(+) and O2 over TMC could correlate with their corresponding surface acidity. It is found that certain materials with an appropriate surface acidity can achieve the high catalytic activity in reducing charging voltage and activation barrier of rate-determinant step. According to this correlation, CoO should have as active catalysis as Co3O4 in reducing charging overpotential, which is further confirmed by our comparative experimental studies. Co3O4, Mo2C, TiC, and TiN are predicted to have a relatively high catalytic activity, which is consistent with the previous experiments. The present study enables the rational design of catalysts with greater activity for charging reactions of Li-O2 battery.

  20. Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

    Institute of Scientific and Technical Information of China (English)

    Kebing Wang; Jie Yao; Yue Wang; Gongying Wang

    2007-01-01

    The coupling reaction of formaldehyde (FA) and methyl formate (MF) to form methyl glycolate (MG) and methyl methoxy acetate(MMAc),catalyzed by p-toluenesulfonic acid(p-TsOH) as well as assisted by different kinds of solvents or Ni-containing compounds.had been investigated.The results showed that when the reaction was carried out at 140℃ with a molar ratio of FA to MF of 0.65:1,molar fraction of p-TsOH to total feedstock of 11.0%,and reaction time of 3 h,the yield of MG and MMAc Was 31.1% and 17.1%.respectively.p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity.Adding extra solvents to the reaction system Was unfavorable for the reaction.The composite catalytic system consisting of p-TsOH and NiX2(X=Cl,Br,I)exhibited a high catalytic performance for the coupling reaction,and NiX2 acted as a promoter in the reaction,whose promotion for the catalysis increased in the following order:NiCl2<NiBr2<NiI2.The present system is less corrosive when compared with the previous system,in which strong inorganic liquid acids were used as catalysts.

  1. Catalytic self-assembled monolayers on Au nanoparticles: the source of catalysis of a transphosphorylation reaction.

    Science.gov (United States)

    Zaupa, Giovanni; Mora, Claudia; Bonomi, Renato; Prins, Leonard J; Scrimin, Paolo

    2011-04-18

    The catalytic activity of a series of Au monolayer protected colloids (Au MPCs) containing different ratios of the catalytic unit triazacyclononane⋅Zn(II) (TACN⋅Zn(II) ) and an inert triethyleneglycol (TEG) unit was measured. The catalytic self-assembled monolayers (SAMs) are highly efficient in the transphosphorylation of 2-hydroxy propyl 4-nitrophenyl phosphate (HPNPP), an RNA model substrate, exhibiting maximum values for the Michaelis-Menten parameters k(cat) and K(M) of 6.7×10(-3) s(-1) and 3.1×10(-4) M, respectively, normalized per catalytic unit. Despite the structural simplicity of the catalytic units, this renders these nanoparticles among the most active catalysts known for this substrate. Both k(cat) and K(M) parameters were determined as a function of the mole fraction of catalytic unit (x(1)) in the SAM. Within this nanoparticle (NP) series, k(cat) increases up till x(1) ≈0.4, after which it remains constant and K(M) decreases exponentially over the range studied. A theoretical analysis demonstrated that these trends are an intrinsic property of catalytic SAMs, in which catalysis originates from the cooperative effect between two neighboring catalytic units. The multivalency of the system causes an increase of the number of potential dimeric catalytic sites composed of two catalytic units as a function of the x(1) , which causes an apparent increase in binding affinity (decrease in K(M)). Simultaneously, the k(cat) value is determined by the number of substrate molecules bound at saturation. For values of x(1) >0.4, isolated catalytic units are no longer present and all catalytic units are involved in catalysis at saturation. Importantly, the observed trends are indicative of a random distribution of the thiols in the SAM. As indicated by the theoretical analysis, and confirmed by a control experiment, in case of clustering both k(cat) and K(M) values remain constant over the entire range of x(1) .

  2. Catalytic activity of copper (II) oxide prepared via ultrasound assisted Fenton-like reaction.

    Science.gov (United States)

    Angı, Arzu; Sanlı, Deniz; Erkey, Can; Birer, Özgür

    2014-03-01

    Copper (II) oxide nanoparticles were synthesized in an ultrasound assisted Fenton-like aqueous reaction between copper (II) cations and hydrogen peroxide. The reactions were initiated with the degradation of hydrogen peroxide by ultrasound induced cavitations at 0 °C or 5 °C and subsequent generation of the OH radical. The radical was converted into hydroxide anion in Fenton-like reactions and copper hydroxides were readily converted to oxides without the need of post annealing or aging of the samples. The products were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) surface area analysis. Catalytic activity of the nanoparticles for the hydrogen peroxide assisted degradation of polycyclic aromatic hydrocarbons in the dark was tested by UV-visible spectroscopy with methylene blue as the model compound. The rate of the reaction was first order, however the rate constants changed after the initial hour. Initial rate constants as high as 0.030 min(-1) were associated with the high values of surface area, i.e. 70 m(2)/g. Annealing of the products at 150 °C under vacuum resulted in the decrease of the catalytic activity, underlying the significance of the cavitation induced surface defects in the catalytic process.

  3. Catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles.

    Science.gov (United States)

    Zhang, Hong-Hao; Sun, Xiao-Xue; Liang, Jing; Wang, Yue-Ming; Zhao, Chang-Chun; Shi, Feng

    2014-12-21

    The first catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles was established in the presence of chiral phosphoric acid, which tolerates a wide range of substrates with generally excellent diastereoselectivity and good enantioselectivity (up to >95 : 5 dr, 89 : 11 er). This approach will greatly enrich the chemistry of the catalytic asymmetric Povarov reaction, in particular ketone-involved transformations. Furthermore, this protocol represents the first diastereo- and enantio-selective construction of a spiro[indolin-3,2'-quinoline] framework bearing an indole moiety. This novel type of spiro-compound not only contains two chiral centers, including one quaternary stereogenic center, but also integrates two biologically important structures of spiro[indolin-3,2'-quinoline] and indole, which may find medicinal applications after bioassay.

  4. The catalytic reactions in the Cu-Li-Mg-H high capacity hydrogen storage system.

    Science.gov (United States)

    Braga, M H; El-Azab, A

    2014-11-14

    A family of hydrides, including the high capacity MgH2 and LiH, is reported. The disadvantages these hydrides normally display (high absorption/desorption temperatures and poor kinetics) are mitigated by Cu-hydride catalysis. This paper reports on the synthesis of novel CuLi0.08Mg1.42H4 and CuLi0.08Mg1.92H5 hydrides, which are structurally and thermodynamically characterized for the first time. The CuLi0.08Mg1.42H4 hydride structure in nanotubes is able to hold molecular H2, increasing the gravimetric and volumetric capacity of this compound. The catalytic effect these compounds show on hydride formation and decomposition of CuMg2 and Cu2Mg/MgH2, Li and LiH, Mg and MgH2 is analyzed. The Gibbs energy, decomposition temperature, and gravimetric capacity of the reactions occurring within the Cu-Li-Mg-H system are presented for the first time. First principles and phonon calculations are compared with experiments, including neutron spectroscopy. It is demonstrated that the most advantageous sample contains CuLi0.08Mg1.92 and (Li) ∼ Li2Mg3; it desorbs/absorbs hydrogen according to the reaction, 2CuLi0.08Mg1.42H4 + 2Li + 4MgH2 ↔ 2CuLi0.08Mg1.92 + Li2Mg3 + 8H2 at 114 °C (5.0 wt%) - 1 atm, falling within the proton exchange membrane fuel cell applications window. Finally the reaction 2CuLi0.08Mg1.42H4 + MgH2 ↔ 2CuLi0.08Mg1.92 + 5H2 at 15 °C (4.4 wt%) - 1 atm is found to be the main reaction of the samples containing CuLi0.08Mg1.92 that were analyzed in this study.

  5. New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.

    Science.gov (United States)

    Zaera, Francisco

    2014-11-21

    Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are

  6. Effect of reaction time on the characteristics of catalytically grown boron nitride nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Norani Muti, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my; Ahmad, Pervaiz, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my; Saheed, Mohamed Shuaib Mohamed, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my; Burhanudin, Zainal Arif, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my [Center of Innovative Nanostructures and Nanodevices (COINN), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750, Tronoh, Perak (Malaysia)

    2014-10-24

    The paper reports on the growth of boron nitride nanotube (BNNTs) on Si substrate by catalytic chemical vapor deposition technique and the effect of reaction time and temperature on the size and purity were investigated. Scanning electron microscopy image revealed the bamboo-like BNNTs of multiwalled type with interlayer spacing of 0.34 nm. EDX analysis described the presence of a small percentage of Mg in the sample, indicating the combination of base-tip growth model for the sample synthesized at 1200°C. The reaction time has an effect of extending the length of the BNNTs until the catalyst is oxidized or covered by growth precursor.

  7. Lacunary Keggin Polyoxotungstate as Reaction-controlled Phasetransfer Catalyst for Catalytic Epoxidation of Olefins

    Institute of Scientific and Technical Information of China (English)

    LI,Ming-Qiang(李明强); JIAN,Xi-Gao(蹇锡高); YANG,Yong-Qiang(杨永强)

    2004-01-01

    A new reaction-controlled phase-transfer catalyst system, lacunary Keggin polyoxotungstate [C7H7N(CH3)3]9PW9O34 has been synthesized and used for catalytic epoxidation of olefins with H2O2 as the oxidant.Infrared spectra were used to analyze the behavior of the phase transfer of catalyst. In this system, the catalyst not only can act as homogeneous catalyst but also as heterogeneous catalyst to be easily filtered and reused. The epoxidation reaction is clean and exhibits high conversion and selectivity as well as excellent catalyst stability.

  8. In-situ Scanning Transmission X-ray Microscopy of catalytic materials under reaction conditions

    Science.gov (United States)

    de Smit, Emiel; Creemer, J. Fredrik; Zandbergen, Henny W.; Weckhuysen, Bert M.; de Groot, Frank M. F.

    2009-11-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the ability to image materials under realistic conditions opens up new opportunities to study many chemical processes.

  9. In-situ Scanning Transmission X-ray Microscopy of catalytic materials under reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Smit, Emiel de; Weckhuysen, Bert M; Groot, Frank M F de [Inorganic Chemistry and Catalysis group, Debye Institute for Nanomaterials Science, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (Netherlands); Creemer, J Fredrik [DIMES-ECTM, Delft University of Technology, 2600 GB Delft (Netherlands); Zandbergen, Henny W, E-mail: e.desmit@uu.n [Kavli Institute of NanoScience, National Centre for High Resolution Electron Microscopy, Delft University of Technology, 2600 GA Delft (Netherlands)

    2009-11-15

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the ability to image materials under realistic conditions opens up new opportunities to study many chemical processes.

  10. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  11. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  12. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

  13. Chloromethyl chlorosulfate: a new, catalytic method of preparation and reactions with some nucleophiles.

    Science.gov (United States)

    Power, Nicholas P; Bethell, Donald; Proctor, Lee; Latham, Elliot; Dawson, Paul

    2004-05-21

    The reaction of liquid (gamma-) SO3 with CH2Cl2 at room temperature leads to SO3 insertion into the C-Cl bonds, giving the useful chloromethylating agent chloromethyl chlorosulfate (CMCS). The process is very slow but becomes rapid on addition of catalytic quantities of trimethyl borate. The product mixture consists almost entirely of CMCS and the product of further sulfation, methylene bis(chlorosulfate)(MBCS), in a ratio of ca. 2 : 1, but typical yields of CMCS, isolated by distillation, are only 30-35%. The catalysed reaction in the homogeneous liquid phase at -45 degrees C has been followed as a function of time and of reactant concentration by 1H nmr spectroscopy. It is observed that, besides CMCS and MBCS, three additional, transient products (designated A, B and C) are formed. Products A, B and C decompose slowly at -45 degrees C but much more rapidly if the reaction mixture is raised to room temperature, giving additional CMCS and MBCS. From an analysis of the SO3 balance, it is inferred that products A, B and C arise from the reaction of one molecule of CH2Cl2 with respectively two, three and four molecules of SO3; they are suggested to be chloromethyl chloropolysulfates. By measuring initial rates of CMCS formation or total CH2Cl2 consumption, it is shown that the reaction is first order in the catalyst and roughly third order in SO3. A mechanistic scheme is proposed in which SO3 forms equilibrating zwitterionic molecular complexes with CH2Cl2. of 1 : 1, 2 : 1 and higher stoichiometries. The boron-containing catalyst can activate these complexes towards nucleophilic attack at carbon by the negatively charged oxygen of another zwitterion. An analogous mechanism can be written for the conversion of CMCS into MBCS by SO3 in the presence of trimethyl borate. CMCS reacts rapidly with anionic nucleophiles, such as halide or acetate ions (X-), in homogeneous solution of their tetrabutylammonium salts in CD3CN, or in a two-phase system (CDCl3/H2O) using alkali

  14. Cyclosophorohexadecaose and succinoglycan monomers as catalytic carbohydrates for the Strecker reaction.

    Science.gov (United States)

    Lee, Sanghoo; Cho, Eunae; Kwon, Chanho; Jung, Seunho

    2007-12-10

    Some microbial carbohydrates have been used as catalysts for the multicomponent Strecker reaction using trimethylsilyl cyanide (TMSCN). Alpha-Cyclosophorohexadecaose (alpha-C16) derived from Xanthomonas species and succinoglycan monomers derived from Rhizobium species acted as catalytic carbohydrates in the mixture solutions of methanol and water. Malonaldehyde bis(phenylimine) as a substrate was completely converted (yield: 100%) into its product to 100% by both alpha-C16 and the succinoglycan monomer (M2), having acetyl, pyruvyl, and succinyl groups as substituents after 1h. The catalytic abilities of the carbohydrates were dependent on the inherent structures of the substrates used in this study, where substrate 1 having a symmetrical structure rather than the others was favorably reacted with the alpha-C16 and M2. Through this study, we suggest that the microbial carbohydrates used in this study could be expected to be environmentally-benign catalysts for the synthesis of alpha-aminonitriles.

  15. Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

    Institute of Scientific and Technical Information of China (English)

    张光旭; 吴元欣; 马沛生; 田崎峰; 吴广文; 李定或; 王存文

    2003-01-01

    Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was La0.62Pb0.38MnO3 and the average diameter could be about 25.4 nm. The optimum conditions for synthesis of DPC with Pd/LaxPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catMyst/phenol mass ratio 1 to 50, pressure 4.5 MPa,volume concentration of O2 25%, reaction temperature 60° and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

  16. Catalytic Activity of Dual Metal Cyanide Complex in Multi-component Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    Anaswara RAVINDRAN; Rajendra SRIVASTAVA

    2011-01-01

    Several dual metal cyanide catalysts were prepared from potassium ferrocyanide,metal chloride (where metal =Zn2+,Mn2+,Ni2+,Co2+ and Fe2+),t-butanol (complexing agent) and PEG-4000 (co-complexing agent).The catalysts were characterized by elemental analysis (CHN and X-ray fluorescence),X-ray diffraction,N2 adsorption-desorption,scanning electron microscopy,Fourier-transform infiared spectroscopy,and UV-Visible spectroscopy.The dual metal cyanide catalysts were used in several acid catalyzed multi-component coupling reactions for the synthesis of pharmaceutically important organic derivatives.In all these reactions,the Fe-Fe containing dual metal cyanide catalyst was the best catalyst.The catalysts can be recycled without loss in catalytic activity.The advantage of this method is the use of mild,efficient and reusable catalysts for various reactions,which makes them candidates for commercial use.

  17. Flexible catalytic site conformations implicated in modulation of HIV-1 protease autoprocessing reactions

    Directory of Open Access Journals (Sweden)

    Chen Chaoping

    2011-10-01

    Full Text Available Abstract Background The HIV-1 protease is initially synthesized as part of the Gag-Pol polyprotein in the infected cell. Protease autoprocessing, by which the protease domain embedded in the precursor catalyzes essential cleavage reactions, leads to liberation of the free mature protease at the late stage of the replication cycle. To examine autoprocessing reactions in transfected mammalian cells, we previously described an assay using a fusion precursor consisting of the mature protease (PR along with its upstream transframe region (p6* sandwiched between GST and a small peptide epitope. Results In this report, we studied two autoprocessing cleavage reactions, one between p6* and PR (the proximal site and the other in the N-terminal region of p6* (the distal site catalyzed by the embedded protease, using our cell-based assay. A fusion precursor carrying the NL4-3 derived protease cleaved both sites, whereas a precursor with a pseudo wild type protease preferentially autoprocessed the proximal site. Mutagenesis analysis demonstrated that several residues outside the active site (Q7, L33, N37, L63, C67 and H69 contributed to the differential substrate specificity. Furthermore, the cleavage reaction at the proximal site mediated by the embedded protease in precursors carrying different protease sequences or C-terminal fusion peptides displayed varied sensitivity to inhibition by darunavir, a catalytic site inhibitor. On the other hand, polypeptides such as a GCN4 motif, GFP, or hsp70 fused to the N-terminus of p6* had a minimal effect on darunavir inhibition of either cleavage reaction. Conclusions Taken together, our data suggest that several non-active site residues and the C-terminal flanking peptides regulate embedded protease activity through modulation of the catalytic site conformation. The cell-based assay provides a sensitive tool to study protease autoprocessing reactions in mammalian cells.

  18. Deuterium–tritium catalytic reaction in fast ignition: Optimum parameters approach

    Indian Academy of Sciences (India)

    B Khanbabaei; A Ghasemizad; S Khoshbinfar

    2014-09-01

    One of the main concerns about the currentworking on nuclear power reactors is the potential hazard of their radioactive waste. There is hope that this issue will be reduced in next generation nuclear fusion power reactors. Reactors will release nuclear energy through microexplosions that occur in a mixture of hydrogen isotopes of deuterium and tritium. However, there exist radiological hazards due to the accumulation of tritium in the blanket layer. A catalytic fusion reaction of DT mixture may stand between DD and an equimolar DT approach in which the fusion process continues with a small amount of tritium seed. In this paper, we investigate the possibility of DT reaction in the fast ignition (FI) scheme. The kinematic study of the main mechanism of the energy gain–loss term, which may disturb the ignition and burn process, was performed in FI and the optimum values of precompressed fuel and proton beam driver were derived. The recommended values of fuel parameters are: areal density $ρ R ≥ 5\\cdot$cm-2 and initial tritium fraction ≤ 0.025. For the proton beam, the corresponding optimum interval values are proton average energy $3≤ E_p ≤ 10$ MeV, pulse duration $5 ≤ t_p ≤ 15$ ps and power $5≤ W_p ≤ 12 × 10^{22}$ (keV$\\cdot$cm3$\\cdot$ps-1). It was proved that under the above conditions, a fast ignition DT reaction stays in the catalytic regime.

  19. Catalytic methanation reaction over supported nickel-rhodium oxide for purification of simulated natural gas

    Institute of Scientific and Technical Information of China (English)

    Wan Azelee Wan Abu Bakar; Rusmidah Ali; Susilawati Toemen

    2011-01-01

    In this research,new catalyst with high industrial impact is developed,which can catalyze the conversion of CO2 to methane through methanation reaction.A series of catalysts based on nickel oxide were prepared using wetness impregnation technique and ageing,followed by calcination at 400 ℃.Rh/Ni (30∶70)/Al2O3 catalyst was revealed as the most potential catalyst based on the results of catalytic activity measurementmonitored by Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography (GC).The results showed 90.1% CO2 conversion and 70.8% yield at 400 ℃.

  20. Electrical polymerization of a tetrazole polymer-modified electrode and its catalytic reaction toward dopamine

    Science.gov (United States)

    Hsieh, Mu-Tao; Whang, Thou-Jen

    2017-02-01

    A conducting polymer-modified electrode was proposed in this article, which was fabricated by electropolymerization of 5-amino-1H-tetrazole (ATet) on a glassy carbon electrode. Electrochemical studies such as differential pulse voltammetry and chronoamperometry were performed for the evaluation of the rate constant of the catalytic reaction, the diffusion coefficient of the analyte dopamine, and the linear dynamic range of the analyte determination. The film modified electrode has superior resolving power in quantitative determination from the mixture of analytes and it was found to be an efficient functionalized electrode for its sensitivity and selectivity toward the analyte of interest.

  1. Electrochemical Synthesis of Mo2C Catalytical Coatings for the Water-Gas Shift Reaction

    Science.gov (United States)

    Kuznetsov, Sergey A.; Dubrovskiy, Anton R.; Rebrov, Evgeny V.; Schouten, Jaap C.

    2007-11-01

    The electroreduction of CO32- ions on a molybdenum cathode in a NaCl-KCl-Li2CO3 melt was studied by cyclic voltammetry. The electrochemical synthesis of Mo2C on molybdenum substrates has been performed at 1123 K for 7 h with a cathodic current density of 5 mA cm-2. If molybdenum carbide is present as a thin (ca. 500 nm) film on a molybdenum substrate (Mo2C/Mo), its catalytic activity in the water gas-shift reaction is enhanced by at least an order of magnitude compared to that of the bulk Mo2C phase.

  2. Convective stability in the presence of a catalytic chemical reaction. I.

    Science.gov (United States)

    Wankat, P. C.; Schowalter, W. R.

    1971-01-01

    A linear analysis of hydrodynamic stability has been applied to a problem in which a fluid mixture is contained between two horizontal planes. One species diffuses to the lower plane where it is destroyed by a rapid exothermic or endothermic catalytic reaction. Results show that important coupling takes place between thermal and concentration fields. This coupling gives rise to unusual stabilizing or destabilizing effects, depending upon the value of Lewis number. Several examples are discussed. It is also shown how the results can be applied to other problems involving heat and mass transfer.

  3. Synthesis of Functionalized Furans via Chemoselective Reduction/Wittig Reaction Using Catalytic Triethylamine and Phosphine.

    Science.gov (United States)

    Lee, Chia-Jui; Chang, Tzu-Hsiu; Yu, Jhen-Kuei; Madhusudhan Reddy, Ganapuram; Hsiao, Ming-Yu; Lin, Wenwei

    2016-08-05

    An efficient protocol for the synthesis of highly functionalized furans via intramolecular Wittig reaction has been developed using catalytic amounts of phosphine and triethylamine. Silyl chloride served as the initial promoter to activate the phosphine oxide. Reduction of the activated phosphine oxide by hydrosilane resulted in generation of phosphine, while decomposition of Et3N·HCl resulted in regeneration of base, which mediated formation of phosphorus ylide. Remarkably, the in situ generated byproduct, Et3N·HCl, also catalyzes reduction of phosphine oxide.

  4. Synthesis of Novel Chiral Dibenzo [ a, c ] cycloheptadiene Bis(oxazoline) and Catalytic Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    FU Bin; DU Da-Ming; WANG Jian-Bo

    2003-01-01

    @@ Over the last decade, C2-symmetric chiral oxazoline metal complexes have been recognized as an effective classof chiral catalyst in a variety of transition metal catalyzed asymmetric reactions. [1] High catalytic activities and enantiomeric excesses have been obtained using C2-symmetric chiral ligands in conjunction with suitable transition metal ion, for example, the hydrosilylation of ketone, allylic alkylation, Michael addition, Diels-Alder cycloaddition, and cyclopropanation. Thus, the design and synthesis of new chiral oxazoline ligands have inspired many scientists to work with great efforts.

  5. Impact of active phase chemical composition and dispersity on catalytic behavior in PROX reaction

    Science.gov (United States)

    Cherkezova-Zheleva, Z.; Paneva, D.; Todorova, S.; Kolev, H.; Shopska, M.; Yordanova, I.; Mitov, I.

    2014-04-01

    Iron and iron-platinum catalysts supported on activated carbon have been successfully synthesized by wet impregnation method and low-temperature treatment in inert atmosphere. The content of the supported phases corresponds to 10 wt % Fe and 0.5 wt % Pt. Four catalytic samples were synthesized: Sample A—activated carbon impregnated with Fe nitrate; Sample B—activated carbon impregnated with Pt salt; Sample C—activated carbon impregnated consequently with Fe and Pt salts; Sample D—activated carbon impregnated simultaneously with Fe and Pt salts. The as-prepared materials were characterized by Mössbauer spectroscopy, X-ray diffraction, infrared and X-ray photoelectron spectroscopy. The spectra show that the activated carbon support and the preparation procedure give rise to the synthesis of isolated metal Pt ions and ultradispersed Fe and Pt oxide species. Probably the presence of different functional groups of activated carbon gives rise to registered very high dispersion of loaded species on support. The catalytic tests were carried out in PROX reaction. A lower activity of bimetallic Pt-Fe samples was explained with the increase in surface oxygen species as a result of predomination of iron oxide on the support leading to the increase in selectivity to the H2 oxidation. Partial agglomeration of supported iron oxide phase was registered after catalytic tests.

  6. Evidence for the powerful catalytic ability of imidozirconocene complex from its epoxide ring cleavage reactions - A DFT mechanistic view

    Indian Academy of Sciences (India)

    Dhurairajan Senthilnathan; Rajadurai Vijay Solomon; Ponnambalam Venuvanalingam

    2012-01-01

    Imidozirconocene complex is known for its bifunctional reactivity and catalytic ability and this complex mediates ring cleavage of epoxides. Cyclooctene oxide (1) Norbornene oxide (2) and 2,5-dimethyl cyclohexene oxide (3) undergo ring cleavage in the presence of imidozirconocene complex. Epoxide 1 has accessible -hydrogens (type I) while epoxide 2 and 3 do not have them (type II). Normally type I epoxides undergo elimination while type II epoxides prefer insertion. All the insertion reactions lead to five-membered metallacycle formation and elimination results in thermodynamically stable allyl-alkoxy product. The insertion is a two-step process following either diradical or zwitterionic pathway, while elimination is a one-step concerted reaction. DFT (density functional theory) modelling of these reactions at B3LYP/LANL2DZ level show that epoxide 1 undergoes elimination in agreement with experiment. However, calculations indicate that epoxide (2) proceeds through diradical intermediate in contrast to experimental observations. Surprisingly, epoxide (3) that has both the positions blocked by methyl groups undergoes elimination rather than insertion. AIM and EDA analyses offer further insights on the reaction mechanism and bifunctional reactivity of imidozirconozene complex.

  7. On the catalytic effects of UO 2(s) and Pd(s) on the reaction between H 2O 2 and H 2 in aqueous solution

    Science.gov (United States)

    Nilsson, Sara; Jonsson, Mats

    2008-01-01

    The possible catalytic effects of UO 2 and Pd (as a model for noble metal particles) on the reaction between H 2O 2 and H 2 have been studied experimentally. The experiments were performed in aqueous solution using an autoclave. The aqueous solutions were pressurized with H 2 or N 2 and the H 2O 2 concentration was measured as a function of time. The experiments clearly showed that Pd catalyzes the reaction between H 2O 2 and H 2 while UO 2 has no catalytic effect. The rate constant of the reaction between H 2O 2 and H 2 catalyzed by Pd was found to be close to diffusion controlled and independent of the H 2 pressure in the range 1-40 bar. The impact of the catalytic effect on the reaction between H 2O 2 and H 2 on spent nuclear fuel dissolution is, however, fairly small. Other possible effects of noble metal particles are also discussed, e.g. reduction of U(VI) to U(IV) in the liquid and solid phase.

  8. Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design.

    Science.gov (United States)

    Madhavan, Nandita; Jones, Christopher W; Weck, Marcus

    2008-09-01

    Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst

  9. Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions.

    Science.gov (United States)

    Aguirre-Díaz, Lina María; Gándara, Felipe; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2015-05-20

    The aim of this research is to establish how metal-organic frameworks (MOFs) composed of more than one metal in equivalent crystallographic sites (solid solution MOFs) exhibit catalytic activity, which is tunable by virtue of the metal ions ratio. New MOFs with general formula [InxGa1-x(O2C2H4)0.5(hfipbb)] were prepared by the combination of Ga and In. They are isostructural with their monometal counterparts, synthesized with Al, Ga, and In. Differences in their behavior as heterogeneous catalysts in the three-component, one pot Strecker reaction illustrate the potential of solid solution MOFs to provide the ability to address the various stages involved in the reaction mechanism.

  10. Rapid-reaction kinetic characterization of the pathway of streptokinase-plasmin catalytic complex formation.

    Science.gov (United States)

    Verhamme, Ingrid M; Bock, Paul E

    2008-09-19

    Binding of the fibrinolytic proteinase plasmin (Pm) to streptokinase (SK) in a tight stoichiometric complex transforms Pm into a potent proteolytic activator of plasminogen. SK binding to the catalytic domain of Pm, with a dissociation constant of 12 pm, is assisted by SK Lys(414) binding to a Pm kringle, which accounts for a 11-20-fold affinity decrease when Pm lysine binding sites are blocked by 6-aminohexanoic acid (6-AHA) or benzamidine. The pathway of SK.Pm catalytic complex formation was characterized by stopped-flow kinetics of SK and the Lys(414) deletion mutant (SKDeltaK414) binding to Pm labeled at the active site with 5-fluorescein ([5F]FFR-Pm) and the reverse reactions by competitive displacement of [5F]FFR-Pm with active site-blocked Pm. The rate constants for the biexponential fluorescence quenching caused by SK and SKDeltaK414 binding to [5F]FFR-Pm were saturable as a function of SK concentration, reporting encounter complex affinities of 62-110 nm in the absence of lysine analogs and 4900-6500 and 1430-2200 nm in the presence of 6-AHA and benzamidine, respectively. The encounter complex with SKDeltaK414 was approximately 10-fold weaker in the absence of lysine analogs but indistinguishable from that of native SK in the presence of 6-AHA and benzamidine. The studies delineate for the first time the sequence of molecular events in the formation of the SK.Pm catalytic complex and its regulation by kringle ligands. Analysis of the forward and reverse reactions supports a binding mechanism in which SK Lys(414) binding to a Pm kringle accompanies near-diffusion-limited encounter complex formation followed by two slower, tightening conformational changes.

  11. Determination of iron and aluminum based on the catalytic effect on the reaction of xylene cyanol FF with hydrogen peroxide and potassium periodate

    OpenAIRE

    Cai, Longfei; Xu, Chunxiu

    2011-01-01

    A simple, sensitive and selective method for the simultaneous determination of trace iron and aluminum by catalytic spectrophotometry is presented. This method is based on the catalytic effects of iron and aluminum on the reaction of xylene cyanol FF with hydrogen peroxide and potassium periodate. Both iron and aluminum did not show catalytic effects on the oxidation reaction of xylene cyanol FF in the presence of either hydrogen peroxide or potassium periodate. However, significant catalytic...

  12. Catalytic performance of Metal‐Organic‐Frameworks vs. extra‐large pore zeolite UTL incondensation reactions

    Directory of Open Access Journals (Sweden)

    Mariya eShamzhy

    2013-08-01

    Full Text Available Catalytic behavior of isomorphously substituted B‐, Al‐, Ga‐, and Fe‐containing extra‐large pore UTLzeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensationof 1‐naphthol with ethylacetoacetate, and Prins reaction of β‐pinene with formaldehyde andcompared with large‐pore aluminosilicate zeolite BEA and representative Metal‐Organic‐FrameworksCu3(BTC2 and Fe(BTC. The yield of the target product over the investigated catalysts in Knoevenagelcondensation increases in the following sequence: (AlBEA < (AlUTL < (GaUTL < (FeUTL < Fe(BTC <(BUTL < Cu3(BTC2 being mainly related to the improving selectivity with decreasing strength ofactive sites of the individual catalysts. The catalytic performance of Fe(BTC, containing the highestconcentration of Lewis acid sites of the appropriate strength is superior over large‐pore zeolite(AlBEA and B‐, Al‐, Ga‐, Fe‐substituted extra‐large pore zeolites UTL in Prins reaction of β‐pinene withformaldehyde and Pechmann condensation of 1‐naphthol with ethylacetoacetate.

  13. Improvement of hydrogen isotope exchange reactions on Li4SiO4 ceramic pebble by catalytic metals

    Institute of Scientific and Technical Information of China (English)

    Cheng Jian Xiao; Chun Mei Kang; Xiao Jun Chen; Xiao Ling Gao; Yang Ming Luo; Sheng Hu; Xiao Lin Wang

    2012-01-01

    Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module (CH HCSB TBM) for the International Thermonuclear Experimental Reactor (ITER).In this paper,Li4SiO4 ceramic pebbles deposited with catalytic metals,including Pt,Pd,Ru and Ir,were prepared by wet impregnation method.The metal particles on Li4SiO4 pebble exhibit a good promotion of hydrogen isotope exchange reactions in H2-DzO gas system,with conversion equilibrium temperature reduction of 200-300 ℃.The out-of-pile tritium release experiments were performed using 1.0 wt% Pt/Li4SiO4 and Li4SiO4 pebbles irradiated in a thermal neutron reactor.The thermal desorption spectroscopy shows that Pt was effective to increase the tritium release rate at lower temperatures,and the ratio of tritium molecule (HT) to tritiated water (HTO) of 1.0 wt% Pt/Li4SiO4 was much more than that of Li4SiO4,which released mainly as HTO.Thus,catalytic metals deposited on Li4SiO4 pebble may help to accelerate the recovery of bred tritium particularly in low temperature region,and increase the tritium molecule form released from the tritium breeding materials.

  14. Study of Catalytic Reaction at Electrode-Electrolyte Interfaces by a CV-XAFS Method

    Science.gov (United States)

    Kusano, Shogo; Matsumura, Daiju; Asazawa, Koichiro; Kishi, Hirofumi; Sakamoto, Tomokazu; Yamaguchi, Susumu; Tanaka, Hirohisa; Mizuki, Jun'ichiro

    2017-01-01

    A method combining cyclic voltammetry (CV) with x-ray absorption fine structure (XAFS) spectroscopy, viz. CV-XAFS, has been developed to enable in situ real-time investigation of atomic and electronic structures related to electrochemical reactions. We use this method to study the reaction of a Pt/C cathode catalyst in the oxygen reduction reaction (ORR) in an alkaline electrolyte, using x-ray energies near the Pt LIII edge for XAFS measurements. It was found that the current induced by the ORR was first observed at approximately 0.08 V versus Hg/HgO, although the Pt valence, which is reflected in the oxidation states, remained almost unchanged. The electronic structure of the catalytic surface in the ORR was observed to be different in the negative and positive scan directions of CV measurements. Hydrogen adsorption is also discussed on the basis of the observation of this spectral change. We have demonstrated that CV-XAFS provides dynamical structural and electronic information related to electrochemical reactions and can be used for in situ real-time measurements of a catalyst.

  15. Electric Field-Enhanced Catalytic Conversion of Methane: AN Experimental Study on the Effects of Corona Discharge on Methane Reactions

    Science.gov (United States)

    Marafee, Abdulathim M. J.

    reactions, while the C _2 selectivity slightly decreased with increasing O_2 partial pressure. Experiments were conducted with Sr/La_2O _3, Sm_2O _3, Li/MgO and NaOH/CaO catalysts (under identical operating conditions) to evaluate the catalytic performance in the presence of a DC corona discharge. The results show that the Sr/La_2O _3 catalyst yields are the best results. This suggests that the corona heterogeneous technique has potential for improving the process economics. Methane conversion to higher hydrocarbon was achieved with temperatures from 100 to 500^circ C with DC corona-discharge heterogeneous reactions. In the absence of the corona discharge, the catalytic process over NaY zeolite produces no C_2 hydrocarbons over the entire range of temperatures. The corona discharge heterogeneous reaction, however, resulted in both high C_2 yield (6-15%) and high methane conversion (14-53%) 100^circ C. Increasing the gas temperature was found to have a negative effect on both C_2 formation and C_2H_4 /C_2H_6 ratio. Experiments conducted in both remote and direct corona discharges showed that the remote corona showed better enhancement than the direct corona under the identical experimental conditions. A study of the zeolite stability shows only slight changes in the methane conversion and C_2 selectivity over a period of two hours. The present methane conversion results (over NaY zeolite in the presence of DC corona discharges) suggests that the yield of CO and C_2H _4 are high. (Abstract shortened by UMI.).

  16. Palladium nanoparticle anchored polyphosphazene nanotubes: preparation and catalytic activity on aryl coupling reactions

    Indian Academy of Sciences (India)

    V Devi; A Ashok Kumar; S Sankar; K Dinakaran

    2015-06-01

    Highly accessible-supported palladium (Pd) nanoparticles anchored polyphosphazene (PPZ) nanotubes (NTs) having average diameter of 120 nm were synthesized rapidly at room temperature and homogeneously decorated with Pd nanoparticles. The resultant PPZ–Pd nanocomposites were morphologically and structurally characterized by means of transmission electron microscope equipped with energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PPZ NTs. The PPZ–Pd NTs show enhanced catalytic activity for the Suzuki coupling of aryl bromides with arylboronic acid. In addition, these PPZ–Pd NTs show excellent behaviour as reusable catalysts of the Suzuki and Heck coupling reactions.

  17. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng

    2010-04-13

    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  18. Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

    Institute of Scientific and Technical Information of China (English)

    Shicheng XU; Junhua LI; Dong YANG; Jiming HAO

    2009-01-01

    The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH4)over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Bronsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Bronsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NOy species and the corresponding reaction routes were determined by the overall acidity strength of the support.The reaction routes where NO2 moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts,reactions between appropriate couples of active NOy species and activated hydrocarbon intermediates should be realized by modification of the support acidity.

  19. Temperature Non-Homogeneieties in a Catalytic Reactor With a Periodic Change in the Direction of the Reaction Mixture Feed

    Directory of Open Access Journals (Sweden)

    Zheleva Ivanka

    2015-06-01

    Full Text Available Temperature non-homogeneities in a catalytic reactor with periodic change in the direction of the reaction mixture feed is investigated in the present work. The temperature of the reaction mixture is described using a numerical algorithm for simulation of the work of the catalytic reactor, graphically shown and commented. The influence of the higher catalyst layer porosity in the wall area upon the temperature distribution in the reactor is studied. The existence of two different regimes is shown - a high temperature one in the middle part of the layer and a low temperature one in the high porosity area of the layer in contact with the reactor wall. This leads to not very effective usage of the catalyst in these parts of the catalyst layer in the reactor. This simulation can be used for better understanding and controlling of the examined catalytic process.

  20. Simultaneous determination of trace iron and aluminum by catalytic spectrophotometry based on a novel oxidation reaction of xylene cyanol FF.

    Science.gov (United States)

    Cai, Longfei; Xu, Chunxiu

    2008-06-01

    A new, simple, sensitive and selective method for the simultaneous determination of trace iron and aluminum by catalytic spectrophotometry was presented, based on the catalytic effects of iron and aluminum on the discoloring reaction of xylene cyanol FF proceeded by hydrogen peroxide and potassium periodate in weak nitric acid medium. No catalytic effect was obtained in the presence of hydrogen peroxide or potassium periodate only. With the conditional rate constants determined in reaction systems catalyzed by Al or Fe only, the concentrations of Fe and Al in the samples can be calculated. The method was applied to the simultaneous determination of trace Fe and Al in tap water, lake water, river water and tea leaves without separation and preconcentration.

  1. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    KAUST Repository

    Yin, S. M.

    2017-01-18

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  2. Pyranone natural products as inspirations for catalytic reaction discovery and development.

    Science.gov (United States)

    McDonald, Benjamin R; Scheidt, Karl A

    2015-04-21

    Natural products continue to provide a wealth of opportunities in the areas of chemical and therapeutic development. These structures are effective measuring sticks for the current state of chemical synthesis as a field and constantly inspire new approaches and strategies. Tetrahydropryans and tetrahydropyran-4-ones are found in numerous bioactive marine natural products and medicinal compounds. Our interest in exploring the therapeutic potential of natural products containing these motifs provided the impetus to explore new methods to access highly functionalized, chiral pyran molecules in the most direct and rapid fashion possible. This goal led to exploration and development of a Lewis acid-mediated Prins reaction between a chiral β-hydroxy-dioxinone and aldehyde to produce a pyran-dioxinone fused product that can be processed in a single pot operation to the desired tetrahydropyran-4-ones in excellent yield and stereoselectivity. Although the Prins reaction is a commonly employed approach toward pyrans, this method uniquely provides a 3-carboxy-trisubstituted pyran and utilizes dioxinones in a manner that was underexplored at the time. The 3-carboxy substituent served as a key synthetic handhold when this method was applied to the synthesis of highly functionalized pyrans within the macrocyclic natural products neopeltolide, okilactiomycin, and exiguolide. When employed in challenging macrocyclizations, this tetrahydropyranone forming reaction proved highly stereoselective and robust. Another major thrust in our lab has been the synthesis of benzopyranone natural products, specifically flavonoids, because this broad and diverse family of compounds possesses an equally broad range of biological and medicinal applications. With the goal of developing a broad platform toward the synthesis of enantioenriched flavonoid analogs and natural products, a biomimetic, asymmetric catalytic approach toward the synthesis of 2-aryl benzopyranones was developed. A

  3. Catalytic reaction mechanism of L-lactate dehydrogenase: an ab initio study

    Institute of Scientific and Technical Information of China (English)

    侯若冰; 陈志达; 义祥辉; 卞江; 徐光宪

    2000-01-01

    Studies on the catalytic reaction mechanism of L-lactate dehydrogenase have been carried out by using quantum chemical ab initio calculation at HF/6-31G* level. It is found that the interconversion reaction of pyruvate to L-lactate is dominated by the hydride ion HR- transfer, and the transfers of the hydride ion HR and proton HR+ are a quasi-coupled process, in which the energy barrier of the transition state is about 168.37 kJ/mol. It is shown that the reactant complex is 87.61 kJ/mol lower, in energy, than the product complex. The most striking features in our calculated results are that pyridine ring of the model cofactor is a quasi-boat-like configuration in the transited state, which differs from a planar conformation in some previous semiempirical quantum chemical studies. On the other hand, the similarity in the structure and charge between the HR transfer process and the hydrogen bonding with lower barrier indicates that the HR transfer process occurs by means of an unusual manner. In addition,

  4. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl

    2015-01-01

    of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided in an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore both NO and NH3...... are required in the reduction, and, nally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst, by combining in situ X-ray absorption spectrosocpy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....

  5. Synthesis of novel chiral tridentate Schiff-base ligands and their applications in catalytic asymmetric Henry reaction.

    Science.gov (United States)

    Qiang, Gen-Rong; Shen, Tian-Hua; Zhou, Xiao-Cong; An, Xiao-Xia; Song, Qing-Bao

    2014-12-01

    A series of chiral tridentate Schiff-bases were prepared and used as ligands in the catalytic asymmetric Henry reaction. Under the optimal conditions, a variety of arylaldehydes were smoothly converted into corresponding adducts with high yields (up to 98%) and excellent enantioselectivities (up to 97% ee).

  6. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

  7. Catalytic Studies Featuring Palladium(II Benzoylthiourea Derivative as Catalyst in Sonogashira Reaction

    Directory of Open Access Journals (Sweden)

    Wan M. Khairul

    2014-10-01

    Full Text Available A benzoylthiourea derivative (LTU and its metal complexation of palladium(II chloride (MLTU has been successfully synthesized and characterized via typical spectroscopic and analytical techniques namely IR, 1H and 13C Nuclear Magnetic Resonance, UV-Visible and Gas Chromatography Flame Ionization Detector (GC-FID. The Infrared spectrum for LTU shows four significant bands of interest namely ν(N-H, ν(C=O, ν(C-N and ν(C=S and the values were observed within the range. The 1H NMR spectrum for the compound shows expected protons for N-H at δH 10.95 ppm and δH 11.15 ppm while the 13C NMR spectrum shows resonances of carbonyl (C=O carbon and thiones (C=S at δC 168.26 ppm and δC 180.56 ppm, respectively. From UV-Vis spectrum, it shows the presence of n-pi* and pi→pi*electronic transitions which are expected to be attributed from the phenyl ring, carbonyl (C=O and thiones (C=S chromophores. Complexation of LTU with palladium(II chloride was done to afford MLTU which in turn, was tested as homogeneous catalyst in Sonogashira cross-coupling reaction. The reaction was monitored by GC-FID at 6 hours reaction period. The percentage conversion of 4-bromoacetophenone to the coupled product was 75.73% indicated that MLTU can act as an ideal potential catalyst in the Sonogashira reaction. © 2014 BCREC UNDIP. All rights reservedReceived: 14th May 2014; Revised: 30th August 2014; Accepted: 3rd September 2014 How to Cite: Khairul, W.M., Faisol, S.L.M., Jasman, S.M., Shamsuddin, M. (2014. Catalytic Studies Featuring Palladium(II Benzoylthiourea Derivative as Catalyst in Sonogashira Reaction. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (3: 241-248 (doi:10.9767/bcrec.9.3.6880.241-248Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.3.6880.241-248

  8. Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

    Science.gov (United States)

    Li, Yaping; Liu, Zhimin; Xue, Wenhua; Crossley, Steven P.; Jentoft, Friederike C.; Wang, Sanwu

    2017-01-01

    Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2-methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the sbnd OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.

  9. Structural Basis on the Catalytic Reaction Mechanism of Novel 1,2-Alpha L-Fucosidase (AFCA) From Bifidobacterium Bifidum

    Energy Technology Data Exchange (ETDEWEB)

    Nagae, M.; Tsuchiya, A.; Katayama, T.; Yamamoto, K.; Wakatsuki, S.; Kato, R.

    2009-06-03

    1,2-alpha-L-fucosidase (AfcA), which hydrolyzes the glycosidic linkage of Fucalpha1-2Gal via an inverting mechanism, was recently isolated from Bifidobacterium bifidum and classified as the first member of the novel glycoside hydrolase family 95. To better understand the molecular mechanism of this enzyme, we determined the x-ray crystal structures of the AfcA catalytic (Fuc) domain in unliganded and complexed forms with deoxyfuconojirimycin (inhibitor), 2'-fucosyllactose (substrate), and L-fucose and lactose (products) at 1.12-2.10 A resolution. The AfcA Fuc domain is composed of four regions, an N-terminal beta region, a helical linker, an (alpha/alpha)6 helical barrel domain, and a C-terminal beta region, and this arrangement is similar to bacterial phosphorylases. In the complex structures, the ligands were buried in the central cavity of the helical barrel domain. Structural analyses in combination with mutational experiments revealed that the highly conserved Glu566 probably acts as a general acid catalyst. However, no carboxylic acid residue is found at the appropriate position for a general base catalyst. Instead, a water molecule stabilized by Asn423 in the substrate-bound complex is suitably located to perform a nucleophilic attack on the C1 atom of L-fucose moiety in 2'-fucosyllactose, and its location is nearly identical near the O1 atom of beta-L-fucose in the products-bound complex. Based on these data, we propose and discuss a novel catalytic reaction mechanism of AfcA.

  10. β-Alanine-DBU" A Highly Efficient Catalytic System forKnoevenageI-Doebner Reaction under Mild Conditionsβ-Alanine-DBU" A Highly Efficient Catalytic System forKnoevenageI-Doebner Reaction under Mild Conditions

    Institute of Scientific and Technical Information of China (English)

    祝令建; 雷宁; 缪震元; 盛春泉; 庄春林; 姚建忠; 张万年

    2012-01-01

    A mild and efficient Knoevenagel-Doebner reaction from malonic acid and a wide range of aldehydes was catalyzed by a catalytic system consisting offlalanine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), affording the corresponding (E)-a,fl-unsaturated carboxylic acids in good to excellent yields and with high stereoselectivity. The advantage of the method is that the reaction could proceed smoothly at ambient temperature so that it can tolerate a variety of functional groups and avoid unnecessary side reactions.

  11. Catalytic Spectrophotometric Method for Determination of Formaldehyde Based on its Catalytic Effect on the ReactionBetween Bromate and Safranin

    OpenAIRE

    2010-01-01

    The reaction monitored spectrophotometrically by measuring the decrease in absorbance of the reaction mixture at 533 nm. The fixed-time method was used for the first 60s. For initiation of the reaction, under the optimum conditions, in the concentration range of 0.02-1.5 μg mL–1 formaldehyde can be determined with a limit of detection 9.5 ng mL–1. The relative standard deviation of five replicate measurements is 2.3% for 0.5 μg mL–1 of formaldehyde. The method was used for the determination o...

  12. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Science.gov (United States)

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  13. NO-CO-O2 Reaction on a Metal Catalytic Surface using Eley-Rideal Mechanism

    Institute of Scientific and Technical Information of China (English)

    Waqar Ahmad

    2008-01-01

    Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal (ER) mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood (LH) thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.

  14. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    Science.gov (United States)

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts.

  15. Water-gas shift reaction on CuO-ZnO catalysts: I. Structure and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Kalchev, M.G.; Andreev, A.A. [Institute of Catalysis, Sofia (Bulgaria); Zotov, N.S. [Institute of Applied Mineralogy, Sofia (Bulgaria)

    1995-11-01

    The physicochemical properties of CuO-ZnO samples with different CuO contents were investgated by a complex of physical methods: DSC, XPS, EPR, TPR, and XRD. The samples containing {approximately}25 wt % CuO exhibited a maximum catalytic activity in the water-gas shift reaction. The catalytic activity was attributed to copper ions aggregated on the highly dispersed and defective CuO surface and to an anion-modified ZnO surface. Aggregates of copper ions, formed on metal species and probably modified with hydroxyl and carbonate groups, were shown to play a decisive role in the catalytic activity of the samples containing more than 15 wt % CuO.

  16. Catalytic antibody light chain capable of cleaving a chemokine receptor CCR-5 peptide with a high reaction rate constant.

    Science.gov (United States)

    Mitsuda, Yukie; Hifumi, Emi; Tsuruhata, Kumi; Fujinami, Hiroko; Yamamoto, Naoki; Uda, Taizo

    2004-04-20

    A monoclonal antibody (MAb), ECL2B-2, was obtained by immunizing a peptide possessing a part of a sequence of a chemokine receptor, CCR-5, which is present as a membrane protein on the macrophage surface, and which plays an important role in human immunodeficiency virus (HIV) infection. From the DNA and the deduced amino acid sequences of the light and heavy chains of ECL2B-2 MAb, molecular modeling was conducted to calculate the steric conformation of the antibody. Modeling suggested that the structure of ECL2B-2 could possess one or two catalytic triad(s), composed of Asp(1), Ser(27a) (or Ser(27e)), and His(93) (or His(27d)), in the light chain of ECL2B-2. The three amino acid residues, Asp(1), Ser(27a), and His(93), are identical to those of catalytic antibody light chains such as VIPase and i41SL1-2. The light chain of ECL2B-2 MAb degraded the antigenic peptide CCR-5 within about 100 h. Surprisingly, the light chain had a very high catalytic reaction rate constant (k(cat)) of 2.23 min(-1), which is greater by factors of tens to hundreds than those of natural catalytic antibodies obtained previously. The heavy chain of ECL2B-2 MAb, which has no catalytic triad because of a lack of His residue, did not degrade the CCR-5 peptide.

  17. Exploring the learnings derived from catalytic experiences in a leadership context

    Directory of Open Access Journals (Sweden)

    Daphna S. Horowitz

    2015-03-01

    Full Text Available Orientation: Personal leadership comprises self-awareness, authenticity, inspiration and passion. The concept of personal leadership was explored together with its relationship with leadership-related learnings derived from a catalytic experience.Research purpose: The objective of the study was to explore the leadership-related learnings derived from a catalytic experience and any connection between these learnings, personal leadership and leadership in an organisational context.Motivation for the study: Measurement of leaders’ performance remains largely focused on the results achieved. The importance of personal leadership in the corporate environment is often ignored and even questioned. Recognising that there is a relationship between personal leadership and professional leadership enables leaders to connect who they are being and what they are doing. This can enhance their leadership.Research design, approach and method: The study was conducted using a qualitative approach, specifically narrative enquiry. The sample comprised seven leaders who have had catalytic experiences in their lives. In-depth interviews were conducted and thematic analysis was used to identify themes on the leadership-related learnings gained from the leaders’catalytic experiences.Main findings: Elements of personal leadership and the processes involved in the development of personal leadership were identified. It was furthermore shown that challenging experiences serve as learning opportunities and that time for reflection is essential in this learning process.Practical/managerial implications: Leadership lessons are best learnt through experience.Using challenging experiences as learning opportunities may assist leaders in their growth and development.Contribution: Leadership effectiveness and organisational effectiveness may be enhanced by a more holistic view of leadership that includes elements of personal leadership.

  18. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  19. Preparation of porous paper composites with ruthenium hydroxide and catalytic alcohol oxidation in a multiphase gas–liquid–solid reaction

    Energy Technology Data Exchange (ETDEWEB)

    Homma, Taichi [Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, and Biotron Application Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Processing Development Research Laboratory, Kao Corporation, 2606 Akabane, Ichikai-machi, Haga-gun, Tochigi 321-3497 (Japan); Kitaoka, Takuya, E-mail: tkitaoka@agr.kyushu-u.ac.jp [Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, and Biotron Application Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan)

    2014-05-01

    Highlights: • Flexible and porous paper-structured Ru(OH){sub x} catalysts were prepared successfully. • Ru(OH){sub x} catalysts were dispersed on the ceramic fiber networks of paper composites. • Catalytic oxidation of benzyl alcohol proceeded efficiently in three-phase reactions. • Paper catalysts exhibited much higher performance than conventional solid catalysts. - Abstract: In situ synthesis of ruthenium hydroxide catalysts on a microporous fiber-network structure of ceramic paper composites was achieved. The efficient catalytic oxidation of alcohol was investigated in a heterogeneous, multiphase gas–liquid–solid reaction. A simple papermaking technique and subsequent immersion in a ruthenium chloride solution allowed us to fabricate novel-concept microstructured catalysts. The paper-structured catalysts possess micropores ca. 30 μm in diameter with high porosity of ca. 90%. They exhibited much higher catalytic efficiency in the O{sub 2}-mediated oxidation in toluene of benzyl alcohol to benzaldehyde in a fixed bed external loop reactor, as compared with conventional pellet- and bead-type solid catalysts. This excellent catalytic effect is possibly attributed to the porous paper composite microstructure like microreactors.

  20. Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

    Institute of Scientific and Technical Information of China (English)

    Masoud Hasany; Mohammad Malakootikhah; Vahid Rahmanian; Soheila Yaghmaei

    2015-01-01

    A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction, removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production. For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used. Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogena-tion method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and significant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

  1. Catalytic synthesis of 2-methylpyrazine over Cr-promoted copper based catalyst via a cyclo-dehydrogenation reaction route

    Indian Academy of Sciences (India)

    Fangli Jing; Yuanyuan Zhang; Shizhong Luo; Wei Chu; Hui Zhang; Xinyu Shi

    2010-07-01

    The cyclo-dehydrogenation of ethylene diamine and propylene glycol to 2-methylpyrazine was performed under the atmospheric conditions at 380°C. The Cr-promoted Cu-Zn/Al2O3 catalysts were prepared by impregnation method and characterized by ICP-AES, N2 adsorption/desorption, XRD, XPS, N2O chemisorption, TPR and NH3-TPD techniques. The amorphous chromium species existing in Cu-Zn-Cr/Al2O3 catalyst enhanced the dispersion of active component Cu, promoted the reduction of catalyst. Furthermore, the catalytic performance was significantly improved. The acidity of the catalyst played an important role in increasing the 2-MP selectivity. To optimize the reaction parameters, influences of different chromium content, reaction temperature, liquid hourly space velocity (LHSV), reactants molar ratio and time on stream on the product pattern were studied. The results demonstrated that addition of chromium promoter revealed satisfying catalytic activity, stability and selectivity of 2-methylpyrazine.

  2. Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering

    Science.gov (United States)

    Rajagopalan, S.; Asthalter, T.; Rabe, V.; Laschat, S.

    2016-12-01

    Nuclear inelastic scattering (NIS) of synchrotron radiation, also known as nuclear resonant vibrational spectroscopy (NRVS), has been shown to provide valuable insights into metal-centered vibrations at Mössbauer-active nuclei. We present a study of the iron-centered vibrational density of states (VDOS) during the first step of the Gif-type oxidation of cyclohexene with a novel trinuclear Fe3(μ 3-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe3(μ 3-O) in pyridine solution, Fe3(μ 3-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe3(μ 3-O)/Zn/acetic acid/pyridine/cyclohexene (reaction mixture) for reaction times of 1 min, 5 min, and 30 min. The projected VDOS of the Fe atoms was calculated on the basis of pseudopotential density functional calculations. Two possible reaction intermediates were identified as [Fe(III)(C5H5N)2(O2CCH3)2]+ and Fe(II)(C5H5N)4(O2CCH3)2, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.

  3. Effect of Precursor Mechanism on CO-NO Catalytic Reaction on Body-Centred Cubic Structure: Monte Carlo Simulation

    Institute of Scientific and Technical Information of China (English)

    A. U. Qaisrani; M. Khalid; M. K.Khan

    2005-01-01

    @@ The CO-NO catalytic reaction on body-centred cubic (bcc) lattice is studied by Monte Carlo simulation. The simple Langmuir-Hinshelwood (LH) mechanism yields a steady reactive window, which is separated by continuous and discontinuous irreversible phase transitions. The effect of precursor mechanism on the phase diagram of the system is also studied. According to this mechanism, the precursor motion of CO molecules is considered only on the surface of bcc lattice. Some interesting observations are reported.

  4. Transient Non-Thermal Mobility of CO for CO-NO Catalytic Reaction on Square Lattice: Monte Carlo Simulation

    Institute of Scientific and Technical Information of China (English)

    M. Khalid; A. U. Qaisrani; M. G. Ullah

    2008-01-01

    @@ We study a model based on precursor mechanism for CO-NO catalytic reaction on square lattice with Monte Carlo simulation. The precursor mechanism clearly demonstrates its impact on the phase diagram. The steady reactive state (SRS) gets established. The width of reactive region increases by increasing the range of precursor mobility. When the precursor mobility is increased to third-nearest neighboarhood, the second-order transition disappears.

  5. Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin (UC); (Xiamen)

    2016-08-10

    Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.

  6. Kinetic Study of the Heck Reaction: An Interdisciplinary Experiment

    Science.gov (United States)

    Gozzi, Christel; Bouzidi, Naoual

    2008-01-01

    The aim of this experiment is to study and calculate the kinetic constant of a Heck reaction: the arylation of but-3-en-2-ol by iodobenzene catalyzed by palladium acetate in presence of triethylamine in DMF. The reaction leads to a mixture of two ketones. Students use GC analysis to quantify reagents and products of reaction. They control the…

  7. High catalytic efficiency of palladium nanoparticles immobilized in a polymer membrane containing poly(ionic liquid) in Suzuki–Miyaura cross-coupling reaction

    OpenAIRE

    Gu, Yingying; Favier, Isabelle; Pradel, Christian; Gin, Douglas L.; Lahitte, Jean-Francois; Noble, Richard D.; Gómez, Montserrat; Remigy, Jean-Christophe

    2015-01-01

    International audience; The elaboration of a polymeric catalytic membrane containing palladium nanoparticles is presented. The membrane was prepared using a photo-grafting process with imidazolium-based ionic liquid monomers as modifying agent and microPES® as support membrane. Ionic liquid serves as a stabilizer and immobilizer for the catalytic species, i.e. palladium nanoparticles. The Suzuki–Miyaura cross-coupling reaction was carried out on the catalytic membrane in flow-through configur...

  8. An effective route to improve the catalytic performance of SAPO-34 in the methanol-to-olefin reaction

    Institute of Scientific and Technical Information of China (English)

    Guangyu Liu; Peng Tian; Qinhua Xia; Zhongmin Liu

    2012-01-01

    An effective route to improve the catalytic performance of SAPO-34 in the methanol-to-olefin reaction by simple oxalic acid treatment was investigated.The samples were characterized by XRD,SEM,N2 adsorption-desorption,XRF,TG,29Si MAS NMR and NH3-TPD techniques.The results indicated that the external surface acidity of SAPO-34 was finely tuned by oxalic acid treatment,and the selectivity to C2H4 on SAPO-34 and the catalyst lifetime in the methanol-to-olefin reaction were greatly improved.

  9. CFD modeling of reaction and mass transfer through a single pellet:Catalytic oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    Siavash Seyednej adian; Nakisa Yaghobi; Ramin Maghrebi; Leila Vafajoo

    2011-01-01

    In this study a mathematical model of a small scale single pellet for the oxidative coupling of methane (OCM) over titanite pervoskité isdeveloped.The method is based on a computational fluid dynamics (CFD) code which known as Fluent may be adopted to model the reactions that take place inside the porous catalyst pellet.The steady state single pellet model is coupled with a kinetic model and the intra-pellet concentration profiles of species are provided.Subsequent to achieving this goal,a nonlinear reaction network consisting of nine catalytic reactions and one gas phase reaction as an external program is successfully implemented to CFD-code as a reaction term in solving the equations.This study is based on the experimental design which is conducted in a differential reactor with a Sn/BaTiO3 catalyst (7-8 mesh) at atmospheric pressure,GHSV of 12000 h-1,ratio of methane to oxygen of 2,and three different temperatures of 1023,1048 and 1073 K.The modeling results such as selectivity and conversion at the pellet exit are in good agreement with the experimental data.Therefore,it is suggested that to achieve high yield in OCM process the modeling of the single pellet should be considered as the heart of catalytic fixed bed reactor.

  10. Study of liquid-solid catalytic reaction of epichlorohydrin with sodium butyrate in the presence of tetrabutylammonium bromide

    Science.gov (United States)

    Huang, Qiang; Meng, Qingyi; Ban, Chunlan; Zhang, Rui; Gao, Yingyu

    2016-08-01

    The liquid-solid catalytic reaction of epichlorohydrin and sodium butyrate with tetrabutylammonium bromide as a phase transfer catalyst was studied in this paper. The shrinking core model was applied. The analysis of the reaction based on the kinetic model showed a reaction-controlled regime at temperatures varying from 90 to 100°C. The exterior diffusivity was removed between 300 and 400 rpm. The internal diffusivity was removed when the particle size was 2 × 10-4 m. Reaction rate constants were calculated at different temperatures. The correlation was obtained when the proposed kinetic model was applied to all the experimental data for predictive evaluations and the activation energy was 37.01 kJ mol-1.

  11. Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions.

    Science.gov (United States)

    Dybeck, Eric Christopher; Plaisance, Craig Patrick; Neurock, Matthew

    2017-02-14

    A novel algorithm has been developed to achieve temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate timescales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC have been designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the timescales of the slow kinetically relevant non-equilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation and the reaction rate constants are rescaled accordingly. The algorithm has been utilized here to model the Fischer-Tropsch synthesis reaction over ruthenium nanoparticles. This reaction network has multiple timescale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to give reaction rates and selectivities indistinguishable from those calculated by an equivalent mean-field kinetic model. The computational savings of the algorithm can span many orders of magnitude in realistic systems and the computational cost is not limited by the magnitude of the timescale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.

  12. Effect of diluent and reaction parameter on selective oxidation of propane over MoVTeNb catalyst using nanoflow catalytic reactor

    Institute of Scientific and Technical Information of China (English)

    Restu Kartiko Widi; Sharifah Bee Abdul Hamid; Robert Schl(o)gl

    2008-01-01

    The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity (GHSV) and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.

  13. Enhancement in the Catalytic Activity of Pd/USY in the Heck Reaction Induced by H2 Bubbling

    Directory of Open Access Journals (Sweden)

    Miki Niwa

    2010-12-01

    Full Text Available Pd was loaded on ultra stable Y (USY zeolites prepared by steaming NH4-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H2 bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc2. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H2O gave the highest activity (TOF = 61,000 h−1, which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OHstrong generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  14. Resonance scattering spectral detection of ultratrace IgG using immunonanogold-HAuCl4-NH2OH catalytic reaction

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Nanogold particles of 10 nm were used to label goat anti-human IgG (GIgG) to obtain nanogold-labeled GIgG (AuGIgG). In a citrate-HCl buffer solution of pH 2.27,AuGIgG showed a strong catalytic effect on the reaction between HAuCl4 and NH2OH to form big gold particles that exhibited a resonance scatter-ing (RS) peak at 796 nm. Under the chosen conditions,AuGIgG combined with IgG to form immuno-complex AuGIgG-IgG that can be removed by centrifuging at 16000 r/min. AuGIgG in the centrifuging solution also showed catalytic effect on the reaction. On those grounds,an immunonanogold catalytic RS assay for IgG was designed. With addition of IgG,the amount of AuGIgG in the centrifuging solution decreased; the RS intensity at 796 nm (I796 nm) decreased linearly. The decreased intensity ΔI796 nm was linear with respect to the IgG concentration in the range of 0.08-16.0 ng·mL-1 with a detection limit of 0.02 ng·mL-1. This assay was applied to analysis of IgG in sera with satisfactory sensitivity,selectivity and rapidity.

  15. Photo catalytic reduction of benzophenone on TiO{sub 2}: Effect of preparation method and reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I., E-mail: mavalenz@ipn.m [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Laboratorio de Catalisis y Materiales, Zacatenco, 07738 Mexico D. F. (Mexico)

    2010-07-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO{sub 2} was synthesized by means of a hydrothermal technique. TiO{sub 2} (Degussa TiO{sub 2}-P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp ({lambda}= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO{sub 2} depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO{sub 2} was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO{sub 2} (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO{sub 2}-P25. (Author)

  16. Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    Yongki Choi

    2011-12-01

    Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

  17. Key nuclear reaction experiments discoveries and consequences

    CERN Document Server

    Paetz gen. Schieck, Hans

    2015-01-01

    In this book the author charts the developments in nuclear physics since its inception around a century ago by reviewing the key experiments that helped drive and shape our understanding of the field, especially in the context of the wider developments in physics in the early 20th Century. In addition to providing a path through the field and the crucial events it looks at how these experiments not only answered key questions at the time but presented new challenges to the contemporary perception of the nuclear and sub-atomic worlds and how they helped develop our present understanding of nuclear physics.

  18. Nuclear reaction modeling, verification experiments, and applications

    Energy Technology Data Exchange (ETDEWEB)

    Dietrich, F.S.

    1995-10-01

    This presentation summarized the recent accomplishments and future promise of the neutron nuclear physics program at the Manuel Lujan Jr. Neutron Scatter Center (MLNSC) and the Weapons Neutron Research (WNR) facility. The unique capabilities of the spallation sources enable a broad range of experiments in weapons-related physics, basic science, nuclear technology, industrial applications, and medical physics.

  19. Upward Trend in Catalytic Efficiency of Rare-Earth Triflate Catalysts in Friedel-Crafts Aromatic Sulfonylation Reactions

    DEFF Research Database (Denmark)

    Duus, Fritz; Le, Thach Ngoc; Nguyen, Vo Thu An

    2014-01-01

    A series of 14 lanthanide (Ln) triflates were investigated as sustainable catalysts for aromatic sulfonylation reactions under microwave irradiation. The catalytic efficiency of the early triflates La(OTf)3–Eu(OTf)3 is good for long irradiation times. For the later lanthanides, yields reaching over...... 90 % were achieved for short irradiation periods. This was the case especially for Tm(OTf)3, Yb(OTf)3, and Lu(OTf)3, of which Yb(OTf)3 was the most efficient. The upward trend in catalytic efficiency therefore correlates with the lanthanide sequence in the periodic table. The results can be explained......(OTf)3, which matched the “gadolinium break”; the well-known discontinuity in lanthanide properties...

  20. Molecular studies of model surfaces of metals from single crystals to nanoparticles under catalytic reaction conditions. Evolution from prenatal and postmortem studies of catalysts.

    Science.gov (United States)

    Somorjai, Gabor A; Aliaga, Cesar

    2010-11-01

    Molecular level studies of metal crystal and nanoparticle surfaces under catalytic reaction conditions at ambient pressures during turnover were made possible by the use of instruments developed at the University of California at Berkeley. Sum frequency generation vibrational spectroscopy (SFGVS), owing to its surface specificity and sensitivity, is able to identify the vibrational features of adsorbed monolayers of molecules. We identified reaction intermediates, different from reactants and products, under reaction conditions and for multipath reactions on metal single crystals and nanoparticles of varying size and shape. The high-pressure scanning tunneling microscope (HP-STM) revealed the dynamics of a catalytically active metallic surface by detecting the mobility of the adsorbed species during catalytic turnover. It also demonstrated the reversible and adsorbate-driven surface restructuring of platinum when exposed to molecules such as CO and ethylene. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) detected the reversible changes of surface composition in rhodium-palladium, platinum-palladium, and other bimetallic nanoparticles as the reactant atmosphere changed from oxidizing to reducing. It was found that metal nanoparticles of less than 2 nm in size are present in higher oxidation states, which alters and enhances their catalytic activity. The catalytic nanodiode (CND) confirmed that a catalytic reaction-induced current flow exists at oxide-metal interfaces, which correlates well with the reaction turnover.

  1. A Study on the Kinetics of the Catalytic Reforming Reaction of CH4 with CO2: Determination of the Reaction Order

    Institute of Scientific and Technical Information of China (English)

    Chunyang Ji; Lihong Gong; Jiawei Zhang; Keying Shi

    2003-01-01

    The kinetics of the catalytic reforming reaction of methane with carbon dioxide to produce synthesis gas on a Ni/α-Al2O3 and a HSD-2 type commercial catalyst has been studied. The results indicate that the reaction orders are one and zero for methane and carbon dioxide, respectively, when the carbon dioxide partial pressure was about 12.5-30.0 kPa and the temperature was at 1123-1173 K. However,when the carbon dioxide partial pressure was changed to 30.0-45.0 kPa under the same temperature range of 1123 1173 K, the reaction orders of methane and carbon dioxide are one. Furthermore, average rate constants at different temperatures were determined.

  2. Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification.

    Science.gov (United States)

    Ji, Bolin; Tang, Peixin; Yan, Kelu; Sun, Gang

    2015-11-05

    1,2,3,4-Butanetetracarboxylic acid (BTCA) reacts with cellulose in two steps with catalysis of alkaline salts such as sodium hypophosphite: anhydride formation and esterification of anhydride with cellulose. The alkali metal ions were found effective in catalyzing formation of BTCA anhydride in a previous report. In this work, catalytic functions of the alkaline salts in the esterification reaction between BTCA anhydride and cellulose were investigated. Results revealed that acid anions play an important role in the esterification reaction by assisting removal of protons on intermediates and completion of the esterification between cellulose and BTCA. Besides, alkaline salts with lower pKa1 values of the corresponding acids are more effective ones for the reaction since addition of these salts could lead to lower pH values and higher acid anion concentrations in finishing baths. The mechanism explains the results of FTIR and wrinkle recovery angles of the fabrics cured under different temperatures and times.

  3. Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

    Science.gov (United States)

    Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2014-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

  4. New Chiral Pyridine Prolinol Derivatives and Preliminary Study on Asymmetric Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    Xiao CHEN; Yong Xin ZHANG; Da Ming DU; Wen Ting HUA

    2004-01-01

    Two new chiral pyridine prolinol derivatives have been synthesized from N-alkylation of (S)-α,α-diphenyl-2-pyrrolidinemethanol with 2-bromomethylpyridine and 2, 6-dibromo-methyl-pyridine. The catalytic asymmetric borane reduction of prochiral ketones and the asymmetric addition of diethylzinc to benzaldehyde were investigated.

  5. Biogenic synthesis of palladium nanoparticles using Pulicaria glutinosa extract and their catalytic activity towards the Suzuki coupling reaction.

    Science.gov (United States)

    Khan, Mujeeb; Khan, Merajuddin; Kuniyil, Mufsir; Adil, Syed Farooq; Al-Warthan, Abdulrahman; Alkhathlan, Hamad Z; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H

    2014-06-28

    Green synthesis of nanomaterials finds the edge over chemical methods due to its environmental compatibility. Herein, we report a facile and eco-friendly method for the synthesis of palladium (Pd) nanoparticles (NPs) using an aqueous solution of Pulicaria glutinosa, a plant widely found in a large region of Saudi Arabia, as a bioreductant. The as-prepared Pd NPs were characterized using ultraviolet-visible (UV-vis) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform-infrared spectroscopy (FT-IR). The hydroxyl groups of the plant extract (PE) molecules were found mainly responsible for the reduction and growth of Pd NPs. FT-IR analysis confirmed the dual role of the PE, both as a bioreductant as well as a capping ligand, which stabilizes the surface of Pd NPs. The crystalline nature of the Pd NPs was identified using XRD analysis which confirmed the formation of a face-centered cubic structure (JCPDS: 87-0641, space group: Fm3m (225)). Furthermore, the as-synthesized Pd NPs demonstrated excellent catalytic activity towards the Suzuki coupling reaction under aqueous and aerobic conditions. Kinetic studies of the catalytic reaction monitored using GC confirmed that the reaction completes in less than 5 minutes.

  6. Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues

    Directory of Open Access Journals (Sweden)

    Hamza Boufroura

    2017-01-01

    Full Text Available The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four new catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine- and azetidine-based catalytic systems allowed Suzuki-Miyaura reactions from aryl halides including chlorides with catalytic loadings until 0.001% at temperatures ranging from 100 °C to r.t. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or an imidate pendant arm impacted the Suzuki-Miyaura reaction issue.

  7. Non-Thermal Effects on CO-NO Surface Catalytic Reaction on Square Surface: Monte Carlo Study

    Institute of Scientific and Technical Information of China (English)

    M. Khalid; A. U. Qaisrani; W. Ahmad

    2005-01-01

    @@ A Monte Carlo simulation of the CO-NO heterogeneous catalytic reaction over a square surface has already been studied with a model based on the Langmuir-Hinshelwood (LH) mechanism. The results of this study are well known. Here we study the effects of transient non-thermal mobility of monomer (CO) based on precursor mechanism, diffusion of adsorbed nitrogen and oxygen atoms, on the phase diagram. The interesting feature of this model is the yield of a steady reactiw window, while simple LH mechanism is not capable of producing a steady reactive state.

  8. Monomeric Cu(Ⅱ) Complex Containing Chiral Phase-transfer Catalyst as Ligand and Its Asymmetrically Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    QU Zhi-Rong; XIONG Ren-Gen

    2008-01-01

    The thermal treatment of CuCl2 with N-(4'-vinylbenzyl)cinchonidinitim chloride(L1)afforded a monomeric discrete homochiral copper(Ⅱ)complex N-4'-(vinylbenzyl)cinchonidinium trichlorocoprate(Ⅱ)(1).Their applications to the enantioselectively catalytic alkylation reaction of N-(diphenylmethylidene)glycine tert-butyl ester(3)show that the higher ee value observed in catalyst 1 than that in the corresponding free ligand L1 is probably due to the rigidity enhancement after the coordination of N atom of quinoline ring to the copper ion.

  9. Evaluation of the Cu dopping effects in CeO{sub 2} catalytic supports obtained by combustion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Neiva, Laedna Souto; Leal, Elvia; Costa, Ana Cristina F.M.; Gama, Lucianna, E-mail: lsoutoneiva@yahoo.com.br, E-mail: elvialeal@gmail.com, E-mail: anacristina@dema.ufcg.edu.br, E-mail: lucianna@dema.ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), Campina Grande, PB (Brazil). Departamento de Engenharia de Materiais; Mascarenhas, Artur Jose S.; Andrade, Heloysa M.C., E-mail: artur@ufba.br, E-mail: handrade@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil)

    2009-07-01

    This work has for aim to synthesize CeO{sub 2} catalytic supports doped with Cu{sup 2+} by combustion reaction method. Thus were obtained catalytic supports with the composition Ce{sub 1-x}Cu{sub x}O{sub 2} and the effect caused by doped element in the structure of the CeO{sub 2} was evaluated. The concentration value (x) of the Cu doped took over the values of 0.0; 0.3 and 0.5 mol. The catalytic supports developed were submitted to the structural characterization by X-ray diffraction, morphologic analysis by SEM and textural analysis by means of adsorption-desorption of N{sub 2} by BET method. The results showed that the doped element (Cu) was not completely incorporated in the CeO{sub 2} structure and was evidenced that how much larger the quantity of Cu larger maid the disorder of the atomic structure of the obtained material. The analyzed supports present mesoporous nature structure. (author)

  10. Simulation experiments on the reaction system of CH4-MgSO4-H2O

    Institute of Scientific and Technical Information of China (English)

    DING KangLe; LI ShuYuan; YUE ChangTao; ZHONG NingNing

    2008-01-01

    H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction (TSR). In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃-525℃. The threshold temperature for initiating TSR is much lower than our previous studies (550℃). Properties of the reaction products were analyzed by microcoulometry, gas-chromatography (GC), Fourier transform-infrared spectrometry (FT-IR) and X-ray diffraction (XRD) methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon diox-ide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac-cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg2+ may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.

  11. Apparent Rate Constant for Diffusion-Controlled Three molecular (catalytic) reaction

    OpenAIRE

    Burlatsky, S. F.; Moreau, M

    1996-01-01

    We present simple explicit estimates for the apparent reaction rate constant for three molecular reactions, which are important in catalysis. For small concentrations and $d> 1$, the apparent reaction rate constant depends only on the diffusion coefficients and sizes of the particles. For small concentrations and $d\\le 1$, it is also time -- dependent. For large concentrations, it gains the dependence on concentrations.

  12. Catalytic Reaction of Aryldiazoacetates with Indole and Its Derivatives: Profound Effect of N-1 Substitutent on the Reaction Pathways

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xue-Jing; LIU Sheng-Ping; YAN Ming

    2008-01-01

    The reaction of indole and its derivatives with aryldiazoacetates has been studied in the presence of copper and The electron-donating group favored the formation of the β-alkylation products, while the electron-withdrawing group favored the formation of the cyclopropane products. A reaction mechanism was proposed based on the experimental data and previous research results. The structure of aryl group in diazo compounds also affected the yield of the β-alkylation products or the cyclopropane products.

  13. Catalytic enantioselective Michael addition reactions of alpha-nitroesters to alpha,beta-unsaturated ketones

    NARCIS (Netherlands)

    Keller, E; Veldman, N; Spek, AL; Feringa, BL

    1997-01-01

    Enantioselective Michael additions of alpha-nitroesters 2a-d with alpha,beta-unsaturated ketones were carried out in the presence of a catalytic amount of chiral Al-Li-(R,R')-2,2'-dihydroxy-1,1'-binaphthyl ('AlLiBINOL') complex prepared in situ from LiAlH4 and 2.45 equiv. of (R,R')-BINOL. The enanti

  14. Catalytic enantioselective Michael addition reactions of α-nitroesters to α,β-unsaturated ketones

    NARCIS (Netherlands)

    Keller, Erik; Veldman, Nora; Spek, Anthony L.; Feringa, Bernard

    1997-01-01

    Enantioselective Michael additions of α-nitroesters 2a-d with α,β-unsaturated ketones were carried out in the presence of a catalytic amount of chiral Al-Li-(R,R')-2,2'-dihydroxy-1,1'-binaphthyl (‘AlLiBINOL’) complex prepared in situ from LiAlH4 and 2.45 equiv. of (R,R')-BINOL. The enantioselectivit

  15. Synthesis of 1-alkyl triazolium triflate room temperature ionic liquids and their catalytic studies in multi-component Biginelli reaction

    Indian Academy of Sciences (India)

    Sankaranarayanan Nagarajan; Tanveer M Shaikh; Elango Kandasamy

    2015-09-01

    Synthesis of three Brønsted acid-based ionic liquids, namely, 1-ethyl-1,2,4-triazolium triflate (1a), 1-propyl-1,2,4-triazolium triflate (1b) and 1-butyl-1,2,4-triazolium triflate (1c), is described. These ionic liquids have been employed as catalysts for convenient and high-yielding one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones and 3,4-dihydropyrimidin-2(1H)-thiones, which are Biginelli reaction products. Advantages of the methodology are operational convenience, short reaction times, avoidance of chromatographic purification and non-production of toxic waste. Further, the catalysts are easily recovered and reused without any noticeable diminution in their catalytic activity.

  16. Recent developments in the production of liquid fuels via catalytic conversion of microalgae: experiments and simulations

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Fan; Wang, Pin; Duan, Yuhua; Link, Dirk; Morreale, Bryan

    2012-01-01

    Due to continuing high demand, depletion of non-renewable resources and increasing concerns about climate change, the use of fossil fuel-derived transportation fuels faces relentless challenges both from a world markets and an environmental perspective. The production of renewable transportation fuel from microalgae continues to attract much attention because of its potential for fast growth rates, high oil content, ability to grow in unconventional scenarios, and inherent carbon neutrality. Moreover, the use of microalgae would minimize ‘‘food versus fuel’’ concerns associated with several biomass strategies, as microalgae do not compete with food crops in the food chain. This paper reviews the progress of recent research on the production of transportation fuels via homogeneous and heterogeneous catalytic conversions of microalgae. This review also describes the development of tools that may allow for a more fundamental understanding of catalyst selection and conversion processes using computational modelling. The catalytic conversion reaction pathways that have been investigated are fully discussed based on both experimental and theoretical approaches. Finally, this work makes several projections for the potential of various thermocatalytic pathways to produce alternative transportation fuels from algae, and identifies key areas where the authors feel that computational modelling should be directed to elucidate key information to optimize the process.

  17. Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.

    Directory of Open Access Journals (Sweden)

    Daniel E Almonacid

    2010-03-01

    Full Text Available Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3 show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1 catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56% suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to

  18. Oxidation of Borneol to Camphor Using Oxone and Catalytic Sodium Chloride: A Green Experiment for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Lang, Patrick T.; Harned, Andrew M.; Wissinger, Jane E.

    2011-01-01

    A new green oxidation procedure was developed for the undergraduate organic teaching laboratories using Oxone and a catalytic quantity of sodium chloride for the conversion of borneol to camphor. This simple 1 h, room temperature reaction afforded high quality and yield of product, was environmentally friendly, and produced negligible quantities…

  19. Memorable experiences with sad music-reasons, reactions and mechanisms of three types of experiences.

    OpenAIRE

    Tuomas Eerola; Henna-Riikka Peltola

    2016-01-01

    Reactions to memorable experiences of sad music were studied by means of a survey administered to a convenience (N = 1577), representative (N = 445), and quota sample (N = 414). The survey explored the reasons, mechanisms, and emotions of such experiences. Memorable experiences linked with sad music typically occurred in relation to extremely familiar music, caused intense and pleasurable experiences, which were accompanied by physiological reactions and positive mood changes in about a third...

  20. A design-of-experiments approach for the optimization and understanding of the cross-metathesis reaction of methyl ricinoleate with methyl acrylate.

    Science.gov (United States)

    Ho, Thao T T; Jacobs, Tina; Meier, Michael A R

    2009-01-01

    A design-of-experiments approach for the investigation of the cross-metathesis of methyl ricinoleate with methyl acrylate is described. Two second-generation metathesis initiators were studied using different reaction conditions, revealing optimal reaction conditions for each catalyst. Interestingly, the two catalysts showed completely different temperature response profiles. As a result of these investigations, suitable reaction conditions for the sustainable production of two value-added chemical intermediates were derived. Moreover, the design-of-experiments approach provided valuable information for a thorough understanding of catalytic reactions that would be more difficult to obtain by classic approaches.

  1. An undergraduate level experiment on the synthesis of Au nanoparticles and their size-dependent optical and catalytic properties

    Directory of Open Access Journals (Sweden)

    Anderson G. M. da Silva

    2014-01-01

    Full Text Available The synthesis of gold nanoparticles (Au NPs 15, 26, and 34 nm in diameter, followed by the investigation of their size-dependent optical and catalytic properties, is described herein as an undergraduate level experiment. The proposed experiment covers concepts on the synthesis, stabilization, and characterization of Au NPs, their size-dependent optical and catalytic properties at the nanoscale, chemical kinetics, and the role of a catalyst. The experiment should be performed by groups of two or three students in three lab sessions of 3 h each and organized as follows: i synthesis of Au NPs of different sizes and investigation of their optical properties; ii evaluation of their catalytic activity; and iii data analysis and discussion. We believe that this activity enables students to integrate these multidisciplinary concepts in a single experiment as well as to become introduced/familiarized with an active research field and current literature in the areas of nanoparticle synthesis and catalysis.

  2. Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(III) corrole 1-Fe.

    Science.gov (United States)

    Avidan-Shlomovich, Shlomit; Gross, Zeev

    2015-07-21

    The amphipolar iron(III) corrole 1-Fe is one of the most efficient catalysts for the decomposition of peroxynitrite, the toxin involved in numerous diseases. This research focused on the mechanism of that reaction at physiological pH, where peroxynitrite is in equilibrium with its much more reactive conjugated acid, by focusing on the elementary steps involved in the catalytic cycle. Kinetic investigations uncovered the formation of a reaction intermediate in a process that is complete within a few milliseconds (k1 ∼ 3 × 10(7) M(-1) s(-1) at 5 °C, about 7 orders of magnitude larger than the first order rate constant for the non-catalyzed process). Multiple evidence points towards iron-catalyzed homolytic O-O bond cleavage to form nitrogen dioxide and hydroxo- or oxo-iron(iv) corrole. The iron(iv) intermediate was found to decay via multiple pathways that proceed at similar rates (k2 about 10(6) M(-1) s(-1)): reaction with nitrogen dioxide to form nitrate, nitration of the corrole macrocyclic, and dimerization to binuclear iron(iv) corrole. Catalysis in the presence of substrates affects the decay of the iron intermediate by either oxidative nitration (phenolic substrates) or reduction (ascorbate). A large enough excess of ascorbate accelerates the catalytic decomposition of PN by 1-Fe by orders of magnitude, prevents other decay routes of the iron intermediate, and eliminates nitration products as well. This suggests that the beneficial effect of the iron corrole under the reducing conditions present in most biological media might be even larger than in the purely chemical system. The acquired mechanistic insight is of prime importance for the design of optimally acting catalysts for the fast and safe decomposition of reactive oxygen and nitrogen species.

  3. Catalytic reaction energetics by single crystal adsorption calorimetry: hydrocarbons on Pt(111).

    Science.gov (United States)

    Lytken, Ole; Lew, Wanda; Campbell, Charles T

    2008-10-01

    Single crystal adsorption calorimetry provides essential information about the energetics of surface reactions on well-defined surfaces where the adsorbed reaction products can be clearly identified. In this tutorial review, we cover the essentials of that technique, with emphasis on our lab's recent advances in sensitivity and temperature range, and demonstrate what can be achieved through a review of selected example studies concerning adsorption and dehydrogenation of hydrocarbons on Pt(111). A fairly complete reaction enthalpy diagram is presented for the dehydrogenation of cyclohexane to benzene on Pt(111).

  4. Perturbation theory in the catalytic rate constant of the Henri-Michaelis-Menten enzymatic reaction.

    Science.gov (United States)

    Bakalis, Evangelos; Kosmas, Marios; Papamichael, Emmanouel M

    2012-11-01

    The Henry-Michaelis-Menten (HMM) mechanism of enzymatic reaction is studied by means of perturbation theory in the reaction rate constant k (2) of product formation. We present analytical solutions that provide the concentrations of the enzyme (E), the substrate (S), as well as those of the enzyme-substrate complex (C), and the product (P) as functions of time. For k (2) small compared to k (-1), we properly describe the entire enzymatic activity from the beginning of the reaction up to longer times without imposing extra conditions on the initial concentrations E ( o ) and S ( o ), which can be comparable or much different.

  5. Catalytic Asymmetric Carbon-Carbon Forming Reactions Catalyzed Chiral Schiff Base-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Takanori; Tanaka; Masahiko; Hayashi

    2007-01-01

    1 Results In 1991, we disclosed the novel asymmetric catalysts prepared from chiral Schiff base and titanium alkoxide in the reaction of asymmetric silylcyanation of aldehydes (eq.1)[1]. Since our first report, chiral Schiff base-metal complex was proven to be efficient in a variety of asymmetric reactions. We reported the first example of enantioselective addition of diketene to aldehydes promoted by chiral Schiff base-titanium alkoxide complexes (eq.2)[2]. The products of this reaction have been cove...

  6. Layered materials with coexisting acidic and basic sites for catalytic one-pot reaction sequences.

    Science.gov (United States)

    Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro

    2009-06-17

    Acidic montmorillonite-immobilized primary amines (H-mont-NH(2)) were found to be excellent acid-base bifunctional catalysts for one-pot reaction sequences, which are the first materials with coexisting acid and base sites active for acid-base tamdem reactions. For example, tandem deacetalization-Knoevenagel condensation proceeded successfully with the H-mont-NH(2), affording the corresponding condensation product in a quantitative yield. The acidity of the H-mont-NH(2) was strongly influenced by the preparation solvent, and the base-catalyzed reactions were enhanced by interlayer acid sites.

  7. Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

    Science.gov (United States)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2015-01-01

    Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

  8. Study on Chemisorption, Catalytic Behavior, and Stability of Supported Au Catalyst for the Propylene Epoxidation Reaction

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The supported Au/TiO2 and Au/TiO2-SiO2 catalysts were prepared by deposition precipitation method. The TPD study reveals that propylene oxide competes with propylene to be adsorbed on the same adsorptive center-Tin+ site on the surface of the catalyst and that the adsorbing capacity of the catalyst for propylene oxide is larger than that for propylene. Catalytic behavior for propylene epoxidation with H2 and O2 was tested in a micro-reactor. Under typical conditions, the selectivity for propylene oxide is over 87%. The TG curves show that PO successive oxidation cause carbon deposition on the active center and deactivation of the Au catalysts. Because the amounts of Tin+ site decrease significantly, and consequently the separation between Tin+ sites increases, the Au/TiO2-SiO2 catalyst is more stable than Au/TiO2.

  9. Photo-catalytic oxidation reaction of gaseous mercury over titanium dioxide nanoparticle surfaces

    Science.gov (United States)

    Snider, Graydon; Ariya, Parisa

    2010-05-01

    Hg 0(g) is known to undergo photo-catalytic oxidation by UVA-irradiated TiO 2 surfaces. One micrometre layers of TiO 2 on quartz glass were irradiated within the 240-800 nm range. Gaseous mercury was measured by mass spectrometry single ion monitoring. The surface configuration and elemental characterization of TiO 2 layer was evaluated using scanning electron microcopy with energy dispersive spectroscopy. The LH adsorption constant of was found to be KHg = (5.1 ± 2.4) × 10 -14 cm 3 and an apparent surface deposition rate of k = (7.4 ± 2.5) × 10 14 min -1 cm -2 under experimental conditions. Water did not affect the rate constant. We show TiO 2 could be employed to reduce mercury concentrations in gas streams, even at very high Hg 0 concentrations.

  10. One-pot Solvent-free Catalytic Dimerization Reaction of Phenylacetylene to 1-Phenylnaphthalene

    Indian Academy of Sciences (India)

    Avat (Arman) Taherpour; Sepehr Taban; Ako Yari

    2015-09-01

    In this study, we report a smooth one-pot, solvent-free catalytic dimerization of phenylacetylene (1) to 1-phenylnaphthalene (2) by Cu/C at room temperature in good yield (∼100%). In the computational study, the structure of the 1-phenylnaphthalene was optimized by DFT-B3LYP/6-31G* method. The rotation barrier around C-C of the phenyl and naphthalene parts of the molecule and its UV-Visible spectrum were calculated. The modelling of the mechanism of production of 2 from 1 was performed with and without Cu/C catalyst. The data of EDS and SEM of the Cu/C catalyst surface are also reported.

  11. Hexene catalytic cracking over 30% sapo-34 catalyst for propylene maximization: influence of reaction conditions and reaction pathway exploration

    Directory of Open Access Journals (Sweden)

    Z. Nawaz

    2009-12-01

    Full Text Available Higher olefins are produced as a by product in a number of refinery processes and are one of the potential raw materials to produce propylene. In the present study, FCC model feed compound was considered to explore the olefin cracking features and options to enhance propylene using 30% SAPO-34 zeolite as catalyst in a micro-reactor. The superior selectivity of propylene (73 wt% and higher total olefin selectivity was obtained over 30% SAPO-34 catalyst than over Y or ZSM-5 zeolite catalysts. The thermodynamical constraints were found to be relatively less serious in the case of 1-hexene conversion. Most of the 1-hexene follows a direct cracking pathway to give two propylene molecules, due to weak acid sites and better diffusion opportunities. The higher temperature and short residence time could also suppress the hydrogen transfer reactions. From OPE (olefins performance envelop the products were classified as primary, secondary, or both. Iso-hexene (2-methyl-2-pentene cracking was also analyzed in order to justify a shape selective effect of the SAPO-34 catalyst. A detailed integrated reaction network together with an associated mechanism was proposed and discussed in detail for their fundamental importance in understanding the olefin cracking processes over SAPO-34.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-01

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

  13. Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

    Science.gov (United States)

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature.

  14. [Experiment study on the aqueous removal of SO2 by Mn2+ catalytic ozonation].

    Science.gov (United States)

    Ma, Shuang-Chen; Su, Min; Ma, Jing-Xiang; Sun, Yun-Xue; Jin, Xin; Zhao, Yi

    2009-11-01

    The removal of SO2 by Mn2+ catalytic aqueous ozonation was investigated by experiment, so as to find the effects of Mn2+ for aqueous removal of SO2 by ozonation. The concentration curve of ozone was drawn by standard iodine method. The operating factors included mole ratio of ozone to sulfur dioxide and concentration of Mn2+. When absorption solution has no Mn2+, the removal efficiency of SO2 was 35% at [O3 ]/[SO2 ] = 0.5,but the efficiency was 70% when Mn2+ was put into absorption solution at the same value of [O3 ]/[SO2].With the increasing of [3O]/[SO2], the removal efficiency of SO2 increases. And as concentration of Mn2+ increases, the efficiency also increases. There is an appropriate concentration range which is 1.2 x 10(-2)-1.2 x 10(-1) mol/L for Mn2+.

  15. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    Directory of Open Access Journals (Sweden)

    Wan Azelee Wan Abu Bakar

    2015-09-01

    Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

  16. Effect of size of copper nanoparticles on its catalytic behaviour in Ullman reaction

    Indian Academy of Sciences (India)

    Mohd Samim; N K Kaushik; Amarnath Maitra

    2007-10-01

    The condensation of iodobenzene to biphenyl is an industrially important reaction due to its significant role in organic synthesis as drug intermediates. The reaction takes place in the presence of copper powder as catalyst. We have shown in this paper that the size of the copper nanoparticles as well as its exposed surface area is responsible for the yield of chemical reaction. The uncapped copper powder showed a 43% conversion of iodobenzene to biphenyl in 5 h under our experimental conditions. Same amount of copper nanoparticles (size, ∼ 66 nm diameter) prepared by citrate capping showed 88% conversion of iodobenzene to biphenyl, which increased to about 95% when 8 nm diameter capped copper nanoparticles are used. Surprisingly, 5 nm size copper nanoparticles showed no change in the yield of about 95%.

  17. Catalytic hydroconversion of tricaprylin and caprylic acid as model reaction for biofuel production from triglycerides

    Energy Technology Data Exchange (ETDEWEB)

    Boda, L.; Thernesz, A. [MOL Hungarian Oil and Gas Co. Plc., Szazhalombatta (Hungary); Onyestyak, G.; Solt, H.; Lonyi, F.; Valyon, J. [Hungarian Academy of Sciences, Budapest (Hungary). Inst. of Nanochemistry and Catalysis

    2010-07-01

    Palladium/activated carbon (Pd/C) and non-sulfided Ni,Mo/{gamma}-Al{sub 2}O{sub 3} catalysts were used. The hydroconversion was found to proceed in consecutive steps of tricaprylin (TC) hydrogenolysis (HYS) to caprylic acid (CA) and propane, and hydrodeoxygenation (HDO) of the acid intermediate to get hydrocarbon. Two HDO routes were distinguished: (i) over Pd/C the prevailing reaction route was the decarbonylation, whereas (ii) over molybdena-alumina catalysts the main reaction was the reduction of oxygen to get water. (orig.)

  18. Spatially resolved characterization of catalyst-coated membranes by distance-controlled scanning mass spectrometry utilizing catalytic methanol oxidation as gas-solid probe reaction.

    Science.gov (United States)

    Li, Nan; Assmann, Jens; Schuhmann, Wolfgang; Muhler, Martin

    2007-08-01

    The spatially resolved catalytic activity of a catalyst-coated membrane (CCM), which is the essential part of PEM fuel cells, was visualized rapidly without any damage by a distance-controlled scanning mass spectrometer with an improved resolution of 250 microm. Methanol oxidation was identified as a suitable gas-solid probe reaction for the characterization of local catalytic activity. In addition, defects were manually generated in the CCM to simulate inhomogeneous coating and pinholes. The measurements successfully demonstrated that catalytically active and less active regions can be clearly distinguished. Simultaneously, the local topography was recorded, providing additional information on the location of the scratches and pinholes. The catalytic results were highly reproducible due to the constant-distance feedback loop rendering scanning mass spectrometry a promising tool for the quantitative quality control of CCMs.

  19. Two-phase (bio)catalytic reactions in a table-top centrifugal contact separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Zwol, Floris van; Schuur, Boelo; Heeres, Hero J.; Vries, Johannes G. de

    2008-01-01

    A new spin on catalysis: A table-top centrifugal contact separator allows for fast continuous two-phase reactions to be performed by intimately mixing two immiscible phases and then separating them. Such a device has been used to produce biodiesel from sunflower oil and MeOH/NaOMe. A lipase-catalyze

  20. A catalytically active membrane reactor for fast, exothemic, heterogeneously catalysed reactions

    NARCIS (Netherlands)

    Veldsink, J.W.; Damme, R.M.J. van; Versteeg, G.F.; Swaaij, W.P.M. van

    1992-01-01

    A membrane reactor with separated feed of reactants is demonstrated as a promising contactor type when dealing with heterogeneously catalysed, very fast and exothermic gas phase reactions. Due to the separation of reactants a good control of the system is obtained, because process variables can be v

  1. Catalytic Enantioselective Synthesis of Tetrahydocarbazoles and Exocyclic Pictet-Spengler-Type Reactions

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Ohm, Ragnhild Gaard; Olsen, Lasse Bohn;

    2016-01-01

    A synthetic strategy for the synthesis of chiral tetrahydrocarbazoles (THCAs) has been developed. The strategy relies on two types of 6-exo-trig cyclization of 3-substituted indole substrates. Enantioselective domino Friedel-Crafts-type reactions leading to THCAs can be catalyzed by chiral phosph...

  2. Catalytic and DRIFTS study of the WGS reaction on Pt-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Vignatti, Ch.; Avila, M.S.; Apesteguia, C.R.; Garetto, T.F. [Catalysis Science and Engineering Research Group (GICIC), Instituto de Investigaciones en Catalisis y Petroquimica - INCAPE - (UNL-CONICET), Santiago del Estero 2654, 3000 Santa Fe (Argentina)

    2010-07-15

    The water-gas shift (WGS) activity of Pt/SiO{sub 2}, Pt/CeO{sub 2} and Pt/TiO{sub 2} catalysts was studied by in-situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). Samples contained a similar amount of Pt, between 0.34 and 0.50%, and were characterized by employing a variety of physical and spectroscopic techniques. The catalyst activities were evaluated through both CO conversion versus temperature and CO conversion versus time tests. The DRIFTS spectra were obtained on stream during the WGS reaction at increasing temperatures, from 303 to 573 K. Reduced ceria was the only active support and promoted the WGS reaction on surface bridging OH groups that react with CO to form formate intermediates. Pt/SiO{sub 2} was more active than CeO{sub 2} and catalyzed the WGS reaction through a monofunctional redox mechanism on metallic Pt sites. The CO conversion turnover rate was more than one order of magnitude greater on Pt/CeO{sub 2} than on Pt/SiO{sub 2} showing that the reaction proceeds faster via a bifunctional metal-support mechanism. Platinum on Pt/CeO{sub 2} increased the concentration of OH groups by increasing the ceria reduction extent and also provided a faster pathway for the formation of formate intermediates in comparison to CeO{sub 2} support. Pt/TiO{sub 2} catalysts were clearly more active than Pt/CeO{sub 2}. The WGS reaction on Pt/TiO{sub 2} was catalyzed via a bifunctional metal-support mechanism, probably involving the activation of CO and water on the metal and the support, respectively. The role of platinum on Pt/TiO{sub 2} was critical for promoting the reduction of Ti{sup 4+} ions to Ti{sup 3+} which creates oxygen vacancies in the support to efficiently activate water. (author)

  3. Catalytic role of TiO(2) terminal oxygen atoms in liquid-phase photocatalytic reactions: oxidation of aromatic compounds in anhydrous acetonitrile.

    Science.gov (United States)

    Montoya, Juan F; Bahnemann, Detlef W; Peral, José; Salvador, Pedro

    2014-08-04

    On the basis of experiments carried out with controlled amounts of residual oxygen and water, or by using oxygen-isotope-labeled Ti(18) O2 as the photocatalyst, we demonstrate that (18) Os atoms behave as real catalytic species in the photo-oxidation of acetonitrile-dissolved aromatic compounds such as benzene, phenol, and benzaldehyde with TiO2 . The experimental evidence allows a terminal-oxygen indirect electron-transfer (TOIET) mechanism to be proposed, which is a new pathway that involves the trapping of free photogenerated valence-band holes at Os species and their incorporation into the reaction products, with simultaneous generation of oxygen vacancies at the TiO2 surface and their subsequent healing with oxygen atoms from either O2 or H2 O molecules that are dissolved in the liquid phase. According to the TOIET mechanism, the TiO2 surface is not considered to remain stable, but is continuously changing in the course of the photocatalytic reaction, challenging earlier interpretations of TiO2 photocatalytic phenomena.

  4. Immobilization and catalytic properties of lipase on chitosan for hydrolysis and esterification reactions

    OpenAIRE

    2003-01-01

    The objective of this study was to evaluate the immobilization of lipase on a chitosan support by physical adsorption, aiming at its application in hydrolytic and synthetic reactions. Two types of chitosan (flakes and porous) were used for immobilizing lipase from a microbial source (Candida rugosa) and animal cells (porcine pancreas). The best results for recovery of total activity after immobilization were obtained for microbial lipase and porous chitosan beads. This set was selected for fu...

  5. Immobilization and catalytic properties of lipase on chitosan for hydrolysis and esterification reactions

    Directory of Open Access Journals (Sweden)

    Pereira E.B.

    2003-01-01

    Full Text Available The objective of this study was to evaluate the immobilization of lipase on a chitosan support by physical adsorption, aiming at its application in hydrolytic and synthetic reactions. Two types of chitosan (flakes and porous were used for immobilizing lipase from a microbial source (Candida rugosa and animal cells (porcine pancreas. The best results for recovery of total activity after immobilization were obtained for microbial lipase and porous chitosan beads. This set was selected for further immobilization studies, including full characterization of the immobilized derivative in aqueous and organic media. In aqueous medium, the operational and thermal stabilities of this preparation were quantified. In organic medium, the direct synthesis of n-butyl butyrate in organic solvent was chosen as a model reaction. The influence of several parameters, such as temperature, initial butyric acid concentration and amount of enzyme in the reaction system, was analyzed. Production of n-butyl butyrate was optimized and an ester yield response equation was obtained, making it possible to predict ester yields from known values of the three main factors. Use of this immobilized preparation was extended to the direct esterification of a large range of carboxylic acids (from C2 to C12 with a variety of alcohols (from C2 to C10.

  6. Multiphasic Reaction Modeling for Polypropylene Production in a Pilot-Scale Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-06-01

    Full Text Available In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas–solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%–11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas

  7. Immobilized Pd nanoparticles on Tris-modified SiO2:Synthesis, characterization, and catalytic activity in Heck cross-coupling reactions

    Institute of Scientific and Technical Information of China (English)

    Abdol R.Hajipour; Ghobad Azizi

    2014-01-01

    The preparation of supported Pd nanoparticles on Tris (tris(hydroxymethyl)aminomethane)-modi-fied SiO2 gel and their catalytic application in Heck coupling are investigated. The catalyst was char-acterized using a combination of X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and scanning electron microscopy/energy-dispersive X-ray spec-troscopy. The supported Pd nanoparticles were found to be a highly active and reusable catalyst for the Heck reaction at a low Pd loading (0.02 mol%) because of stabilization by the Tris moieties. Several reaction parameters, including the type and amount of solvent, base, and temperature, were evaluated. The heterogeneity of the catalytic system was investigated using different approaches, and showed that slight Pd leaching into the reaction solution occurred under the reaction condi-tions. Despite this metal leaching, the catalyst can be reused seven times without significant loss of its activity.

  8. Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

    KAUST Repository

    Huang, Jianfeng

    2013-06-12

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. © 2013 American Chemical Society.

  9. A model of protocell based on the introduction of a semi-permeable membrane in a stochastic model of catalytic reaction networks

    Directory of Open Access Journals (Sweden)

    Marco Villani

    2013-09-01

    Full Text Available In this work we introduce some preliminary analyses on the role of a semi-permeable membrane in the dynamics of a stochastic model of catalytic reaction sets (CRSs of molecules. The results of the simulations performed on ensembles of randomly generated reaction schemes highlight remarkable differences between this very simple protocell description model and the classical case of the continuous stirred-tank reactor (CSTR. In particular, in the CSTR case, distinct simulations with the same reaction scheme reach the same dynamical equilibrium, whereas, in the protocell case, simulations with identical reaction schemes can reach very different dynamical states, despite starting from the same initial conditions.

  10. Copper(I) complexes with trispyrazolylmethane ligands: synthesis, characterization, and catalytic activity in cross-coupling reactions.

    Science.gov (United States)

    Haldón, Estela; Álvarez, Eleuterio; Nicasio, M Carmen; Pérez, Pedro J

    2012-08-01

    Three novel Cu(I) complexes bearing tris(pyrazolyl)methane ligands, Tpm(x), have been prepared from reactions of equimolar amounts of CuI and the ligands Tpm, (HC(pz)(3)), Tpm*, (HC(3,5-Me(2)-pz)(3)), and Tpm(Ms), (HC(3-Ms-pz)(3)). X-ray diffraction studies have shown that the Tpm and Tpm(Ms) derivatives exhibit a 2:1 Cu:ligand ratio, whereas the Tpm* complex is a mononuclear species in nature. The latter has been employed as a precatalyst in the arylation of amides and aromatic thiols with good activity. The synthesis of a Tpm*Cu(I)-phthalimidate, a feasible intermediate in this catalytic process, has also been performed. Low temperature (1)H NMR studies in CDCl(3) have indicated that this complex exists in solution as a mixture of two, neutral and ionic forms. Conductivity measurements have reinforced this proposal, the ionic form predominating in a very polar solvent such as DMSO. The reaction of Tpm*Cu(I)-phthalimidate with iodobenzene afforded the expected C-N coupling product in 76% yield accounting for its role as an intermediate in this transformation.

  11. Structural and catalytic properties of a novel vanadium containing solid core mesoporous silica shell catalysts for gas phase oxidation reaction

    Indian Academy of Sciences (India)

    N Venkatathri; Vijayamohanan K Pillai; A Rajini; M Nooka Raju; I A K Reddy

    2013-01-01

    A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with microporosity are formed by incorporation of octadecyltrichloro silane and triethylamine in the catalyst and it was found out from E-DAX and BET—surface area analysis. The material was found to be nanocrystalline. Vanadium is present as V4+ species in as-synthesized samples and convert to V5+ on calcination. Most of the vanadium is present in tetrahedral or square pyramidal environment. Incorporation of vanadium in silica framework was confirmed by 29Si MAS NMR analysis. Among the various vanadium containing solid core mesoporous silica shell catalysts, the Si/V =100 ratio exhibited maximum efficiency towards diphenyl methane to benzophenone gas phase reaction. The optimum condition required for maximum conversion and selectivity was found out from the catalytic studies.

  12. Catalytic degradation of methylene blue by Fenton like system:model to the environmental reaction

    Institute of Scientific and Technical Information of China (English)

    Sanjay R. Thakare

    2004-01-01

    To develop more efficient chemical methods for the demineralization of organic pollutants from waterbodies, which one was also mimic to the nature, a degradation of methylene blue by Fe( Ⅲ ) and H2O2 in theabsence of light instead of Fe( Ⅱ ) and H2O2 was studied. Results showed that use of Fe ( Ⅲ ) is more promisingthan Fe( Ⅱ ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount ofsalicylic acid is added which is a one of the priority pollutant.

  13. The Synthesis, Characterization and Catalytic Reaction Studies of Monodisperse Platinum Nanoparticles in Mesoporous Oxide Materials

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, Robert M. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    A catalyst design program was implemented in which Pt nanoparticles, either of monodisperse size and/or shape were synthesized, characterized and studied in a number of hydrocarbon conversion reactions. The novel preparation of these materials enables exquisite control over their physical and chemical properties that could be controlled (and therefore rationally tuned) during synthesis. The ability to synthesize rather than prepare catalysts followed by thorough characterization enable accurate structure-function relationships to be elucidated. This thesis emphasizes all three aspects of catalyst design: synthesis, characterization and reactivity studies. The precise control of metal nanoparticle size, surface structure and composition may enable the development of highly active and selective heterogeneous catalysts.

  14. A Ternary Catalytic System for the Room Temperature Suzuki-Miyaura Reaction in Water

    Directory of Open Access Journals (Sweden)

    Aires da Conceição Silva

    2013-01-01

    Full Text Available The formation of Pd(0 in the absence of any classical reducing agent in a medium containing Mg2+/Al3+ layered double hydroxide (LDH and N,N-dimethylformamide was evidenced. XRD analysis showed the presence of crystalline phases of palladium in the Pd/LDH composite. Suzuki-Miyaura reactions in aqueous medium were carried out at room temperature, and good yields were obtained with bromoarenes and iodoarenes using the ternary system LDH-Pd-CD (cyclodextrin as catalyst.

  15. Fuel-rich, catalytic reaction experimental results. [fuel development for high-speed civil transport aircraft

    Science.gov (United States)

    Rollbuhler, Jim

    1991-01-01

    Future aeropropulsion gas turbine combustion requirements call for operating at very high inlet temperatures, pressures, and large temperature rises. At the same time, the combustion process is to have minimum pollution effects on the environment. Aircraft gas turbine engines utilize liquid hydrocarbon fuels which are difficult to uniformly atomize and mix with combustion air. An approach for minimizing fuel related problems is to transform the liquid fuel into gaseous form prior to the completion of the combustion process. Experimentally obtained results are presented for vaporizing and partially oxidizing a liquid hydrocarbon fuel into burnable gaseous components. The presented experimental data show that 1200 to 1300 K reaction product gas, rich in hydrogen, carbon monoxide, and light-end hydrocarbons, is formed when flowing 0.3 to 0.6 fuel to air mixes through a catalyst reactor. The reaction temperatures are kept low enough that nitrogen oxides and carbon particles (soot) do not form. Results are reported for tests using different catalyst types and configurations, mass flowrates, input temperatures, and fuel to air ratios.

  16. Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.

    Science.gov (United States)

    Denmark, Scott E; Heemstra, John R

    2007-07-20

    The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.

  17. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xin, E-mail: chenxin830107@pku.edu.cn; Chen, Shuangjing; Wang, Jinyu

    2016-08-30

    Highlights: • The screened M-G structures are very thermodynamically stable, and the stability is even higher than that of the corresponding bulk metal surfaces. • The binding energies of ORR intermediates suggest that they are not linear dependence, which are different form the cases found on some metal-based catalysts. • The Au-, Co-, and Ag-G structures could be used as the ORR catalysts. - Abstract: Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  18. High Intrinsic Catalytic Activity of Two-Dimensional Boron Monolayers for Hydrogen Evolution Reaction

    CERN Document Server

    Shi, Li; Ouyang, Yixin; Wang, Jinlan

    2016-01-01

    Two-dimensional (2D) boron monolayers have been successfully synthesized on silver substrate very recently. Their potential application is thus of great significance. In this work, we explore the possibility of boron monolayers (BMs) as electrocatalysts for hydrogen evolution reaction (HER) by first-principle method. Our calculations show that the BMs are active catalysts for HER with nearly zero free energy of hydrogen adsorption, metallic conductivity and plenty of active sites in the basal plane. The effect of the substrate on the HER activity is further assessed. It is found that the substrate has a positive effect on the HER performance caused by the competitive effect of mismatch strain and charge transfer. The indepth understanding of the structure dependent HER activity is also provided.

  19. Copper(I Complexes of Mesoionic Carbene: Structural Characterization and Catalytic Hydrosilylation Reactions

    Directory of Open Access Journals (Sweden)

    Stephan Hohloch

    2015-04-01

    Full Text Available Two series of different Cu(I-complexes of “click” derived mesoionic carbenes are reported. Halide complexes of the type (MICCuI (with MIC = 1,4-(2,6-diisopropyl-phenyl-3-methyl-1,2,3-triazol-5-ylidene (for 1b, 1-benzyl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene (for 1c and cationic complexes of the general formula [Cu(MIC2]X (with MIC =1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene, X = CuI2− (for 2á, 1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene, X = BF4− (for 2a, 1,4-(2,6-diisopropylphenyl-3-methyl-1,2,3-triazol-5-ylidene, X = BF4− (for 2b, 1-benzyl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene, X = BF4− (for 2c have been prepared from CuI or [Cu(CH3CN4](BF4 and the corresponding ligands, respectively. All complexes were characterized by elemental analysis and standard spectroscopic methods. Complexes 2á and 1b were studied by single-crystal X-ray diffraction analysis. Structural analysis revealed 2á to adopt a cationic form as [Cu(MIC2](CuI2 and comparison of the NMR spectra of 2á and 2a confirmed this conformation in solution. In contrast, after crystallization complex 1b was found to adopt the desired neutral form. All complexes were tested for the reduction of cyclohexanone under hydrosilylation condition at elevated temperatures. These complexes were found to be efficient catalysts for this reaction. 2c was also found to catalyze this reaction at room temperature. Mechanistic studies have been carried out as well.

  20. Memorable Experiences with Sad Music-Reasons, Reactions and Mechanisms of Three Types of Experiences.

    Directory of Open Access Journals (Sweden)

    Tuomas Eerola

    Full Text Available Reactions to memorable experiences of sad music were studied by means of a survey administered to a convenience (N = 1577, representative (N = 445, and quota sample (N = 414. The survey explored the reasons, mechanisms, and emotions of such experiences. Memorable experiences linked with sad music typically occurred in relation to extremely familiar music, caused intense and pleasurable experiences, which were accompanied by physiological reactions and positive mood changes in about a third of the participants. A consistent structure of reasons and emotions for these experiences was identified through exploratory and confirmatory factor analyses across the samples. Three types of sadness experiences were established, one that was genuinely negative (Grief-Stricken Sorrow and two that were positive (Comforting Sorrow and Sweet Sorrow. Each type of emotion exhibited certain individual differences and had distinct profiles in terms of the underlying reasons, mechanisms, and elicited reactions. The prevalence of these broad types of emotional experiences suggested that positive experiences are the most frequent, but negative experiences were not uncommon in any of the samples. The findings have implications for measuring emotions induced by music and fiction in general, and call attention to the non-pleasurable aspects of these experiences.

  1. Memorable Experiences with Sad Music-Reasons, Reactions and Mechanisms of Three Types of Experiences.

    Science.gov (United States)

    Eerola, Tuomas; Peltola, Henna-Riikka

    2016-01-01

    Reactions to memorable experiences of sad music were studied by means of a survey administered to a convenience (N = 1577), representative (N = 445), and quota sample (N = 414). The survey explored the reasons, mechanisms, and emotions of such experiences. Memorable experiences linked with sad music typically occurred in relation to extremely familiar music, caused intense and pleasurable experiences, which were accompanied by physiological reactions and positive mood changes in about a third of the participants. A consistent structure of reasons and emotions for these experiences was identified through exploratory and confirmatory factor analyses across the samples. Three types of sadness experiences were established, one that was genuinely negative (Grief-Stricken Sorrow) and two that were positive (Comforting Sorrow and Sweet Sorrow). Each type of emotion exhibited certain individual differences and had distinct profiles in terms of the underlying reasons, mechanisms, and elicited reactions. The prevalence of these broad types of emotional experiences suggested that positive experiences are the most frequent, but negative experiences were not uncommon in any of the samples. The findings have implications for measuring emotions induced by music and fiction in general, and call attention to the non-pleasurable aspects of these experiences.

  2. Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols.

    Science.gov (United States)

    Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K

    2010-09-07

    The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

  3. The importance of hinge sequence for loop function and catalytic activity in the reaction catalyzed by triosephosphate isomerase.

    Science.gov (United States)

    Xiang, J; Sun, J; Sampson, N S

    2001-04-01

    We have determined the sequence requirements for the N-terminal protein hinge of the active-site lid of triosephosphate isomerase. The codons for the hinge (PVW) were replaced with a genetic library of all possible 8000 amino acid combinations. The most active of these 8000 mutants were selected using in vivo complementation of a triosephosphate isomerase-deficient strain of Escherichia coli, DF502. Approximately 0.3 % of the mutants complement DF502 with an activity that is between 10 and 70 % of wild-type activity. They all contain Pro at the first position. Furthermore, the sequences of these hinge mutants reveal that hydrophobic packing is very important for efficient formation of the enediol intermediate. However, the reduced catalytic activities observed are not due to increased rates of loop opening. To explore the relationship between the N-terminal and C-terminal hinges, three semi-active mutants from the N-terminal hinge selection experiment (PLH, PHS and PTF), and six active C-terminal hinge mutants from previous work (NSS, LWA, YSL, KTK, NPN, KVA) were combined to form 18 "double-hinge" mutants. The activities of these mutants suggest that the N-terminal and C-terminal hinge structures affect one another. It appears that specific side-chain interactions are important for forming a catalytically active enzyme, but not for preventing release of the unstable enediol intermediate from the active site of the enzyme. The independence of intermediate release on amino acid sequence is consistent with the absence of a "universal" hinge sequence in structurally related enzymes.

  4. Evolution of a spallation reaction: experiment and Monte Carlo simulation

    CERN Document Server

    Enke, M; Hilscher, D; Jahnke, U; Schapiro, O; Letourneau, A; Galin, J; Goldenbaum, F; Lott, B; Peghaire, A; Filges, D; Neef, R D; Nünnighoff, K; Paul, N; Schaal, H; Sterzenbach, G; Tietze, A; Pienkowski, L

    1999-01-01

    Reaction cross sections and production cross sections for neutrons, hydrogen, and helium have been measured for 1.2, 1.8 GeV p+Fe, Ni, Ag, Ta, W, Au, Pb and U and are compared with different intra-nuclear-cascade- combined with evaporation-models. Agreement for neutrons and considerable differences for light charged particles are observed between experiment and calculation as well as between different models. The discrepancies are associated with specific deficiencies in the models. The exclusive data measured with two 4 pi-detectors for neutron and charged particle detection allowed furthermore a systematic comparison of observables characteristic of different stages of the temporal evolution of a spallation reaction: inelastic collision probability, excitation energy distribution, pre-equilibrium emission, and inclusive production cross sections.

  5. A dual arylboronic acid--aminothiourea catalytic system for the asymmetric intramolecular hetero-Michael reaction of α,β-unsaturated carboxylic acids.

    Science.gov (United States)

    Azuma, Takumi; Murata, Akihiro; Kobayashi, Yusuke; Inokuma, Tsubasa; Takemoto, Yoshiji

    2014-08-15

    A bifunctional aminoboronic acid has been used to facilitate for the first time the intramolecular aza- and oxa-Michael reactions of α,β-unsaturated carboxylic acids. The combination of an arylboronic acid with a chiral aminothiourea allowed for these reactions to proceed successfully in an enantioselective manner to afford the desired heterocycles in high yields and ee's (up to 96% ee). The overall utility of this dual catalytic system was demonstrated by a one-pot enantioselective synthesis of (+)-erythrococcamide B, which proceeded via sequential Michael and amidation reactions.

  6. Synthesis, characterization, crystal structure determination and catalytic activity in epoxidation reaction of two new oxidovanadium(IV) Schiff base complexes

    Science.gov (United States)

    Tahmasebi, Vida; Grivani, Gholamhossein; Bruno, Giuseppe

    2016-11-01

    The five coordinated vanadium(IV) Schiff base complexes of VOL1 (1) and VOL2 (2), HL1 = 2-{(E)-[2-bromoethyl)imino]methyl}-2- naphthol, HL2 = 2-{(E)-[2-chloroethyl)imino]methyl}-2- naphthol, have been synthesized and they were characterized by using single-crystal X-ray crystallography, elemental analysis (CHN) and FT-IR spectroscopy. Crystal structure determination of these complexes shows that the Schiff base ligands (L1 and L2) act as bidentate ligands with two phenolato oxygen atoms and two imine nitrogen atoms in the trans geometry. The coordination geometry around the vanadium(IV) is distorted square pyramidal in which vanadium(IV) is coordinated by two nitrogen and two oxygen atoms of two independent ligands in the basal plane and by one oxygen atom in the apical position. The catalytic activity of the Schiff base complexes of 1 and 2 in the epoxidation of alkenes were investigated using different reaction parameters such as solvent effect, oxidant, alkene/oxidant ratio and the catalyst amount. The results showed that in the presence of TBHP as oxidant in 1: 4 and 1:3 ratio of the cyclooctene/oxidant ratio, high epoxide yield was obtained for 1 (76%) and 2 (80%) with TON(= mole of substrate/mole of catalyst) of 27 and 28.5, respectively, in epoxidation of cyclooctene.

  7. Kinetic of Catalytic CO{sub 2} Gasification for Cyprus Coal by Gas-Solid Reaction Model

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Soon Choel; Lee, Do Kyun; Kim, Sang Kyum; Rhee, Young Woo [Chungnam National University, Daejeon (Korea, Republic of); Lee, Si Hyun [Korea Institute of Energy Research, Daejeon (Korea, Republic of)

    2015-10-15

    In general, the coal gasification has to be operated under high temperature (1300~1400 .deg. C) and pressure (30~40 bar). However, to keep this conditions, it needs unnecessary and excessive energy. In this work, to reduce the temperature of process, alkali catalysts such as K{sub 2}CO{sub 3} and Na{sub 2}CO{sub 3} were added into Cyprus coal. We investigated the kinetic of Cyprus char-CO{sub 2} gasification. To determine the gasification conditions, the coal (with and without catalysts) gasified with fixed variables (catalyst loading, catalytic effects of Na{sub 2}CO{sub 3} and K{sub 2}CO{sub 3}, temperatures) by using TGA. When catalysts are added by physical mixing method into Cyprus coal the reaction rate of coal added 7 wt% Na{sub 2}CO{sub 3} is faster than raw coal for Cyprus char-CO{sub 2} gasification. The activation energy of coal added 7 wt% Na{sub 2}CO{sub 3} was calculated as 63 kJ/mol which was lower than raw char. It indicates that Na{sub 2}CO{sub 3} can improve the reactivity of char-CO{sub 2} gasification.

  8. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Directory of Open Access Journals (Sweden)

    Ruth Gomes

    2014-11-01

    Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  9. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction

    Science.gov (United States)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian; Shen, Yuhua

    2017-01-01

    Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) -doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m2/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and addresses the disposal issue of waste biomass simultaneously for environment clean.

  10. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  11. Quantum chemical study on the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process

    Institute of Scientific and Technical Information of China (English)

    Zheng-cheng WEN; Zhi-hua WANG; Jun-hu ZHOU; Ke-fa CEN

    2009-01-01

    Quantum chemical simulation was used to investigate the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process. Both NO-char and NO-NaYK reactions were considered as three-step processes in this calculation. Based on geometry optimizations made using the UB3LYP/6-31 G(d) method, the activation energies of NO-char and NO-Na/K reactions were calculated using the QC1SD(T)/6-3 i 1G(d, p) method; Results showed that the activation energy of the NO-Na/K reaction (107.9/82.0 kJ/mol) was much lower than that of the NO-char reaction (245.1 kJ/mol). The reactions of NaO/KO and Na2P/K2O reduced by char were also studied, and their thermodynamics were calculated using the UB3LYP/6-31G(d) method; Results showed that both Na and K can be refreshed easily and rapidly by char at high temperature during the coal rebuming process. Based on the calculations and analyses, the catalytic mechanism of Na/K on NO-char het-erogeneous reactions during the coal reburning process was clarified.

  12. Synthesis of magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts and their catalytic performance for Knoevenagel reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qingyuan; Jiang, Sai; Ji, Shengfu, E-mail: jisf@mail.buct.edu.cn; Ammar, Muhammad; Zhang, Qingmin; Yan, Junlei

    2015-03-15

    Novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 through in situ method. The structures of the catalysts were characterized by TEM, SEM, XRD, FT-IR, VSM, N{sub 2} adsorption/desorption and CO{sub 2}-TPD technology. The catalytic activity and recovery properties of the catalysts for the Knoevenagel reaction of p-chlorobenzaldehyde with malononitrile were evaluated. The results showed that the magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts had the larger surface areas, the suitable superparamagnetism, and good catalytic activity for Knoevenagel reaction. The conversion of p-chlorobenzaldehyde can reach ~98% and the selectivity of the production can reach ~99% over35.8%ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} (MZC-5) catalyst under the reaction condition of 25 °C and 4 h. The magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts also had good substrates adaptation. After reaction, the catalyst can be easily separated from the reaction mixture by an external magnet. The recovery catalyst can be reused five times and the conversion of p-chlorobenzaldehyde can be kept over 90%. - Graphical abstract: Novel magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 and the as-synthesized catalysts exhibited a good catalytic activity for the Knoevenagel reaction. - Highlights: • A series of novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized. • The catalysts had the larger surface areas and the suitable superparamagnetism. • The catalysts exhibited good catalytic activity for the Knoevenagel reaction. • After reaction the catalyst can be easily separated by an external magnet. • The recovery catalyst can be reused five times and can keep its catalytic activity.

  13. Catalytic soot oxidation in microscale experiments: Simulation of interactions between co-deposited graphitic nanoparticle agglomerates and platinum nanoparticles

    Science.gov (United States)

    Seipenbusch, Martin; Friedlander, Sheldon K.

    2004-12-01

    Continuously regenerating catalytic soot traps are under development to reduce particulate emissions from diesel exhaust. A good understanding of the processes that take place during soot oxidation is needed to optimize diesel soot trap performance. To gain insight into these processes from the perspective of nanoparticle technology, the effects of catalyst particle size and the interparticle distance between soot and catalyst particles were measured. A model catalyst was prepared by depositing Pt nanoparticles on a SiO/SiO2-coated transmission electron microscope (TEM) grid. A soot surrogate composed of graphitic nanoparticle agglomerates generated by laser ablation was deposited on the same surface. This system simulates, morphologically, catalytic soot traps used in practice. The reaction was carried out in a tubular flow reactor in which the gas phase simulated diesel exhaust gas, composed of a mixture of 10% O2 and 1000 ppm NO with the remainder N2. The progress of the carbon nanoparticle oxidation was monitored off-line by analysis of electron microscopy images of the agglomerates before and after reaction. This experimental method permitted the correlation of reaction rate with particle sizes and separation distances as well as catalyst surface area in the direct environs of the soot particles. The experimental results revealed no effect of Pt catalyst particle size in the range 7-31 nm on the rate of reaction. Also observed were a decrease in the rate of reaction with increasing distance between carbon agglomerates and catalyst particles and a linear dependence of the reaction rate on the fractional catalyst surface area coverage.

  14. Study on hexaaluminate MnLaAl11O19-δcatalyst for catalytic combustive reaction of dimethyl ether as a new fuel

    Institute of Scientific and Technical Information of China (English)

    YU Qian; YU Lin; HUANG Yingmin; SUN Ming; CHEN Xiaokang; WANG Yuanna; ZHANG Qini

    2006-01-01

    Study on catalytic combustive reaction of dimethyl ether as a new fuel was presented. Hexaaluminate catalysts were used to reduce ignition temperature so that dimethyl ether completely combusted at low temperature. Hexaaluminate catalysts MnLaAl11O19-δ were prepared by reverse microemulsion method. Crystalline phase and structure of the catalyst were analysed by means of TG-DTA, XRD and BET. The results show that the hexaalunminate is of magnetoplumbite structure when La is taken as mirror plane cation. Hexaalunminate phase is formed slowly via 1050 ℃ calcined for 4 h and it can keep hexaaluminate phase and high surface area of 48 m2·g-1 even calcined at 1200 ℃ for 2h. Catalytic activity of MnLaAl11O19-δ was tested in combustion reaction of dimethyl ether. It shows that hexaaluminate is of high activity with T 10% at 170 ℃ and almost 100% conversion at 370 ℃.

  15. Characterization of the efficiency of the gas-solid contact in circulating bed at by the use of a test reaction: the cumene catalytic cracking

    Energy Technology Data Exchange (ETDEWEB)

    Bayle, J.; Gauthier, T.; Pontier, R. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France); Briens, C.L.; Bergougnou, M. [University of Western Ontario, London, ON (Canada). Dept. of Physics

    1995-12-31

    The gas-solid down with the stream reactor, the ``downer``, presents a main interest for the high-speed reactions because it is well adapted to hard conditions uses: very short residence times, high temperatures and feeds of catalyst. This reactor type already presents a certain advantage to estimate the charges or new catalysts potential. But, it particularly constitutes an interesting option for some processes as petroleum cuts catalytic cracking. In order to intensify the contact between the catalyst and the reagents, the temperature increase of the reagents has to be almost instantaneous and the initial contact between the gas and the solid particles particularly effective. So as to validate these two hypothesis, the test reaction of the cumene catalytic cracking is carried out in the pilot unit ``downer`` of the Western Ontario University. (O.M.). 11 refs., 3 figs.

  16. Effect of Mg/Al atom ratio of support on catalytic performance of Co-Mo/MgO-Al2O3 catalyst for water gas shift reaction

    Institute of Scientific and Technical Information of China (English)

    Yixin Lian; Huifang Wang; Quanxing Zheng; Weiping Fang; Yiquan Yang

    2009-01-01

    Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO(x)-Al2O3 catalyst and the contents of Mo5+, Mo4+, S2- and S2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.

  17. The effect of preparation factors on the structural and catalytic properties of mesoporous nanocrystalline iron-based catalysts for high temperature water gas shift reaction

    Energy Technology Data Exchange (ETDEWEB)

    Meshkani, Fereshteh; Rezaei, Mehran [University of Kashan, Kashan (Iran, Islamic Republic of)

    2015-07-15

    A systematic study was done on the effect of preparation factors on the structural and catalytic properties of mesoporous nanocrystalline iron-based catalysts in high temperature water gas shift reaction. The catalysts were prepared by coprecipitation method, and the effect of the main preparation factors (pH, refluxing temperature, refluxing time, concentration of the precursors solution) was studied. The catalysts were characterized by powder X-ray diffraction (XRD), N{sub 2} adsorption (BET), Temperature programmed reduction (TPR), transmission and scanning electron microscopies (TEM, SEM) techniques. The results revealed that the preparation factors affected the textural and catalytic properties of the Fe-Cr-Cu catalyst. The results showed that the prepared catalyst with the highest activity showed higher specific surface area compared to commercial catalyst and consequently exhibited higher activity in high temperature water gas shift reaction. The TEM analysis showed a nanostructure for this sample with crystallite size less than 20 nm.

  18. General base catalysis in the urate oxidase reaction: evidence for a novel Thr-Lys catalytic diad.

    Science.gov (United States)

    Imhoff, Rebecca D; Power, Nicholas P; Borrok, M Jack; Tipton, Peter A

    2003-04-15

    Urate oxidase catalyzes the oxidation of urate without the involvement of any cofactors. The gene encoding urate oxidase from Bacillus subtilis has been cloned and expressed, and the enzyme was purified and characterized. Formation of the urate dianion is believed to be a key step in the oxidative reaction. Rapid-mixing chemical quench studies provide evidence that the dianion is indeed an intermediate; at 15 degrees C the dianion forms within the mixing time of the rapid-quench instrument, and it disappears with a rate constant of 8 s(-)(1). Steady-state kinetic studies indicate that an ionizable group on the enzyme with a pK of 6.4 must be unprotonated for catalysis, and it is presumed that the role of this group is to abstract a proton from the substrate. Surprisingly, examination of the active site provided by the previously reported crystal structure does not reveal any obvious candidates to act as the general base. However, Thr 69 is hydrogen-bonded to the ligand at the active site, and Lys 9, which does not contact the ligand, is hydrogen-bonded to Thr 69. The T69A mutant enzyme has a V(max) that is 3% of wild type, and the K9M mutant enzyme has a V(max) that is 0.4% of wild type. The ionization at pH 6.4 that is observed with wild-type enzyme is absent in both of these mutants. It is proposed that these residues form a catalytic diad in which K9 deprotonates T69 to allow it to abstract the proton from the N9 position of the substrate to generate the dianion.

  19. Design and Synthesis of Chiral Zn2+ Complexes Mimicking Natural Aldolases for Catalytic C–C Bond Forming Reactions in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Susumu Itoh

    2014-01-01

    Full Text Available Extending carbon frameworks via a series of C–C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C–C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C–C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented.

  20. First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface

    Science.gov (United States)

    Xue, Wenhua

    Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL

  1. Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions

    Science.gov (United States)

    Baran, Talat; Menteş, Ayfer

    2017-04-01

    In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.

  2. Studies of Electrochemical Catalytic Reduction Reactions of Tetraphenylporphinatocobalt/1,2-Dibromoethane and 1,2-Dichloroethane Systems in Nonaqueous Media

    Institute of Scientific and Technical Information of China (English)

    林祥钦; 刘殿骏; 汪尔康

    1994-01-01

    Electrochemical catalytic reactions of tetraphenylporphmatocobalt were studied in DMF and EtCl2 solutions in the presence of 1,2 dibroraoethane and 1,2-dichloroethane utilizing cyclic voltamme-try, thin-layer electrochemistry, in situ UV-visible spectroelectrochemistry and computer digital simulation methods. Homogeneous rate constants for reactions of electrogenerated Co(Ⅰ)TPP species with 1,2-dibro-moethane and 1,2-dichloroethane were determined as 1. 2×103 and 5 mol-1 · dm3 × s-1, respectively. Neither alkylation nor degradation of CoTPP was observed.

  3. Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

    KAUST Repository

    Yang, Wenguo

    2012-02-08

    Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E configuration in good to excellent yields. The Michael product could also be easily prepared by tuning the β-C-substituent group of the α-methylene ester under the same reaction conditions. Calculated relative energies of various transition states by DFT methods strongly support the observed chemoselectivity and diastereoselectivity. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  4. Studies on the Catalytic Activities of Cyclopalladated Ferrocenylimine in the Suzuki Reaction of Pyridylboronic Acid Derivative with Arylhalides

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jin-Li; YANG Liang-Ru; ZHAO Liang; GUI Xiu-Ling; GONG Jun-Fang; WU Yang-Jie

    2003-01-01

    @@ Heterobiaryls have important biologicalproperties. [1] The use of catalytic cross-coupling methodologies forpreparing aryl functionalized heterocycles with pharmaceutical, agrochemical, materials, and supermolecular appli-cations is a burgeoning field of study. [2

  5. Kinetic method for the determination of traces of thyroxine by its catalytic effect on the Mn(III) metaphosphate-As(III) reaction.

    Science.gov (United States)

    Pastor, Ferenc T; Milovanović, Gordana A; Todorović, Marija

    2008-02-15

    A new, highly sensitive and simple kinetic method for the determination of thyroxine was proposed. The method was based on the catalytic effect of thyroxine on the oxidation of As(III) by Mn(III) metaphosphate. The kinetics of the reaction was studied in the presence of orthophosphoric acid. The reaction rate was followed spectrophotometrically at 516 nm. It was established that orthophosphoric acid increased the reaction rate and that the extent of the non-catalytic reaction was extremely small. A kinetic equation was postulated and the apparent rate constant was calculated. The dependence of the reaction rate on temperature was investigated and the energy of activation and other kinetic parameters were determined. Thyroxine was determined under the optimal experimental conditions in the range 7.0 x 10(-9) to 3.0 x 10(-8) mol L(-1) with a relative standard deviation up to 6.7% and a detection limit of 2.7 x 10(-9) molL(-1). In the presence of 0.08 mol L(-1) chloride, the detection limit decreased to 6.6 x 10(-10) mol L(-1). The proposed method was applied for the determination of thyroxine in tablets. The accuracy of the method was evaluated by comparison with the HPLC method.

  6. Catalytic effects of mutations of distant protein residues in human DNA polymerase β: theory and experiment.

    Science.gov (United States)

    Klvaňa, Martin; Murphy, Drew L; Jeřábek, Petr; Goodman, Myron F; Warshel, Arieh; Sweasy, Joann B; Florián, Jan

    2012-11-06

    We carried out free-energy calculations and transient kinetic experiments for the insertion of the right (dC) and wrong (dA) nucleotides by wild-type (WT) and six mutant variants of human DNA polymerase β (Pol β). Since the mutated residues in the point mutants, I174S, I260Q, M282L, H285D, E288K, and K289M, were not located in the Pol β catalytic site, we assumed that the WT and its point mutants share the same dianionic phosphorane transition-state structure of the triphosphate moiety of deoxyribonucleotide 5'-triphosphate (dNTP) substrate. On the basis of this assumption, we have formulated a thermodynamic cycle for calculating relative dNTP insertion efficiencies, Ω = (k(pol)/K(D))(mut)/(k(pol)/K(D))(WT) using free-energy perturbation (FEP) and linear interaction energy (LIE) methods. Kinetic studies on five of the mutants have been published previously using different experimental conditions, e.g., primer-template sequences. We have performed a presteady kinetic analysis for the six mutants for comparison with wild-type Pol β using the same conditions, including the same primer/template DNA sequence proximal to the dNTP insertion site used for X-ray crystallographic studies. This consistent set of kinetic and structural data allowed us to eliminate the DNA sequence from the list of factors that can adversely affect calculated Ω values. The calculations using the FEP free energies scaled by 0.5 yielded 0.9 and 1.1 standard deviations from the experimental log Ω values for the insertion of the right and wrong dNTP, respectively. We examined a hybrid FEP/LIE method in which the FEP van der Waals term for the interaction of the mutated amino acid residue with its surrounding environment was replaced by the corresponding van der Waals term calculated using the LIE method, resulting in improved 0.4 and 1.0 standard deviations from the experimental log Ω values. These scaled FEP and FEP/LIE methods were also used to predict log Ω for R283A and R283L Pol

  7. Pressure Regulations on the Surface Properties of CeO2 Nanorods and Their Catalytic Activity for CO Oxidation and Nitrile Hydrolysis Reactions.

    Science.gov (United States)

    Li, Jing; Zhang, Zhiyun; Gao, Wei; Zhang, Sai; Ma, Yuanyuan; Qu, Yongquan

    2016-09-07

    Surface properties of nanoscale CeO2 catalysts in terms of the surface Ce(3+) fraction and concentration of oxygen vacancy can affect their catalytic performance significantly. Continual adjustment on surface properties of CeO2 with the morphological preservation has not been realized by synthetic methods. The revisited studies show that surface properties of CeO2 nanorods can be effectively regulated by synthetic pressures while the rodlike morphology is well-preserved. Such phenomena are ascribed to the contact possibility between Ce(3+) species and dissolved O2, which is balanced by the rapidly increased and gradually saturated dissolution/recrystallization rate of Ce(OH)3 and linearly increased concentration of dissolved O2 with the increase of total air pressure or partial pressure of O2. Surface-property-dependent catalytic activity of CeO2 nanorods synthesized under various pressures was also demonstrated in two benchmark reactions-catalytic oxidation of CO and hydrolysis of nitrile. Such a finding of the pressure regulation on the reducible metal oxides provides an effective approach to rationally design novel catalysts for specific reactions, where ceria are supports, promoters, or actives.

  8. Effect of calcination temperature on structural properties and catalytic activity in oxidation reactions of LaNiO3 perovskite prepared by Pechini method

    Institute of Scientific and Technical Information of China (English)

    K.Rida; M.A.Pe(n)a; E.Sastre; A.Martínez-Arias

    2012-01-01

    The study presented the preparation of the perovskite oxide LaNiO3 by the complex citrate method,paying particular attention to evolution of its formation from the amorphous precursor with varied calcination temperatures.The products obtained after heat treatment under air between 200 and 800 ℃ were characterized by X-ray diffraction (XRD),thermogravimetric and differential thermal analysis (TG-DTA),Fourier transform infrared spectroscopy (FTIR),SBET measurements and X-ray photoelectron spectroscopy (XPS).The results showed the formation of a single phase with perovskite structure from ca.550 ℃.Tests on the two catalytic oxidation reactions of C3H6 and CO over the system calcined between mentioned temperatures were examined on the basis of characterization results and showed that optimum catalytic properties for such reactions were achieved for the perovskite calcined at 600 ℃.In turn,correlations between redox and catalytic properties were established on the basis of thermogravimetric temperature programmed reduction (TPR) analysis.

  9. Liquid Phase Hydrogenation of Benzalacetophenone:Effect of Solvent,Catalyst Support,Catalytic Metal and Reaction Conditions%Liquid Phase Hydrogenation of Benzalacetophenone: Effect of Solvent, Catalyst Support, Catalytic Metal and Reaction Conditions

    Institute of Scientific and Technical Information of China (English)

    Achim STOLLE; Christine SCHMOGER; Bernd ONDRUSCHKA; Werner BONRATH; Thomas F. KELLER; Klaus D. JANDT

    2011-01-01

    Innovative catalysts based on a “porous glass” support material were developed and investigated for the reduction of benzalacetophenone.The easy preparation conditions and possibility to use different metals (e.g.Pd,Pt,Rh) for impregnation gave a broad variety of these catalysts.Hydrogenation experiments with these supported catalysts were carried out under different hydrogen pressures and temperatures.Porous glass catalysts with Pd as the active component gave chemoselective hydrogenation of benzalacetophenone,while Pt- and Rh-catalysts tended to further reduce the carbonyl group,especially at elevated hydrogen pressures and temperatures.Kinetic analysis of the reactions revealed these had zero order kinetics,which was independent of the type of porous glass support and solvent used.

  10. A combined experimental and computational study of the catalytic dehydration of glycerol on microporous zeolites: an investigation of the reaction mechanism and acrolein selectivity.

    Science.gov (United States)

    Lin, Xufeng; Lv, Yanhong; Qu, Yuanyuan; Zhang, Guodong; Xi, Yanyan; Phillips, David L; Liu, Chenguang

    2013-12-14

    The catalytic activity and the acrolein selectivity for liquid phase glycerol dehydration on β zeolites (HNa-β-k) were found to be dependent on the reaction temperature as well as on the amount of acid sites on the zeolites. An increase in the reaction temperature favors the acrolein selectivity. The acrolein selectivity increases with the Na(+)/H(+) ratio and the glycerol conversion decreases with it so that a maximum acrolein yield is obtained when a certain amount of acidic sites are replaced by non-active Na(+) sites. The computational results indicate that 3-hydoxylpropanal (HPA) is an important intermediate that determines the final product selectivity. The relative rates of the different reaction pathways for HAP can be affected by the amount of water molecules involved in its homogeneous reaction. Based on the reaction mechanism proposed, it was hypothesized that smaller pores reduce activity but increase selectivity to acrolein, and results of the H-MFI zeolite were consistent with this hypothesis. Our work provides important insight into the overall landscape of the reaction mechanism and can be used to help design reaction systems that have good acrolein selectivity for the liquid phase glycerol dehydration reactions.

  11. A Monte Carlo Simulation of a Monomer Dimer CO-O2 Catalytic Reaction on the Surface and Subsurface of a Face-centered Cubic Lattice

    Institute of Scientific and Technical Information of China (English)

    K.Iqbal; A.Basit

    2011-01-01

    @@ The presence of oxygen in the subsurface in monomer-dimer reactions(CO-O2 and NO-CO)is observed experimentally.The effect of subsurface oxygen on a CO-O2 catalytic reaction on a face-centered cubic(FCC)lattice is studied using Monte Carlo simulation.The effect of adding subsurface neighbours on the phase diagram is also extensively explored.It is observed that the subsurface oxygen totally eliminates the typical second order phase transition.It is also shown that the introduction of the diffusion of O atoms and the subsurface of the FCC lattice shifts the single transition point towards the stoichiometric ratio.%The presence of oxygen in the subsurface in monomer-dimer reactions (CO-O2 and NO-CO) is observed experimentally. The effect of subsurface oxygen on a CO-O2 catalytic reaction on a face-centered cubic (FCC) lattice is studied using Monte Carlo simulation. The effect of adding subsurface neighbours on the phase diagram is also extensively explored. It is observed that the subsurface oxygen totally eliminates the typical second order phase transition. It is also shown that the introduction of the diffusion of O atoms and the subsurface of the FCC lattice shifts the single transition point towards the stoichiometric ratio.

  12. HYDROGEN TRANSFER IN CATALYTIC CRACKING

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Hydrogen transfer is an important secondary reaction of catalytic cracking reactions, which affects product yield distribution and product quality. It is an exothermic reaction with low activation energy around 43.3 kJ/mol. Catalyst properties and operation parameters in catalytic cracking greatly influence the hydrogen transfer reaction. Satisfactory results are expected through careful selection of proper catalysts and operation conditions.

  13. Effect of Ni+2-substituted Fe2TiO5 on the H2-reduction and CO2 Catalytic Decomposition Reactions at 500℃

    Institute of Scientific and Technical Information of China (English)

    M.H.Khedr

    2006-01-01

    CO2 is a major component of the greenhouse gases, which causes the global warming. To reduce CO2 gas,high activity nanosized Ni+2 substituted Fe2TiO5 samples were synthesized by conventional ceramic method.The effect of the composition of the synthesized ferrite on the H2-reduction and CO2-catalytic decomposition was investigated. Fe2TiO5 (iron titanate) phase that has a nanocrystallite size of ~80 nm is formed as a result of heating Fe2O3 and TiO2 while the addition of NiO leads to the formation of new phases (~80 nm)NiTiO3 and NiFe2O4, but the mixed solid of NiO and Fe2O3 results in the formation of NiFe2O4 only.Samples with Ni+2=0 shows the lowest reduction extent (20%); as the extent of Ni+2 increases, the extent of reduction increases. The increase in the reduction percent is attributed to the presence of NiTiO3 and NiFe2O4 phases, which are more reducible phases than Fe2TiO5. The CO2 decomposition reactions were monitored by thermogravimetric analysis (TGA) experiments. The oxidation of the H2-reduced Ni+2 substituted Fe2TiO5 at 500℃ was investigated. As Ni+2 increases, the rate of reoxidation increases. Samples with the highest reduction extents gave the highest reoxidation extent, which is attributed to the highly porous nature and deficiency in oxygen due to the presence of metallic Fe, Ni and/or FeNi alloy. X-ray diffraction (XRD) and transmission electron microscopy (TEM) of oxidized samples show also the presence of carbon in the sample containing Ni+2>0, which appears in the form of nanotubes (25 nm).

  14. Characterization of Ni and W co-loaded SBA-15 catalyst and its hydrogen production catalytic ability on ethanol steam reforming reaction

    Science.gov (United States)

    Kim, Dongjin; Kwak, Byeong Sub; Min, Bong-Ki; Kang, Misook

    2015-03-01

    This study evaluated the application of advanced bimetallic catalytic species of Ni and W to effectively produce hydrogen gases from ethanol steam reforming. The highest reactivity was achieved using the Ni0.95W0.05/SBA-15 catalyst. The maximum H2 production and ethanol conversion of 90% and 85%, respectively, were obtained for 0.4 g catalyst at 600 °C after 10 h with a EtOH:H2O ratio of 1:3 and a gas hourly space velocity of 6000 h-1. This highlights a synergy between the Ni and W loading on SBA-15 during ethanol steam reforming that occurs through the inhibition of Ni particle agglomeration and consequent decrease in catalytic deactivation. Additionally, the supplied W ingredients promoted CO2 selectivity, which was generated from the CO-water gas shift reaction.

  15. Zeolite-Y entrapped Ru(III and Fe(III complexes as heterogeneous catalysts for catalytic oxidation of cyclohexane reaction

    Directory of Open Access Journals (Sweden)

    Chetan K. Modi

    2017-02-01

    Full Text Available Catalysis is probably one of the greatest contributions of chemistry to both economic growth and environmental protection. Herein we report the catalytic behavior of zeolite-Y entrapped Ru(III and Fe(III complexes with general formulae [M(VTCH2·2H2O]+-Y and [M(VFCH2·2H2O]+-Y [where, VTCH = vanillin thiophene-2-carboxylic hydrazone and VFCH = vanillin furoic-2-carboxylic hydrazone] over the oxidation of cyclohexane forming cyclohexanone and cyclohexanol. The samples were corroborated by various physico-chemical techniques. These zeolite-Y based complexes are stable and recyclable under current reaction conditions. Amongst them, [Ru(VTCH2⋅2H2O]+-Y showed higher catalytic activity (41.1% with cyclohexanone (84.6% selectivity.

  16. Nonaqueous catalytic fluorometric trace determination of vanadium based on the pyronine B-hydrogen peroxide reaction and flow injection after cloud point extraction.

    Science.gov (United States)

    Paleologos, E K; Koupparis, M A; Karayannis, M I; Veltsistas, P G

    2001-09-15

    The catalytic effect of vanadium on the pyronine B-H2O2 system is examined. Enhancement of the catalytic reaction rate along with the efficiency and selectivity against vanadium is achieved in a formic acid environment in the presence of a nonionic surfactant (Triton X-114). Elimination of drastic interference caused by inorganic acids and aqueous matrix along with a 50-fold preconcentration of vanadium are facilitated through cloud point extraction of its neutral complex with 8-quinolinol in an acidic solution. Subsequent flow injection analysis (FIA) with fluorometric detection renders the proposed method ideal for selective and cost-effective determination of as little as 0.020 microng L(-1) vanadium in environmental, biological, and food substrates. The preconcentration step can be applied simultaneously to multiple samples, allowing for massive preparation prior to analysis, compensating, thus, for the time-consuming procedure.

  17. Catalytic distillation process

    Science.gov (United States)

    Smith, Jr., Lawrence A.

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  18. Catalytic distillation process

    Science.gov (United States)

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  19. The effect of microwave-assisted for photo-catalytic reaction in aqueous nano TiO2 particles dispersions.

    Science.gov (United States)

    Chae, Jeong-Seok; Chung, Minchul; Ahn, Ho-Geun; Jung, Sang-Chul

    2010-05-01

    In this study, the photo-catalytic degradation of methylene blue in TiO2 particles-dispersed aqueous solution was carried out by irradiating microwave and UV light simultaneously. The results of photocatalytic degradation of methylene blue showed that the decomposition rate increased with the microwave intensity, UV intensity, TiO2 particle dosages and the circulating fluid velocity. From the result of microwave-assisted photo-catalytic degradation of methylene blue, decomposition rate were shown gradually increased according to the increase of pH. The photo-catalytic degradation rate constant obtained under simultaneous irradiation of microwave and UV light case was about 1.5 times higher than irradiation of UV light only case. This result suggests that there is a synergy effect when the constituent techniques are applied together and that the additional irradiation of microwave can play a very important role in photo-catalysis of organic water pollutants.

  20. Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study.

    Science.gov (United States)

    Han, You; Sun, Mengxia; Li, Wei; Zhang, Jinli

    2015-03-28

    The catalytic mechanism of Ru-based catalysts in the acetylene hydrochlorination reaction has been investigated via the density functional theory (DFT) method. To study the effect of the chlorine coordination number on the catalytic mechanism, Ru3Cl9, Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 clusters were chosen as the catalytic models. Our results show that the energy barrier for acetylene hydrochlorination on Ru3Cl9 was as high as 1.51 eV at 458 K. When the chlorine coordination number decreased, the energy barriers on Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 were 1.29, 0.89, 1.01 and 1.42 eV, respectively. On Ru3Cl9, the H and Cl atoms of HCl were simultaneously added to C2H2 to form C2H3Cl, while the reaction was divided into two steps on Ru3Cl7, Ru3Cl3 and Ru3 clusters. The first step was the addition of H atom of HCl to C2H2 to form C2H3˙, and the second step was the addition of Cl atom to C2H3˙ to form C2H3Cl. The step involving the addition of Cl was the rate-controlling step during the whole reaction. On Ru5Cl7 cluster, there was an additional step before the steps involving the addition of H and Cl: the transfer of H atom from HCl to Ru atom. This step was the rate-controlling step during the reaction of acetylene hydrochlorination on Ru5Cl7 and its energy barrier was the lowest among all the above-mentioned catalytic models. Therefore, the Ru5Cl7 cluster played the most predominant role in acetylene hydrochlorination with the largest reaction rate constant kTST of 10(3).

  1. Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

    Science.gov (United States)

    Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

    2007-01-01

    A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

  2. 催化水煤气变换反应的计算模拟进展%Progress of theoretical simulation of catalytic water-gas-shift reaction

    Institute of Scientific and Technical Information of China (English)

    陈玉; 张福丽; 姚辉超; 刘植昌; 崔佳; 徐春明

    2012-01-01

    The progress of theoretical simulation of catalytic water-gas-shift(WGS) reaction is reviewed,by focusing on the reaction mechanism.As to traditional Cu-Zn-,Fe-Cr-,and Co-Mo-based heterogeneous catalysts,carboxyl and redox mechanisms dominate.Promoters and supports also affect the entire reaction process,and may take part in the reaction process directly.Improved or novel catalysts,such as gold or gold-loaded catalyst have also been explored theoretically,and there is also no end to apprehending respective catalytic reaction mechanism.For those homogeneous catalytic reactions like WGS catalyzed by carbonyls of iron group,the understanding of the reaction mechanism is getting deeper.Theoretical studies are expected to expand from those simple model systems to more complex and real WGS model systems.Theoretical studies will show their advantages,such as convenience and low cost,in comparison with experimental investigation,and also provide successful examples for the design of catalysts.%综述了对具有广泛工业应用的水煤气变换(WGS)反应进行理论模拟所取得的进展,重点讨论反应机理方面获得的成果。对于传统的铜锌、铁铬和钴钼等非均相催化剂而言,羧基机理和氧化还原机理占统治地位,而助剂和载体对反应机理也有影响,有时甚至直接参与反应过程。对改进型、新型催化剂如金或负载金等催化WGS反应机理的认识过程尚未结束。对铁族羰基络合均相催化WGS反应机理的理解逐步深入。理论模拟研究将从少数简单的WGS模型体系扩展到更多复杂的真实体系;在预言新的催化体系反应机理上,与实验研究相比,有望体现出费用低和非常便利的优势,并能为催化剂的设计提供理论依据和成功案例。

  3. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  4. Thieme Chemistry Journal Awardees - Where are They Now? Catalytic Transport with an Amine Carrier in a Fluorous Triphasic Reaction.

    Science.gov (United States)

    Montanari, Vittorio; Yu, Marvin S; Curran, Dennis P

    2009-03-01

    Several aromatic aldehydes are transported by a fluorous amine from one organic phase through a fluorous phase to another organic phase. The derived imines react with phenylhydrazine to immobilize the transported product as a hydrazone and release the amine for reuse. In this way, catalytic transport is accomplished for the first time.

  5. The oxygen evolution reaction on cobalt Part I. Reaction order experiments and impedance measurements

    NARCIS (Netherlands)

    Kobussen, A.G.C.; Willems, H.; Wit, J.H.W. de; Broers, G.H.J.

    1984-01-01

    It was found that the oxygen evolution reaction on cobalt in concentrated KOH solutions can be described differently for low and high overpotentials. In the overpotential range from 150 to 280 mV, the reaction has a Tafel slope of approximately 40 mV and a reaction order with respect to the KOH acti

  6. Ultraviolet-Visible (UV-Vis) Microspectroscopic System Designed for the In Situ Characterization of the Dehydrogenation Reaction Over Platinum Supported Catalytic Microchannel Reactor.

    Science.gov (United States)

    Suarnaba, Emee Grace Tabares; Lee, Yi Fuan; Yamada, Hiroshi; Tagawa, Tomohiko

    2016-11-01

    An ultraviolet visible (UV-Vis) microspectroscopic system was designed for the in situ characterization of the activity of the silica supported platinum (Pt) catalyst toward the dehydrogenation of 1-methyl-1,4-cyclohexadiene carried out in a custom-designed catalytic microreactor cell. The in situ catalytic microreactor cell (ICMC) with inlet/outlet ports was prepared using quartz cover as the optical window to facilitate UV-Vis observation. A fabricated thermometric stage was adapted to the UV-Vis microspectrophotometer to control the reaction temperature inside the ICMC. The spectra were collected by focusing the UV-Vis beam on a 30 × 30 µm area at the center of ICMC. At 393 K, the sequential measurement of the spectra recorded during the reaction exhibited a broad absorption peak with maximum absorbance at 260 nm that is characteristic for gaseous toluene. This result indicates that the silica supported Pt catalyst is active towards the dehydrogenation of 1-methyl-1,4-cyclohexadiene at the given experimental conditions. The onset of coke formation was also detected based on the appearance of absorption bands at 300 nm. The UV-Vis microspectroscopic system developed can be used further in studying the mechanism of the dehydrogenation reaction.

  7. Preparation of acid-base bifunctional mesoporous KIT-6 (KIT: Korea Advanced Institute of Science and Technology) and its catalytic performance in Knoevenagel reaction

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Ling [College of Chemistry and Chemical Engineering, Inner Mongolia University for Nationalities, Tongliao 028000 (China); Wang, Chunhua [Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun 130023 (China)

    2014-05-01

    Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH{sub 2} containing different aluminum content have been synthesized through post synthetic grafting method. The materials were characterized by X-ray diffraction (XRD), scanning electron micrographs (SEM), transmission electron micrographs (TEM), Fourier-transform infrared spectroscopy (FTIR), IR spectra of pyridine adsorption, NH{sub 3}-TPD and TG analysis. The characterization results indicated that the pore structure of KIT-6 was well kept after the addition of aluminum and grafting of aminopropyl groups. The acid amount of Al-KIT-6 increased with enhancing aluminum content. Catalytic results showed that weak acid and weak base favor the Knoevenagel reaction, while catalysts with strong acid and weak base exhibited worse catalytic behavior. - Graphical abstract: The postulated steps of mechanism for the acid-base catalyzed process are as follows: (1) the aldehyde gets activated by the surface acidic sites which allow the amine undergoes nucleophilic to attack the carbonyl carbon of benzaldehyde. (2) Water is released in the formation of imine intermediate. (3) The ethyl cyanoacetate reacts with the intermediate. (4) The benzylidene ethyl cyanoacetate is formed and the amine is regenerated. - Highlights: • KIT-6 and Al-KIT-6-NH{sub 2} with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH{sub 2} within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH{sub 2} shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction.

  8. Catalytic titrations of silver(I) applying the iodide-catalysed manganese(IV)-arsenic(III) indicator reaction in the presence of sulphuric acid

    OpenAIRE

    TIBOR J. PASTOR; VOJKA V. ANTONIJEVIC; FERENC T. PASTOR

    1999-01-01

    A new catalytic potentiometric titration method for the determination of silver(I), applying the iodide-catalysed manganese(IV)-arsenic(III) indicator reaction in the presence of sulphuric acid, has been developed. The effect of the concentration of sulphuric acid and different ions, and of the mole ratio of manganese(IV) to arsenic(III) in the titrated solution, as well as of the titrand temperature on the conditions for the determination of silver(I) in solutions of various concentrations, ...

  9. Superior catalytic activity derived from a two-dimensional Ti3C2 precursor towards the hydrogen storage reaction of magnesium hydride.

    Science.gov (United States)

    Liu, Yongfeng; Du, Hufei; Zhang, Xin; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

    2016-01-14

    The superior catalytic effects derived from a 2D Ti3C2 (MXene), synthesized by the exfoliation of Ti3AlC2 powders, towards the hydrogen storage reaction of MgH2 were demonstrated. The 5 wt% Ti3C2-containing MgH2 releases 6.2 wt% H2 within 1 min at 300 °C and absorbs 6.1 wt% H2 within 30 s at 150 °C, exhibiting excellent dehydrogenation/hydrogenation kinetics.

  10. Online psychophysics: reaction time effects in cognitive experiments.

    Science.gov (United States)

    Semmelmann, Kilian; Weigelt, Sarah

    2016-08-05

    Using the Internet to acquire behavioral data is currently on the rise. However, very basic questions regarding the feasibility of online psychophysics are still open. Here, we aimed to replicate five well-known paradigms in experimental psychology (Stroop, Flanker, visual search, masked priming, attentional blink) in three settings (classical "lab", "web-in-lab", "web") to account for possible changes in technology and environment. Lab and web-in-lab data were both acquired in an in-lab setting with lab using "Gold Standard" methods, while web-in-lab used web technology. This allowed for a direct comparison of potential differences in acquisition software. To account for additional environmental differences, the web technology experiments were published online to participate from home (setting web), thereby keeping the software and experimental design identical and only changing the environmental setting. Our main results are: First, we found an expected fixed additive timing offset when using web technology (M = 37 ms, SD = 8.14) and recording online (M = 87 ms, SD = 16.04) in comparison to lab data. Second, all task-specific effects were reproduced except for the priming paradigm, which couldn't be replicated in any setting. Third, there were no differences in error rates, which are independent of the timing offset. This finding further supports the assumption of data equality over all settings. Fourth, we found that browser type might be influencing absolute reaction times. Together, these results contribute to the slowly but steadily growing literature that online psychophysics is a suitable complement - or even substitute - to lab data acquisition.

  11. Performance of nitrogen-containing macroporous carbon supported cobalt catalyst synthesized through in-situ construction of catalytic sites for oxygen reduction reaction

    Science.gov (United States)

    He, Fan; Yang, Jun; Li, Rui; Liu, Bin Hong; Li, Zhou Peng

    2015-01-01

    A novel method of in-situ catalytic site (CoNx) construction in macroporous carbon (MPC) is developed. The nitrogen-containing MPC-supported cobalt (Co/N-MPC) catalysts are synthesized via the pyrolysis of a mixture of glucose-urea resin, nano-CaCO3, and cobalt nitrate. The nano-CaCO3 functions as a template to fabricate MPC that provides high electric conductivity and large specific surface area. The catalytic CoNx sites are simultaneously created during the formation of N-MPC. The use of glucose-urea resin as the carbon and nitrogen sources significantly increases the nitrogen content as high as 8.8 at% in the MPC. The synthesized Co/N-MPC demonstrates superb catalytic activity toward oxygen reduction reaction. The direct borohydride fuel cell using the Co/N-MPC shows a power density as high as 170 mW cm-2 which is much higher than the cell using 10 wt.% Pt/C but slightly lower than the cell using 20 wt.% Pt/C as the cathode catalyst at ambient conditions.

  12. Research on Macro-kinetics of Phase Transfer Catalytic Reaction for Benzyl Acetate%相转移催化合成乙酸苄酯宏观动力学研究

    Institute of Scientific and Technical Information of China (English)

    张国华

    2012-01-01

    The macro-kinetics of phase transfer catalytic reaction for benzyl acetate from benzyl chloride and sodium acetate with benzyltriethylammonium chloride as catalyst was researched. In the kinetics experiments, the concentration of phase transfer catalyst benzyltriethylammonium was keep unchanged, and excess sodium acetate was used to keep constant acetate concentration by dissolution equilibrium. The kinetics experiments were carried out to obtained the reaction order of benzyl chloride at 50-60℃. The results indicated that the reaction orders for benzyl chloride was 1, and the activation energy was 36.4kJ/mol.%研究了氯化苄与乙酸钠在相转移催化剂苄基三乙基氯化铵作用下合成乙酸苄酯的宏观动力学。研究中固定相转移催化剂用量,并使乙酸钠大量过量以维持反应体系中乙酸钠浓度为定值。在50~60℃的温度下进行实验。实验结果表明,反应对氯化苄为1级,反应表观活化能为36.4kJ/mol。

  13. Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

    Science.gov (United States)

    Grodzka, P.; Facemire, B.

    1977-01-01

    Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

  14. Catalytic combustor for hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Mercea, J.; Grecu, E.; Fodor, T.; Kreibik, S.

    1982-01-01

    The performance of catalytic combustors for hydrogen using platinum-supported catalysts is described. Catalytic plates of different sizes were constructed using fibrous and ceramic supports. The temperature distribution as well as the reaction efficiency as a function of the fuel input rate was determined, and a comparison between the performances of different plates is discussed.

  15. Epitaxial Growth of Multimetallic Pd@PtM (M = Ni, Rh, Ru) Core-Shell Nanoplates Realized by in Situ-Produced CO from Interfacial Catalytic Reactions.

    Science.gov (United States)

    Yan, Yucong; Shan, Hao; Li, Ge; Xiao, Fan; Jiang, Yingying; Yan, Youyi; Jin, Chuanhong; Zhang, Hui; Wu, Jianbo; Yang, Deren

    2016-12-14

    Pt-based multimetallic core-shell nanoplates have received great attention as advanced catalysts, but the synthesis is still challenging. Here we report the synthesis of multimetallic Pd@PtM (M = Ni, Rh, Ru) nanoplates including Pd@Pt nanoplates, in which Pt or Pt alloy shells with controlled thickness epitaxially grow on plate-like Pd seeds. The key to achieve high-quality Pt-based multimetallic nanoplates is in situ generation of CO through interfacial catalytic reactions associated with Pd nanoplates and benzyl alcohol. In addition, the accurate control in a trace amount of CO is also of great importance for conformal growth of multimetallic core-shell nanoplates. The Pd@PtNi nanoplates exhibit substantially improved activity and stability for methanol oxidation reaction (MOR) compared to the Pd@Pt nanoplates and commercial Pt catalysts due to the advantages arising from plate-like, core-shell, and alloy structures.

  16. Synthesis, characterization and catalytic properties of nanocrystaline Y2O3-coated TiO2 in the ethanol dehydration reaction

    Directory of Open Access Journals (Sweden)

    Humberto Vieira Fajardo

    2012-04-01

    Full Text Available In the present study, TiO2 nanopowder was partially coated with Y2O3 precursors generated by a sol-gel modified route. The system of nanocoated particles formed an ultra thin structure on the TiO2 surfaces. The modified nanoparticles were characterized by high resolution transmission electron microscopy (HR-TEM, X-ray diffraction (XRD analysis, Zeta potential and surface area through N2 fisisorption measurements. Bioethanol dehydration was used as a probe reaction to investigate the modifications on the nanoparticles surface. The process led to the obtainment of nanoparticles with important surface characteristics and catalytic behavior in the bioethanol dehydration reaction, with improved activity and particular selectivity in comparison to their non-coated analogs. The ethylene production was disfavored and selectivity toward acetaldehyde, hydrogen and ethane increased over modified nanoparticles.

  17. Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like shape for oxygen evolution reaction with enhanced catalytic activity

    Directory of Open Access Journals (Sweden)

    Tao Ding

    2016-01-01

    Full Text Available Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like wire shape has been achieved via a facile and moderate hydrothermal process at 120 °C for 1 h from the reaction of nickel nitrate and chloroplatinic acid in alkaline solution in the presence of ethanediamine and hydrazine hydrate. The holothuria-like alloyed NiPt wires are Ni-rich in composition (Ni23.6Pt and uniform in diameter with many tiny tips outstretched from the wires surface. The holothuria-like wires are assembled from granular subunits with the assistance of capping molecular of ethanediamine and the wires display an improved oxygen evolution reaction catalytic activity.

  18. Synthesis, characterization and catalytic properties of nanocrystaline Y{sub 2}O{sub 3}-coated TiO{sub 2} in the ethanol dehydration reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fajardo, Humberto Vieira [Universidade Federal de Ouro Preto (UFOP), MG (Brazil). Departamento de Quimica; Longo, Elson [Universidade Estadual Paulista (UNESP), Araraquara, SP (Brazil). Departamento de Fisico-Quimica; Leite, Edson Roberto; Libanori, Rafael [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica; Probst, Luiz Fernando Dias [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Departamento de Quimica; Carreno, Neftali Lenin Villarreal [Universidade Federal de Pelotas (UFPel), RS (Brazil). Departamento de Quimica Analitica e Inorganica

    2012-03-15

    In the present study, TiO{sub 2} nano powder was partially coated with Y{sub 2}O{sub 3} precursors generated by a sol-gel modified route. The system of nanocoated particles formed an ultra thin structure on the TiO{sub 2} surfaces. The modified nanoparticles were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) analysis, Zeta potential and surface area through N{sub 2} physisorption measurements. Bioethanol dehydration was used as a probe reaction to investigate the modifications on the nanoparticles surface. The process led to the obtainment of nanoparticles with important surface characteristics and catalytic behavior in the bioethanol dehydration reaction, with improved activity and particular selectivity in comparison to their non-coated analogs. The ethylene production was disfavored and selectivity toward acetaldehyde, hydrogen and ethane increased over modified nanoparticles. (author)

  19. Nickel(II) complexes containing ONS donor ligands: Synthesis, characterization, crystal structure and catalytic application towards C-C cross-coupling reactions

    Indian Academy of Sciences (India)

    Panneerselvam Anitha; Rajendran Manikandan; Paranthaman Vijayan; Govindan Prakash; Periasamy Viswanathamurthi; Ray Jay Butcher

    2015-04-01

    Nickel(II) complexes containing thiosemicarbazone ligands [Ni(L)2] (1-3) (L = 9,10-phenanthrenequinonethiosemicarbazone (HL1), 9,10-phenanthrenequinone-N-methylthio semicarbazone (HL2) and 9, 10-phenanthrenequinone-N-phenylthiosemicarbazone (HL3)) have been synthesized and characterized by elemental analysis and spectroscopic (IR, UV-Vis, 1H, 13C-NMR and ESI mass) methods. The molecular structures of complexes 1 and 2 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate ONS fashion. The catalytic activity of complexes towards some C–C coupling reactions (viz., Kumada-Corriu, Suzuki-Miyaura and Sonogashira) has been examined. The complexes behave as efficient catalysts in the Kumada-Corriu and Sonogashira coupling reactions rather than Suzuki-Miyaura coupling.

  20. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction

    Energy Technology Data Exchange (ETDEWEB)

    Vallet, Ana [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Ovejero, Gabriel, E-mail: govejero@quim.ucm.es [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Rodríguez, Araceli [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Peres, José A. [Centro de Química de Vila Real, Universidade de Trás-os-Montes e Alto Douro, Apartado 1013, 5001-801 Vila Real (Portugal); García, Juan, E-mail: juangcia@quim.ucm.es [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain)

    2013-01-15

    Highlights: ► Ni supported over hydrotalcite calcined precursors as catalyst. ► Catalytic wet air oxidation in trickle bed reactor for Chromotrope 2R removal. ► Dye removal depends on temperature, initial dye concentration and flow rate. ► The catalyst proved to bare-usable after in situ regeneration. -- Abstract: Active nickel catalysts (7 wt%) supported over Mg–Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min{sup −1} and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min{sup −1}, respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T{sub r} = 0.098 g{sub Ni} min mL{sup −1}. After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T{sub r} = 0.098 g{sub Ni} min mL{sup −1}, attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity.

  1. Structural studies of Saccharomyces cerevesiae mitochondrial NADP-dependent isocitrate dehydrogenase in different enzymatic states reveal substantial conformational changes during the catalytic reaction.

    Science.gov (United States)

    Peng, Yingjie; Zhong, Chen; Huang, Wei; Ding, Jianping

    2008-09-01

    Isocitrate dehydrogenases (IDHs) catalyze oxidative decarboxylation of isocitrate (ICT) into alpha-ketoglutarate (AKG). We report here the crystal structures of Saccharomyces cerevesiae mitochondrial NADP-IDH Idp1p in binary complexes with coenzyme NADP, or substrate ICT, or product AKG, and in a quaternary complex with NADPH, AKG, and Ca(2+), which represent different enzymatic states during the catalytic reaction. Analyses of these structures identify key residues involved in the binding of these ligands. Comparisons among these structures and with the previously reported structures of other NADP-IDHs reveal that eukaryotic NADP-IDHs undergo substantial conformational changes during the catalytic reaction. Binding or release of the ligands can cause significant conformational changes of the structural elements composing the active site, leading to rotation of the large domain relative to the small and clasp domains along two hinge regions (residues 118-124 and residues 284-287) while maintaining the integrity of its secondary structural elements, and thus, formation of at least three distinct overall conformations. Specifically, the enzyme adopts an open conformation when bound to NADP, a quasi-closed conformation when bound to ICT or AKG, and a fully closed conformation when bound to NADP, ICT, and Ca(2+) in the pseudo-Michaelis complex or with NADPH, AKG, and Ca(2+) in the product state. The conformational changes of eukaryotic NADP-IDHs are quite different from those of Escherichia coli NADP-IDH, for which significant conformational changes are observed only between two forms of the apo enzyme, suggesting that the catalytic mechanism of eukaryotic NADP-IDHs is more complex than that of EcIDH, and involves more fine-tuned conformational changes.

  2. Steam reforming of methane over Ni catalysts prepared from hydrotalcite-type precursors:Catalytic activity and reaction kinetics

    Institute of Scientific and Technical Information of China (English)

    Yang Qi; Zhenmin Cheng; Zhiming Zhou

    2015-01-01

    Ni/Mg–Al catalysts derived from hydrotalcite-type precursors were prepared by a co-precipitation technique and applied to steam reforming of methane. By comparison with Ni/γ-Al2O3 and Ni/α-Al2O3 catalysts prepared by in-cipient wetness impregnation, the Ni/Mg–Al catalyst presented much higher activity as a result of higher specific surface area and better Ni dispersion. The Ni/Mg–Al catalyst with a Ni/Mg/Al molar ratio of 0.5:2.5:1 exhibited the highest activity for steam methane reforming and was selected for kinetic investigation. With external and inter-nal diffusion limitations eliminated, kinetic experiments were carried out at atmospheric pressure and over a temperature range of 823–973 K. The results demonstrated that the overal conversion of CH4 and the conversion of CH4 to CO2 were strongly influenced by reaction temperature, residence time of reactants as wel as molar ratio of steam to methane. A classical Langmuir–Hinshelwood kinetic model proposed by Xu and Froment (1989) fitted the experimental data with excellent agreement. The estimated adsorption parameters were consistent thermodynamical y.

  3. The catalytic effect of water, water dimers and water trimers on H2S + (3)O2 formation by the HO2 + HS reaction under tropospheric conditions.

    Science.gov (United States)

    Zhang, Tianlei; Yang, Chen; Feng, Xukai; Kang, Jiaxin; Song, Liang; Lu, Yousong; Wang, Zhiyin; Xu, Qiong; Wang, Wenliang; Wang, Zhuqing

    2016-06-29

    In this article, the reaction mechanisms of H2S + (3)O2 formation by the HO2 + HS reaction without and with catalyst X (X = H2O, (H2O)2 and (H2O)3) have been investigated theoretically at the CCSD(T)/6-311++G(3df,2pd)//B3LYP/6-311+G(2df,2p) level of theory, coupled with rate constant calculations by using conventional transition state theory. Our results show that in the presence of catalyst X (X = H2O, (H2O)2 and (H2O)3) into the channel of H2S + (3)O2 formation, the reactions between the SH radical and HO2(H2O)n (n = 1-3) complexes are more favorable than the corresponding reactions of the HO2 radical with HS(H2O)n (n = 1-3) complexes due to the lower barrier of the former reactions and the higher concentrations of HO2(H2O)n (n = 1-3) complexes. Meanwhile, the catalytic effect of water, water dimers and water trimers is mainly taken from the contribution of a single water vapor molecule, since the total effective rate constant of HO2H2O + HS and H2OHO2 + HS reactions was, respectively, larger by 7-9 and 9-12 orders of magnitude than that of SH + HO2(H2O)2 and SH + HO2(H2O)3 reactions. Besides, the enhancement factor of water vapor is only 0.37% at 240 K, while at high temperatures, such as 425 K, the positive water vapor effect is enhanced up to 38.00%, indicating that at high temperatures the positive water effect is obvious under atmospheric conditions. Overall, these results show how water and water clusters catalyze the gas phase reactions under atmospheric conditions.

  4. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction.

    Science.gov (United States)

    Vallet, Ana; Ovejero, Gabriel; Rodríguez, Araceli; Peres, José A; García, Juan

    2013-01-15

    Active nickel catalysts (7 wt%) supported over Mg-Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min(-1) and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min(-1), respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T(r)=0.098 g(Ni) min mL(-1). After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T(r)=0.098 g(Ni) min mL(-1), attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity.

  5. Microwave-induced synthesis and characterization of nanometer Ce0.5Zr0.5O2 solid solution for the acidic catalytic reaction

    Institute of Scientific and Technical Information of China (English)

    HU Yucai; YIN Ping; LIANG Tao; JIANG Wei; DU Zhengkun; CHEN Yonghua

    2008-01-01

    Ce0.5Zr0.5O2 solid solution was successfully synthesized using cerium nitrate,zirconium nitrate,and urea as raw materials by the microwave irradiation method and charactefizde by X-ray diffraction,fluorescence spectrum,transmission electron microscopy,and infrared spectrum.Its acid catalytic activity was evaluated in the esterification reaction of acetic acid and n-butyl alcohol.The results show that Ce0.5Zr0.5O2 solid solution has cubic fluorite structure,and its particle diameter is in the nanometer scale.As a sort of solid acid,it possesses a higher acid catalytic activity and can be easily separated from reaction liquids.It can be used for several times,and basically,its activity keeps constant.The proton acid sites and Lewis acid sites exist in the structure of Ce0.5Zr0.5O2 solid solution.

  6. Dinuclear NHC-palladium complexes containing phosphine spacers: synthesis, X-ray structures and their catalytic activities towards the Hiyama coupling reaction.

    Science.gov (United States)

    Yang, Jin; Li, Pinhua; Zhang, Yicheng; Wang, Lei

    2014-05-21

    Six dinuclear N-heterocyclic carbene (NHC) palladium complexes, [PdCl2(IMes)]2(μ-dppe) (1), [PdCl2(IPr)]2(μ-dppe) (2), [PdCl2(IMes)]2(μ-dppb) (3), [PdCl2(IPr)]2(μ-dppb) (4), [PdCl2(IMes)]2(μ-dpph) (5), and [PdCl2(IPr)]2(μ-dpph) (6) [IMes = N,N'-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = N,N'-bis-(2,6-di(iso-propyl)phenyl)imidazol-2-ylidene; dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane; and dpph = 1,6-bis(diphenylphosphino)hexane], have been synthesized through bridge-cleavage reactions of chloro-bridged dimeric compounds, [Pd(μ-Cl)(Cl)(NHC)]2, with the corresponding diphosphine ligands. The obtained compounds were fully characterized by (1)H NMR, (13)C NMR and (31)P NMR spectroscopy, FT-IR, elemental analysis and single-crystal X-ray crystallography. Moreover, further explorations of the catalytic potential of the dinuclear carbene palladium complexes as catalysts for the Pd-catalyzed transformations have been performed under microwave irradiation conditions, and the complexes exhibited moderate to good catalytic activity in the Hiyama coupling reaction of trimethoxyphenylsilane with aryl chlorides.

  7. Experiments shed new light on nickel-fluorine reactions

    Science.gov (United States)

    Fischer, J.; Gunther, W.; Jarry, R. L.

    1967-01-01

    Isotopic tracer experiments and scale-impingement experiments show fluorine to be the migrating species through the nickel fluoride scale formed during the fluorination of nickel. This is in contrast to nickel oxide scales, where nickel is the migrating species.

  8. 脱灰生物质焦的催化气化反应及动力学%Catalytic gasification reaction and kinetics of deashing biomass char

    Institute of Scientific and Technical Information of China (English)

    张建良; 李净; 胡正文; 付亚清; 左海滨

    2013-01-01

    The physical structure and chemical composition of deashing biomass char coated with potash, as well as its gasification reaction with CO2 were investigated by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometry (EDS) and thermal gravimetry. Experimental data were processed with both the homogeneous model and the shrinking unreacted-core model, and kinetic parameters were obtained for the gasification reaction. It is found that there is an obvious catalytic effect of potash on the gasification reaction. This catalysis improves the overall reaction rate and shortens the reaction time. As the potash content increases from 0%to 4%, more adhering catalytic points, rich in kalium, can be detected on the biomass char surface, and the activation energy of the gasification reaction decreased gradually with increasing potash content. Compared with the shrinking unreacted-core model, the homegeneous model is more suitable for describing the gasification reaction of deashing biomass char with CO2 due to its extremely low ash content.%利用扫描电镜-能谱仪及热重分析仪研究了添加钾盐催化剂的脱灰生物质焦的物理结构、化学成分及其与CO2的气化反应,并分别采用均相模型和收缩未反应核模型对实验数据进行处理,得到动力学参数。研究发现钾盐对脱灰生物质焦-CO2气化反应有明显催化作用,可提高整体反应速率,并减少反应时间。随着钾盐的增加(质量分数在0%∼4%的范围内),附着在生物质焦表面的富钾催化点增多,催化作用逐渐增大,反应的活化能逐渐降低。由于(脱灰)生物质焦的灰分含量很低,与未反应核模型相比,均相模型更适合于描述生物质焦-CO2的气化反应过程。

  9. Organic synthesis by quench reactions. [in prebiotic simulation experiment

    Science.gov (United States)

    Park, W. K.; Hochstim, A. R.; Ponnamperuma, C.

    1975-01-01

    Study of the effects of chemical quench reactions on the formation of organic compounds at a water surface under simulated primordial earth conditions. A mixture of gaseous methane and ammonia over a water surface was exposed to an arc discharge between an electrode and the water surface, generating reactive species. Various organic molecules were formed by a subsequent quenching of these species generated on the water surface. The effects of these water-surface quench reactions were assessed by comparing the amounts of synthesized molecules to the amounts which formed during the discharge of an arc above the water level. It is concluded that the quench (or wet) discharge led to faster rates of reactions, higher-molecular-weight organic compounds, and one-order-of-magnitude larger yields than the dry discharge.

  10. Catalytic distillation structure

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  11. Activation of organozinc reagents with t-Bu-P4 base for transition metal-free catalytic SN2' reaction.

    Science.gov (United States)

    Kobayashi, Koji; Ueno, Masahiro; Naka, Hiroshi; Kondo, Yoshinori

    2008-08-28

    The t-Bu-P4 base was found to be an excellent catalyst for activating organozinc reagents and was used to promote the S(N)2' reaction of alpha,beta-unsaturated esters bearing a gamma-chloride using various organozinc reagents: these reactions proceeded in high yields with excellent chemo-and regioselectivity.

  12. Supersonic molecular beam experiments on surface chemical reactions.

    Science.gov (United States)

    Okada, Michio

    2014-10-01

    The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces.

  13. SOFC system with integrated catalytic fuel processing

    Science.gov (United States)

    Finnerty, Caine; Tompsett, Geoff. A.; Kendall, Kevin; Ormerod, R. Mark

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm -2 at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H 2/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack.

  14. SOFC system with integrated catalytic fuel processing

    Energy Technology Data Exchange (ETDEWEB)

    Finnerty, C.; Tompsett, G.A.; Kendall, K.; Ormerod, R.M. [Birchall Centre for Inorganic Chemistry and Materials Science, Keele Univ. (United Kingdom)

    2000-03-01

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm{sup -2} at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H{sub 2}/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack. (orig.)

  15. Spectroscopic investigation of the reaction mechanism of CopB-B, the catalytic fragment from an archaeal thermophilic ATP-driven heavy metal transporter.

    Science.gov (United States)

    Völlmecke, Christian; Kötting, Carsten; Gerwert, Klaus; Lübben, Mathias

    2009-11-01

    The mechanism of ATP hydrolysis of a shortened variant of the heavy metal-translocating P-type ATPase CopB of Sulfolobus solfataricus was studied. The catalytic fragment, named CopB-B, comprises the nucleotide binding and phosphorylation domains. We demonstrated stoichiometric high-affinity binding of one nucleotide to the protein (K(diss) 1-20 microm). Mg is not necessary for nucleotide association but is essential for the phosphatase activity. Binding and hydrolysis of ATP released photolytically from the caged precursor nitrophenylethyl-ATP was measured at 30 degrees C by infrared spectroscopy, demonstrating that phosphate groups are not involved in nucleotide binding. The hydrolytic kinetics was biphasic, and provides evidence for at least one reaction intermediate. Modelling of the forward reaction gave rise to three kinetic states connected by two intrinsic rate constants. The lower kinetic constant (k(1) = 4.7 x 10(-3) s(-1) at 30 degrees C) represents the first and rate-limiting reaction, probably reflecting the transition between the open and closed conformations of the domain pair. The subsequent step has a faster rate (k(2) = 17 x 10(-3) s(-1) at 30 degrees C), leading to product formation. Although the latter appears to be a single step, it probably comprises several reactions with presently unresolved intermediates. Based on these data, we suggest a model of the hydrolytic mechanism.

  16. Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

    Institute of Scientific and Technical Information of China (English)

    Xue Zhang; Yu-ping Li; Song-bai Qiu; Tie-jun Wang; Long-long Ma; Qi Zhang; Ming-yue Ding

    2013-01-01

    The effect of calcination temperature on the catalytic activity for the dimethyl ether (DME) carbonylation into methyl acetate (MA) was investigated over mordenite supported copper (Cu/HMOR) prepared by ion-exchange process.The results showed that the catalytic activity was obviously affected by the calcination temperature.The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃,1.5 MPa,and GSHV of 4883 h-1.The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction,N2 absorption,NH3 temperature program desorption,CO temperature program desorption,and Raman techniques.Proper calcination temperature was effective to promote copper ions migration and diffusion,and led the support HMOR to possess more acid activity sites,which exhibited the complete decomposing of copper nitrate,large surface area and optimum micropore structure,more amount of CO adsorption site and proper amount of weak acid centers.

  17. Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

    Science.gov (United States)

    Park, Jisu; Cha, Song-Hyun; Cho, Seonho; Park, Youmie

    2016-06-01

    In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of -41.98 mV for the gold nanoparticles and -53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV-visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7-99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.

  18. Spontaneous adverse drug reaction monitoring in oncology: Our experience

    Directory of Open Access Journals (Sweden)

    K Kaur

    2015-01-01

    Full Text Available Background: Adverse drug reaction (ADR monitoring is slowly developing as an important aspect of healthcare. The aim of the study was to study the pattern of adverse drug reactions in the Oncology department of a tertiary care hospital. Materials And Methods: This was a prospective study conducted in the Oncology department of a tertiary care hospital in which ADRs were reported spontaneously. The ADRs were noted from 1st January, 2007 to 30th June, 2011. Following were noted: demographics, premedication (if any, diagnosis, chemotherapy (regimen, cycles, medication history, and alteration in the treatment or co morbidities, ADRs (severity and management. Adverse drug reactions were noted by patient interview, collaborating with information on file, recording changes in the prescribing chart and investigations, consulting the doctor on duty. Results: During this study period, there were total of 14,475 visits of patients from which 2500 ADRs were recorded. Maximum number of ADRs were noted with platinum compounds (25.52% followed by pyrimidine antagonists (19.88%. The most common malignancy reported in our hospital was Carcinoma breast (20% followed by leukemia (12% and Ca ovary (12%. Alopecia (27.76% was the most common ADR followed by anemia (7.48%, thrombocytopenia (6.96% and constipation (6.16%. Conclusion: Alopecia is the most common ADR and platinum compounds were responsible for the maximum number of ADRs. The most common carcinoma reported during this period was carcinoma breast.

  19. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel

    2015-09-25

    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  20. Influence of the particle size of zeolite HZSM-5 on the catalytic performance in the ethene-to-propene reaction

    Energy Technology Data Exchange (ETDEWEB)

    Follmann, S.; Ernst, S. [Kaiserslautern Univ. (Germany). Dept. of Chemistry; Vetter, A.; Ripperger, S. [Kaiserslautern Univ. (Germany). Dept. of Mechanical and Process Engineering

    2013-11-01

    In this study, HZSM-5-type zeolites with comparable nSi/nAl-ratios but different crystallite sizes (6 {mu}m, 27 {mu}m, 40 {mu}m and 62 {mu}m) were synthesized and their physicochemical properties characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and nitrogen physisorption. Their catalytic properties were explored in the acid-catalyzed conversion of ethene to propene (and higher hydrocarbons). The results show that there is a significant influence of the crystallite size of the zeolite catalyst on the activity and time-on-steam stability. While the yields of short-chain olefins do not significantly differ for all materials investigated, the formation of aromatics is significantly suppressed over the catalyst with the largest crystallite size. (orig.)

  1. Preparation and Characterization of A New Dinuclear Ruthenium Complex with BDPX Ligand and Its Catalytic Hydrogenation Reactions for Cinnamaldehyde

    Institute of Scientific and Technical Information of China (English)

    TANG,Yuan-You(唐元友); LI,Rui-Xiang(李瑞祥); LI,Xian-Jun(李贤均); WONG,Ning-Bew(黄宁表); TIN,Kim-Chung(田金忠); ZHANG,Zhe-Ying(张哲英); MAK,Thomas C.W.(麦松威)

    2004-01-01

    A new anionic dinuclear ruthenium complex bearing 1,2-bis(diphenylphosphinomethyl)benzene (BDPX)[NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallographic analysis. This result indicated that complex 1 consisted of an anion dinuclear BDPX-Ru and a cationic diethylammonium. The crystal belonged to monoclinic system, C2/c space group with a=3.3552(7) nm, b= 1.8448(4)nm, c=2.4265(5) nm, β= 101.89(3)° and Z=8. The catalytic hydrogenation activities and selectivities of complex 1 for cinnamaldehyde were investigated.

  2. Quantification and evaluation of kinetic bio-catalytic pathway of horseradish peroxidase in an electron mediated reaction system and its applications in plant extracts.

    Science.gov (United States)

    Krishna, Honnur; Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Chamaraja, Nelligere A; Aradhana, Narayan

    2013-02-01

    The intermolecular coupling of 2,5-dimethoxyaniline (DMA) as mediated electron transfer reaction in presence of H(2)O(2) and peroxidase in acetate buffer of pH 4.2 resulting green colored product having maximum absorption at λ(max)=740 nm was investigated by spectrophotometer. Under optimum conditions, linearity range for the quantification of H(2)O(2) was 2.0-288.0 μM and for peroxidase were 0.59-9.46 and 0.443-9.46 nM by kinetic and fixed-time method, respectively. The catalytic efficiency and catalytic power were K(eff)(D)=2.354 × 10(5)M(-1)min(-1) and K(pow)(D)=4.59 × 10(-4)min(-1), respectively. From the plot of d(1/D(o)) vs d(1/V(o)) and d(1/H(o)) vs d(1/V(o)), Michaelis-Menten constants for DMA and H(2)O(2)were found that K(m)(D)=1,458 μM and [Formula: see text] =301 μM. Applicability of the method was tested for peroxidase activity in some plant extracts and compared with guaiacol/peroxidase system. Regarding superiority of the method, it is suggested that DMA/peroxidase system can be a better hydrogen donor for HRP assay than guaiacol system as evident from kinetic data.

  3. Quantification and evaluation of kinetic bio-catalytic pathway of horseradish peroxidase in an electron mediated reaction system and its applications in plant extracts

    Science.gov (United States)

    Krishna, Honnur; Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Chamaraja, Nelligere A.; Aradhana, Narayan

    2013-02-01

    The intermolecular coupling of 2,5-dimethoxyaniline (DMA) as mediated electron transfer reaction in presence of H2O2 and peroxidase in acetate buffer of pH 4.2 resulting green colored product having maximum absorption at λmax = 740 nm was investigated by spectrophotometer. Under optimum conditions, linearity range for the quantification of H2O2 was 2.0-288.0 μM and for peroxidase were 0.59-9.46 and 0.443-9.46 nM by kinetic and fixed-time method, respectively. The catalytic efficiency and catalytic power were KeffD = 2.354 × 105 M-1 min-1 and KpowD = 4.59 × 10-4 min-1, respectively. From the plot of d(1/Do) vs d(1/Vo) and d(1/Ho) vs d(1/Vo), Michaelis-Menten constants for DMA and H2O2were found that KmD = 1458 μM and KmHO = 301 μM. Applicability of the method was tested for peroxidase activity in some plant extracts and compared with guaiacol/peroxidase system. Regarding superiority of the method, it is suggested that DMA/peroxidase system can be a better hydrogen donor for HRP assay than guaiacol system as evident from kinetic data.

  4. Catalytic, Conjugate Reduction-Aldol Addition Reaction of β'Oxoal kyl α, β-Unsatu rated Carboxylates%Catalytic, Conjugate Reduction-Aldol Addition Reaction of β'Oxoal kyl α, β-Unsatu rated Carboxylates

    Institute of Scientific and Technical Information of China (English)

    郑爱军; 姜岚; 李争宁

    2012-01-01

    Intramolecular conjugate reduction-aldol addition reactions of β'-oxoalkyl a,fl-unsaturated carboxylates were performed in the presence of copper catalysts generated in situ from copper salts, phosphine ligands and silanes. Moderate to good yields and high diastereoselectivities were obtained in 15 min to 3 h using bis[(2-diphenyl- phosphino)phenyl] ether as the ligand.

  5. Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

    Science.gov (United States)

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

    2015-06-15

    We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.

  6. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification.

    Science.gov (United States)

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G; Kazantzis, Nikolaos K; Ma, Yi Hua

    2016-09-19

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H₂ to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H₂, CO and CO₂. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H₂O, CO₂ and H₂. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H₂ and induce higher methane and CO conversions while yielding ultrapure H₂ and compressed CO₂ ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H₂ permeance and purity, high CH₄ conversion levels and reduced CO yields.

  7. Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:Model reaction for upgrading of bio-oil

    Institute of Scientific and Technical Information of China (English)

    Minghao; Zhou; Zuo; Zeng; Hongyan; Zhu; Guomin; Xiao; Rui; Xiao

    2014-01-01

    A series of Cu-Mg-Al hydrotalcites derived oxides with a(Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio(from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 ?C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.

  8. NH3-SCR performance of fresh and hydrothermally aged Fe-ZSM-5 in standard and fast selective catalytic reduction reactions.

    Science.gov (United States)

    Shi, Xiaoyan; Liu, Fudong; Xie, Lijuan; Shan, Wenpo; He, Hong

    2013-04-02

    Hydrothermal stability is one of the challenges for the practical application of Fe-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with NH3 (NH(3)-SCR) for diesel engines. The presence of NO(3) in the exhaust gases can enhance the deNOx activity because of the fast SCR reaction. In this work, a Fe-ZSM-5 catalyst was prepared by a solid-state ion-exchange method and was hydrothermally deactivated at 800 °C in the presence of 10% H(2)O. The activity of fresh and hydrothermal aged Fe-ZSM-5 catalysts was investigated in standard SCR (NO(2)/NOx = 0) and in fast SCR with NO(2)/NOx = 0.3 and 0.5. In standard SCR, hydrothermal aging of Fe-ZSM-5 resulted in a significant decrease of low-temperature activity and a slight increase in high-temperature activity. In fast SCR, NOx conversion over aged Fe-ZSM-5 was significantly increased but was still lower than that over fresh catalyst. Additionally, production of N(2)O in fast SCR was much more apparent over aged Fe-ZSM-5 than over fresh catalyst. We propose that, in fast SCR, the rate of key reactions related to NO is slower over aged Fe-ZSM-5 than over fresh catalyst, thus increasing the probabilities of side reactions involving the formation of N(2)O.

  9. An efficient route for catalytic activity promotion via hybrid electro-depositional modification on commercial nickel foam for hydrogen evolution reaction in alkaline water electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Guanshui; He, Yongwei; Wang, Mei; Zhu, Fuchun; Tang, Bin [Research Institute of Surface Engineering, Taiyuan University of Technology, Yingze West Road 79, Taiyuan 030024 (China); Wang, Xiaoguang, E-mail: wangxiaog1982@163.com [Research Institute of Surface Engineering, Taiyuan University of Technology, Yingze West Road 79, Taiyuan 030024 (China); International Iberian Nanotechnology Laboratory (INL), 4715-330 Braga (Portugal)

    2014-09-15

    Highlights: • Mono-Cu surface modification depress the HER activity of Ni-foam. • Hybrid Ni-foam/Cu0.01/Co0.05 exhibits superior HER performance. • Layer-by-layer structure may contribute to a synergistic promoting effect. - Abstract: In this paper, the single- and hybrid-layered Cu, Ni and Co thin films were electrochemically deposited onto the three-dimensional nickel foam as composite cathode catalyst for hydrogen evolution reaction in alkaline water electrolysis. The morphology, structure and chemical composition of the electrodeposited composite catalysts were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Electrochemical measurement depicted that, for the case of the monometallic layered samples, the general activity for hydrogen evolution reaction followed the sequence: Ni-foam/Ni > Ni-foam/Co > bare Ni-foam > Ni-foam/Cu. It is noteworthy that, the hybrid-layered Ni-foam/Cu0.01/Co0.05 exhibited the highest catalytic activity towards hydrogen evolution reaction with the current density as high as 2.82 times that of the bare Ni-foam. Moreover, both excellent electrochemical and physical stabilities can also be acquired on the Ni-foam/Cu0.01/Co0.05, making this hybrid-layered composite structure as a promising HER electro-catalyst.

  10. Synthesis and characterization of Sn/zeolite and catalytic activity test in the esterification reaction of sludge oil

    Science.gov (United States)

    Alimuddin, Andi Hairil; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Prawatya, Yopa Eka; Astar, Ismail; Yustira, Yudi

    2017-03-01

    Synthesis of Sn-Zeolite has been made to use for esterification reaction of free fatty acids in sludge oil. Catalyst characterization was accomplished using X-Ray Diffraction (XRD), X-Ray Flourecence (XRF), and Fourier Transform Infra Red (FTIR). Catalyst Sn/zeolite was synthesized by impregnated Sn of SnCl2 into the zeolite. The amount of Sn impregnated base on the value of cation exchange capacity (CEC) of zeolites. Esterification reaction of fatty acids from sludge oil using Sn/Zeolite catalyst was did by variated the reaction time. XRD analysis results showed that the catalyst Sn/zeolite was dominated by modernit and quartz. XRF analysis results was increasing amount of Sn metal and the Si/Al ratio on Sn/zeolite catalyst along with addition of Sn metal. FTIR analysis results showed that the catalyst synthesized had Bronsted acid side (the spectrum 1639.4; 1656.7; 1654.8 cm-1) and the Lewis acid (spectrum 1400.2 and 1402.2 cm-1). The results showed that the optimum conditions of esterification reaction in 4 hours reaction time, 5% concentration of the catalyst, and molar ratio was about 1:10 with a conversion percentage of products reached 96.00%, which can be achieved with a ratio was about 4:1 between Sn and zeolite on Sn/zeolite catalyst.

  11. Studies of the Catalytic Activity and Deactivation of Calcined Layered Double Hydroxides in the Reaction of Ethanol with Propylene Oxide

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The reaction of ethanol with propylene oxide over calcined layered double hydroxides(CLDH) was investigated. The results show that CLDH has a good activity and a good selectivity, but the activity and the selectivity of CLDH decrease when CLDH reforms LDH- the so called "memory effect". The influence of the "memory effect" on the CLDH returning to LDH was studied by the hydration reaction. It is shown that the "memory effect" is not complete, and the decreases of the Mg/Al molar ratio of LDH and the crystallite size due to the increase of the hydration reaction time result in the drop of the activity and the selectivity.Keyworcds Ethanol, Propylene oxide, Calcined layered double hydroxide, "Memory effect", Hydration

  12. Reaction mechanism and kinetics of the NCN +NO reaction: Comparison of theory and experiment

    Science.gov (United States)

    Huang, Chih-Liang; Tseng, Shiang Yang; Wang, Tzu Yi; Wang, Niann S.; Xu, Z. F.; Lin, M. C.

    2005-05-01

    The rate constants for the NCN +NO reaction have been measured by laser photolysis/laser-induced fluorescence technique in the temperature range of 254-353K in the presence of He (40-600Torr) and N2 (30-528Torr) buffer gases. The NCN radical was produced from the photodissociation of NCN3 at 193nm and monitored with a dye laser at 329.01nm. The reaction was found to be strongly positive-pressure dependent with negative-temperature dependence, as was reported previously. The experimental data could be reasonably accounted for by dual-channel Rice-Ramsperger-Kassel-Marcus calculations based on the predicted potential-energy surface using the modified Gaussian-2 method. The reaction is predicted to occur via weak intermediates, cis- and trans-NCNNO, in the A″2 state which crosses with the A'2 state containing more stable cis- and trans-NCNNO isomers. The high barriers for the fragmentation of these isomers and their trapping in the A'2 state by collisional stabilization give rise to the observed positive-pressure dependence and negative-temperature effect. The predicted energy barrier for the fragmentation of the cis-NCNNO (A'2) to CN +N2O also allows us to quantitatively account for the rate constant previously measured for the reverse process CN +N2O→NCN+NO.

  13. Resting Study of Tracer Experiment on Catalytic Wet Oxidation Reactor under Micro-gravity and Earth Gravity Conditions

    Institute of Scientific and Technical Information of China (English)

    YANG Ji; JIA Jin-ping

    2005-01-01

    The International Space Station(ISS) employs catalytic wet oxidation carried out in a Volatile Reactor Assembly (VRA) for water recycling. Previous earth gravity experiments show that the VRA is very effective at removing polar,low molecular weight organics. To compare the reactor performance under micro-gravity and Earth gravity conditions,a tracer study was performed on a space shuttle in 1999 by using 0. 2% potassium carbonate as the chemical tracer.In this paper, the experimental data were analyzed and it is indicated that the reactor can be considered as a plug flow one under both micro-gravity and earth gravity experimental conditions. It has also been proved that dispersion is not important in the VRA reactor under the experimental conditions. Tracer retardation was observed in the experiments and it is most likely caused by catalyst adsorption. It is concluded that the following reasons may also have influence on the retardation of mean residence time: (1) the liquid can be held by appurtenances, which will retard the mean residence time; (2) the pores can hold the tracer, which can also retard the mean residence time.

  14. Rh nanoparticles supported on ultrathin carbon nanosheets for high-performance oxygen reduction reaction and catalytic hydrogenation.

    Science.gov (United States)

    Lin, Chong; Wu, Guanghao; Li, Huiqin; Geng, Yanmin; Xie, Gang; Yang, Jianhui; Liu, Bin; Jin, Jian

    2017-02-02

    We reported a facile and scalable salt-templated approach to produce monodisperse Rh nanoparticles (NPs) on ultrathin carbon nanosheets with the assistance of calcination under inert gas. More importantly, in spite of the essentially poor ORR activity of Rh/C, the acquired Rh/C hybrid nanosheets display a comparable ORR activity to the optimal commercial Pt/C catalyst, which may be due to the extra-small size of Rh NPs and the 2D defect-rich amorphous carbon nanosheets that can facilitate the charge transfer and reactive surface exposure. Moreover, Rh/C nanosheets present the optimal current density and best durability with the minimum decline during the entire test, so that ∼93% activity after 20 000 s is achieved, indicating a good lifetime for ORR. In contrast, commercial Pt/C and commercial Rh/C exhibited worse durability, so that ∼74% and ∼85% activities after 20 000 s are maintained. What's more, in the model system of reduction of 4-nitrophenol (4-NP), the kinetic constant k for Rh/C nanosheets is 3.1 × 10(-3), which is 4.5 times than that of the commercial Rh/C catalyst, revealing that our Rh/C hybrid nanosheets can be potentially applied in industrial catalytic hydrogenation. This work opens a novel and facile way for the rest of the precious metal NPs to be supported on ultrathin carbon nanosheets for heterogeneous catalysis.

  15. Studies on Anion Promoted Titania.1: Preparation, Characterization, and Catalytic Activity toward Alcohol and Cumene Conversion Reactions of Phosphated Titania.

    Science.gov (United States)

    Parida; Acharya; Samantaray; Mishra

    1999-09-15

    Phosphate impregnated titania samples with varying amount of phosphate have been prepared by solid-solid kneading as well as aqueous impregnation method. All the samples are characterized by XRD, TG-DTA, and N(2) adsorption-desorption isotherm. Surface area is found to increase with the increase in phosphate content up to 7.5 wt% loading and thereafter decreases. The average pore diameter and crystallite size of titania decreases with the addition of phosphate. However, total acidity (determined by base adsorption method) and the catalytic activity increases with the increase in phosphate content up to 10 wt%. Phosphated samples prepared using phosphoric acid as the source of phosphate exhibit higher acidity compared to the samples prepared using (NH(4))(3)PO(4). However, the sample prepared from (NH(4))(3)PO(4) shows the presence of both acid and basic sites. Though from the cumene conversion study it is understood that phosphated samples contain both Lewis and Brønsted acid sites, the latter predominates over the former. Copyright 1999 Academic Press.

  16. A Molecular Reaction Cycle with a Solvatochromic Merocyanine Dye: An Experiment in Photochemistry, Kinetics, and Catalysis.

    Science.gov (United States)

    Abdel-Kader, M. H.; Steiner, U.

    1983-01-01

    Three experiments using merocyanine M suitable as an integrated laboratory experience for undergraduates are described. Experiments demonstrate: complete molecular cycle composed of photochemical, thermal, and protolytic reaction steps; kinetics of cis-trans isomerization of the dye; and mechanism of base catalysis for thermal isomerization of the…

  17. Composite polymer/oxide hollow fiber contactors: versatile and scalable flow reactors for heterogeneous catalytic reactions in organic synthesis.

    Science.gov (United States)

    Moschetta, Eric G; Negretti, Solymar; Chepiga, Kathryn M; Brunelli, Nicholas A; Labreche, Ying; Feng, Yan; Rezaei, Fateme; Lively, Ryan P; Koros, William J; Davies, Huw M L; Jones, Christopher W

    2015-05-26

    Flexible composite polymer/oxide hollow fibers are used as flow reactors for heterogeneously catalyzed reactions in organic synthesis. The fiber synthesis allows for a variety of supported catalysts to be embedded in the walls of the fibers, thus leading to a diverse set of reactions that can be catalyzed in flow. Additionally, the fiber synthesis is scalable (e.g. several reactor beds containing many fibers in a module may be used) and thus they could potentially be used for the large-scale production of organic compounds. Incorporating heterogeneous catalysts in the walls of the fibers presents an alternative to a traditional packed-bed reactor and avoids large pressure drops, which is a crucial challenge when employing microreactors.

  18. An Environmentally-Friendly and Catalytic Procedure for Mukaiyama Aldol Reaction Using Organic Catalyst DBU under Solvent Free Conditions

    Institute of Scientific and Technical Information of China (English)

    SHEN,Zhi-Liang; JI,Shun-Jun; LOH,Teck Peng

    2004-01-01

    @@ Recently, methods based exclusively on organic catalysts have become of major significance in synthetic chemistry.Mukaiyama-aldol reaction, as one of the most important and frequently utilized methods for C-C bond formation, is well documented in literatures recently. A variety of reagents, particularly metal-containing Lewis acids or bases, are known to promote the nucleophilic process. However, many of the reported strategies might have the following limitations from environmental viewpoints: (1) the use of metal-containing catalyst. Some of the catalysts are air or moisture sensitive (such as lithium amide), and crucial reaction conditions are needed; Some of the catalysts derived from poisonous metal (for example: SnCl4, SmI2 etc.) may cause harmful influence on humane body and environment; (2) the use of organic solvent (such as DMF, CH2Cl2 etc.) may bring about environmental pollution and solvent waste.

  19. Characterization of catalytic supports based in mixed oxides for control reactions of NO and N{sub 2}O; Caracterizacion de soportes cataliticos basados en oxidos mixtos para reacciones de control de NO y N{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Garcia C, M.A.; Perez H, R.; Gomez C, A.; Diaz, G. [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    1999-07-01

    The catalytic supports Al{sub 2}O{sub 3}, La{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-La{sub 2}O{sub 3} were prepared by the Precipitation and Coprecipitation techniques. The catalytic supports Al{sub 2}O{sub 3}, La{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-La{sub 2}O{sub 3} were characterized by several techniques to determine: texture (Bet), crystallinity (XRD), chemical composition (Sem)(Ftir) and it was evaluated their total acidity by reaction with 2-propanol. The investigation will be continued with the cobalt addition and this will be evaluated for its catalytic activity in control reactions of N O and N{sub 2}O. (Author)

  20. Discrimination of Inner- and Outer-Sphere Electrode Reactions by Cyclic Voltammetry Experiments

    Science.gov (United States)

    Tanimoto, Sachiko; Ichimura, Akio

    2013-01-01

    A laboratory experiment for undergraduate students who are studying homogeneous and heterogeneous electron-transfer reactions is described. Heterogeneous or electrode reaction kinetics can be examined by using the electrochemical reduction of three Fe[superscript III]/Fe[superscript II] redox couples at platinum and glassy carbon disk electrodes.…

  1. 催化裂化提升管反应器中颗粒聚团裂化反应的数值模拟%Numerical Predication of Cracking Reaction of Particle Clusters in Fluid Catalytic Cracking Riser Reactors

    Institute of Scientific and Technical Information of China (English)

    王淑彦; 陆慧林; 高金森; 徐春明; 孙丹

    2008-01-01

    Behavior of catalytic cracking reactions of particle cluster in fluid catalytic cracking(FCC)riser reac-tors was numerically analyzed using a four-lump mathematical model.Effects of the cluster porosity.inlet gas ve-locity and temperature,and coke deposition on cracking reactions of the cluster were investigated. Distributions of temperature,gases,and gasoline from both catalyst particle cluster and an isolated catalyst particle are presented.The reaction rates from vacuum gas oil(VGO)to gasoline,gas and coke of individual particle in the cluster arehigher than those of the isolated particle,but it reverses for the reaction rates from gasoline to gas and coke.Less gasoline is produccd bv particle clustering.Simulated results show that the produced mass fluxes of gas and gasolineincrease with the operating temperature and molar concentration of VGO,and decrease due to the formation of coke.

  2. Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism.

    Science.gov (United States)

    Rossin, Andrea; Bottari, Giovanni; Lozano-Vila, Ana M; Paneque, Margarita; Peruzzini, Maurizio; Rossi, Andrea; Zanobini, Fabrizio

    2013-03-14

    Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH(2)-NR(2)](n) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-borane equivalent. The processes were followed through multinuclear ((31)P, (1)H, (11)B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.

  3. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions.

    Science.gov (United States)

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-07-06

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd(2+) precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal.

  4. Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Minjae [Kunsan National Univ., Gunsan (Korea, Republic of); Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B. [Chonbuk National Univ., Jeonju (Korea, Republic of)

    2014-07-15

    We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in H{sub 2} and O{sub 2} gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

  5. Qualitative Aspects of the Solutions of a Mathematical Model for the Dynamic Analysis of the Reversible Chemical Reaction SO2(g)+1/2O2(g)<=>SO3(g) in a Catalytic Reactor

    CERN Document Server

    Wilfredo, Angulo

    2014-01-01

    We present some qualitative aspects concerning the solution to the mathematical model describing the dynamical behavior of the reversible chemical reaction SO2(g)+1/2O2(g)SO3(g) carried out in a catalytic reactor used in the process of sulfuric acid production.

  6. 碳纳米管管腔在催化反应中的应用%Application of carbon nanotube channels in catalytic reactions

    Institute of Scientific and Technical Information of China (English)

    郭淑静

    2015-01-01

    The research progress in modification effect of carbon nanotubes for catalytic reactions confined inside their channels was summarized. The application of space confinement effect,spatial concentration effect and electronic modulation effect of carbon nanotubes was especially introduced. Carbon nanotubes could not only tune the particle size of the catalysts by changing the channel diameter,but also provide spatial restriction on metal catalyst encapsulated in their channels,which hampered particles aggregation during the reaction,thus maintaining good catalytic activity and stability. The spatial concentration effect of carbon nanotubes channels influenced on diffusion behavior of reactants and products around active particles by means of shape selectivity of carbon nanotubes channels,selective adsorption and desorption, thus modulating catalytic performance and the selectivity to product. Deviation from planarity caused electron density to shift from the concave inner to the convex outer surface,leading to the electron potential difference between inside and outside of carbon nanotubes,and therefore the electron density of the catalysts inside and outside carbon nanotubes was modified. The catalytic activity and the selectivity to products could be improved effectively.%综述近年来碳纳米管管腔对催化反应性能调变作用的研究进展,重点介绍碳纳米管管腔空间限域效应、空间富集效应和电子调变效应在催化反应中的应用,碳纳米管管腔的空间限域效应能够调节催化剂粒子大小,在反应过程中限制粒子团聚,有效维持反应活性和稳定性。碳纳米管管腔的空间富集效应通过管腔择形、选择吸附及脱附等影响催化反应中反应物和产物分子在管腔内活性位周围的扩散行为,从而影响反应活性和目标产物选择性。石墨烯片卷曲形成碳纳米管的过程中,造成碳纳米管管腔内缺电子管腔外富电子的特殊电子结

  7. Modification of the adsorption and catalytic properties of micro-and mesoporous materials by reactions with organometallic complexes

    Institute of Scientific and Technical Information of China (English)

    LEFEBVRE; Frédéric; PUTAJ; Piotr; BASSET; Jean-Marie

    2010-01-01

    This review describes the work of two laboratories in the field of the modification of micro-and mesoporous molecular sieves through reactions with organometallic complexes.The modification of zeolites can occur inside the pore channels or on the external surface,depending on the size of the organometallic complex.When the modification occurs on the external surface,it results in a decrease of the pore entrance,which will lead in turn to a modification of the sorption properties of the zeolite,by decreasing the rate of the adsorption(mainly by a kinetic control).Such a material can be also used in catalysis,because the external acid sites,which are responsible for side-reactions,have been removed upon grafting.When small organometallic complexes are used,they can fill the channels and cages of the zeolite and react with internal hydroxyl groups.Due to the high acidity of zeolites,the reaction occurs very easily(for example at-100℃ on faujasite),in contrast to what is observed on the external surface,therefore leading to high metal loadings.In that case,the modification of the sorption properties will be mainly related to a thermodynamic control.The resulting materials can be useful in catalysis,by combining the activity of the organometallic complex and properties(for example shape-selectivity) of the zeolite.Modification of mesoporous molecular sieves occurs always in the pores and results in altering of the sorption properties of the solid,by changing the interaction type between the sorbent and the sorbate.For example the sorption isotherm of alkanes is changed from type II to type III according to the IUPAC nomenclature.

  8. Study of the structure of unstable nuclei through the reaction experiments

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Along with the development of the radioactive nuclear beam facility, the study of the structure of unstable nuclei has progressed rapidly over the last few decades. Due to the weakly binding property, the structure information of the unstable nuclei comes primarily from the scattering or reaction experiments. Therefore it would be very important to understand clearly the reaction mechanism involved in the experiment. We outlined here the major reaction mechanisms which are adequate to the study of unstable nuclei, with the focus on the new phenomena and methods in comparison with those with traditional stable nucleus beam. Especially emphasized are the breakup and knockout reactions, developed as accurate tools for spectroscopy investigation into the nuclear structure with low intensity secondary beam. Couplings of the breakup channel to the elastic scattering and the fusion and transfer reactions are also reviewed.

  9. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    Science.gov (United States)

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P.; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G.; Kazantzis, Nikolaos K.; Ma, Yi Hua

    2016-01-01

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields. PMID:27657143

  10. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    Directory of Open Access Journals (Sweden)

    Bernardo Castro-Dominguez

    2016-09-01

    Full Text Available Palladium-based catalytic membrane reactors (CMRs effectively remove H2 to induce higher conversions in methane steam reforming (MSR and water-gas-shift reactions (WGS. Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i a conventional packed bed reactor packed (PBR for MSR, (ii a PBR with five layers of two catalysts in series and (iii a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields.

  11. Experiments on melt-rock reaction in the shallow mantle wedge

    Science.gov (United States)

    Mitchell, Alexandra L.; Grove, Timothy L.

    2016-12-01

    This experimental study simulates the interaction of hotter, deeper hydrous mantle melts with shallower, cooler depleted mantle, a process that is expected to occur in the upper part of the mantle wedge. Hydrous reaction experiments ( 6 wt% H2O in the melt) were conducted on three different ratios of a 1.6 GPa mantle melt and an overlying 1.2 GPa harzburgite from 1060 to 1260 °C. Reaction coefficients were calculated for each experiment to determine the effect of temperature and starting bulk composition on final melt compositions and crystallizing assemblages. The experiments used to construct the melt-wall rock model closely approached equilibrium and experienced phase equilibria, melt compositions, and reaction coefficients provide a framework for understanding how melt-wall rock reaction occurs in the natural system during melt ascent in the mantle wedge.

  12. Note: CO₂-mineral dissolution experiments using a rocking autoclave and a novel titanium reaction cell.

    Science.gov (United States)

    Purser, Gemma; Rochelle, Christopher A; Wallis, Humphrey C; Rosenqvist, Jörgen; Kilpatrick, Andrew D; Yardley, Bruce W D

    2014-08-01

    A novel titanium reaction cell has been constructed for the study of water-rock-CO2 reactions. The reaction cell has been used within a direct-sampling rocking autoclave and offers certain advantages over traditional "flexible gold/titanium cell" approaches. The main advantage is robustness, as flexible cells are prone to rupture on depressurisation during gas-rich experiments. The reaction cell was tested in experiments during an inter-laboratory comparison study, in which mineral kinetic data were determined. The cell performed well during experiments up to 130 °C and 300 bars pressure. The data obtained were similar to those of other laboratories participating in the study, and also to previously published data.

  13. Catalytic hydrogen/oxygen reaction assisted the proton exchange membrane fuel cell (PEMFC) startup at subzero temperature

    Science.gov (United States)

    Sun, Shucheng; Yu, Hongmei; Hou, Junbo; Shao, Zhigang; Yi, Baolian; Ming, Pingwen; Hou, Zhongjun

    Fuel cells for automobile application need to operate in a wide temperature range including freezing temperature. However, the rapid startup of a proton exchange membrane fuel cell (PEMFC) at subfreezing temperature, e.g., -20 °C, is very difficult. A cold-start procedure was developed, which made hydrogen and oxygen react to heat the fuel cell considering that the FC flow channel was the characteristic of microchannel reactor. The effect of hydrogen and oxygen reaction on fuel cell performance at ambient temperature was also investigated. The electrochemical characterizations such as I- V plot and cyclic voltammetry (CV) were performed. The heat generated rate for either the single cell or the stack was calculated. The results showed that the heat generated rate was proportional to the gas flow rate when H 2 concentration and the active area were constant. The fuel cell temperature rose rapidly and steadily by controlling gas flow rate.

  14. The strong catalytic effect of Pb(II) on the oxygen reduction reaction on 5 nm gold nanoparticles.

    Science.gov (United States)

    Wang, Ying; Laborda, Eduardo; Plowman, Blake J; Tschulik, Kristina; Ward, Kristopher R; Palgrave, Robert G; Damm, Christine; Compton, Richard G

    2014-02-21

    Citrate-capped gold nanoparticles (AuNPs) of 5 nm in diameter are synthesized via wet chemistry and deposited on a glassy carbon electrode through electrophoresis. The kinetics of the oxygen reduction reaction (ORR) on the modified electrode is determined quantitatively in oxygen-saturated 0.5 M sulphuric acid solution by modelling the cathode as an array of interactive nanoelectrodes. Quantitative analysis of the cyclic voltammetry shows that no apparent ORR electrocatalysis takes place, the kinetics on AuNPs being effectively the same as on bulk gold. Contrasting with the above, a strong ORR catalysis is found when Pb(2+) is added to the oxygen saturated solution or when the modified electrode is cycled in lead alkaline solution such that lead dioxide is repeatedly electrodeposited and stripped off on the nanoparticles. In both cases, the underpotential deposition of lead on the gold nanoparticles is found to be related to the catalysis.

  15. Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions.

    Science.gov (United States)

    Wang, Meihua; Gao, Zhe; Zhang, Bin; Yang, Huimin; Qiao, Yan; Chen, Shuai; Ge, Huibin; Zhang, Jiankang; Qin, Yong

    2016-06-13

    Metal-support interfaces play a prominent role in heterogeneous catalysis. However, tailoring the metal-support interfaces to realize full utilization remains a major challenge. In this work, we propose a graceful strategy to maximize the metal-oxide interfaces by coating confined nanoparticles with an ultrathin oxide layer. This is achieved by sequential deposition of ultrathin Al2 O3 coats, Pt, and a thick Al2 O3 layer on carbon nanocoils templates by atomic layer deposition (ALD), followed by removal of the templates. Compared with the Pt catalysts confined in Al2 O3 nanotubes without the ultrathin coats, the ultrathin coated samples have larger Pt-Al2 O3 interfaces. The maximized interfaces significantly improve the activity and the protecting Al2 O3 nanotubes retain the stability for hydrogenation reactions of 4-nitrophenol. We believe that applying ALD ultrathin coats on confined catalysts is a promising way to achieve enhanced performance for other catalysts.

  16. Catalytic hydrotreating process

    Science.gov (United States)

    Karr, Jr., Clarence; McCaskill, Kenneth B.

    1978-01-01

    Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  17. Adverse drug reaction reporting by patients in the Netherlands - Three years of experience

    NARCIS (Netherlands)

    de Langen, Joyce; van Hunsel, Florence; Passier, Anneke; de Jong-van den Berg, Lolkje; van Grootheest, Kees

    2008-01-01

    Background: There has been discussion about the acceptance of adverse drug reactions (ADRs) reported by patients to spontaneous reporting systems. Lack of experience with patient reporting in real life was one of the main drawbacks in this debate. This study covers 3 years of experience with patient

  18. Palladacyclic imidazoline-naphthalene complexes: synthesis and catalytic performance in Pd(II)-catalyzed enantioselective reactions of allylic trichloroacetimidates.

    Science.gov (United States)

    Cannon, Jeffrey S; Frederich, James H; Overman, Larry E

    2012-02-17

    A new family of air- and moisture-stable enantiopure C,N-palladacycles (PIN-acac complexes) were prepared in good overall yield in three steps from 2-iodo-1-naphthoic acid and enantiopure β-amino alcohols. Three of these PIN complexes were characterized by single-crystal X-ray analysis. As anticipated, the naphthalene and imidazoline rings of PIN-acac complexes 18a and 18b were canted significantly from planarity and projected the imidazoline substituents R(1) and R(2) on opposite faces of the palladium square plane. Fifteen PIN complexes were evaluated as catalysts for the rearrangement of prochiral (E)-allylic trichloroacetimidate 19 (eq 2) and the S(N)2' allylic substitution of acetic acid with prochiral (Z)-allylic trichloroacetimidate 23. Although these complexes were kinetically poor catalysts for the Overman rearrangement, they were good catalysts for the allylic substitution reaction, providing branched allylic esters in high yield. However, enantioselectivities were low to moderate and significantly less than that realized with palladacyclic complexes of the COP family. Computational studies support an anti-acetoxypalladation/syn-deoxypalladation mechanism analogous to that observed with COP catalysts. The computational study further suggests that optimizing steric influence in the vicinity of the carbon ligand of a chiral C,N-palladacycle, rather than near the nitrogen heterocycle, is the direction to pursue in future development of improved enantioselective catalysts of this motif.

  19. Kinetic modelling of hydrocracking catalytic reactions by the single events theory; Modelisation cinetique des reactions catalytiques d`hydrocraquage par la theorie des evenements constitutifs

    Energy Technology Data Exchange (ETDEWEB)

    Schweitzer, J.M.

    1998-11-23

    Kinetic modelling of petroleum hydrocracking is particularly difficult given the complexity of the feedstocks. There are two distinct classes of kinetics models: lumped empirical models and detailed molecular models. The productivity of lumped empirical models is generally not very accurate, and the number of kinetic parameters increases rapidly with the number of lumps. A promising new methodology is the use of kinetic modelling based on the single events theory. Due to the molecular approach, a finite and limited number of kinetic parameters can describe the kinetic behaviour of the hydrocracking of heavy feedstock. The parameters are independent of the feedstock. However, the available analytical methods are not able to identify the products on the molecular level. This can be accounted for by means of an posteriori lamping technique, which incorporates the detailed knowledge of the elementary step network. Thus, the lumped kinetic parameters are directly calculated from the fundamental kinetic coefficients and the single event model is reduced to a re-lumped molecular model. Until now, the ability of the method to extrapolate to higher carbon numbers had not been demonstrated. In addition, no study had been published for three phase (gas-liquid-solid) systems and a complex feedstock. The objective of this work is to validate the `single events` method using a paraffinic feedstock. First of all, a series of experiments was conducted on a model compound (hexadecane) in order to estimate the fundamental kinetic parameters for acyclic molecules. To validate the single event approach, these estimated kinetic coefficients were used to simulate hydrocracking of a paraffinic mixture ranging from C11 to C18. The simulation results were then compared to the results obtained from the hydrocracking experiments. The comparison allowed to validate the model for acyclic molecules and to demonstrate that the model is applicable to compounds with higher carbon numbers. (author

  20. Medical Students’ Experience of and Reaction to Stress: The Role of Depression and Anxiety

    Directory of Open Access Journals (Sweden)

    Coumaravelou Saravanan

    2014-01-01

    Full Text Available Background. Medical school is recognized as a stressful environment that often has a negative effect on students’ academic performance, physical health, and psychosocial well-being. Previous studies have not identified differences between depressed and nondepressed and anxious and nonanxious medical students’ experiences of stress or their reactions to stressors. The present study aimed to identify the prevalence of depression and anxiety among a sample of 358 medical students attending a private university in Malaysia and to examine differences according to participants’ gender, year of study, and stage of training (preclinical and clinical. Additionally, this study examined the extent to which stress predicts depression and anxiety, differences between depressed and nondepressed medical students’ experiences of and reactions to stressors, and differences between anxious and nonanxious medical students’ experiences of and reactions to stressors. Methods. The Student Life Stress Inventory was used to measure stress and reaction to stressors and the Depression, Anxiety, and Stress Scale was used to measure depression and anxiety. Results. The results showed that 44% (n=158 of the students were anxious and 34.9% (n=125 were depressed. More female students exhibited anxiety compared to male students. Stress is a predictor for depression and anxiety. A significant difference was found between depressed and nondepressed and anxious and nonanxious students’ experience of stressors due to frustration, change, and their emotional reaction to stressors. Conclusion. Overall, depressed and anxious students were found to experience more stress and react differently to stressors compared to nondepressed and nonanxious students.

  1. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    Science.gov (United States)

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-09-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

  2. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed

    2014-11-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts\\' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  3. The reaction kinetics of 3-hydroxybenzoate 6-hydroxylase from Rhodococcus jostii RHA1 provide an understanding of the para-hydroxylation enzyme catalytic cycle.

    Science.gov (United States)

    Sucharitakul, Jeerus; Tongsook, Chanakan; Pakotiprapha, Danaya; van Berkel, Willem J H; Chaiyen, Pimchai

    2013-12-06

    3-Hydroxybenzoate 6-hydroxylase (3HB6H) from Rhodococcus jostii RHA1 is an NADH-specific flavoprotein monooxygenase that catalyzes the para-hydroxylation of 3-hydroxybenzoate (3HB) to form 2,5-dihydroxybenzoate (2,5-DHB). Based on results from stopped-flow spectrophotometry, the reduced enzyme-3HB complex reacts with oxygen to form a C4a-peroxy flavin with a rate constant of 1.13 ± 0.01 × 10(6) m(-1) s(-1) (pH 8.0, 4 °C). This intermediate is subsequently protonated to form a C4a-hydroperoxyflavin with a rate constant of 96 ± 3 s(-1). This step shows a solvent kinetic isotope effect of 1.7. Based on rapid-quench measurements, the hydroxylation occurs with a rate constant of 36 ± 2 s(-1). 3HB6H does not exhibit substrate inhibition on the flavin oxidation step, a common characteristic found in most ortho-hydroxylation enzymes. The apparent kcat at saturating concentrations of 3HB, NADH, and oxygen is 6.49 ± 0.02 s(-1). Pre-steady state and steady-state kinetic data were used to construct the catalytic cycle of the reaction. The data indicate that the steps of product release (11.7 s(-1)) and hydroxylation (36 ± 2 s(-1)) partially control the overall turnover.

  4. Hydrogen Effect on Coke Removal and Catalytic Performance in Pre-Carburization and Methane Dehydro-Aromatization Reaction on Mo/HZSM-5

    Institute of Scientific and Technical Information of China (English)

    Hongtao Ma; Ryoichi Kojima; Satoshi Kikuchi; Masaru Ichikawa

    2005-01-01

    In this study,the effects of pre-carburization of catalyst,hydrogen addition to methane feed and the space velocity of methane on the catalytic performance in methane to benzene (MTB) reaction were discussed in detail over Mo/HZSM-5 catalyst at 1023 K and 0.3 MPa. Compared with the non-precarburized catalyst,the Mo catalyst pre-carburized under the flow of CH4+4H2 at 973 K was found to have the higher activity and better stability. Further 6% H2 addition to the methane feed suppressed the aromatic type of coke formation effectively,and improved the stability of catalyst markedly,moreover gave a much longer reaction life of catalyst (53 h at 1023 K and 5400 ml/(g·h)) and much more formation amounts of benzene and hydrogen. With increase of methane space velocity,both the naphthalene formation selectivity and the coke formation selectivity were decreased by the shortened contact time;the benzene formation selectivity and total formation amount before the complete deactivation of catalyst were increased ly,while the total naphthalene and coke formation amounts did not change much.At high methane space velocity (≥5400 ml/(g·h)),a new middle temperature coke derived from the high temperature aromatic coke was formed on the catalyst; all the coke formed could be burnt off at lower temperature in oxygen,compared with those obtained at low space velocity. Considering the benzene formation amount and catalyst stability together,5400 ml/(g·h) was proved to be the most efficient methane space velocity for benzene production.

  5. EPR Spectroscopy of catalytic systems based on nickel complexes of 1,4-diaza-1,3-butadiene (α-diimine) ligands in hydrogenation and polymerization reactions

    Science.gov (United States)

    Titova, Yu. Yu.; Belykh, L. B.; Schmidt, F. K.

    2015-01-01

    EPR spectroscopy is used to study catalytic hydration and polymerization reaction systems based on α-diimine complexes of Ni(0) and Ni(II) with the general formula NiBr2(DAD-R) (R = -C3H7 or -CH3) or Ni(DAD-CH3)2 (DAD(-C3H7) = 1,4-bis(2,6-diiso-propylphenyl)-2,3-(dimethyl-1,4-diazabuta-1,3-diene, DAD(-CH3) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene)), in combination with Lewis acids (AlEt3, AlEt2Cl, AlEtCl2, B(F5C6)3, BF3.OEt2). Ni(I) complexes of the form (DAD-R)NiX2AlX'y(C2H5)3-y composition (an aluminum atom can be replaced by a boron atom) were identified, where R = -CH3 or -C3H7, X = Br, and X' = Cl or -C2H5 and α-diimine anion radicals are included in derivatives of aluminum or boron. Oxidation reactions of the Ni(DAD-CH3)2 complex with aluminum alkyl halides and boron derivatives with formation of paramagnetic nickel complexes are observed. It is found that there is no direct relationship between the polymerization activity of ethylene or hydration of the alkenes and the concentration of paramagnetic particles.

  6. Sodium chloride precipitation reaction coefficient from crystallization experiment in a microfluidic device

    Science.gov (United States)

    Naillon, A.; Joseph, P.; Prat, M.

    2017-04-01

    The crystal growth of sodium chloride from an aqueous solution is studied from evaporation experiments in microfluidic channels in conjunction with analytical and numerical computations. The crystal growth kinetics is recorded using a high speed camera in order to determine the intrinsic precipitation reaction coefficient. The study reveals that the crystal growth rates determined in previous studies are all affected by the ions transport phenomena in the solution and thus not representative of the precipitation reaction. It is suggested that accurate estimate of sodium chloride precipitation reaction coefficient presented here offers new opportunities for a better understanding of important issues involved in the damages of porous materials induced by the salt crystallization.

  7. Some Aspects of the Catalytic Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Anil; K.Saikia

    2007-01-01

    1 Results Catalytic reactions are gaining importance due to its low cost, operational simplicity, high efficiency and selectivity. It is also getting much attention in green synthesis. Many useful organic reactions, including the acylation of alcohols and aldehydes, carbon-carbon, carbon-nitrogen, carbon-sulfur bond forming and oxidation reactions are carried out by catalyst. We are exploring the catalytic acylation of alcohols and aldehydes in a simple and efficient manner. Catalytic activation of unr...

  8. Produção de etilenoglicóis e derivados por reações catalíticas do óxido de eteno Production of ethyleneglycols and derivates by catalytic reactions of ethylene oxide

    Directory of Open Access Journals (Sweden)

    Leandro Martins

    2005-03-01

    Full Text Available Products resulting from the ethoxylation of hydroxylated compounds, especially water and ethanol, are of great commercial importance. This work presents several aspects concerning the catalytic reactions of ethylene oxide, a chemical substance used in the production of a wide variety of products. Mechanisms of ethoxylation, distribution of products, formation of undesired by-products and perspectives for new processes using heterogeneous catalysis are also reviewed and discussed.

  9. Produção de etilenoglicóis e derivados por reações catalíticas do óxido de eteno Production of ethyleneglycols and derivates by catalytic reactions of ethylene oxide

    OpenAIRE

    2005-01-01

    Products resulting from the ethoxylation of hydroxylated compounds, especially water and ethanol, are of great commercial importance. This work presents several aspects concerning the catalytic reactions of ethylene oxide, a chemical substance used in the production of a wide variety of products. Mechanisms of ethoxylation, distribution of products, formation of undesired by-products and perspectives for new processes using heterogeneous catalysis are also reviewed and discussed.

  10. Shape and catalytic mechanism of RuO{sub 2} particles at CO oxidation reaction conditions. First-principles based multi-scale modeling

    Energy Technology Data Exchange (ETDEWEB)

    Reuter, Karsten [TU Muenchen (Germany). Lehrstuhl fuer Theoretische Chemie

    2016-11-01

    For model catalyst studies on low-index single-crystal surfaces close agreement between detailed measurements and quantitative microkinetic modeling can increasingly be achieved. However, for 'real' catalyst particles, such structure-morphology-activity relationships are only scarcely established. This is prototypically reflected by the situation for RuO{sub 2}, as a most active catalyst for CO oxidation. Here, existing first-principles kinetic modeling is restricted to just one facet, namely the RuO{sub 2}(110) surface, which is not able to fully account for activity data obtained from polycrystalline RuO{sub 2} powder catalysts. The overarching objective of this project was correspondingly to close this gap and demonstrate that similarly close agreement as for individual single-crystal model catalysts can also be achieved for catalyst particles. Specifically, we addressed experiments where an intact RuO{sub 2} bulk structure is conserved, and establish the atomic-scale structure and reactivity of other RuO{sub 2} low-index facets under the gas-phase conditions characteristic for catalytic CO oxidation.

  11. An oxyferrous heme/protein-based radical intermediate is catalytically competent in the catalase reaction of Mycobacterium tuberculosis catalase-peroxidase (KatG).

    Science.gov (United States)

    Suarez, Javier; Ranguelova, Kalina; Jarzecki, Andrzej A; Manzerova, Julia; Krymov, Vladimir; Zhao, Xiangbo; Yu, Shengwei; Metlitsky, Leonid; Gerfen, Gary J; Magliozzo, Richard S

    2009-03-13

    A mechanism accounting for the robust catalase activity in catalase-peroxidases (KatG) presents a new challenge in heme protein enzymology. In Mycobacterium tuberculosis, KatG is the sole catalase and is also responsible for peroxidative activation of isoniazid, an anti-tuberculosis pro-drug. Here, optical stopped-flow spectrophotometry, rapid freeze-quench EPR spectroscopy both at the X-band and at the D-band, and mutagenesis are used to identify catalase reaction intermediates in M. tuberculosis KatG. In the presence of millimolar H2O2 at neutral pH, oxyferrous heme is formed within milliseconds from ferric (resting) KatG, whereas at pH 8.5, low spin ferric heme is formed. Using rapid freeze-quench EPR at X-band under both of these conditions, a narrow doublet radical signal with an 11 G principal hyperfine splitting was detected within the first milliseconds of turnover. The radical and the unique heme intermediates persist in wild-type KatG only during the time course of turnover of excess H2O2 (1000-fold or more). Mutation of Met255, Tyr229, or Trp107, which have covalently linked side chains in a unique distal side adduct (MYW) in wild-type KatG, abolishes this radical and the catalase activity. The D-band EPR spectrum of the radical exhibits a rhombic g tensor with dual gx values (2.00550 and 2.00606) and unique gy (2.00344) and gz values (2.00186) similar to but not typical of native tyrosyl radicals. Density functional theory calculations based on a model of an MYW adduct radical built from x-ray coordinates predict experimentally observed hyperfine interactions and a shift in g values away from the native tyrosyl radical. A catalytic role for an MYW adduct radical in the catalase mechanism of KatG is proposed.

  12. Agreement and Null Subjects in German L2 Development: New Evidence from Reaction-Time Experiments.

    Science.gov (United States)

    Clahsen, Harald; Hong, Upyong

    1995-01-01

    Reports on reaction time experiments investigating subject-verb agreement and null subjects in 33 Korean learners of German and a control group of 20 German native speakers. Results found that the two phenomena do not covary in the Korean learners, indicating that properties of agreement and null subjects are acquired separately from one another.…

  13. Unraveling the reaction mechanisms governing methanol-to-olefins catalysis by theory and experiment.

    Science.gov (United States)

    Hemelsoet, Karen; Van der Mynsbrugge, Jeroen; De Wispelaere, Kristof; Waroquier, Michel; Van Speybroeck, Veronique

    2013-06-03

    The conversion of methanol to olefins (MTO) over a heterogeneous nanoporous catalyst material is a highly complex process involving a cascade of elementary reactions. The elucidation of the reaction mechanisms leading to either the desired production of ethene and/or propene or undesired deactivation has challenged researchers for many decades. Clearly, catalyst choice, in particular topology and acidity, as well as the specific process conditions determine the overall MTO activity and selectivity; however, the subtle balances between these factors remain not fully understood. In this review, an overview of proposed reaction mechanisms for the MTO process is given, focusing on the archetypal MTO catalysts, H-ZSM-5 and H-SAPO-34. The presence of organic species, that is, the so-called hydrocarbon pool, in the inorganic framework forms the starting point for the majority of the mechanistic routes. The combination of theory and experiment enables a detailed description of reaction mechanisms and corresponding reaction intermediates. The identification of such intermediates occurs by different spectroscopic techniques, for which theory and experiment also complement each other. Depending on the catalyst topology, reaction mechanisms proposed thus far involve aromatic or aliphatic intermediates. Ab initio simulations taking into account the zeolitic environment can nowadays be used to obtain reliable reaction barriers and chemical kinetics of individual reactions. As a result, computational chemistry and by extension computational spectroscopy have matured to the level at which reliable theoretical data can be obtained, supplying information that is very hard to acquire experimentally. Special emphasis is given to theoretical developments that open new perspectives and possibilities that aid to unravel a process as complex as methanol conversion over an acidic porous material.

  14. An ab initio study on the chemical reactions in the Cl-ClO catalytic cycle%Cl-ClO催化循环圈的从头算研究

    Institute of Scientific and Technical Information of China (English)

    毛连港; 邴单; 赵永芳; 李根全; 李新营; 蒿凤有; 刘凤丽

    2006-01-01

    One of processes of the ozone depletion in the polar stratosphere is investigated by using an ab initio calculation at the B3LYP/6-311+G (3df) and the G2 levels. The calculated result obviously supported the theory on destroying ozone mechanism of the Cl-ClO catalytic cycle, and explained basic reason of the destroying ozone from the energy point of view. The reactional energy, the enthalpy of formation, and relative Gibbs free energy of the reactions in the ClClO catalytic cycle are calculated exactly, and provided thermodynamics quantities for the reactions in the Cl-ClO catalytic cycle.%采用分子轨道从头算方法,在B3LYP/6-311+G(3df)和G2水平上研究了极地平流层臭氧损耗的一个基本过程.计算结果明显支持Cl-ClO催化循环圈机理,并且从能量角度解释了了臭氧破坏的基本原因.还对循环圈中各个反应的反应能,生成焓,相对吉布斯自由能做了计算,计算结果相互协调都说明了Cl-ClO催化循环圈破坏臭氧机理的正确性.

  15. Morphology of melt-rich channels formed during reaction infiltration experiments on partially molten mantle rocks

    Science.gov (United States)

    Pec, Matej; Holtzman, Benjamin; Zimmerman, Mark; Kohlstedt, David

    2016-04-01

    Geochemical, geophysical and geological observations suggest that melt extraction from the partially molten mantle occurs by some sort of channelized flow. Melt-solid reactions can lead to melt channelization due to a positive feedback between melt flow and reaction. If a melt-solid reaction increases local permeability, subsequent flow is increased as well and promotes further reaction. This process can lead to the development of high-permeability channels which emerge from background flow. In nature, anastomozing tabular dunite bodies within peridotitic massifs are thought to represent fossilized channels that formed by reactive flow. The conditions under which such channels can emerge are treated by the reaction infiltration instability (RII) theory (e.g. Szymczak and Ladd 2014). In this contribution, we report the results of a series of Darcy type experiments designed to study the development of channels due to RII in mantle lithologies (Pec et al. 2015). We sandwiched a partially molten rock between a melt source and a porous sink and annealed it at high-pressures (P = 300 MPa) and high-temperatures (T = 1200° or 1250° C) under a controlled pressure gradient (∇P = 0-100 MPa/mm) for up to 5 hours. The partially molten rock is formed by 50:50 mixtures of San Carlos olivine (Ol, Fo ˜ 88) and clinopyroxene (Cpx) with either 4, 10 or 20 vol% of alkali basalt added. The source and sink are disks of alkali basalt and porous alumina, respectively. During the experiments, silica undersaturated melt from the melt source dissolves Cpx and precipitates an iron rich Ol (Fo ˜ 82) thereby forming a Cpx-free reaction layer at the melt source - partially molten rock interface. The melt fraction in the reaction layer increases significantly (40% melt) compared to the protolith, confirming that the reaction increases the permeability of the partially molten rock. In experiments annealed under a low pressure gradient (and hence slow melt flow velocity) the reaction layer is

  16. Catalytic degradation of high-density polyethylene on an ultrastable-Y zeolite. Nature of initial polymer reactions, pattern of formation of gas and liquid products, and temperature effects

    Energy Technology Data Exchange (ETDEWEB)

    Manos, G.; Garforth, A.; Dwyer, J.

    2000-05-01

    The catalytic degradation of high-density polyethylene (hdPE) over ultrastable Y zeolite in a semibatch reactor was studied at different heating rates and reaction temperatures. Catalytic degradation of the polymer occurred at much lower temperatures than pure thermal degradation. When gel permeation chromatography was used to determine the molar mass distribution, it was found that solid state reactions occur only in the presence of a catalyst. These reactions change the polymer structure well before the formation of significant amounts of volatile products. The pattern of formation of gaseous and liquid products was studied and found to follow the temperature increase. After the system reached its final temperature, the reaction rate of formation of volatile products decreased rapidly. The product range was typically between C{sub 3} and C{sub 15}. Isobutane and isopentane were the main gaseous products. The liquid product fraction was alkane-rich, as alkenes rapidly undergo bimolecular hydrogen transfer reactions to give alkanes as secondary products.

  17. [Platelet transfusion and allergic transfusion reactions: experiences at Lille Hospital over a four year period].

    Science.gov (United States)

    Wibaut, B; Vannier, V; Renom, P; Goudemand, J

    2000-04-01

    Among the immediate transfusion reactions caused by the utilization of blood products, those suggesting immuno-allergic mechanisms posed problems for frequency, gravity, laboratory diagnosis and safety. We report here the Lille Hospital's experience over a four-year period concerning these manifestations after platelet concentrate transfusion. Eight hundred and fifty-two immediate transfusion reactions have been declared, of which 230 were allergic, which appeared in 181 patients (27%). Among the most frequent clinical signs, rash was often described (158 cases: 68.7%); less frequent were respiratory problems such as dyspnea (34 cases: 14.8%) and hypotensive reactions (18 cases: 7.8%). Seven patients presented severe reactions (3%). Twenty percent of them presented multiple allergic reactions and in 43.2%, the recurrence was more serious than the initial problem in spite of preventive medication; the use of washed blood components was necessary. The age of platelet concentrates does not appear to play a part in provoking these events (67% of platelet concentrates had been collected within four days). These allergic transfusion reactions posed problems for those who prescribe medication, because they are frequent, sometimes serious, can recur and at present, the proposed medication prevention is not always efficient.

  18. One-pot synthesis of imines from nitroaromatics and alcohols by tandem photocatalytic and catalytic reactions on Degussa (Evonik) P25 titanium dioxide.

    Science.gov (United States)

    Hirakawa, Hiroaki; Katayama, Miyu; Shiraishi, Yasuhiro; Sakamoto, Hirokatsu; Wang, Kunlei; Ohtani, Bunsho; Ichikawa, Satoshi; Tanaka, Shunsuke; Hirai, Takayuki

    2015-02-18

    Photoirradiation (λ > 300 nm) of Degussa (Evonik) P25 TiO2, a mixture of anatase and rutile particles, in alcohols containing nitroaromatics at room temperature produces the corresponding imines with very high yields (80-96%). Other commercially available anatase or rutile TiO2 particles, however, exhibit very low yields (anatase and rutile particles were isolated from P25 TiO2 by the H2O2/NH3 and HF treatments to clarify the activity of these two step reactions. Photocatalysis experiments revealed that the active sites for photocatalytic reactions on P25 TiO2 are the rutile particles, promoting efficient reduction of nitrobenzene on the surface defects. In contrast, catalysis experiments showed that the anatase particles isolated from P25 TiO2 exhibit very high activity for condensation of aldehyde and aniline, because the number of Lewis acid sites on the particles (73 μmol g(-1)) is much higher than that of other commercially available anatase or rutile particles (rutile and anatase particles, thus producing imines with very high yields.

  19. Characterization of Sodium Ion Electrochemical Reaction with Tin Anodes: Experiment and Theory

    Energy Technology Data Exchange (ETDEWEB)

    Baggetto, Loic [ORNL; Meisner, Roberta A [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Ganesh, Panchapakesan [ORNL; Unocic, Raymond R [ORNL; Bridges, Craig A [ORNL; Jumas, Dr. Jean-Claude [Institut Charles Gerhardt, University of Montpellier II, FRANCE; Veith, Gabriel M [ORNL

    2013-01-01

    Tin anodes show a rich structure and reaction chemistry which we have investigated in detail. Upon discharge five plateaus are observed corresponding to -Sn, an unidentified phase (Na/Sn = 0.6), an amorphous phase (Na/Sn = 1.2), a hexagonal R-3m Na5Sn2, and fully sodiated Na15Sn 4. With charging there are six plateaus, which are related to the formation of Na5Sn2 followed by the formation of amorphous phases and -Sn. Upon cycling the formation of metastable Na5Sn2 seems to be suppressed, leading to a single charge plateau at 0.2 V. Theoretical voltages calculated from existing crystal structures using DFT provide a good match with constant current measurements, however, the voltage is more negative compared to quasi-equilibrium measurements (GITT). Search for additional (meta)stable phases using cluster-expansion method predicts many phases lower in energy than the convex hull, including the R-3m Na5Sn2 phase characterized experimentally. The presence of multiple phases in varying lattices with very similar formation energy suggests why the reaction mechanism is non-reversible. Interpretation of M ssbauer spectroscopy data is not yet elucidated due to the very low recoil-free fraction of the materials. The electrode surface is terminated with a SEI layer rich in carbonates such as Na2CO3 and Na alkyl carbonates as evidenced by XPS. After a full charge at 2V, strong evidence for the formation of oxidized Sn4+ is obtained. Subjecting the electrode to a rest after a full charge at 2 V reveals that aging in the electrolyte reduces the oxidized Sn4+ into Sn2+ and Sn0, and concomitantly suppresses the electrolyte decomposition represented by an anomalous discharge plateau at 1.2 V. Thereby, the catalytic decomposition of the electrolyte during discharge is caused by nanosized Sn particles covered by oxidized Sn4+ and not by pure metallic Sn.

  20. Catalysis of Photochemical Reactions.

    Science.gov (United States)

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  1. QRTEngine: An easy solution for running online reaction time experiments using Qualtrics.

    Science.gov (United States)

    Barnhoorn, Jonathan S; Haasnoot, Erwin; Bocanegra, Bruno R; van Steenbergen, Henk

    2015-12-01

    Performing online behavioral research is gaining increased popularity among researchers in psychological and cognitive science. However, the currently available methods for conducting online reaction time experiments are often complicated and typically require advanced technical skills. In this article, we introduce the Qualtrics Reaction Time Engine (QRTEngine), an open-source JavaScript engine that can be embedded in the online survey development environment Qualtrics. The QRTEngine can be used to easily develop browser-based online reaction time experiments with accurate timing within current browser capabilities, and it requires only minimal programming skills. After introducing the QRTEngine, we briefly discuss how to create and distribute a Stroop task. Next, we describe a study in which we investigated the timing accuracy of the engine under different processor loads using external chronometry. Finally, we show that the QRTEngine can be used to reproduce classic behavioral effects in three reaction time paradigms: a Stroop task, an attentional blink task, and a masked-priming task. These findings demonstrate that QRTEngine can be used as a tool for conducting online behavioral research even when this requires accurate stimulus presentation times.

  2. Using a dual plasma process to produce cobalt--polypyrrole catalysts for the oxygen reduction reaction in fuel cells -- part I: characterisation of the catalytic activity and surface structure

    CERN Document Server

    Walter, Christian; Vyalikh, Denis; Brüser, Volker; Quade, Antje; Weltmann, Klaus-Dieter; 10.1149/2.078208jes

    2012-01-01

    A new dual plasma coating process to produce platinum-free catalysts for the oxygen reduction reaction in a fuel cell is introduced. The catalysts thus produced were analysed with various methods. Electrochemical characterisation was carried out by cyclic voltammetry, rotating ring- and rotating ring-disk electrode. The surface porosity of the different catalysts thus obtained was characterised with the nitrogen gas adsorption technique and scanning electron microscopy was used to determine the growth mechanisms of the films. It is shown that catalytically active compounds can be produced with this dual plasma process. Furthermore, the catalytic activity can be varied significantly by changing the plasma process parameters. The amount of H$_2$O$_2$ produced was calculated and shows that a 2 electron mechanism is predominant. The plasma coating mechanism does not significantly change the surface BET area and pore size distribution of the carbon support used. Furthermore, scanning electron microscopy pictures o...

  3. LaMn1-xFe xO3 and LaMn0.1-xFe0.90Mo x O3 perovskites: synthesis, characterization and catalytic activity in H2O2 reactions

    Directory of Open Access Journals (Sweden)

    Fabiano Magalhães

    2008-09-01

    Full Text Available In this work two perovskites were prepared: LaMn1-xFe xO3, and LaMn0.1-x Fe0.90Mo xO3. XRD and Mössbauer spectroscopy suggest the formation of pure phase perovskite with the incorporation of Fe and Mo in the structure. The catalytic activity of these materials was studied in two reactions with H2O2: the decomposition to O2, and the oxidation of the model organic contaminant methylene blue. The perovskite composition strongly affects the catalytic activity, while Fe decreases the H2O2 decomposition Mo strongly improves dye oxidation.

  4. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  5. 非均相羰基氧化一步合成碳酸二苯酯的研究(Ⅴ)筛选催化剂及优化合成条件%Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (Ⅴ) Screening Catalysts and Optimizing Synthesis Conditions

    Institute of Scientific and Technical Information of China (English)

    张光旭; 吴元欣; 马沛生; 田崎峰; 吴广文; 李定或; 王存文

    2003-01-01

    Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was La0.62Pb0.38MnO3 and the average diameter could be about 25.4nm. The optimum conditions for synthesis of DPC with Pd/LaxPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio 1 to 50, pressure 4.5 MPa,volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

  6. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)

    2013-11-01

    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  7. Gas-solid catalytic reactions over ruthenium-based catalysts%钌基催化剂催化的气固相反应

    Institute of Scientific and Technical Information of China (English)

    施文博; 刘霄龙; 曾俊淋; 王健; 魏耀东; 朱廷钰

    2016-01-01

    防止高温焙烧导致催化剂烧结.对于 HCl氧化虽然研究较少,但是 Over等人对 HCl氧化机理进行了深入研究,并且日本住友化工设计的 Ru基催化剂已经商业化. Ru基催化剂可以有效降低甲烷部分氧化的反应温度和压力,并具有高的选择性和稳定性,避免副产物生成.现有催化系统以及新型催化剂开发仍面临诸多挑战,例如:对于单一 VOC氧化过程和多元 VOCs催化氧化的机理和动力学需要进一步研究;对于氨合成需要寻求具有高电导率的载体,从而将电子快速转移到 Ru颗粒表面,使得氨合成在更低温度下进行;为了避免副产物生成,需确保新型 Ru基催化剂上PROX和甲烷部分氧化在低温低压条件下进行; Ru基催化剂理化性质对活性的影响以及失活等问题需要进一步研究.%Ruthenium (Ru)‐based catalysts are widely employed in several types of gas‐solid reactions because of their high catalytic activities. This review provides theoretical research on Ru‐based catalysts and an analysis of their basic properties and oxidation behavior. There is particular emphasis on Ru‐catalyzed gas‐solid catalytic reactions, including the catalytic oxidation of VOCs, preferential oxidation of CO, synthesis of ammonia, oxidation of HCl and partial oxidation of CH4. Recent litera‐ture on catalysis is summarized and compared. Finally, we describe current challenges in the field and propose approaches for future development of Ru‐based catalysts.

  8. Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst Ⅱ. Experimental results of catalytic decarboxylation over acidic catalysts

    Institute of Scientific and Technical Information of China (English)

    Fu Xiaoqin; Tian Songbai; Hou Shuandi; Longjun; Wang Xieqing

    2008-01-01

    The energy barriers of thermal decarboxylation reactions of petroleum acids and catalytic decarboxylation reactions of Br(o)nsted acid and Lewis acid were analyzed using molecular simulation technology.Compared with thermal decarboxylation reactions of petroleum acids, the decarboxylation reactions by acid catalysts were easier to occur. The decarboxylaton effect by Lewis acid was better than Br(o)nsted acid. The mechanisms of catalytic decarboxylation over acid catalyst were also verified by experiments on a fixed bed and a fluidized bed, the experimental results showed that the rate of acid removal could reach up to 97% over the acidic catalyst at a temperature above 400℃.

  9. Preparation of Rh-TPPTS complex intercalated layered double hydroxide and influences of host and guest compositions on its catalytic performances in hydroformylation reaction

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xian; LU Jun; JIN Lan; WEI Min

    2008-01-01

    Based on the concept of intercalation chemistry of layered double hydroxides (LDHs), RhCI(GO)-(TPPTS)2 (TPPTS: P(m-C6H4SO3Na)3) and TPPTS co-intercalated LDHs were successfully synthesized by in situ complexation method. Characterizations of structure and composition of composite materials by powder XRD, FT-IR, and ICP-AES techniques confirmed the supramolecular structures of the catalytic species intercalated LDHs. The correlation between catalytic performance of intercalated catalyst and the composition of both host layers and interlayer guest species was also investigated.

  10. Reactions

    DEFF Research Database (Denmark)

    Søndergaard, Morten

    2011-01-01

      My concern is to understand augmentation as an emergent modality - among many others in ‘the expanding digital field' (Søndergaard M. , Transformative Creativity in the Expanded Digital Field, 2009)' - attributed to the production of contemporary art and the ‘archive of knowledge' in the (art...... construction; and 2) As a construction of a new reactive modality of the (art) museum as ‘archive of reality' - showing the outline of a cultural institution that oscillates between the instituting and institutionalizing competences of the (art) museum - between knowledge-based and experience-based exhibiting......; It is in this negotiation, I would claim, that the foundation of a possible critique of the role of the (art) museum in the age of post-bourgeois public space and experience-based culture should be located....

  11. The impact of CrOx loading on reaction behaviors of dichloromethane (DCM) catalytic combustion over Cr-O/HZSM-5 catalysts

    Science.gov (United States)

    Su, Jie; Yao, Weiyuan; Liu, Yue; Wu, Zhongbiao

    2017-02-01

    A series of HZSM-5 supported CrOx catalysts at different loadings were prepared by wet impregnation method for catalytic combustion of dichloromethane (DCM) in this paper. The catalytic activity tests indicated that both DCM conversion and product selectivity varied greatly with Cr doping contents. The sample at 2 wt% loading showed the highest DCM conversion, while the selectivity toward CO/CO2 increased at an elevated CrOx loading. The characterization results revealed that the surface acidity and the chemical states of Cr were strongly affected by the doping content. The surface acidity would decline at an elevated Cr loading owing to the interactions between surface OH groups and chromium ions. And higher surface Cr(VI)/Cr(III) ratios could be observed on the catalysts at lower CrOx doping, leading to the improvement of reducibility. The activity and selectivity of DCM catalytic degradation were found to be highly depended on the balance of surface acidity and redox property. The increased surface acidity could result in the enhancement of dissociated adsorption of DCM, which are beneficial to the catalytic activity. However, higher surface acidity meant lower Cr loading, which might lead the adsorbed intermediates incompletely oxidized and the decrease in COx selectivity due to the limit redox ability.

  12. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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 X-ra

  14. Status of The Facility for Experiments of Nuclear Reactions in Stars

    Science.gov (United States)

    Longland, Richard; Kelley, John; Marshall, Caleb; Portillo, Federico; Setoodehnia, Kiana; Underwood, Daniel

    2016-09-01

    To make connections between observations of stellar atmospheres and the processes occurring deep inside stars, me must rely on accurate nuclear cross sections. Often, the Coulomb barrier makes these cross sections immeasurably small in the laboratory. Particle transfer reactions are one tool in our inventory that can be used to infer the necessary properties of nuclear reactions, thus opening an avenue to calculate their cross sections. Enge split-pole magnetic spectrographs are one tool in our inventory that have been used successfully to perform these experiments. However, after a rash of closures, there were no operational spectrographs of this kind in North America to provide these valuable capabilities. Over the last few years, we have revived the Enge split-pole spectrograph at TUNL. We have also upgraded much of the equipment, ranging from the data acquisition system to the control system and detector package. These upgrades have enabled a powerful, flexible, and modern facility - the Facility for Experiments of Nuclear Reactions in Stars (FENRIS). In this talk, I will present a status upgrade of FENRIS, highlighting our upgrades, capabilities, and first science results. I will also highlight future upgrade plans for the facility.

  15. Electromagnetic simulations of microwave heating experiments using reaction vessels made out of silicon carbide.

    Science.gov (United States)

    Robinson, John; Kingman, Sam; Irvine, Derek; Licence, Peter; Smith, Alastair; Dimitrakis, Georgios; Obermayer, David; Kappe, C Oliver

    2010-09-28

    There is a growing body of literature which reports the use of silicon carbide vessels to shield reaction mixtures during microwave heating. In this paper we use electromagnetic simulations and microwave experiments to show that silicon carbide vessels do not exclude the electric field, and that dielectric heating of reaction mixtures will take place in addition to heat transfer from the silicon carbide. The contribution of dielectric heating and heat transfer depends on the dielectric properties of the mixture, and the temperature at which the reaction is carried out. Solvents which remain microwave absorbent at high temperatures, such as ionic liquids, will heat under the direct influence of the electric field from 30-250 degrees C. Solvents which are less microwave absorbent at higher temperatures will be heated by heat-transfer only at temperatures in excess of 150 degrees C. The results presented in this paper suggest that the influence of the electric field cannot be neglected when interpreting microwave assisted synthesis experiments in silicon carbide vessels.

  16. Deterministic chaos in the Belousov-Zhabotinsky reaction: Experiments and simulations

    Science.gov (United States)

    Zhang, Dongmei; Györgyi, László; Peltier, William R.

    1993-10-01

    An account of the experimental discovery of complex dynamical behavior in the continuous-flow, stirred tank reactor (CSTR) Belousov-Zhabotinsky (BZ) reaction, as well as numerical simulations based on the BZ chemistry are given. The most recent four- and three-variable models that are deduced from the well-accepted, updated chemical mechanism of the BZ reaction and which exhibit robust chaotic states are summarized. Chaos has been observed in experiments and simulations embedded in the regions of complexities at both low and high flow rates. The deterministic nature of the observed aperiodicities at low flow rates is unequivocally established. However, controversy still remains in the interpretation of certain aperiodicities observed at high flow rates.

  17. Study on the adsorptive catalytic voltammetry of aloe-emodin at a carbon paste electrode

    Institute of Scientific and Technical Information of China (English)

    LI; Ju'nan; GAO; Peng; LI; Xiangling; YAN; Zhihong; MAO; Xu

    2005-01-01

    A new catalytic voltammetric method for the determination of anthraqunone medicines at a carbon paste electrode (CPE) was described for the first time. The mechanism of the catalytic reaction was investigated by using linear sweep voltammetry, cyclic voltammetry, constant potential electrolysis and so on. The experiment results indicate that aloe-emodin was efficiently accumulated at a CPE by adsorption. In the following potential scan, aloe-emodin was reduced to homologous anthrahydroquinone compound, then the compound was immediately oxidized to aloe-emodin by the dissolved oxygen, and the aloe-emodin was again reduced at the CPE. As a result, a cyclic catalytic reaction was established. But a reversible redox reaction of aloe-emodin can only be observed at a mercury electrode, no catalytic reaction occurs there. A sensitive catalytic voltammetric peak of aloe-emodin was obtained at about -0.60 V (vs. SCE) in 0.56 mol/L NH3-NH4Cl buffer (pH 8.9). The proposed method was applied to the determination of aloe-emodin in the Radix Rhei with satisfactory results. The determination results were in good agreement with reference values obtained by the HPLC. The adsorptive catalytic voltammetry for the determination of organic compound at CPE, chemically modified electrode and other solid electrodes could be significant in the studies on pharmacology, pharmacodynamics, toxicity of medicine, clinical medicine and biochemistry.

  18. 曲克芦丁钯配合物的制备及其对Heck反应的催化性能%Synthesis of troxerutin-Pd complex and its catalytic properties for Heck reaction

    Institute of Scientific and Technical Information of China (English)

    徐启杰; 时文中; 刘雷英; 王文豪; 崔元臣

    2011-01-01

    The complex of troxerutin-Pd was synthesized. The structure of the complex was characterized by means of infrared spectrometry and ultraviolet spectrometry. Besides, the catalytic performance of the complex for the Heck arylation reaction of bromobenzene and acrylic acid was examined. Results showed that the complex had good catalytic performance for the Heck arylation reaction of bromobenzene and acrylic acid under optimized reaction conditions.Namely, a yield of above 70% was reached at bromobenzene to acrylic acid molar ratio of 1∶ 2,reaction time of 8 h, and reaction temperature of 120 ℃ in the presence of tri-n-butylamine as the alkali and tetrabutylammonium bromide as the solvent.%制备了曲克芦丁钯配合物,利用红外光谱和紫外光谱表征了配合物的结构;同时考察了其对溴苯和丙烯酸的Heck芳基化反应的催化性能.结果表明:在反应物的物质的量之比(溴苯与丙烯酸)为1:2、反应温度120℃、反应时间8 h、三正丁胺为碱、四丁基溴化铵为溶剂的条件下,曲克芦丁钯配合物对溴苯和丙烯酸的Heck芳基化反应有较好的催化作用,产率可达70%以上.

  19. Reações de Etanol com CO/H2 na Presença do Sistema Catalítico Ru(acac3/I- Ethanol, reactions with co/h2 in the presence of the ru(acac3/i- catalytic system

    Directory of Open Access Journals (Sweden)

    Elizeu Trabuco

    1997-06-01

    Full Text Available The hydrocarbonylation reaction of ethanol with a CO/H2 mixture assisted by Ru(acac3/iodide was investigated. Bronsted and Lewis acids and iodides salt were used as homogeneous promoters. The etherification reaction was the main reaction under typical acidic conditions of the catalytic system. When a hydrocarbon solvent (toluene was added to the initial reaction, the alcohol conversion and the carbonylation products were increased. The catalytic activity of the Bronsted acids (conv. EtOH = 71-92% was higher than that of the Lewis acids promoters (conv. EtOH = 65-85%. The salt present the lower catalytic activity among the promoters used. The long time reaction carried out with ethanol showed an increase of the product selectivity of the homologation and carbonylation reactions while the etherification reaction selectivity decreased. The recycled ether led to 60-65% ethanol conversion to C5 and C6 products. The main catalytic species are H+[Ru(CO3I3]-, [HRu3(CO11]- and [HRu(CO4]-. The first one is active in the carbonylation and homologation reactions of alcohols while the two others take part only in the homologation reaction.

  20. Methanol to Olefins (MTO) Reaction over SAPO-34 Catalyst——Deactivation Kinetics of Catalytic Reaction%SAPO-34催化剂上甲醇制烯烃反应——催化反应失活动力学

    Institute of Scientific and Technical Information of China (English)

    齐国祯; 谢在库; 陈庆龄

    2013-01-01

    甲醇制烯烃(MTO)催化剂SAPO-34在反应过程中存在失活现象,为了合理设计MTO反应器,需要了解该反应的本征动力学以及催化剂的失活规律,为此在固定床等温积分反应器内进行了甲醇制烯烃反应失活动力学的研究.通过测定不同催化反应时间下反应物和各产物的浓度,考察了催化剂不同使用时间后的催化活性,研究了SAPO-34催化剂的失活规律,建立了5集总反应和失活动力学模型,该模型充分考虑到水和积炭对反应过程的影响.根据实验测定的动力学数据拟合得到了失活反应的动力学常数,该动力学模型预测得到的SAPO-34催化剂上MTO反应产物组成随反应时间的变化规律与实验值吻合很好,说明了获得的动力学模型的可靠性.%The SAPO-34 catalyst used for converting methanol to olefins (MTO) would be suffering deactivation by coking. In order to perform the rational design of MTO reactor, it is important to understand the intrinsic kinetics as well as the physics of catalyst deactivation. Experiments on MTO reaction in a fixed-bed isothermal integral reactor were carried out to study the deactivation of SAPO-34 catalyst. At different reaction time, the concentration of reactants and products were measured on stream, and catalytic activities were then determined. A kinetic model based on five-reaction deactivation mechanism was proposed, in which the influence of water and coke deposition was incorporated. The kinetic constants of deactivation reactions were obtained by regression of experimental data. A very good agreement between the model predictions and experimental data in terms of on-stream product concentration has been reached, which indicates that the kinetic model is reliable.

  1. Catalytic microrotor driven by geometrical asymmetry

    Science.gov (United States)

    Yang, Mingcheng; Ripoll, Marisol; Chen, Ke

    2015-02-01

    An asymmetric gear with homogeneous surface properties is, here, presented as a prototype to fabricate catalytic microrotors. The driving torque arises from the diffusiophoretic effect induced by the concentration gradients generated by catalytic chemical reactions at the gear surface. This torque produces a spontaneous and unidirectional rotation of the asymmetric gear. By means of mesoscopic simulations, we prove and characterize this scenario. The gear rotational velocity is determined by the gear-solvent interactions, the gear geometry, the solvent viscosity, and the catalytic reaction ratio. Our work presents a simple way to design self-propelled microrotors, alternative to existing catalytic bi-component, or thermophoretic ones.

  2. Black applicants' reactions to affirmative action plans: effects of plan content and previous experience with discrimination.

    Science.gov (United States)

    Slaughter, Jerel E; Sinar, Evan F; Bachiochi, Peter D

    2002-04-01

    This study examined the effects of plan content and previous experience with discrimination on Black respondents' reactions to affirmative action plans. Black engineering students (N = 1,173) were randomly assigned to 1 of 6 plans implemented by a hypothetical organization and were asked to provide ratings of perceived fairness and intention to pursue a position at the organization. There were significant effects of plan content on perceived faimess and job pursuit intentions. Perceived fairness mediated the effect of content on intentions. Furthermore, previous experience with discrimination interacted with content to affect intentions. Individuals who had experienced relatively more discrimination in the workplace reported stronger intentions to pursue a position at an organization whose plan specified special training opportunities for minorities.

  3. Interfacial reactions in the Sb-Sn/(Cu, Ni) systems: Wetting experiments

    Energy Technology Data Exchange (ETDEWEB)

    Novakovic, R., E-mail: r.novakovic@ge.ieni.cnr.it [National Research Council (CNR) - Institute for Energetics and Interphases (IENI), Via De Marini, 6-16149 Genoa (Italy); Lanata, T. [National Research Council (CNR) - Institute for Energetics and Interphases (IENI), Via De Marini, 6-16149 Genoa (Italy); Delsante, S.; Borzone, G. [DCCI-University of Genoa, Via Dodecaneso, 31 - 16146-Genoa (Italy)

    2012-12-14

    Interfacial reactions in the Sb-Sn/Cu and Sb-Sn/Ni systems have been investigated by means of wetting experiments. The wetting behaviour of two lead-free alloys, namely, Sb{sub 2.5}Sn{sub 97.5} and Sb{sub 14.5}Sn{sub 85.5} (at.%), in contact with Cu and Ni-substrates has been studied in view of possible applications as high-temperature solders in the electronics industry. The contact angle measurements on Cu and Ni plates were performed by using a sessile drop apparatus. The solder/substrate interface was characterised by the SEM-EDS analyses. -- Highlights: Black-Right-Pointing-Pointer Sb-Sn alloys are used as high temperature lead-free solders. Black-Right-Pointing-Pointer Sb-Sn alloys have good wetting properties on Cu and Ni substrates. Black-Right-Pointing-Pointer Interfacial reactions and products are important for joint properties. Black-Right-Pointing-Pointer Interfacial reactions/products data can be used to study the phase diagrams.

  4. Ignition and growth modeling of detonation reaction zone experiments on single crystals of PETN and HMX

    Science.gov (United States)

    White, Bradley W.; Tarver, Craig M.

    2017-01-01

    It has long been known that detonating single crystals of solid explosives have much larger failure diameters than those of heterogeneous charges of the same explosive pressed or cast to 98 - 99% theoretical maximum density (TMD). In 1957, Holland et al. demonstrated that PETN single crystals have failure diameters of about 8 mm, whereas heterogeneous PETN charges have failure diameters of less than 0.5 mm. Recently, Fedorov et al. quantitatively determined nanosecond time resolved detonation reaction zone profiles of single crystals of PETN and HMX by measuring the interface particle velocity histories of the detonating crystals and LiF windows using a PDV system. The measured reaction zone time durations for PETN and HMX single crystal detonations were approximately 100 and 260 nanoseconds, respectively. These experiments provided the necessary data to develop Ignition and Growth (I&G) reactive flow model parameters for the single crystal detonation reaction zones. Using these parameters, the calculated unconfined failure diameter of a PETN single crystal was 7.5 +/- 0.5 mm, close to the 8 mm experimental value. The calculated failure diameter of an unconfined HMX single crystal was 15 +/- 1 mm. The unconfined failure diameter of an HMX single crystal has not yet been determined precisely, but Fedorov et al. detonated 14 mm diameter crystals confined by detonating a HMX-based plastic bonded explosive (PBX) without initially overdriving the HMX crystals.

  5. Heats of transfer in the diffusion layer before the surface and the surface temperature for a catalytic hydrogen oxidation (H2 + (1/2)O2 --> H2O) reaction.

    Science.gov (United States)

    Zhu, Lianjie; Koper, Ger J M; Bedeaux, Dick

    2006-03-23

    The surface temperature and surface mole fractions are calculated for a catalytic hydrogen oxidation reaction over a Pt/Al2O3 catalyst pellet. The thermodynamics of irreversible processes was used in order to ensure the correct introduction of coupled heat and mass transfer. Two pathways, one using the 4 x 4 resistivity matrix and the other using a simplified effective conductivity matrix, were proven to yield equivalent results. By using expressions for the thermal diffusion coefficients, heats of transfer, and the Maxwell-Stefan diffusion coefficients given in the literature, available experimental data could be reproduced. The Dufour effect was found to be negligible for the prediction of the surface temperature. Neglecting the Soret effect would increase the predicted value of the surface temperature significantly-more than 30 K out of an average of about 400 K. It is found that the reaction rate can be used to predict the surface temperature.

  6. A surface enhanced Raman scattering quantitative analytical platform for detection of trace Cu coupled the catalytic reaction and gold nanoparticle aggregation with label-free Victoria blue B molecular probe.

    Science.gov (United States)

    Li, Chongning; Ouyang, Huixiang; Tang, Xueping; Wen, Guiqing; Liang, Aihui; Jiang, Zhiliang

    2017-01-15

    With development of economy and society, there is an urgent need to develop convenient and sensitive methods for detection of Cu(2+) pollution in water. In this article, a simple and sensitive SERS sensor was proposed to quantitative analysis of trace Cu(2+) in water. The SERS sensor platform was prepared a common gold nanoparticle (AuNP)-SiO2 sol substrate platform by adsorbing HSA, coupling with the catalytic reaction of Cu(2+)-ascorbic acid (H2A)-dissolved oxygen, and using label-free Victoria blue B (VBB) as SERS molecular probes. The SERS sensor platform response to the AuNP aggregations by hydroxyl radicals (•OH) oxidizing from the Cu(2+) catalytic reaction, which caused the SERS signal enhancement. Therefore, by monitoring the increase of SERS signal, Cu(2+) in water can be determined accurately. The results show that the SERS sensor platforms owns a linear response with a range from 0.025 to 25μmol/L Cu(2+), and with a detection limit of 0.008μmol/L. In addition, the SERS method demonstrated good specificity for Cu(2+), which can determined accurately trace Cu(2+) in water samples, and good recovery and accuracy are obtained for the water samples. With its high selectivity and good accuracy, the sensitive SERS quantitative analysis method is expected to be a promising candidate for determining copper ions in environmental monitoring and food safety.

  7. Standard and Nonstandard Neutrino-Nucleus Reactions Cross Sections and Event Rates to Neutrino Detection Experiments

    Directory of Open Access Journals (Sweden)

    D. K. Papoulias

    2015-01-01

    Full Text Available In this work, we explore ν-nucleus processes from a nuclear theory point of view and obtain results with high confidence level based on accurate nuclear structure cross sections calculations. Besides cross sections, the present study includes simulated signals expected to be recorded by nuclear detectors and differential event rates as well as total number of events predicted to be measured. Our original cross sections calculations are focused on measurable rates for the standard model process, but we also perform calculations for various channels of the nonstandard neutrino-nucleus reactions and come out with promising results within the current upper limits of the corresponding exotic parameters. We concentrate on the possibility of detecting (i supernova neutrinos by using massive detectors like those of the GERDA and SuperCDMS dark matter experiments and (ii laboratory neutrinos produced near the spallation neutron source facilities (at Oak Ridge National Lab by the COHERENT experiment. Our nuclear calculations take advantage of the relevant experimental sensitivity and employ the severe bounds extracted for the exotic parameters entering the Lagrangians of various particle physics models and specifically those resulting from the charged lepton flavour violating μ-→e- experiments (Mu2e and COMET experiments.

  8. The Reaction of Carbonates in Contact with Superheated Silicate Melts: New Insights from MEMIN Laser Melting Experiments

    Science.gov (United States)

    Hamann, C.; Hecht, L.; Schäffer, S.; Deutsch, A.; Lexow, B.

    2016-08-01

    The reaction of carbonates in contact with silicate impact melts is discussed quite controversially in the impact community. Here, we discuss four MEMIN laser melting experiments involving carbonates in contact with superheated silicate melts.

  9. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  10. Study of catalytic upgrading of biomass tars using Indonesian iron ore

    Science.gov (United States)

    Wicakso, Doni Rahmat; Sutijan, Rochmadi, Budiman, Arief

    2017-03-01

    Catalytic decomposition is a promising way for chemical upgrading process of low quality oil such as biomass tars. In this experiment, catalytic decomposition of biomass tars was performed over Indonesian low grade iron ore catalyst. This process is carried out in a fixed bedreactor which is equipped with preheater to convert the tars into vapor form. The reaction was studied at the temperature range of 500 - 700°C. The kinetic study of catalytic decomposition of biomass tars is represented using first order reaction. The results show that value of constant of chemical reaction is in range 0.2514 - 0.9642 cm3.gr-1.min-1 with value of the frequency factor (A) and the activation energy (E) are 48.98 min-1 and 5724.94 cal.mol-1, respectively.

  11. Catalytic Hydrogenation of Organic Compounds without H2 Supply: An Electrochemical System

    Science.gov (United States)

    Navarro, Daniela Maria do Amaral Ferraz; Navarro, Marcelo

    2004-01-01

    An experiment developed for an undergraduate organic chemistry laboratory course that can be used to introduce the catalytic hydrogenation reaction, catalysis electrochemical principles and gas chromatography is presented. The organic compounds hydrogenated by the electrocatalytic hydrogenation (ECH) process were styrene, benzaldehyde and…

  12. Monopropellant engine investigation for space shuttle reaction control. Volume 2: Design, fabrication, and demonstration test of a catalytic gas generator for the space shuttle APU

    Science.gov (United States)

    1975-01-01

    The capability of a catalytic gas generator to meet the requirement specified for the space shuttle APU is established. A full-scale gas generator, designed to operate at a chamber pressure of 750 psia and a flow rate of 0.36 lbm/sec, was fabricated and subjected to three separate life test series. The nickel foam metal used for catalyst retention was investigated. Inspection of the foam metal following the first life test revealed significant degradation. Consequently an investigation was conducted to determine the mechanism of degradation and to provide an improved foam metal.

  13. Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2 -Scrubbing Solutions.

    Science.gov (United States)

    Scott, Martin; Blas Molinos, Beatriz; Westhues, Christian; Franciò, Giancarlo; Leitner, Walter

    2017-03-22

    Aqueous biphasic systems were investigated for the production of formate-amine adducts by metal-catalyzed CO2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis-[Ru(dppm)2 Cl2 ] (dppm=bis-diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate-amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOFav of approximately 35 000 h(-1) and an initial TOF of approximately 180 000 h(-1) was achieved in the presence of NEt3 . Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO2 -scrubbing processes. Saturated aqueous solutions (CO2 overpressure 5-10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×10(3)  h(-1) with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization.

  14. Oxidative photoredox-catalytic activation of aliphatic nucleophiles for C(sp(3))-C(sp(2)) cross-coupling reactions.

    Science.gov (United States)

    Jahn, Emanuela; Jahn, Ullrich

    2014-12-01

    In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions.

  15. Removal performance and mechanism of ibuprofen from water by catalytic ozonation using sludge-corncob activated carbon as catalyst.

    Science.gov (United States)

    Wang, Hongjuan; Zhang, Liqiu; Qi, Fei; Wang, Xue; Li, Lu; Feng, Li

    2014-09-01

    To discover the catalytic activity of sludge-corncob activated carbon in catalytic ozonation of Ibuprofen, the performance of sludge-corncob activated carbon and three selected commercial activated carbons as catalysts in catalytic ozonation was investigated. The observation indicates the degradation rate of Ibuprofen increases significantly in the presence of sludge-corncob activated carbon and the catalytic activity of sludge-corncob activated carbon is much higher than that of the other three commercial activated carbons. Ibuprofen's removal rate follows pseudo-first order kinetics model well. It is also found that the adsorption removal of Ibuprofen by sludge-corncob activated carbon is less than 30% after 40 min. And the removal efficiency of Ibuprofen in the hybrid ozone/sludge-corncob activated carbon system is higher than the sum of sludge-corncob activated carbon adsorption and ozonation alone, which is a supportive evidence for catalytic reaction. In addition, the results of radical scavenger experiments demonstrate that catalytic ozonation of Ibuprofen by sludge-corncob activated carbon follows a hydroxyl radical reaction pathway. During ozonation of Ibuprofen in the presence of activated carbon, ozone could be catalytically decomposed to form hydrogen peroxide, which can promote the formation of hydroxyl radical. The maximum amount of hydrogen peroxide occurs in the presence of sludge-corncob activated carbon, which can explain why sludge-corncob activated carbon has the best catalytic activity among four different activated carbons.

  16. Amphibole reaction rim textures and mineralogy from the 2006 eruption of Augustine Volcano, Alaska: Nature vs. experiment

    Science.gov (United States)

    Henton, S.; Larsen, J. F.; Coombs, M. L.

    2011-12-01

    Augustine Volcano forms a small island located in Alaska's Cook Inlet, approximately 180 miles southwest of Anchorage. The 2006 eruption began January 11, 2006, and evolved from an initial phase of explosive activity, through continuous and effusive phases, ending approximately mid-March 2006. We present data on the textural and mineralogical make-up of amphibole reaction rims from 2006 andesites from Augustine. Naturally formed reaction rims are compared to rims formed through decompression and heating experiments. Amphiboles make up less than 1 modal % of most samples. However, variations in composition and texture help to explain pre-and syn-eruptive magma histories. The Augustine 2006 amphiboles contain a mixture of rimmed and unrimmed grains. In order of decreasing abundance (by tally), the dominant phases in reaction rims are orthopyroxene, oxides, plagioclase, and clinopyroxene. Most amphibole reaction rims are between 1- 40 microns in thickness. Thicker rims (> 40 microns) were primarily erupted in the later effusive phase of the eruption. In general, the thickest reactions rims (> 60 microns average thickness) contain coarser individual reaction rim grains (with feret diameters of 15-50 microns). Reaction rims with average thickness of less than 60 microns tend to contain finer reaction rim grains (with feret diameters of 10 microns or less). Some reactions rims show a coarsening of rim grains across the rim, from the amphibole boundary to the glass boundary. Preliminary results show no systematic changes in the aspect ratios of reaction rim grains, either across the rim, or between the different rims. Some rims show a decrease in the An content of plagioclase across the rim, from the amphibole boundary to the glass boundary. Reaction rim textures and mineralogy are complex and suggest that multiple forcing factors (including heating and decompression) were responsible for their formation. This study will compare these natural reaction rims to those formed

  17. 乙基环己烷催化裂解制低碳烯烃反应动力学%Reaction kinetics of ethylcyclohexane catalytic pyrolysis for production of light olefins

    Institute of Scientific and Technical Information of China (English)

    张睿; 郭少鹏; 刘贵丽; 刘海燕; 刘植昌; 孟祥海

    2016-01-01

    The cracking performance of ethylcyclohexane on a mesoporous catalyst based on ZSM-5 molecular sieve was investigated in an apparatus with a fixed-bed reactor. The results showed that ethylcyclohexane had good cracking performance, the conversion was above 80%, the yield of ethylene and propylene reached 41% (mass), the yield of total light olefins was near 50% (mass), and the main components of liquid products were benzene, toluene and xylene. As reaction temperature increased, the yield of ethylene increased monotonously, and those of propylene and butene showed maxima. With the consideration of both thermal and catalytic reactions, a kinetic model involving 14 reactions was established for the catalytic pyrolysis of ethylcyclohexane. The experimental data were obtained at reaction temperatures of 600, 620, 640 and 660℃, and the reaction rate constants were estimated by genetic algorithm regression analysis. Apparent activation energies and pre-exponential factors were subsequently calculated according to the Arrhenius equation. All of the apparent activation energies obtained were below 90 kJ·mol−1, indicating that the mesoporous ZSM-5 catalyst provides high catalytic activity for ethylcyclohexane catalytic pyrolysis. The model predicted values were in good agreement with the experimental data, and the average relative errors of the main products were below 10%.%利用小型固定床实验装置研究了乙基环己烷在基于ZSM-5分子筛介孔催化剂上的裂解性能,发现乙基环己烷具有较好的裂解性能,原料转化率在80%以上,乙丙烯收率(质量分数)可达41%,低碳烯烃收率(质量分数)接近50%,液体产物主要是苯、甲苯、二甲苯等芳香烃。同时考虑乙基环己烷催化裂解过程中的热反应与催化反应,建立了包含14个反应的动力学模型。基于4个反应温度下的裂解实验数据,求取了反应动力学模型的参数。求得的表观活化能均在90 k

  18. Psy Toolkit: A Novel Web-Based Method for Running Online Questionnaires and Reaction-Time Experiments

    Science.gov (United States)

    Stoet, Gijsbert

    2017-01-01

    This article reviews PsyToolkit, a free web-based service designed for setting up, running, and analyzing online questionnaires and reaction-time (RT) experiments. It comes with extensive documentation, videos, lessons, and libraries of free-to-use psychological scales and RT experiments. It provides an elaborate interactive environment to use (or…

  19. First-principles quantum-mechanical investigations: The role of water in catalytic conversion of furfural on Pd(111)

    Science.gov (United States)

    Xue, Wenhua; Borja, Miguel Gonzalez; Resasco, Daniel E.; Wang, Sanwu

    2015-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of water has attracted wide attention. Recent experiments showed that the proportion of alcohol product from catalytic reactions of furfural conversion with palladium in the presence of water is significantly increased, when compared with other solvent including dioxane, decalin, and ethanol. We investigated the microscopic mechanism of the reactions based on first-principles quantum-mechanical calculations. We particularly identified the important role of water and the liquid/solid interface in furfural conversion. Our results provide atomic-scale details for the catalytic reactions. Supported by DOE (DE-SC0004600). This research used the supercomputer resources at NERSC, of XSEDE, at TACC, and at the Tandy Supercomputing Center.

  20. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne;

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  1. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    Science.gov (United States)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  2. Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (Ⅵ) Effect of Sn Loading Method and Content on Activity of Sn-Pd Supported Catalyst

    Institute of Scientific and Technical Information of China (English)

    张光旭; 吴元欣; 马沛生; 田崎峰; 吴广文; 李定或

    2004-01-01

    The compound metal oxide LaxPbyMnzO used as support was prepared by the sol-gel method, and the catalyst in which Pd was used as active component and Sn as co-active component for direct synthesis of diphenyl carbonate (DPC) with heterogeneous catalytic reaction was obtained by co-calcination and precipitation respectively.The catalyst was characterized by XRD, SEM and TEM respectively. The specific surface area of catalysts was measured by ChemBET3000 instrument, and the activity of the catalysts was tested by the synthesis of DPC in a pressured reactor. The results showed that when the co-active component Sn was added by co-calcination method A, its loading content was equal to 14.43% and active component Pd was loaded by precipitation, the yield and selectivity of DPC could reach 26.78% and 99% respectively.

  3. Simulation studies of the Cl- + CH3I SN2 nucleophilic substitution reaction: Comparison with ion imaging experiments

    Science.gov (United States)

    Zhang, Jiaxu; Lourderaj, Upakarasamy; Sun, Rui; Mikosch, Jochen; Wester, Roland; Hase, William L.

    2013-03-01

    In the previous work of Mikosch et al. [Science 319, 183 (2008)], 10.1126/science.1150238, ion imaging experiments were used to study the Cl- + CH3I → ClCH3 + I- reaction at collision energies Erel of 0.39, 0.76, 1.07, and 1.9 eV. For the work reported here MP2(fc)/ECP/d direct dynamics simulations were performed to obtain an atomistic understanding of the experiments. There is good agreement with the experimental product energy and scattering angle distributions for the highest three Erel, and at these energies 80% or more of the reaction is direct, primarily occurring by a rebound mechanism with backward scattering. At 0.76 eV there is a small indirect component, with isotropic scattering, involving formation of the pre- and post-reaction complexes. All of the reaction is direct at 1.07 eV. Increasing Erel to 1.9 eV opens up a new indirect pathway, the roundabout mechanism. The product energy is primarily partitioned into relative translation for the direct reactions, but to CH3Cl internal energy for the indirect reactions. The roundabout mechanism transfers substantial energy to CH3Cl rotation. At Erel = 0.39 eV both the experimental product energy partitioning and scattering are statistical, suggesting the reaction is primarily indirect with formation of the pre- and post-reaction complexes. However, neither MP2 nor BhandH/ECP/d simulations agree with experiment and, instead, give reaction dominated by direct processes as found for the higher collision energies. Decreasing the simulation Erel to 0.20 eV results in product energy partitioning and scattering which agree with the 0.39 eV experiment. The sharp transition from a dominant direct to indirect reaction as Erel is lowered from 0.39 to 0.20 eV is striking. The lack of agreement between the simulations and experiment for Erel = 0.39 eV may result from a distribution of collision energies in the experiment and/or a shortcoming in both the MP2 and BhandH simulations. Increasing the reactant rotational

  4. Verification experiment of EPR paradox by (d, {sup 2}He) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sakai, Hideyuki [Tokyo Univ., Graudate School of Science, Tokyo (Japan)

    2003-01-01

    FBR paradox which was brought forward by Einstein, Podolsky and Rosen is expressed by Bell's inequality of spin correlation theoretically. In principle it is possible to verify the inequality by measuring spin correlation between two particles having spin 1/2 from a decay of {sup 1}S{sub 0} experimentally. Most of the past experiments to verify the inequality, however, have been performed by using photons. On the other hand, only one experiment by using hadron system was carried out by Lamehi and Mitting, where the [{sup 1}S{sub 0}] state was produced by proton-proton scattering at first, and then the spin orientations after the scattering were measured. Unfortunately, there exit some sources of ambiguity to reach definite conclusion from their result because the experiment was done at rather high energy of 13.5 MeV. In the experiment planned by the present author it is designed to overcome the experimental difficulties, which Lamehi and Mitting encountered, by (1) generating high purity singlet [{sup 1}S{sub 0}] state of two protons by (d, {sup 2}He) type nuclear reaction at intermediate energy range, and by (2) developing high performance spin-correlation polarimeter which can analyze spins of two protons simultaneously to minimize the systematic errors. The excitation energy of {sup 2}He corresponding to the proton-proton relative energy can be experimentally controlled. An idea singlet is realized by choosing the state with sufficiently small relative energy. It is planned to measure the spin correlation function by using SMART (Swinger and Magnetic Analyzer with Rotator and Twister) at RIKEN Accelerator Research Facility. Einstein POLarimeter (EPOL) to be installed on the second focal plane of SMART is under development, with which high precision measurements of spin orientations of two high energy protons simultaneously coming into limited space from {sup 2}He decay are made selecting the subject events from very many background events. Monte Carlo

  5. Performance of a Novel Hydrophobic Mesoporous Material for High Temperature Catalytic Oxidation of Naphthalene

    Directory of Open Access Journals (Sweden)

    Guotao Zhao

    2014-01-01

    Full Text Available A high surface area, hydrophobic mesoporous material, MFS, has been successfully synthesized by a hydrothermal synthesis method using a perfluorinated surfactant, SURFLON S-386, as the single template. N2 adsorption and TEM were employed to characterize the pore structure and morphology of MFS. Static water adsorption test indicates that the hydrophobicity of MFS is significantly higher than that of MCM-41. XPS and Py-GC/MS analysis confirmed the existence of perfluoroalkyl groups in MFS which led to its high hydrophobicity. MFS was used as a support for CuO in experiments of catalytic combustion of naphthalene, where it showed a significant advantage over MCM-41 and ZSM-5. SEM was helpful in understanding why CuO-MFS performed so well in the catalytic combustion of naphthalene. Experimental results indicated that MFS was a suitable support for catalytic combustion of large molecular organic compounds, especially for some high temperature catalytic reactions when water vapor was present.

  6. Experiment E89-044 on the Quasielastic 3He(e,e'p) Reaction at Jefferson Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    E. Penel-Nottaris

    2004-07-07

    The Jefferson Lab Hall A E89-044 experiment has measured the 3He(e,e'p) reaction cross-sections. The extraction of the longitudinal and transverse response functions for the two-body break-up 3He(e,e'p)d reaction in parallel kinematics allows the study of the bound proton electromagnetic properties inside the 3He nucleus and the involved nuclear mechanisms beyond plane wave approximations.

  7. Data discrepancies in and new experiments for D+D, D+T, and T+T fusion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jarmie, N.; Hardekopf, R.A.; Brown, R.E.; Correll, F.D.; Ohlsen, G.G.

    1979-01-01

    The purpose of this work is to investigate the accuracy of the basic fusion reaction data for the reactions T(d,n)/sup 4/He, T(t,2n)/sup 4/He, D(d,n)/sup 3/He, and D(d,p)T, and to describe an elaborate experiment in progress at the Los Alamos Scientific Laboratory to remeasure the cross sections with improved accuracy.

  8. Cross Sections for Neutron-induced Reactions on Actinide Targets Extracted from Surrogate Experiments: A Status Report

    Energy Technology Data Exchange (ETDEWEB)

    Escher, J E; Burke, J T; Dietrich, F S; Lesher, S R; Scielzo, N D; Thompson, I J; Younes, W

    2009-10-01

    The Surrogate nuclear reactions method, an indirect approach for determining cross sections for compound-nuclear reactions involving difficult-to-measure targets, is reviewed. Focusing on cross sections for neutron-induced reactions on actinides, we review the successes of past and present applications of the method and assess its uncertainties and limitations. The approximations used in the analyses of most experiments work reasonably well for (n,f) cross sections for neutron energies above 1-2 MeV, but lead to discrepancies for low-energy (n,f) reactions, as well as for (n,{gamma}) applications. Correcting for some of the effects neglected in the approximate analyses leads to improved (n,f) results. We outline steps that will further improve the accuracy and reliability of the Surrogate method and extend its applicability to reactions that cannot be approached with the present implementation of the method.

  9. High Surface Area Tungsten Carbides: Synthesis, Characterization and Catalytic Activity towards the Hydrogen Evolution Reaction in Phosphoric Acid at Elevated Temperatures

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Li, Qingfeng; Jensen, Jens Oluf

    2014-01-01

    Tungsten carbide powders were synthesized as a potential electrocatalyst for the hydrogen evolution reaction in phosphoric acid at elevated temperatures. With ammonium metatungstate as the precursor, two synthetic routes with and without carbon templates were investigated. Through the intermediate...... nitride route and with carbon black as template, the obtained tungsten carbide samples had higher BET area. In 100% H3PO4 at temperatures up to 185°C, the carbide powders showed superior activity towards the hydrogen evolution reaction. A deviation was found in the correlation between the BET area...

  10. Highly efficient catalytic enantioselective Mannich reaction of malonates with N-tert-butoxycarbonyl imines by using Yb(OTf)3/pybox catalysts at room temperature.

    Science.gov (United States)

    Karimi, Babak; Jafari, Ehsan; Enders, Dieter

    2013-07-29

    Go Mannich! A highly efficient and enantioselective method for the direct asymmetric reaction of dibenzyl malonate with N-tert-butoxycarbonyl aldimines in the presence of Yb(OTf)3 and iPr-pybox complexes is described (see scheme; pybox = pyridine bisoxazoline).

  11. Influence of catalytic activity and reaction conditions on the product distribution in coal liquefaction; Sekitan ekikayu no seiseibutsu bunpu ni taisuru shokubai kassei oyobi hanno joken no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Hasuo, H.; Sakanishi, K.; Mochida, I. [Kyushu University, Fukuoka (Japan). Institute of Advanced Material Study

    1996-10-28

    The NiMo sulfide supported on Ketjen Black (KB) was more effective and yielded lighter oil products containing light fractions with their boiling point below 300{degree}C during the two stage liquefaction combining low temperature and high temperature hydrogenation the conventional NiMo/alumina catalyst and FeS2 catalyst. Although the NiMo/alumina yielded increased oil products during the two stage liquefaction, the lighter oil fractions did not increase and the heavier fractions increased mainly. This suggests that the hydrogenation of aromatic rings and successive cleavage of the rings are necessary for producing the light oil, which is derived from the sufficient hydrogenation of aromatic rings using catalysts. For the two stage reaction with NiMo/KB catalyst, it was considered that sufficient hydrogen was directly transferred to coal molecules at the first stage of the low temperature reaction, which promoted the solubilization of coal and the successive hydrogenation at the high temperature reaction. Thus, high activity of the catalyst must be obtained. It is expected that further high quality distillates can be produced through the optimization of catalysts and solvents at the two stage reaction. 1 ref., 4 figs., 1 tab.

  12. Non-equilibrium model for catalytic distillation process

    Institute of Scientific and Technical Information of China (English)

    Feng WANG; Ning ZHAO; Junping LI; Fukui XIAO; Wei WEI; Yuhan SUN

    2008-01-01

    A new improved tri-diagonal method was developed for the non-equilibrium stage model of the catalytic distillation by coupling consumptive reaction coefficient. The reactions in the distillation column were divided into generative reaction and consumptive reac-tion. The non-equilibrium stage model was introduced for the catalytic distillation process of the dimethyl car-bonate (DMC) synthesis by urea methanolysis over solid based catalyst, and the improved tri-diagonal method was used to solve the model equations. Comparison of pre-dicted results with experiment data shows that the mean relative error of the yield of DMC was 3.78% under dif-ferent conditions such as different operating pressures and reaction temperatures. The improved tri-diagonal matrix method could avoid the negative values of the liquid com-positions during the calculations and restrain the fluc-tuation of compositions by slowing down the variations of the values in the iteration. The modeling results show that the improved tri-diagonal method was appropriate for system containing a wide range of boiling point com-ponents and a different rate of reactions.

  13. Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Qingwen Wang

    2013-09-01

    Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

  14. Shock tube experiments on nitromethane and Promotion of chemical reactions by non-thermal plasma

    Energy Technology Data Exchange (ETDEWEB)

    Seljeskog, Morten

    2002-06-01

    This dissertation was undertaken to study two different subjects both related to molecular decomposition by applying a shock tube and non-thermal plasma to decompose selected hydrocarbons. The first approach to molecular decomposition concerned thermal decomposition and oxidation of highly diluted nitromethane (NM) in a shock tube. Reflected shock tube experiments on NM decomposition, using mixtures of 0.2 to 1.5 vol% NM in nitrogen or argon were performed over the temperature range 850-1550 K and pressure range 190-900 kPa, with 46 experiments diluted in nitrogen and 44 diluted in argon. By residual error analysis of the measured decomposition profiles it was found that NM decomposition (CH{sub 3}NO{sub 2} + M {yields} CH{sub 3} + NO{sub 2} + M, where M = N{sub 2} /Ar) corresponds well to a law of first order. Arrhenius expressions corresponding to NM diluted either in N{sub 2} or in Ar were found as k{sub N2} = 10{sup 17.011} * exp(- 182.6 kJ/mole / R*T) and k{sub Ar} = 10{sup 17.574}*exp(-207 kJ/mole / R*T ) , respectively. A new reaction mechanism was then proposed, based on new experimental data for NM decomposition both in Ar and N{sub 2} and on three previously developed mechanisms. The new mechanism predicts well the decomposition of NM diluted in both N{sub 2} and Ar within the pressure and temperature range covered by the experiments. In parallel to, and following the decomposition experiments, oxidative experiments on the ignition delay times of NM/O{sub 2}/Ar mixtures were investigated over high temperature and low to high pressure ranges. These experiments were carried out with eight different mixtures of gaseous NM and oxygen diluted in argon, with pressures ranging between 44.3-600 kPa, and temperatures ranging between 842-1378 K. The oxidation experiments were divided into different categories according to the type of decomposition signals achieved. For signals with and without emission, the apparent quasi

  15. Shock tube experiments on nitromethane and Promotion of chemical reactions by non-thermal plasma

    Energy Technology Data Exchange (ETDEWEB)

    Seljeskog, Morten

    2002-06-01

    This dissertation was undertaken to study two different subjects both related to molecular decomposition by applying a shock tube and non-thermal plasma to decompose selected hydrocarbons. The first approach to molecular decomposition concerned thermal decomposition and oxidation of highly diluted nitromethane (NM) in a shock tube. Reflected shock tube experiments on NM decomposition, using mixtures of 0.2 to 1.5 vol% NM in nitrogen or argon were performed over the temperature range 850-1550 K and pressure range 190-900 kPa, with 46 experiments diluted in nitrogen and 44 diluted in argon. By residual error analysis of the measured decomposition profiles it was found that NM decomposition (CH{sub 3}NO{sub 2} + M {yields} CH{sub 3} + NO{sub 2} + M, where M = N{sub 2} /Ar) corresponds well to a law of first order. Arrhenius expressions corresponding to NM diluted either in N{sub 2} or in Ar were found as k{sub N2} = 10{sup 17.011} * exp(- 182.6 kJ/mole / R*T) and k{sub Ar} = 10{sup 17.574}*exp(-207 kJ/mole / R*T ) , respectively. A new reaction mechanism was then proposed, based on new experimental data for NM decomposition both in Ar and N{sub 2} and on three previously developed mechanisms. The new mechanism predicts well the decomposition of NM diluted in both N{sub 2} and Ar within the pressure and temperature range covered by the experiments. In parallel to, and following the decomposition experiments, oxidative experiments on the ignition delay times of NM/O{sub 2}/Ar mixtures were investigated over high temperature and low to high pressure ranges. These experiments were carried out with eight different mixtures of gaseous NM and oxygen diluted in argon, with pressures ranging between 44.3-600 kPa, and temperatures ranging between 842-1378 K. The oxidation experiments were divided into different categories according to the type of decomposition signals achieved. For signals with and without emission, the apparent quasi

  16. Method of fabricating a catalytic structure

    Science.gov (United States)

    Rollins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2009-09-22

    A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

  17. K+ nucleus reaction and total cross sections: New analysis of transmission experiments

    Science.gov (United States)

    Friedman, E.; Gal, A.; Weiss, R.; Aclander, J.; Alster, J.; Mardor, I.; Mardor, Y.; May-Tal Beck, S.; Piasetzky, E.; Yavin, A. I.; Bart, S.; Chrien, R. E.; Pile, P. H.; Sawafta, R.; Sutter, R. J.; Barakat, M.; Johnston, K.; Krauss, R. A.; Seyfarth, H.; Stearns, R. L.

    1997-03-01

    The attenuation cross sections measured in transmission experiments at the alternating-gradient synchrotron for K+ on 6Li, C, Si, and Ca at pL = 488, 531, 656, and 714 MeV/c are reanalyzed in order to derive total (σT) and reaction (σR) cross sections. The effect of plural (Molière) scattering is properly accounted for, leading to revised values of σT. We demonstrate the model dependence of these values, primarily due to the choice of K+ nuclear optical potential used to generate the necessary Coulomb-nuclear and nuclear elastic corrections. Values of σR are also derived, for the first time, from the same data and exhibit a remarkable degree of model independence. The derived values of σT and σR exceed those calculated by the first-order tρ optical potential for C, Si, and Ca, but not for 6Li, particularly at 656 and 714 MeV/c where the excess is 10-25%. Relative to 6Li, this excess is found to be nearly energy independent and its magnitude of 15-25% is not reproduced by any nuclear medium effect studied so far.

  18. Catalytic CO Oxidation over Au Nanoparticles Loaded Nanoporous Nickel Phosphate Composite

    Directory of Open Access Journals (Sweden)

    Xiaonan Leng

    2015-01-01

    Full Text Available Au/nickel phosphate-5 (Au/VSB-5 composite with the noble metal loading amount of 1.43 wt.% is prepared by using microporous VSB-5 nanocrystals as the support. Carbon monoxide (CO oxidation reaction is carried out over the sample with several catalytic cycles. Complete conversion of CO is achieved at 238°C over the catalyst at the first catalytic cycle. The catalytic activity improved greatly at the second cycle with the complete conversion fulfilled at 198°C and preserved for the other cycles. A series of experiments such as X-ray diffraction (XRD, high resolution transmission electron microscopy (HRTEM, ultraviolet-visible (UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS are carried out to characterize the catalysts before and after the reaction to study the factors influencing this promotion at the second cycle.

  19. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    , alternative path to acetonitrile from ethanol via the oxidative dehydrogenation of ethylamine. The catalytic activity and product ratios of the batch and continuous flow reactions are compared and the effect of reaction conditions on the reaction is investigated. The effects of ammonia in the reaction...... dehydrogenation of ethylamine and post-reaction purging.Chapter 4 outlines the application of RuO2/Al2O3 catalysts to the oxidative dehydrogenation of benzylamine in air, utilizing a new reaction setup. Again, batch and continuous flow reactions are compared and the effects of reaction conditions, ammonia...

  20. Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

    Science.gov (United States)

    Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

    2016-03-01

    A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

  1. Carbogenic molecular sieves for reaction and separation by design: A novel approach to shape selective super base, super acid and catalytic membranes. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Foley, Henry C.

    2002-03-18

    This report details the findings of three years of research plus one year of a no-cost extension. Primary results are the work with supported nanoporous carbon membranes for separation and reaction as well as with cesium-nanoporous carbon catalysts. The work resulted in 17 plus 2 papers (2 are in progress) and partial or full support for five Ph.D. students. Two patents were filed based on this research.

  2. NaIO4/LiBr-mediated diastereoselective dihydroxylation of olefins: a catalytic approach to the Prevost-Woodward reaction.

    Science.gov (United States)

    Emmanuvel, Lourdusamy; Shaikh, Tanveer Mahammad Ali; Sudalai, Arumugam

    2005-10-27

    [reaction: see text] LiBr catalyzes efficiently the dihydroxylation of alkenes to afford syn and anti diols with excellent diastereoselectivity depending upon the use of NaIO(4) (30 mol %) or PhI(OAc)(2) (1 equiv), respectively, as the oxidants. The oxidation of non-benzylic halides has been achieved for the first time to afford the corresponding diols in excellent yields.

  3. A computational study of detoxification of lewisite warfare agents by British anti-lewisite: catalytic effects of water and ammonia on reaction mechanism and kinetics.

    Science.gov (United States)

    Sahu, Chandan; Pakhira, Srimanta; Sen, Kaushik; Das, Abhijit K

    2013-04-25

    trans-2-Chlorovinyldichloroarsine (lewisite, L agent, Lew-I) acts as a blistering agents. British anti-lewisite (BAL, 2,3-dimercaptopropanol) has long been used as an L-agent antidote. The main reaction channels for the detoxification proceed via breaking of As-Cl bonds and formation of As-S bonds, producing stable, nontoxic ring product [(2-methyl-1,3,2-dithiarsolan-4-yl)methanol]. M06-2X/GENECP calculations have been carried out to establish the enhanced rate of detoxification mechanism in the presence of NH3 and H2O catalysts in both gas and solvent phases, which has been modeled by use of the polarized continuum model (PCM). In addition, natural bond orbital (NBO) and atoms in molecules (AIM) analysis have been performed to characterize the intermolecular hydrogen bonding in the transition states. Transition-state theory (TST) calculation establishes that the rates of NH3-catalyzed (2.88 × 10(-11) s(-1)) and H2O-catalyzed (2.42 × 10(-11) s(-1)) reactions are reasonably faster than the uncatalyzed detoxification (5.44 × 10(-13) s(-1)). The results obtained by these techniques give new insight into the mechanism of the detoxification process, identification and thermodynamic characterization of the relevant stationary species, the proposal of alternative paths on modeled potential energy surfaces for uncatalyzed reaction, and the rationalization of the mechanistic role played by catalysts and solvents.

  4. Catalytic Oxidized Reaction of Paraffin Wax Based on BP Neural Network%基于BP神经网络的石蜡催化氧化反应的研究

    Institute of Scientific and Technical Information of China (English)

    黄玮; 丛玉凤; 郭大鹏

    2012-01-01

    The oxidized wax was prepared by catalytic oxidized reaction of paraffin wax which used BP neural network to build mathematical model of acid value and saponification value influenced by the amount of reactive catalyst and accessory ingredient, airflow rate, reaction temperature and time, and utilized the model of neutral network to calculate the technology condition of preparing oxidized wax through catalyzing and oxidizing paraffin wax. Consequently, optimum technology conditions were gained in order to achieve the objective of reducing experimental number of times.%在石蜡催化氧化反应制备氧化蜡的研究中,利用BP神经网络建立反应催化剂用量、助剂用量、空气流量、反应温度和反应时间对酸值和皂化值影响的数学模型,并利用该神经网络模型对石蜡催化氧化制备氧化蜡的工艺条件进行预测,从而获得最优工艺条件,达到缩短实验次数的目的.

  5. Kinetic Modeling of Complex Catalytic Reactions Modélisation cinétique des réactions catalytiques complexes

    Directory of Open Access Journals (Sweden)

    Froment G. F.

    2006-11-01

    Full Text Available The paper deals with hydrocracking on metal-loaded zeolites. A fundamental approach is presented in which the detailed reaction network of the feed components of a complex feedstock is retained to a maximum extent. The kinetics are developed in terms of the elementary steps and single events involved in the reactions. Plausible assumptions and thermodynamic constraints limit the number of kinetic parameters. These do not depend on the chain length of the hydrocarbons and are not affected by the feed composition. Certainly, chemical analysis still imposes a certain degree of lumping of components and reaction networks, but not to the extent reflected by present day models. L'article traite de l'hydrocraquage sur des zéolites chargés en métaux. Dans l'approche fondamentale qui est présentée, le réseau de réaction des composants d'une charge complexe est retenu au maximum. La cinétique est établie en suivant pas à pas le déroulement et les étapes élémentaires des réactions. Des hypothèses plausibles et des contraintes thermodynamiques limitent le nombre de paramètres cinétiques. Ceux-ci ne dépendent pas de la longueur de la chaîne des hydrocarbures et ne sont pas affectés par la composition de la charge. L'analyse chimique impose bien sûr encore un certain agrégat des composants et des réseaux de réaction, mais moins que ne reflètent les modèles actuels.

  6. Using potassium catalytic gasification to improve the performance of solid oxide direct carbon fuel cells: Experimental characterization and elementary reaction modeling

    OpenAIRE

    Yu, Xiankai; Shi, Yixiang; Wang, Hongjian; Cai, Ningsheng; Li, Chen; Ghoniem, Ahmed F

    2013-01-01

    The performance of a solid oxide electrolyte direct carbon fuel cell (SO-DCFC) is limited by the slow carbon gasification kinetics at the typical operating temperatures of cell: 650–850 °C. To overcome such limitation, potassium salt is used as a catalyst to speed up the dry carbon gasification reactions, increasing the power density by five-fold at 700–850 °C. The cell performance is shown to be sensitive to the bed temperature, emphasizing the role of gasification rates and that of CO produ...

  7. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    OpenAIRE

    2016-01-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to st...

  8. Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

    KAUST Repository

    Chinnusamy, Tamilselvi R.

    2012-05-09

    The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Western Conceptualizations and Eastern Experience : A Cross-cultural Study of Traumatic Stress Reactions among Tibetan Refugees in India

    NARCIS (Netherlands)

    Terheggen, M.A.; Stroebe, M.S.; Kleber, R.J.

    2001-01-01

    This study investigated the nature and impact of traumatic experiences among Tibetan refugees in India. It explored the applicability of western conceptualizations of reactions to traumatic events among this cultural group. A randomly selected sample of refugee camp students was assessed on measures

  10. Western conceptualizations and Eastern experience: A cross-cultural study of traumatic stress reactions among Tibetan refugees in India

    NARCIS (Netherlands)

    Terheggen, M.A.; Stroebe, M.S.; Kleber, R.J.

    2001-01-01

    This study investigated the nature and impact of traumatic experiences among Tibetan refugees in India. It explored the applicability of western conceptualizations of reactions to traumatic events among this cultural group. A randomly selected sample of refugee camp students was assessed on measures

  11. Western conceptualizations and Eastern experience : a cross-cultural study of traumatic stress reactions among Tibetan refugees in India

    NARCIS (Netherlands)

    Terheggen, M A; Stroebe, M S; Kleber, R J

    2001-01-01

    This study investigated the nature and impact of traumatic experiences among Tibetan refugees in India. It explored the applicability of western conceptualizations of reactions to traumatic events among this cultural group. A randomly selected sample of refugee camp students was assessed on measures

  12. Involvement of metals in enzymatic and nonenzymatic decomposition of C-terminal alpha-hydroxyglycine to amide: an implication for the catalytic role of enzyme-bound zinc in the peptidylamidoglycolate lyase reaction.

    Science.gov (United States)

    Takahashi, Kenichi; Harada, Saori; Higashimoto, Yuichiro; Shimokawa, Chizu; Sato, Hideaki; Sugishima, Masakazu; Kaida, Yasuhiko; Noguchi, Masato

    2009-02-24

    The peptide C-terminal amide group essential for the full biological activity of many peptide hormones is produced by consecutive actions of peptidylglycine alpha-hydroxylating monooxygenase (PHM) and peptidylamidoglycolate lyase (PAL); PHM catalyzes the hydroxylation of C-terminal glycine, and PAL decomposes the peptidyl-alpha-hydroxyglycine to an amidated peptide and glyoxylate. PAL contains 1 mol of zinc, but its role, catalytic or structural, has not yet been clarified. In this study, we found that a series of transition metals, Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), and Cd(2+), catalyze the nonenzymatic decomposition of the hydroxyglycine intermediate in a concentration-dependent manner. The second-order rate constant of the metal catalysis increased with elevation of pH, indicating that the hydrated metal acts as a general base. Extensive removal of the enzyme-bound metals remarkably diminished the PAL activity; k(cat) of the metal-depleted enzyme retaining 0.1 mol of zinc decreased to 3.2 s(-1) from 25.7 s(-1) of the wild-type enzyme. Among a series of divalent metals tested, Zn(2+), Co(2+), and Cd(2+) could fully restore the PAL activity of the metal-depleted enzyme. Especially, Zn substitution reproduced the steady-state parameters of the wild-type enzyme. On the other hand, Co and Cd substitution largely altered the kinetic parameters; the k(cat) increased 3- and 5-fold and the K(m) for the substrate increased 2.5- and 4-fold, respectively. These observations support that the enzyme-bound zinc plays a catalytic role, rather than a structural role, in the PAL reaction through the action of zinc-bound water as a general base.

  13. Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Ye Wang

    2015-09-01

    Full Text Available The ethanol oxidation reaction (EOR has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to CO2. This mini review is aimed at presenting an overview of the advances in the study of reaction mechanisms and electrocatalytic materials for EOR over the past two decades with a focus on Pt- and Pd-based catalysts. We start with discussion on the mechanistic understanding of EOR on Pt and Pd surfaces using selected publications as examples. Consensuses from the mechanistic studies are that sufficient active surface sites to facilitate the cleavage of the C–C bond and the adsorption of water or its residue are critical for obtaining a higher electro-oxidation activity. We then show how this understanding has been applied to achieve improved performance on various Pt- and Pd-based catalysts through optimizing electronic and bifunctional effects, as well as by tuning their surface composition and structure. Finally we point out the remaining key problems in the development of anode electrocatalysts for EOR.

  14. Phosphorus/sulfur Co-doped porous carbon with enhanced specific capacitance for supercapacitor and improved catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Zhou, Yao; Ma, Ruguang; Candelaria, Stephanie L.; Wang, Jiacheng; Liu, Qian; Uchaker, Evan; Li, Pengxi; Chen, Yongfang; Cao, Guozhong

    2016-05-01

    Phosphorus (P)/sulfur (S) co-doped porous carbon derived from resorcinol and furaldehyde are synthesized through one-step sol-gel processing with the addition of phosphorus pentasulfide as P and S source followed with freeze-drying and pyrolysis in nitrogen. The P/S co-doping strategy facilitates the pore size widening both in micropore and mesopore regions, together with the positive effect on the degree of graphitization of porous carbon through elimination of amorphous carbon through the formation and evaporation of carbon disulfide. As an electrode for supercapacitor application, P/S co-doped porous carbon demonstrates 43.5% improvement on specific capacitance of the single electrode compared to pristine porous carbon in organic electrolyte at a current of 0.5 mA due to the P-induced pseudocapacitive reactions. As for electrocatalytic use, promoted electrocatalytic activity and high resistance to crossover effects of oxygen reduction reaction (ORR) in alkaline media are observed after the introduction of P and S into porous carbon. After air activation, the specific capacitance of the single electrode of sample PS-pC reaches up to 103.5 F g-1 and an improved oxygen reduction current density.

  15. Direct dynamics simulations of the product channels and atomistic mechanisms for the OH(-) + CH3I reaction. Comparison with experiment.

    Science.gov (United States)

    Xie, Jing; Sun, Rui; Siebert, Matthew R; Otto, Rico; Wester, Roland; Hase, William L

    2013-08-15

    Electronic structure and direct dynamics calculations were used to study the potential energy surface and atomic-level dynamics for the OH(-) + CH3I reactions. The results are compared with crossed molecular beam, ion imaging experiments. The DFT/B97-1/ECP/d level of theory gives reaction energetics in good agreement with experiment and higher level calculations, and it was used for the direct dynamics simulations that were performed for reactant collision energies of 2.0, 1.0, 0.5, and 0.05 eV. Five different pathways are observed in the simulations, forming CH3OH + I(-), CH2I(-) + H2O, CH2 + I(-) + H2O, IOH(-) + CH3, and [CH3--I--OH](-). The SN2 first pathway and the proton-transfer second pathway dominate the reaction dynamics. Though the reaction energetics favor the SN2 pathway, the proton-transfer pathway is more important except for the lowest collision energy. The relative ion yield determined from the simulations is in overall good agreement with experiment. Both the SN2 and proton-transfer pathways occur via direct rebound, direct stripping, and indirect mechanisms. Except for the highest collision energy, 70-90% of the indirect reaction for the SN2 pathway occurs via formation of the hydrogen-bonded OH(-)---HCH2I prereaction complex. For the proton-transfer pathway the indirect reaction is more complex with the roundabout mechanism and formation of the OH(-)---HCH2I and CH2I(-)---HOH complexes contributing to the reaction. The majority of the SN2 reaction is direct at 2.0, 1.0, and 0.5 eV, dominated by stripping. At 0.05 eV the two direct mechanisms and the indirect mechanisms have nearly equal contributions. The majority of the proton-transfer pathway is direct stripping at 2.0, 1.0, and 0.5 eV, but the majority of the reaction is indirect at 0.05 eV. The product relative translational energy distributions are in good agreement with experiment for both the SN2 and proton-transfer pathways. For both, direct reaction preferentially transfers the product

  16. Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells

    Science.gov (United States)

    V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V.; Mitra, Somenath

    2012-01-01

    Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol−1 which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel. PMID:23118490

  17. Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells.

    Science.gov (United States)

    V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V; Mitra, Somenath

    2012-11-30

    Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol(-1) which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel.

  18. Tetradentate N2O2 Chelated Palladium(II Complexes: Synthesis, Characterization, and Catalytic Activity towards Mizoroki-Heck Reaction of Aryl Bromides

    Directory of Open Access Journals (Sweden)

    Siti Kamilah Che Soh

    2013-01-01

    Full Text Available Four air and moisture-stable palladium(II-Schiff base complexes, N,N′-bis(α-methylsalicylidenepropane-1,3-diamine palladium(II (2a, N,N′-bis(4-methyl-α-methylsalicylidenepropane-1,3-diamine palladium(II (2b, N,N′-bis(3,5-di-tert-butylsalicylidenepropane-1,3-diamine palladium(II (2c, and N,N′-bis(4-methoxy-salicylidenepropane-1,3-diamine palladium(II (2d, have been successfully synthesised and characterised by CHN elemental analyses and conventional spectroscopic methods. These complexes were investigated as catalysts in the phosphine-free Mizoroki-Heck cross-coupling reactions of aryl bromides with methyl acrylate.

  19. General Tritium Labelling of Gentamicin C by catalytic hydrogen exchange Reaction with Tritiated Water; Marcado general con tritio de la Gentamicina C por intercambio catalitico con agua triatiada

    Energy Technology Data Exchange (ETDEWEB)

    Suarez, C.; Diaz, D.; Paz, D.

    1991-07-01

    Gentamicin C was labelled with tritium by means of a PtO2 catalyzed hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H2O-3H, and 50 mg of prereduced PtO2) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 degree celsius, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accomplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v) . Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95. Main exchange degradation products show biological activity. (Author) 12 refs.

  20. Catalytic efficiency of enzymes: a theoretical analysis.

    Science.gov (United States)

    Hammes-Schiffer, Sharon

    2013-03-26

    This brief review analyzes the underlying physical principles of enzyme catalysis, with an emphasis on the role of equilibrium enzyme motions and conformational sampling. The concepts are developed in the context of three representative systems, namely, dihydrofolate reductase, ketosteroid isomerase, and soybean lipoxygenase. All of these reactions involve hydrogen transfer, but many of the concepts discussed are more generally applicable. The factors that are analyzed in this review include hydrogen tunneling, proton donor-acceptor motion, hydrogen bonding, pKa shifting, electrostatics, preorganization, reorganization, and conformational motions. The rate constant for the chemical step is determined primarily by the free energy barrier, which is related to the probability of sampling configurations conducive to the chemical reaction. According to this perspective, stochastic thermal motions lead to equilibrium conformational changes in the enzyme and ligands that result in configurations favorable for the breaking and forming of chemical bonds. For proton, hydride, and proton-coupled electron transfer reactions, typically the donor and acceptor become closer to facilitate the transfer. The impact of mutations on the catalytic rate constants can be explained in terms of the factors enumerated above. In particular, distal mutations can alter the conformational motions of the enzyme and therefore the probability of sampling configurations conducive to the chemical reaction. Methods such as vibrational Stark spectroscopy, in which environmentally sensitive probes are introduced site-specifically into the enzyme, provide further insight into these aspects of enzyme catalysis through a combination of experiments and theoretical calculations.

  1. Correlation Models for Light Olefin Yields from Catalytic Pyrolysis of Petroleum Residue

    Institute of Scientific and Technical Information of China (English)

    DongXiaoli; MengXianghai; GaoJinsen; XuChunming

    2005-01-01

    Correlation models for light olefin yields from residue catalytic pyrolysis are studied. Experiments are carried out in a confined fluidized bed reactor for Daqing (China) atmospheric residue catalytic pyrolysis over LCM-5 pyrolyzing catalyst. The influences of reaction temperature, residence time and the weight ratios of catalyst-to-oil and steam-to-oil on light olefin yields are researched. Correlation models for light olefin yields are established, and the model parameters obtained, with the least square method. Results for error analysis and the F-statistical test show that the correlation models have high calculation precision.

  2. Reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene%非催化条件下异丙苯液相过氧化反应动力学

    Institute of Scientific and Technical Information of China (English)

    刘明鑫; 许志美; 孙伟振; 张明华; 赵玲

    2015-01-01

    Both main and side reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene (IPB) were investigated, including byproduct formation such asα-methyl benzyl alchohol (MBA) and acetophenone (ACP), and decomposition pathway of ROOR (DCP). Based on free radical chain reaction mechanism, a kinetic model was developed, in which IPB hydroperoxide (IPBHP), MBA, ACP and DCP were considered. The prediction by this kinetic model is agreed well with the experimental data, if the rate constants were used which were obtained by fitting of the experimental data at 373—404 K. The activation energies estimated were larger for all side reactions than for the main reaction. DCP decomposition requires the presence of oxygen. These data obtained could be helpful for deep understand of the reaction mechanism of liquid phase of alkyl aromatics and could be used as the fundamental data for design and optimization of industrial liquid phase oxidation of IPB.%研究了非催化条件下异丙苯(IPB)液相氧化主副反应动力学,包括主要副产物α-甲基苄醇(MBA)和苯乙酮(ACP)生成规律以及重要链终止产物ROOR (DCP)的分解反应路径。基于烃类链式自由基反应机理,建立了包含反应物IPB、主产物过氧化氢异丙苯(IPBHP)、副产物MBA、ACP以及链终止产物DCP的反应动力学模型。动力学模型预测结果与实验数据吻合良好。通过对373~404 K下实验数据的拟合,得到了不同温度下各基元反应速率常数和活化能。模拟计算表明,两个副反应活化能均大于主反应;链终止产物DCP的分解反应通过氧气的参与进行。研究结果可为异丙苯液相氧化工业反应过程的设计和优化提供基础参数,并且有利于深化对烷基芳烃液相氧化反应机理的认识。

  3. Self-propagating exothermic reaction analysis in Ti/Al reactive films using experiments and computational fluid dynamics simulation

    Science.gov (United States)

    Sen, Seema; Lake, Markus; Kroppen, Norman; Farber, Peter; Wilden, Johannes; Schaaf, Peter

    2017-02-01

    This study describes the self-propagating exothermic reaction in Ti/Al reactive multilayer foils by using experiments and computational fluid dynamics simulation. The Ti/Al foils with different molar ratios of 1Ti/1Al, 1Ti/2Al and 1Ti/3Al were fabricated by magnetron sputtering method. Microstructural characteristics of the unreacted and reacted foils were analyzed by using electronic and atomic force microscopes. After an electrical ignition, the influence of ignition potentials on reaction propagation has been experimentally investigated. The reaction front propagates with a velocity of minimum 0.68 ± 0.4 m/s and maximum 2.57 ± 0.6 m/s depending on the input ignition potentials and the chemical compositions. Here, the 1Ti/3Al reactive foil exhibits both steady state and unsteady wavelike reaction propagation. Moreover, the numerical computational fluid dynamics (CFD) simulation shows the time dependent temperature flow and atomic mixing in a nanoscale reaction zone. The CFD simulation also indicates the potentiality for simulating exothermic reaction in the nanoscale Ti/Al foil.

  4. Computational organic chemistry: bridging theory and experiment in establishing the mechanisms of chemical reactions.

    Science.gov (United States)

    Cheng, Gui-Juan; Zhang, Xinhao; Chung, Lung Wa; Xu, Liping; Wu, Yun-Dong

    2015-02-11

    Understanding the mechanisms of chemical reactions, especially catalysis, has been an important and active area of computational organic chemistry, and close collaborations between experimentalists and theorists represent a growing trend. This Perspective provides examples of such productive collaborations. The understanding of various reaction mechanisms and the insight gained from these studies are emphasized. The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer, are presented along with some conventional developments of mechanistic aspects. Examples of applications are selected to demonstrate the advantages and limitations of these techniques. Some challenges in the mechanistic studies and predictions of reactions are also analyzed.

  5. Employee Reactions to an Open-Plan Office: A Naturally Occurring Quasi-Experiment.

    Science.gov (United States)

    Oldham, Greg R.; Brass, Daniel J.

    1979-01-01

    Examines changes in reactions of employees to work after they moved from a conventional office to an open-plan office. Employee satisfaction and internal motivation decreased significantly after the move to the open office. (Author/IRT)

  6. Reactions of 1-naphthyl radicals with acetylene. Single-pulse shock tube experiments and quantum chemical calculations. Differences and similarities in the reaction with ethylene.

    Science.gov (United States)

    Lifshitz, Assa; Tamburu, Carmen; Dubnikova, Faina

    2009-10-01

    The reactions of 1-naphthyl radicals with acetylene were studied behind reflected shock waves in a single-pulse shock tube, covering the temperature range 950-1200 K at overall densities behind the reflected shocks of approximately 2.5 x 10(-5) mol/cm3. 1-Iodonaphthalene served as the source for 1-naphthyl radicals. The [acetylene]/[1-iodonaphthalene] ratio in all of the experiments was approximately 100 to channel the free radicals into reactions with acetylene rather than iodonaphthalene. Only two major products resulting from the reactions of 1-naphthyl radicals with acetylene and with hydrogen atoms were found in the post shock samples. They were acenaphthylene and naphthalene. Some low molecular weight aliphatic products at rather low concentrations, resulting from an attack of various free radicals on acetylene, were also found in the shocked samples. In view of the relatively low temperatures employed in the present experiments, the unimolecular decomposition rate of acetylene is negligible. One potential energy surface describes the production of acenaphthylene and 1-naphthyl acetylene, although the latter was not found experimentally due to the high barrier (calculated) required for its production. Using quantum chemical methods, the rate constants for three unimolecular elementary steps on the surface were calculated using transition state theory. A kinetics scheme containing 16 elementary steps was constructed, and computer modeling was performed. An excellent agreement between the experimental yields of the two major products and the calculated yields was obtained. Differences and similarities in the potential energy surfaces of 1-naphthyl radical + acetylene and those of ethylene are presented, and the kinetics mechanisms are discussed.

  7. Intersystem crossing and dynamics in O(3P) + C2H4 multichannel reaction: experiment validates theory.

    Science.gov (United States)

    Fu, Bina; Han, Yong-Chang; Bowman, Joel M; Angelucci, Luca; Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio

    2012-06-19

    The O((3)P) + C(2)H(4) reaction, of importance in combustion and atmospheric chemistry, stands out as a paradigm reaction involving triplet- and singlet-state potential energy surfaces (PESs) interconnected by intersystem crossing (ISC). This reaction poses challenges for theory and experiments owing to the ruggedness and high dimensionality of these potentials, as well as the long lifetimes of the collision complexes. Primary products from five competing channels (H + CH(2)CHO, H + CH(3)CO, H(2) + CH(2)CO, CH(3) + HCO, CH(2) + CH(2)O) and branching ratios (BRs) are determined in crossed molecular beam experiments with soft electron-ionization mass-spectrometric detection at a collision energy of 8.4 kcal/mol. As some of the observed products can only be formed via ISC from triplet to singlet PESs, from the product BRs the extent of ISC is inferred. A new full-dimensional PES for the triplet state as well as spin-orbit coupling to the singlet PES are reported, and roughly half a million surface hopping trajectories are run on the coupled singlet-triplet PESs to compare with the experimental BRs and differential cross-sections. Both theory and experiment find almost equal contributions from the two PESs to the reaction, posing the question of how important is it to consider the ISC as one of the nonadiabatic effects for this and similar systems involved in combustion chemistry. Detailed comparisons at the level of angular and translational energy distributions between theory and experiment are presented for the two primary channel products, CH(3) + HCO and H + CH(2)CHO. The agreement between experimental and theoretical functions is excellent, implying that theory has reached the capability of describing complex multichannel nonadiabatic reactions.

  8. Radical-ion-pair reactions are the biochemical equivalent of the optical double slit experiment

    OpenAIRE

    Kominis, I. K.

    2010-01-01

    Radical-ion-pair reactions were recently shown to represent a rich biophysical laboratory for the application of quantum measurement theory methods and concepts. We here show that radical-ion-pair reactions essentially form a non-linear biochemical double slit interferometer. Quantum coherence effects are visible when "which-path" information is limited, and the incoherent limit is approached when measurement-induced decoherence sets in. Based on this analogy with the optical double slit expe...

  9. The influence of anionic ligands on stereoisomerism of Ru carbenes and their importance to efficiency and selectivity of catalytic olefin metathesis reactions.

    Science.gov (United States)

    Torker, Sebastian; Khan, R Kashif M; Hoveyda, Amir H

    2014-03-01

    Investigations detailed herein provide insight regarding the mechanism of stereochemical inversion of stereogenic-at-Ru carbene complexes through a nonolefin metathesis-based polytopal rearrangement pathway. Computational analyses (DFT) reveal that there are two key factors that generate sufficient energy barriers that are responsible for the possibility of isolation and characterization of high-energy, but kinetically stable, intermediates: (1) donor-donor interactions that involve the anionic ligands and the strongly electron donating carbene groups and (2) dipolar effects arising from the syn relationship between the anionic groups (iodide and phenoxide). We demonstrate that a Brønsted acid lowers barriers to facilitate isomerization, and that the positive influence of a proton source is the result of its ability to diminish the repulsive electronic interactions originating from the anionic ligands. The implications of the present studies regarding a more sophisticated knowledge of the role of anionic units on the efficiency of Ru-catalyzed olefin metathesis reactions are discussed. The electronic basis for the increased facility with which allylic alcohols participate in olefin metathesis processes will be presented as well. Finally, we illustrate how a better understanding of the role of anionic ligands has served as the basis for successful design of Ru-based Z-selective catalysts for alkene metathesis.

  10. DNA-binding, catalytic oxidation, C—C coupling reactions and antibacterial activities of binuclear Ru(II thiosemicarbazone complexes: Synthesis and spectral characterization

    Directory of Open Access Journals (Sweden)

    Arumugam Manimaran

    2012-07-01

    Full Text Available New hexa-coordinated binuclear Ru(II thiosemicarbazone complexes of the type {[(B(EPh3(COClRu]2L} (where, E = P or As; B = PPh3 or AsPh3 or pyridine; L = mononucleating NS donor of N-substituted thiosemicarbazones have been synthesized and characterized by elemental analysis, FT-IR, UV–vis and 31P{1H} NMR cyclic voltammetric studies. The DNA-binding studies of Ru(II complexes with calf thymus DNA (CT-DNA were investigated by UV–vis, viscosity measurements, gel-electrophoresis and fluorescence spectroscopy. The new complexes have been used as catalysts in C—C coupling reaction and in the oxidation of alcohols to their corresponding carbonyl compounds by using NMO as co-oxidant and molecular oxygen (O2 atmosphere at ambient temperature. Further, the new binucleating thiosemicarbazone ligands and their Ru(II complexes were also screened for their antibacterial activity against Klebsiella pneumoniae, Shigella sp., Micrococcus luteus, Escherichia coli and Salmonella typhi. From this study, it was found out that the activity of the complexes almost reaches the effectiveness of the conventional bacteriocide.

  11. Investigation of the solid state reaction of LaMnO{sub 3} with Fe{sup 0} and its effect on the catalytic reactions with H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Moura, Flavia C. C.; Araujo, Maria H.; Lago, Rochel M. [Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil). Dept. de Quimica]. E-mail: rochel@ufmg.br; Ardisson, Jose D.; Macedo, Waldemar A. A.; Albuquerque, Adriana S. [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN), Belo Horizonte, MG (Brazil). Lab. de Fisica Aplicada]. E-mail: asa@cdtn.br

    2007-03-15

    In this work, the reaction of the perovskite LaMnO{sub 3.15} with Fe{sup o} has been promoted by thermal treatment of the mixture Fe{sup o}/LaMnO{sub 3.15} at 200, 400 and 600 deg C. Moessbauer spectroscopy, X-ray diffraction (XRD), temperature programmed reduction (TPR) and temperature programmed desorption (O{sub 2}-TPD) analyses suggested that at 400 and 600 deg C oxygen from perovskite is transferred to Fe{sup o} to produce an oxygen deficient perovskite, LaMnO{sub 3-}{delta}, and highly dispersed iron oxides, mainly Fe{sub 3}O{sub 4} and FeO. XRD lattice parameters and crystallite size showed that LaMnO{sub 3} suffers a strong lattice distortion after reaction but no collapse of the perovskite structure. Reactivity studies pointed to a special interface effect of Fe{sup o}/LaMO{sub 3} towards two reactions with H{sub 2}O{sub 2}, the decomposition to O{sub 2} and the oxidation of the model molecule, the methylene blue dye. As the treatment temperature of the Fe{sup o}/LaMnO{sub 3.15} increased, the activity for H{sub 2}O{sub 2} decomposition decreased, whereas the activity for the dye oxidation increased. These results are discussed in terms of a decrease in the concentration of Mn{sup 4+} {sub surf} and Mn{sup 3+} {sub surf} species, active for the H{sub 2}O{sub 2} decomposition, with the formation of Mn{sup 2+} {sub surf} and Fe{sup 2+} {sub surf} species, active for the Fenton reaction. (author)

  12. Catalytic wet air oxidation of high concentration pharmaceutical wastewater.

    Science.gov (United States)

    Zhan, Wei; Wang, Xiaocong; Li, Daosheng; Ren, Yongzheng; Liu, Dongqi; Kang, Jianxiong

    2013-01-01

    In this study, we investigated the pretreatment of a high concentration pharmaceutical wastewater by catalytic wet air oxidation (CWAO) process. Different experiments were conducted to investigate the effects of the catalyst type, operating temperature, initial system pH, and oxygen partial pressure on the oxidation of the wastewater. Results show that the catalysts prepared by the co-precipitation method have better catalytic activity compared to others. Chemical oxygen demand (COD) conversion increased with the increase in temperature from 160 to 220 °C and decreased with the increase in pH. Moreover, the effect of the oxygen partial pressure on the COD conversion was significant only during the first 20 min of the reaction. Furthermore, the biodegradability of the wastewater improved greatly after CWAO, the ratio of BOD5/COD increased less than 0.1-0.75 when treated at 220 °C (BOD: biochemical oxygen demand).

  13. Structures of the Ca2+-regulated photoprotein obelin Y138F mutant before and after bioluminescence support the catalytic function of a water molecule in the reaction.

    Science.gov (United States)

    Natashin, Pavel V; Ding, Wei; Eremeeva, Elena V; Markova, Svetlana V; Lee, John; Vysotski, Eugene S; Liu, Zhi-Jie

    2014-03-01

    Ca(2+)-regulated photoproteins, which are responsible for light emission in a variety of marine coelenterates, are a highly valuable tool for measuring Ca(2+) inside living cells. All of the photoproteins are a single-chain polypeptide to which a 2-hydroperoxycoelenterazine molecule is tightly but noncovalently bound. Bioluminescence results from the oxidative decarboxylation of 2-hydroperoxycoelenterazine, generating protein-bound coelenteramide in an excited state. Here, the crystal structures of the Y138F obelin mutant before and after bioluminescence are reported at 1.72 and 1.30 Å resolution, respectively. The comparison of the spatial structures of the conformational states of Y138F obelin with those of wild-type obelin gives clear evidence that the substitution of Tyr by Phe does not affect the overall structure of both Y138F obelin and its product following Ca(2+) discharge compared with the corresponding conformational states of wild-type obelin. Despite the similarity of the overall structures and internal cavities of Y138F and wild-type obelins, there is a substantial difference: in the cavity of Y138F obelin a water molecule corresponding to W2 in wild-type obelin is not found. However, in Ca(2+)-discharged Y138F obelin this water molecule now appears in the same location. This finding, together with the observed much slower kinetics of Y138F obelin, clearly supports the hypothesis that the function of a water molecule in this location is to catalyze the 2-hydroperoxycoelenterazine decarboxylation reaction by protonation of a dioxetanone anion before its decomposition into the excited-state product. Although obelin differs from other hydromedusan Ca(2+)-regulated photoproteins in some of its properties, they are believed to share a common mechanism.

  14. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Barrio, L.; Kubacka, A; Zhou, G; Estrella, M; Martinez-Arias, A; Hanson, J; Fernandez-Garcia, M; Rodriguez, J

    2010-01-01

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni-O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate-carbonate route is operative for the production of hydrogen.

  15. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, J.A.; Barrio, L.; Kubacka, A.; Zhou, G.; Estrella, M.; Mart& #305; nez-Arias, A.; Hanson, J.C.; Fernandez-Garc& #305; a, M.

    2010-07-29

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni?O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate?carbonate route is operative for the production of hydrogen.

  16. 碳五烃催化裂解制取低碳烯烃反应性能及机理%Reaction Performance and Mechanism for Production of Propylene and Ethylene from C5 Hydrocarbon by Catalytic Cracking

    Institute of Scientific and Technical Information of China (English)

    刘俊涛; 滕加伟

    2015-01-01

    A catalytic cracking process for production of propylene and ethylene from C5 hydrocarbon with a catalyst of the ZSM-5 molecular sieve was investigated, especially the influence of reaction temperature and dilution ratio on product distribution was researched. The results showed that conversion of both C5 alkane and C5 olefins increased constantly with reaction temperature increasing, while the conversion of C5 olefins was much higher than that of C5 alkane. The yield of propylene and ethylene increased continuously from 8.84 % and 2.38 % at 450℃ to 19.67% and 13.86 % at 620℃ under reaction conditions of weight hourly space velocity of 3.06 h-1 and reaction partial pressure of 23.24 kPa. On the other hand, the conversion of C5 olefins, yield of ethylene, propylene and butene all decreased with dilution ratio increasing, while the yield of C6 hydrocarbon increased continuously. The mechanism of C5 hydrocarbon catalytic cracking was discussed. It was assumed that direct cracking of C5 olefins into ethylene and propylene and dimerisation of C5 olefins to C10 intermediate proceeded simultaneously. Then the cracking was carried out from the C10 intermediate. The above-mentioned mechanism can be used to explain experimental data satisfactorily.%以 ZSM-5分子筛为催化剂,碳五烃混合物为裂解原料,考察温度及稀释比对碳五烃催化裂解制丙烯/乙烯反应性能的影响。结果表明:随温度升高碳五烷烃及烯烃的转化率均不断升高,但碳五烯烃的转化率远高于碳五烷烃的转化率。同时乙烯及丙烯的收率也随温度的升高而升高,空速3.06 h-1,分压23.24 kPa时,分别由450℃的2.38%,8.84%升高到620℃时的13.86%和19.67%。另外,随稀释比的增加,碳五烯烃转化率,乙烯、丙烯及丁烯的收率不断下降,但 C6烃的收率随稀释比的增加而升高。碳五烯烃催化裂解机理分析指出:碳五烯烃催化裂解过程中碳五烯烃在直接裂解

  17. SYNTHESIS, CHARACTERIZATION AND CATALYTIC PERFORMANCE OF Cu-CONTAINING SBA-15 CATALYSTS FOR DeNPAC REACTION%含Cu SBA-15催化剂的合成、表征及DeNPAC反应性能评价

    Institute of Scientific and Technical Information of China (English)

    曾厚旭; YU L E; KAWI S

    2008-01-01

    CuO/SBA-15, CuAI/SBA-15 and CuOAI/SBA-15 were synthesized by wet-impregnation and ion-exchange methods. The acidic properties of SBA-15 were improved by incorporating AI with post-synthesis method. The Cu was introduced to SBA-15 and AI/SBA-15 supports by wet-impregnation and ion-exchange method, respectively. CuAI/SBA-15 showed the best catalytic performance by giving the highest conversion of pyridine with the lowest yield of NOx in the reaction of decomposing nitrogen-containing polycyclic aromatic compounds (DeNPAC). The enhanced reaction activity of CuAl/SBA-15 for DeNPAC could be attributed to the hi-functionality of acid and metallic ion of CuAl/SBA-15.%采用浸渍法和离子交换法合成了CuO/SBA-15、CuAl/SBA-15和CuOAl/SBA-15 3种催化剂.SBA-15的酸功能通过负载A1而得以改进.通过浸渍法和离子交换法将Cu引入SBA-15和A1/SBA-15中.3种催化剂相比,CuAl/sBA-15在DeNPAC反应中具有最高的吡啶转化率的同时,具有最低的NOx产率.CuAI/SBA-15具有较好的含氮多环芳烃化合物脱除反应性能的原因,可能是其酸功能和金属离子功能共同作用的结果.

  18. Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

    Science.gov (United States)

    Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

    2016-11-01

    The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input.

  19. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm

    2000-01-01

    The effect of electrochemical polarization on the catalytic SO2 oxidation in the molten V2O5-K2S2O7 system has been studied using a gold working electrode in the temperature range 400-460 degrees C. A similar experiment has been performed with the industrial catalyst VK-58. The aim of the present...... investigation was to study a possible non-Faradaic electrochemical promotion of the liquid-phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately -0.1 and -0.2 V, and one positive potential promotion area with the maximum effect...... caused by the negative charge on the electrode. The Faradaic part of the promoting effect under positive polarization has been explained as the electrochemical pushing of the V(V) V(IV) equilibrium in the direction of V(V) formation. It has also been shown that when using the industrial VK-58 catalyst...

  20. Optimization of reaction parameters for the electrochemical oxidation of lidocaine with a Design of Experiments approach

    NARCIS (Netherlands)

    Gul, Turan; Bischoff, Rainer; Permentier, Hjalmar

    2015-01-01

    Identification of potentially toxic oxidative drug metabolites is a crucial step in the development of new drugs. Electrochemical methods are useful to study oxidative drug metabolism, but are not widely used to synthesize metabolites for follow-up studies. Careful optimization of reaction parameter

  1. Two Experiments to Approach the Boltzmann Factor: Chemical Reaction and Viscous Flow

    Science.gov (United States)

    Fazio, Claudio; Battaglia, Onofrio R.; Guastella, Ivan

    2012-01-01

    In this paper we discuss a pedagogical approach aimed at pointing out the role played by the Boltzmann factor in describing phenomena usually perceived as regulated by different mechanisms of functioning. Experimental results regarding some aspects of a chemical reaction and of the viscous flow of some liquids are analysed and described in terms…

  2. Temperature Modulation of a Catalytic Gas Sensor

    OpenAIRE

    Eike Brauns; Eva Morsbach; Sebastian Kunz; Marcus Baeumer; Walter Lang

    2014-01-01

    The use of catalytic gas sensors usually offers low selectivity, only based on their different sensitivities for various gases due to their different heats of reaction. Furthermore, the identification of the gas present is not possible, which leads to possible misinterpretation of the sensor signals. The use of micro-machined catalytic gas sensors offers great advantages regarding the response time, which allows advanced analysis of the sensor response. By using temperature modulation, additi...

  3. Catalytic liquid marbles: Ag nanowire-based miniature reactors for highly efficient degradation of methylene blue.

    Science.gov (United States)

    Miao, Yue-E; Lee, Hiang Kwee; Chew, Wee Shern; Phang, In Yee; Liu, Tianxi; Ling, Xing Yi

    2014-06-04

    Ag nanowire-based catalytic liquid marbles are fabricated as miniature reactors, which demonstrate highly efficient, support-free and rate-controllable heterogeneous degradation of methylene blue, with catalytic efficiency close to 100%. Our miniature catalytic liquid marbles are essential for reactions involving highly toxic/hazardous or costly reactants, where small volume preliminary reactions are preferred.

  4. The Kemp elimination in membrane mimetic reaction media. Probing catalytic properties of cationic vesicles formed from a double-tailed amphiphile and linear long-tailed alcohols or alkyl pyranosides.

    Science.gov (United States)

    Klijn, Jaap E; Engberts, Jan B F N

    2004-06-21

    . The overall kinetic results are illustrative for the highly complex mix of factors which determines catalytic effects on reactions occurring in biological cell membranes.

  5. Thermal decomposition of NH2OH and subsequent reactions: ab initio transition state theory and reflected shock tube experiments.

    Science.gov (United States)

    Klippenstein, S J; Harding, L B; Ruscic, B; Sivaramakrishnan, R; Srinivasan, N K; Su, M-C; Michael, J V

    2009-09-24

    Primary and secondary reactions involved in the thermal decomposition of NH2OH are studied with a combination of shock tube experiments and transition state theory based theoretical kinetics. This coupled theory and experiment study demonstrates the utility of NH2OH as a high temperature source of OH radicals. The reflected shock technique is employed in the determination of OH radical time profiles via multipass electronic absorption spectrometry. O-atoms are searched for with atomic resonance absorption spectrometry. The experiments provide a direct measurement of the rate coefficient, k1, for the thermal decomposition of NH2OH. Secondary rate measurements are obtained for the NH2 + OH (5a) and NH2OH + OH (6a) abstraction reactions. The experimental data are obtained for temperatures in the range from 1355 to 1889 K and are well represented by the respective rate expressions: log[k/(cm3 molecule(-1) s(-1))] = (-10.12 +/- 0.20) + (-6793 +/- 317 K/T) (k1); log[k/(cm3 molecule(-1) s(-1))] = (-10.00 +/- 0.06) + (-879 +/- 101 K/T) (k5a); log[k/(cm3 molecule(-1) s(-1))] = (-9.75 +/- 0.08) + (-1248 +/- 123 K/T) (k6a). Theoretical predictions are made for these rate coefficients as well for the reactions of NH2OH + NH2, NH2OH + NH, NH + OH, NH2 + NH2, NH2 + NH, and NH + NH, each of which could be of secondary importance in NH2OH thermal decomposition. The theoretical analyses employ a combination of ab initio transition state theory and master equation simulations. Comparisons between theory and experiment are made where possible. Modest adjustments of predicted barrier heights (i.e., by 2 kcal/mol or less) generally yield good agreement between theory and experiment. The rate coefficients obtained here should be of utility in modeling NOx in various combustion environments.

  6. Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

    NARCIS (Netherlands)

    Nordvang, Emily C.; Borodina, Elena; Ruiz-Martinez, Javier; Fehrmann, Rasmus; Weckhuysen, Bert M.

    2015-01-01

    The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ sing

  7. Reaction mechanism and degradation course of azo dyes by catalytic wet peroxide oxidation(CWPO)%催化湿式过氧化(CWPO)偶氮染料反应机理及降解历程研究

    Institute of Scientific and Technical Information of China (English)

    张蕾; 马宏瑞

    2011-01-01

    采用浸渍法制备出具有较高催化活性的催化剂CuO/γ-Al2O3,通过XRD、电镜等手段对催化剂进行了表征。降解了几种不同结构的偶氮染料,并通过改变CWPO的反应条件推断了其催化反应机理。采用紫外/可见分光光度计(UV-Vis)和傅里叶红外光谱仪(IR)等手段对染料降解过程进行跟踪和分析,对比染料处理前后紫外可见光谱与红外光谱图的变化,说明染料分子结构中的偶氮键发生断裂,破坏了分子结构的偶氮-苯环共轭发色体系,从而达到了脱色的目的。并借助水杨酸验证了CWPO体系中.OH的产生及CWPO反应机理。%The catalyst CuO/γ-Al2O3 with high catalytic activity by impregnation was prepared,and were examined by XRD、SEM to characterize the catalyst.Azo dyes of several different structures were degraded,and the reaction conditions were changed to study the reaction mechanism of CWPO.The UV/Visible spectrophotometer(UV-Vis) and the Fourier transform infrared spectrometer(IR) were used to track and analyze the degradation process of the dyes.Compared the UV-Vis and IR spectra before and after wastewater treatment,indicating the structure of the azo dye molecules bond was broken,destroyed azo benzene conjugated chromophoric system of the molecular structure,so as to achieve the purpose of bleaching.The salicylic acid was used to infer the ·OH generation and reaction mechanism in the CWPO system.

  8. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    Science.gov (United States)

    Poux, T; Bonnefont, A; Ryabova, A; Kéranguéven, G; Tsirlina, G A; Savinova, E R

    2014-07-21

    Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.

  9. Vibrational non-equilibrium in the hydrogen-oxygen reaction. Comparison with experiment

    Science.gov (United States)

    Skrebkov, Oleg V.

    2015-03-01

    A theoretical model is proposed for the chemical and vibrational kinetics of hydrogen oxidation based on consistent accounting of the vibrational non-equilibrium of the HO2 radical that forms as a result of the bimolecular recombination H+O2 → HO2. In the proposed model, the chain branching H+O2 = O+OH and inhibiting H+O2+M = HO2+M formal reactions are treated (in the terms of elementary processes) as a single multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and unimolecular decay of the comparatively long-lived vibrationally excited HO2 radical, which is able to react and exchange energy with the other components of the mixture. The model takes into account the vibrational non-equilibrium of the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1Δ), and the main reaction product H2O. It is shown that the hydrogen-oxygen reaction proceeds in the absence of vibrational equilibrium, and the vibrationally excited HO2(v) radical acts as a key intermediate in a fundamentally important chain branching process and in the generation of electronically excited species O2(1Δ), O(1D), and OH(2Σ+). The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 reaction is especially non-equilibrium, and the vibrational non-equilibrium of the HO2 radical is the essence of this process. The quantitative estimation of the vibrational relaxation characteristic time of the HO2 radical in its collisions with H2 molecules has been obtained as a result of the comparison of different experimental data on induction time measurements with the relevant calculations.

  10. Low amplitude insult project: PBX 9501 high explosive violent reaction experiments

    Energy Technology Data Exchange (ETDEWEB)

    Idar, D.J.; Lucht, R.A.; Straight, J.W.; Scammon, R.J.; Browning, R.V.; Middleditch, J.; Dienes, J.K.; Skidmore, C.B.; Buntain, G.A.

    1998-12-31

    The Modified Steven test geometry has been used with several different target designs to investigate the mechanical loading behavior of PBX 9501 to a low velocity impact. A 2 kg. mild steel spigot projectile is launched via a new powder driven gun design, from {approximately} 20 to 105 m/s, at lightly confined, steel targets. Brief descriptions of the gun design and operation are given. The threshold velocity to reaction for various target designs, different PBX 9501 lots, and different high explosive (HE) thicknesses are reported and compared. Various diagnostics have been employed to evaluate the pressure profile and timing, and target strain behavior relative to projectile impact. The violence of reaction, as measured by both passive and active techniques, is reported relative to a steady state detonation in PBX 9501. Experimental results suggest slightly different ignition mechanisms dominate based on (HE) thickness, resulting in delayed reactions from {approximately} 0.2- to 2.8-ms after impact. Post-test analyses of the PBX 9501 are briefly summarized.

  11. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  12. Some issues on soot removal from exhaust gases by means of a catalytic ceramic filter

    Energy Technology Data Exchange (ETDEWEB)

    Ciambelli, P.; Palma, V.; Russo, P. [Dipt. di Ingegneria Chimica e Alimentare, Univ. di Salerno, Fisciano (Italy); Vaccaro, S. [Dipt. di Chemica, Univ. di Napoli Federico II, Napoli (Italy)

    1999-07-01

    A catalytic filter for soot oxidation was made by deposition of a TiO{sub 2} supported Cu/V/K/Cl based catalyst on the surface of a porous ceramic filter. The filter performances were evaluated and compared with those of powder catalyst and uncatalytic filter. Filter testing was performed by either temperature programmed oxidation of soot previously deposited on the filter or simultaneous soot filtration and filter regeneration performed at a gas-oil burner exhaust. Both experiments showed that the catalyst significantly increases the rate of soot combustion and reduces both light-off and burnout temperatures of soot. At 375 C the catalytic filter was continuously regenerated at the burner exhaust with a soot combustion rate of about 0.1 g/min. Tests performed in the presence of NO showed a further increase of the rate of catalytic combustion together with NO consumption. It is suggested that such a consumption was the result of two competitive reactions, i.e. the catalytic oxidation of NO to NO{sub 2} and the reaction of NO{sub x} with soot. A specific feature of the catalyst is that it is active for both reactions. (orig.)

  13. Capture reactions at astrophysically relevant energies: extended gas target experiments and GEANT simulations

    CERN Document Server

    Kölle, V; Braitmayer, S E; Mohr, P J; Wilmes, S; Staudt, G; Hammer, J W; Jäger, M; Knee, H; Kunz, R; Mayer, A

    1999-01-01

    Several resonances of the capture reaction sup 2 sup 0 Ne(alpha, gamma) sup 2 sup 4 Mg were measured using an extended windowless gas target system. Detailed GEANT simulations were performed to derive the strength and the total width of the resonances from the measured yield curve. The crucial experimental parameters, which are mainly the density profile in the gas target and the efficiency of the gamma-ray detector, were analyzed by a comparison between the measured data and the corresponding simulation calculations. The excellent agreement between the experimental data and the simulations gives detailed insight into these parameters. (author)

  14. Looking for the GAP effect in manual responses and the role of contextual influences in reaction time experiments

    Directory of Open Access Journals (Sweden)

    Faria Jr. A.J.P.

    2004-01-01

    Full Text Available When the offset of a visual stimulus (GAP condition precedes the onset of a target, saccadic reaction times are reduced in relation to the condition with no offset (overlap condition - the GAP effect. However, the existence of the GAP effect for manual responses is still controversial. In two experiments using both simple (Experiment 1, N = 18 and choice key-press procedures (Experiment 2, N = 12, we looked for the GAP effect in manual responses and investigated possible contextual influences on it. Participants were asked to respond to the imperative stimulus that would occur under different experimental contexts, created by varying the array of warning-stimulus intervals (0, 300 and 1000 ms and conditions (GAP and overlap: i intervals and conditions were randomized throughout the experiment; ii conditions were run in different blocks and intervals were randomized; iii intervals were run in different blocks and conditions were randomized. Our data showed that no GAP effect was obtained for any manipulation. The predictability of stimulus occurrence produced the strongest influence on response latencies. In Experiment 1, simple manual responses were shorter when the intervals were blocked (247 ms, P < 0.001 in relation to the other two contexts (274 and 279 ms. Despite the use of choice key-press procedures, Experiment 2 produced a similar pattern of results. A discussion addressing the critical conditions to obtain the GAP effect for distinct motor responses is presented. In short, our data stress the relevance of the temporal allocation of attention for behavioral performance.

  15. Simulation Experiments on the Reaction of CH4-CaSO4 and Its Carbon Kinetic Isotope Fractionation

    Institute of Scientific and Technical Information of China (English)

    YueChangtao; LiShuyuan; DingKangle; ZhongNingning

    2005-01-01

    Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H,S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki(kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.

  16. 扫描电化学显微镜研究辣根过氧化物酶催化反应的动力学%Investigation of the Kinetics of Horseradish Peroxidase Catalytic Reaction by Scanning Electrochemical Microscopy

    Institute of Scientific and Technical Information of China (English)

    王晓蕾; 李燕

    2008-01-01

      The horseradish peroxidases (HRP) molecules were immobilized on an insulator substrate with the crosslinked polymer ofβ-cyclodextrin prepolymer and glutaraldhyde. The kinetics of catalytic reaction of hydroquinone (HQ) to p-benzoquinone (BQ) on the surface of immobilized HRP was studied by the scanning electrochemical microscopy with the feedback mode. The one-order enzyme-mediator kinetics was established. The apparent heterogeneous rate constant depended on pH. At pH 7.0, the heterogeneous rate constants had a maximum value of 1.8 × 10-2cm/s.%  本文通过β-环糊精与环氧氯丙烷反应,合成了交联预聚物β-CDP,进而在酸性条件下与戊二醛和辣根过氧化物酶反应,形成把辣根过氧化物酶固定在绝缘体基底上的高聚物.应用扫描电化学显微镜的反馈模式,研究了辣根过氧化物酶的催化反应动力学.通过对扫描电化学显微镜在酶点上的反馈曲线与理论曲线的拟合,测得了一级反应速率常数,并用此方法研究了pH对反应速率常数的影响.在pH=7.0时,辣根过氧化物酶的活性最高,与文献报道一致,结果满意.

  17. Modification of HZSM- 5 Zeolite by Hydrochloric Acid and Catalytic Performance of Mo - based Catalyst for Methane Dehydroaromatization Reaction%盐酸改性HZSM-5及Mo-基催化剂的MDA反应活性

    Institute of Scientific and Technical Information of China (English)

    王红霞; 赵婷婷

    2012-01-01

    采用盐酸溶液在303K对HZSM-5分子筛进行预处理,并以处理后的分子筛制备相应的Mo-基催化剂.分子筛和催化剂采用XRD和NH3-TPD等手段进行表征,利用甲烷无氧芳构化(MDA)反应评价Mo-基催化剂的催化活性.结果表明,指定实验条件下的盐酸处理在一定程度上降低了分子筛的结晶度,降低了分子筛上的B酸量,改性后的Mo-基催化剂在MDA反应中表现很好的稳定性.%The pretreatment with HC1 solution at 303 K was applied to modify HZSM -5 zeolite, and the Mobased catalysts were prepared by using the modified HZSM -5 zeolite as support and tested for catalytic performance of methane dehydroaromatization reaction. The modified Mo - based catalysts show a higher stability than that of Mo/HZSM - 5 catalyst prepared with unmodified with HZSM - 5 zeolite. The effect of acid treatment on the structure and acidity of HZSM - 5 zeolite and Mo - based catalysts were studied by XRD and NH3 - TPD methods. The results show that the acid treatment to HZSM - 5 at given experimental conditions led to a decrease in the crystallinity of HZSM -5 zeolite and the number of the Brnsted acid sites to a certain degree.

  18. Catalytic performance of ZSM-5 zeolite for MTP reaction before and after steam treatment%水热处理前后ZSM-5分子筛MTP反应催化性能研究

    Institute of Scientific and Technical Information of China (English)

    安良成; 王林; 雍晓静; 宋彩霞; 张伟; 罗春桃

    2016-01-01

    以粗孔硅胶为硅源经水热晶化制备了粒径约400nm~1μm的ZSM-5分子筛,并进行水热处理。采用SEM、XRD、NH3-TPD、N2物理吸附等方法对其结构进行了表征。比较研究了其水蒸气处理前后对甲醇制丙烯(MTP)反应的催化性能。结果表明,水热处理使ZSM-5分子筛酸中心数量减少,酸强度减弱,但孔容和孔径增大,从而使丙烯选择性及催化稳定性提高。%A ZSM-5 zeolite with the particle sizes of about 400nm~1μm was synthesized from macroporous silica gel by hy-drothermal crystallization, named as zeolite A, which was treated with steam to obtain zeolite B. The structural properties of both zeo-lites A and B were characterized by SEM, XRD, NH3-TPD and nitrogen adsorption, and their catalytic performances for methanol to propylene (MTP) reaction were comparatively investigated. Results show that steam treatment caused a decrease in the strength and amount of acidic sites and an increase in pore volume and average pore width. As a result, the propylene selectivity and life time of the catalyst were significantly improved.

  19. Facile electrochemical co-deposition of a graphene-cobalt nanocomposite for highly efficient water oxidation in alkaline media: direct detection of underlying electron transfer reactions under catalytic turnover conditions.

    Science.gov (United States)

    Guo, Si-Xuan; Liu, Yuping; Bond, Alan M; Zhang, Jie; Esakki Karthik, P; Maheshwaran, I; Senthil Kumar, S; Phani, K L N

    2014-09-21

    A facile electrochemical co-deposition method has been developed for the fabrication of graphene-cobalt nanocomposite modified electrodes that achieve exceptionally efficient water oxidation in highly alkaline media. In the method reported, a graphene-cobalt nanocomposite film was deposited electrochemically from a medium containing 1 mg ml(-1) graphene oxide, 0.8 mM cobalt nitrate and 0.05 M phytic acid (pH 7). The formation of the nanocomposite film was confirmed using electrochemical, Raman spectroscopic and scanning electron microscopic techniques. The nanocomposite film exhibits excellent activity and stability towards water oxidation to generate oxygen in 1 M NaOH aqueous electrolyte media. A turn over frequency of 34 s(-1) at an overpotential of 0.59 V and a faradaic efficiency of 97.7% were deduced from analysis of data obtained by rotating ring disk electrode voltammetry. Controlled potential electrolysis data suggests that the graphene supported catalyst exhibits excellent stability under these harsh conditions. Phytate anion acts as stabilizer for the electrochemical formation of cobalt nanoparticles. Fourier transformed ac voltammetry allowed the redox chemistry associated with catalysis to be detected directly under catalytic turnover conditions. Estimates of formal reversible potentials obtained from this method and derived from the overall reactions 3Co(OH)2 + 2OH(-) ⇌ Co3O4 + 4H2O + 2e(-), Co3O4 + OH(-) ⇌ 3CoOOH + e(-) and CoOOH + OH(-) ⇌ CoO2 + H2O + e(-) are 0.10, 0.44 and 0.59 V vs. Ag/AgCl, respectively.

  20. Reactions of 1-naphthyl radicals with ethylene. Single pulse shock tube experiments, quantum chemical, transition state theory, and multiwell calculations.

    Science.gov (United States)

    Lifshitz, Assa; Tamburu, Carmen; Dubnikova, Faina

    2008-02-07

    The reactions of 1-naphthyl radicals with ethylene were studied behind reflected shock waves in a single pulse shock tube, covering the temperature range 950-1200 K at overall densities behind the reflected shocks of approximately 2.5 x 10(-5) mol/cm3. 1-Iodonaphthalene served as the source for 1-naphthyl radicals as its C-I bond dissociation energy is relatively small. It is only approximately 65 kcal/mol as compared to the C-H bond strength in naphthalene which is approximately 112 kcal/mol and can thus produce naphthyl radicals at rather low reflected shock temperatures. The [ethylene]/[1-iodo-naphthalene] ratio in all of the experiments was approximately 100 in order to channel the free radicals into reactions with ethylene rather than iodonaphthalene. Four products resulting from the reactions of 1-naphthyl radicals with ethylene were found in the post shock samples. They were vinyl naphthalene, acenaphthene, acenaphthylene, and naphthalene. Some low molecular weight aliphatic products at rather low concentrations, resulting from the attack of various free radicals on ethylene were also found in the shocked samples. In view of the relatively low temperatures employed in the present experiments, the unimolecular decomposition rate of ethylene is negligible. Three potential energy surfaces describing the production of vinyl naphthalene, acenaphthene, and acenaphthylene were calculated using quantum chemical methods and rate constants for the elementary steps on the surfaces were calculated using transition state theory. Naphthalene is not part of the reactions on the surfaces. Acenaphthylene is obtained only from acenaphthene. A kinetics scheme containing 27 elementary steps most of which were obtained from the potential energy surfaces was constructed and computer modeling was performed. An excellent agreement between the experimental yields of the four major products and the calculated yields was obtained.

  1. [A polar expedition in challenging circumstances--experiences and psychological reactions].

    Science.gov (United States)

    Steine, Siri; Steine, Kjetil; Sandbaek, Gunnar; Røseth, Arne G

    2003-12-23

    Four men, in the company of 16 dogs, skied for five weeks from Gåsefjord to Ellef Ringnes Land, North Canada. The expedition met with considerable unforeseen challenges such as extreme and prolonged cold, unmotivated Greenland dogs, and much pack ice. Psychological reactions were described and measured by a qualitative free text analysis and a test battery including GHQ-30 (General Health Questionnaire) and STAI State (State-Trait Anxiety Inventory) before, during, and after the expedition. Five main themes were found: external influences, relations between men and animals, progress and expectations, interpersonal relations, and thoughts at the end of the expedition. Negative emotional reactions were mostly present at the beginning of the expedition and were related to the environment and the pressure of perceived expectations from the outside world. Frustrations were enhanced by forced inactivity. Perceived essential positive elements were a strong group identity and friendship. The acceptance of dissension was low; the group strived to achieve consensus before decisions were made. The psychometric results showed more stress and anxiety immediately before the expedition than after. These parameters also increased significantly at the beginning of the expedition, then there was a reverse. The level of anxiety was higher in the two leaders. The expedition was concluded in an overall atmosphere of mutual affection, satisfaction, and pride.

  2. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    Science.gov (United States)

    Shibata, T.; Nishiyama, H.

    2014-03-01

    Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

  3. Atmospheric Pressure Microwave Assisted Heterogeneous Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Ken Belmore

    2007-07-01

    Full Text Available The newly synthesized 5,10,15,20-tetra[3-(3-trifluoromethylphenoxy]porphyrin, TTFMPP, has been characterized using mass spectroscopy, 1H-, 13C- and 19F-NMR, MALDI-TOF mass spectrometry, UV-Vis and fluorescence spectrophotometry, andcyclic voltammetry. The NMR confirmed the structure of the compound and the massspectrum was in agreement with the proposed molecular formula. The UV-Vis absorptionspectrum of TTFMPP shows characteristic spectral patterns similar to those of tetraphenylporphryin, with a Soret band at 419 nm and four Q bands at 515, 550, 590, and 648 nm.Protonation of the porphyrin with TFA resulted in the expected red shift of the Soret band.Excitation at 419 nm gave an emission at 650 nm. The quantum yield of the porphyrin wasdetermined to be 0.08. Cyclic voltammetry was used to determine the oxidation andreduction potentials of the new porphyrin. Two quasi-reversible one-electron reductions at–1.00 and –1.32 V and a quasi-reversible oxidation at 1.20 V versus the silver/silverchloride reference electrode with tetrabutylammonium tetrafluoroborate as the supportingelectrolyte in methylene chloride were observed.

  4. Mechanisms and Kinetics of Catalytic Reactions

    Science.gov (United States)

    1990-08-01

    Microemulsions", PhD Thesis, Drexel University, Phil ., PA, 1980. 2. R.A. Mackay, F.R. Longo, B.L. Knier, H.D. Durst, J. Phys. Chem. 1987, 91, 861-864. 3. N.J...Am. Chem. Soc. 1978, 100, 117-122. 54. G.D. Hager, G.A. Crosby , J. Am. Chem. Soc. 1975, 97, 7031-7037. 55. S. Oishi, K. Tajime, I. Shiojima, J. Mol...Cat. 1982, 14, 383-386. 56. D.M. Klassen, G.A. Crosby , J. Chem. Phys. 1968, 48, 1853- 1858. 57. J.N. Braddock, T.J. Meyer, J. Am. Chem. Soc. 1973, 95

  5. Diffusion with chemical reaction: An attempt to explain number density anomalies in experiments involving alkali vapor

    Science.gov (United States)

    Snow, W. L.

    1974-01-01

    The mutual diffusion of two reacting gases is examined which takes place in a bath of inert gas atoms. Solutions are obtained between concentric spheres, each sphere acting as a source for one of the reactants. The calculational model is used to illustrate severe number density gradients observed in absorption experiments with alkali vapor. Severe gradients result when sq root k/D R is approximately 5 where k, D, and R are respectively the second order rate constant, the multicomponent diffusion constant, and the geometrical dimension of the experiment.

  6. Reaction kinetics study of coal catalytic gasification in lab scale fixed bed reactor%小型固定床煤催化气化动力学研究

    Institute of Scientific and Technical Information of China (English)

    高攀; 顾松园; 钟思青; 金永明; 曹勇

    2015-01-01

    K2CO3 catalytic gasification of Neimeng brown coal was studied in a fixed bed reactor. The effects of catalyst loading, temperature, gasification agents, such as H2O and H2, and partial pressure of H2O on the carbon conversion and reaction rate were investigated. The results showed that K2CO3 could accelerated the rate of coal-steam gasification obviously, and the carbon conversion reached 70% with the addition of only 10% K2CO3 by mass at 700℃, while H2 inhibited the coal-steam gasification seriously. A kinetic reaction equation was proposed based on an n order and Langmuir-Hinshewood expression by evaluating the carbon conversion behavior. The gasification activity significantly increased with steam partial pressure. In the n order expression, the order nwas 0.87 and the activation energy was 169.2kJ/mol, and, in the L-H expression, the activation energy was 121.9kJ/mol.%以K2CO3和内蒙褐煤为研究对象,在小型固定床上考察了催化剂负载量、温度,氢气以及水蒸气分压对碳转化率和气化反应速率的影响。结果表明,K2CO3对煤焦-水蒸气气化反应有明显的催化作用,700℃,当添加10%的K2CO3,碳的转化率为70%,氢气的含量对煤焦-水蒸气的反应有明显的抑制作用,并采用n级速率方程和Langmuir-Hinshelwood速率方程考察了水蒸气分压的影响,分压提高,煤焦-水蒸气气化反应活性提高,采用n级速率方程得到煤-水蒸气气化反应级数为0.87,活化能为169.2kJ/mol;采用L-H方程得到活化能为121.9kJ/mol。

  7. Statistical Models for the Analysis and Design of Digital Polymerase Chain Reaction (dPCR) Experiments.

    Science.gov (United States)

    Dorazio, Robert M; Hunter, Margaret E

    2015-11-03

    Statistical methods for the analysis and design of experiments using digital PCR (dPCR) have received only limited attention and have been misused in many instances. To address this issue and to provide a more general approach to the analysis of dPCR data, we describe a class of statistical models for the analysis and design of experiments that require quantification of nucleic acids. These models are mathematically equivalent to generalized linear models of binomial responses that include a complementary, log-log link function and an offset that is dependent on the dPCR partition volume. These models are both versatile and easy to fit using conventional statistical software. Covariates can be used to specify different sources of variation in nucleic acid concentration, and a model's parameters can be used to quantify the effects of these covariates. For purposes of illustration, we analyzed dPCR data from different types of experiments, including serial dilution, evaluation of copy number variation, and quantification of gene expression. We also showed how these models can be used to help design dPCR experiments, as in selection of sample sizes needed to achieve desired levels of precision in estimates of nucleic acid concentration or to detect differences in concentration among treatments with prescribed levels of statistical power.

  8. Partial gravity reaction experiment sysytem on graund using multi-Copter

    Science.gov (United States)

    Hasegawa, Katsuya; Maeda, Naoko

    2016-07-01

    In order to enable further space exploration into the space, Moon, Mars, and other planets, it is essential to understand the physiological response to low gravity environments. However, We made low gravity environment for studies using the satellite parabolic flight and drop tower. It is very expensive experiment that low gravity physiological response. Because, it requires rockets and airplanes and dedicated Tower, low gravity conditions test have not been conducted sufficiently due to the extraordinary high cost for conducting experiments. The study present is to develop the radio-controlled multicopter system that is used for the controlled falling flight vehicle (not free fall). During the controlled falling, the payload is exposed to a certain level of low gravity. 1) G profile: low gravity from 0 g to 1 g that will last approximately 5seconds, 50 kg. 2) Supply limited imaging techniques, high-speed or normal video and X ray images. 3) Wireless transmission of up to 64 channels of analog and digital signals. This vehicle is designed for experimentation on various model organisms, from cells to animals and plants. The multicopter flight system enables conducting experiments in low gravity conditions with less than 1% of the budget for spaceflight or parabolic flights. Experiment is possible to perform repeated many times in one day. We can expect reproducible results from many repeated trials at the lowest cost.

  9. On the Use of Interactive Texts in Undergraduate Chemical Reaction Engineering Courses: A Pedagogical Experience

    Science.gov (United States)

    Asensio, Daniela A.; Barassi, Francisca J.; Zambon, Mariana T.; Mazza, Germán D.

    2010-01-01

    This paper describes the results of a pedagogical experience carried out at the University of Comahue, Argentina, with an interactive text (IT) concerning Homogeneous Chemical Reactors Analysis. The IT was built on the frame of the "Mathematica" software with the aim of providing students with a robust computational tool. Students'…

  10. Wavefronts in time-delayed reaction-diffusion systems. Theory and comparison to experiment

    Energy Technology Data Exchange (ETDEWEB)

    Fort, Joaquim [Departament de Fisica, Universitat de Girona, Girona (Spain)]. E-mail: joaquim.fort@udg.es; Mendez, Vicenc [Facultat de Ciencies de la Salut, Universitat Internacional de Catalunya, Ssant Cugat del Valles (Spain)]. E-mail: vmendez@csc.unica.edu

    2002-06-01

    We review the recent theoretical progress in the formulation and solution of the front speed problem for time-delayed reaction-diffusion systems. Most of the review is focused on hyperbolic equations. They have been widely used in recent years, because they allow for analytical solutions and yield a realistic description of some relevant phenomena. The theoretical methods are applied to a range of applications, including population dynamics, forest fire models, bistable systems and combustion wavefronts. We also present a detailed account of successful predictions of the models, as assessed by comparison to experimental data for some biophysical systems, without making use of any free parameters. Areas where the work reviewed may contribute to future progress are discussed. (author)

  11. Experiments to Determine Neighborhood Reactions to Light Airplanes With and Without External Noise Reduction

    Science.gov (United States)

    Elwell, Fred S

    1953-01-01

    The work reported was part of a program of experimentation with external noise reduction on light airplanes. This particular study was in effect a byproduct survey conceived to utilize already available equipment and personnel to further the findings of the original research and to determine reactions in populated neighborhoods to light aircraft with and without noise-reduction equipment. The findings indicate that at the 10 sites within and about metropolitan Boston the degree of noise reduction previously found to be aerodynamically and structurally feasible did eliminate substantially all neighborhood objections to noise per se. The evidence clearly suggests that, when the noise nuisance is minimized to the extent found feasible, the number and severity of other objections also diminish -- evidently because the flight operations are noticed less when heard less.

  12. Bisamino(diphosphonite) with dangling olefin functionalities: synthesis, metal chemistry and catalytic utility of Rh(I) and Pd(II) complexes in hydroformylation and Suzuki-Miyaura reactions.

    Science.gov (United States)

    Naik, Susmita; Kumaravel, Maruthai; Mague, Joel T; Balakrishna, Maravanji S

    2014-01-21

    Bisamino(diphosphonite), p-C6H4{N{P(OC6H4C3H5-o)2}2}2 (1), was prepared by reacting p-C6H4{N(PCl2)2}2 with four equivalents of o-allylphenol in 85% yield. Compound 1 on treatment with [M(CO)4(HNC5H10)2] (M = Mo or W) gave cis-[{M(CO)4}2{p-C6H4{N(P(OC6H4C3H5-o)2)2}2}] (2, M = Mo; 3, M = W). The reaction of 1 with [Fe(η(5)-C5H5)(CO)2]2 yielded the complex [{Fe(η(5)-C5H5)(μ-CO)}2{p-C6H4{N(P(OC6H4C3H5-o)2)2}2}] (4). Treatment of 1 with Fe(CO)5 furnished a mononuclear complex, [{Fe(CO)3}2{p-C6H4{N{P(OC6H4C3H5-o)2}2}2}] (5). The ruthenium(II) complex, [{(η(6)-p-cymene)Ru(μ-Cl)3RuCl}2{p-C6H4{N(P(OC6H4C3H5-o)2)2}2}] (6), was obtained on treatment of ligand 1 with [(η(6)-p-cymene)Ru(Cl)2]2. The reaction between 1 and [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) in dichloromethane resulted in the formation of a dinuclear complex [{RhCl}2{p-C6H4{N(P(OC6H4C3H5-o)2)2}2}] (7), in which the allyl double bond of one of the phenoxy groups coordinates to the metal center. When ligand 1 was reacted with two equivalents of [Pd(COD)Cl2], a dinuclear complex [{PdCl2}2{p-C6H4{N(P(OC6H4C3H5-o)2)2}2}] (8) was obtained. With copper(I) halides, ligand 1 afforded tetranuclear complexes, [{(Cu(μ-X)(NCCH3))2}2{p-C6H4{N(P(OC6H4C3H5-o)2)2}2}] (9, X = Cl; 10, X = Br; 11, X = I). Reaction of 1 with four equivalents of [AuCl(SMe2)] produced a tetranuclear complex, [(AuCl)4{p-C6H4{N{P(OC6H4C3H5-o)2}2}2}] (12). Complex 8 shows excellent catalytic activity in the Suzuki-Miyaura cross-coupling reaction under microwave conditions and complex 7 catalyzes hydroformylation of styrenes with good TONs.

  13. Study and Analysis on Naphtha Catalytic Reforming Reactor Simulation

    Institute of Scientific and Technical Information of China (English)

    Liang Ke min; Song Yongji; Pan Shiwei

    2004-01-01

    A naphtha catalytic reforming unit with four reactors connected in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reaction characteristics based on idealizing the complex naphtha mixture to represent the paraffin, naphthene, and aromatic groups with individual compounds. The simulation results based on above models agree very well with actual operating data of process unit.

  14. A study on naphtha catalytic reforming reactor simulation and analysis

    Institute of Scientific and Technical Information of China (English)

    LIANG Ke-min; GUO Hai-yan; PAN Shi-wei

    2005-01-01

    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

  15. Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2011-01-01

    When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  16. Integrated Simulation Studies of Plasma Performances and Fusion Reactions in the Deuterium Experiment of LHD

    Science.gov (United States)

    Murakami, S.; Yamaguchi, H.; Homma, M.; Maeta, S.; Saito, Y.; Fukuyama, A.; Nagaoka, K.; Takahashi, H.; Nakano, H.; Osakabe, M.; Yokoyama, M.; Tanaka, K.; Ida, K.; Yoshinuma, M.; Isobe, M.; Tomita, H.; Ogawa, K.; LHD Exp Group Team

    2016-10-01

    The deuterium experiment project from 2017 is planned in LHD, where the deuterium NBI heating beams with the power more than 30MW are injected into the deuterium plasma. Principal objects of this project are to clarify the isotope effect on the heat and particle transport in the helical plasma and to study energetic particle confinement in a helical magnetic configuration measuring triton burn-up neutrons. We study the deuterium experiment plasma of LHD applying the integrated simulation code, TASK3D [Murakami, PPCF2015], and the 5-D drift kinetic equation solver, GNET [Murakami, NF2006]. (i) More than 20% of ion temperature increment is obtained in the deuterium plasma (nD /nH +nD = 0.8) due to the isotope effect assuming the turbulent transport model based on the H/He plasma experiment of LHD. (ii) The triton burn-up simulation shows the triton slowing down distribution and the strong magnetic configuration dependency of the triton burn-up ratio in LHD. This work was supported by JSPS KAKENHI Grant Number 26420851.

  17. Novel catalytic and mechanistic studies on wastewater denitrification with hydrogen.

    Science.gov (United States)

    Theologides, C P; Olympiou, G G; Savva, P G; Pantelidou, N A; Constantinou, B K; Chatziiona, V K; Valanidou, L Y; Piskopianou, C T; Costa, C N

    2014-01-01

    The present work reports up-to-date information regarding the reaction mechanism of the catalytic hydrogenation of nitrates in water media. In the present mechanistic study, an attempt is made, for the first time, to elucidate the crucial role of several catalysts and reaction parameters in the mechanism of the NO(3)(-)/H(2) reaction. Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were performed on supported Pd-Cu catalysts for the NO(3)(-)/H(2) and NO(3)(-)/H(2)/O(2) reactions. The latter experiments revealed that the formation and surface coverage of various adsorbed active intermediate N-species on the support or Pd/Cu metal surface is significantly favored in the presence of TiO(2) in the support mixture and in the presence of oxygen in the reaction's gaseous feed stream. The differences in the reactivity of these adsorbed N-species, found in the present work, adequately explain the large effect of the chemical composition of the support and the gas feed composition on catalyst behaviour (activity and selectivity). The present study leads to solid mechanistic evidence concerning the presence of a hydrogen spillover process from the metal to the support. Moreover, this study shows that Cu clusters are active sites for the reduction of nitrates to nitrites.

  18. Neutron-induced reactions relevant for Inertial-Cofinement Fusion Experiments

    Science.gov (United States)

    Boswell, Melissa; Merrill, Frank; Rundberg, R.; Grim, Gary; Wilde, Carl; Hayes, Anna; Fowler, Malcom; Wilhelmy, Jerry

    2012-10-01

    Measuring the fluencies of both the low- & high-energy neutrons is a powerful mechanism for studying the implosion process, and the various parameters that drive inertial confinement fusion. We have developed a number of tools to measure the spectral characteristics of the NIF neutron spectrum. Most of these methods rely on exploiting the energy dependence of (n,γ), (n,2n), (n,3n) and (n,p) reactions on a variety of materials either implicitly present in the NIF implosion or through doping the target capsule or holraum. I will be discussing both prompt activation measurements, and debris activation measurements of these materials currently under development at LANL. Focusing specifically on the development of an in-situ detector to measure short-lived activation products, as well as a low-background counting facility we are developing at the Waste Isolation Pilot Plant (WIPP) to study longer-lived activation products. Furthermore, I will also be discussing several cross section measurements that are important for the interpretation of the data collected from these activation products.

  19. Clinical experiences of intracavitary hyperthermo-radiotherapy. Analysis of treatment results and adverse reactions

    Energy Technology Data Exchange (ETDEWEB)

    Kawamori, Jiro; Hirayama, Michiko; Fukushima, Shoko; Saito, Tsutomu; Tanaka, Yoshiaki [Nihon Univ., Tokyo (Japan). School of Medicine

    1999-09-01

    We have applied intracavitary hyperthermo-radiotherapy to the treatment of various cancers. In this study, early response and acute reaction were analyzed. Eighteen patients treated with intracavitary hyperthermo-radiotherapy were as follows; 4 of esophageal cancer, 6 of uterine cervical cancer, 3 of rectal cancer, and 5 of others. Intracavitary hyperthermia was performed with Endoradiotherm 100A (OLYMPUS) once or twice a week with a total number of heating sessions ranging from 2 to 12 times. The heating was started just after the irradiation, and the temperature measured at the surface of applicator was kept at 42-44 deg C during the treatment for 30-40 min. External irradiation was performed in the majority of these 18 patients. Nine cases achieved complete response (CR), 6 cases did partial response (PR) and 3 cases were no change (NC). Of CR 9 cases, 6 cases showed 2-year local control. There were 2 esophageal tumors, 2 cervical tumors, 1 rectal tumor, and 1 vaginal stump tumor among 2-year local control cases. The treatment was interrupted in 2 patients from severe local pain during the heating. Severe vaginal mucositis occurred in 4 stump tumors. Intracavitary hyperthermoradiotherapy showed good early response for esophageal cancer and stump tumor. The advantages of intracavitary hyperthermia might be the reliability of heating for the treatment of localized tumors. (author)

  20. Enhanced Diffusion of Enzymes that Catalyze Exothermic Reactions

    Science.gov (United States)

    Golestanian, Ramin

    2015-09-01

    Enzymes have been recently found to exhibit enhanced diffusion due to their catalytic activities. A recent experiment [C. Riedel et al., Nature (London) 517, 227 (2015)] has found evidence that suggests this phenomenon might be controlled by the degree of exothermicity of the catalytic reaction involved. Four mechanisms that can lead to this effect, namely, self-thermophoresis, boost in kinetic energy, stochastic swimming, and collective heating are critically discussed, and it is shown that only the last two can be strong enough to account for the observations. The resulting quantitative description is used to examine the biological significance of the effect.