WorldWideScience

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...

  2. Catalytic process for tritium exchange reaction

    International Nuclear Information System (INIS)

    Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

    2001-01-01

    The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

  3. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    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 ...

  4. 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.

  5. Catalytic Organometallic Reactions of Ammonia

    Science.gov (United States)

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  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. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  8. 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.

  9. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    126, No. 2, March 2014, pp. 341–351. c Indian Academy of Sciences. ... enhancement was realized by catalyst design, appropriate choice of reactor, better injection and .... Gas–liquid and liquid–solid transport processes in catalytic reactors.5.

  10. 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....

  11. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-05-04

    The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

  12. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  13. 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....

  14. A kinetic study on non-catalytic reactions in hydroprocessing Boscan crude oil

    Energy Technology Data Exchange (ETDEWEB)

    A. Marafi; E. Kam; A. Stanislaus [Kuwait Institute for Scientific Research, Safat (Kuwait). Petroleum Refining Department, Petroleum Research and Studies Center

    2008-08-15

    Non-catalytic hydrothermal cracking reactions are known to associate with catalytic hydrocracking reactions. In a recent study on hydroprocessing of Boscan crude over a specific catalyst system containing three distinct catalysts, it was found that hydrodesulfurization (HDS) and hydrodemetallation (HDM) reactions continued even when the catalyst is severely deactivated. Since the reactor was packed with considerable amount of inert material besides the three catalysts, it will be advantage to determine if the inert materials can also facilitate hydroprocessing reactions. A series of kinetic experiments for the inert particles was undertaken under different space velocity and temperature conditions. The extent of catalytic and non-catalytic hydroprocessing reactions was assessed. Through statistical analysis, the initial reaction rate constant, reaction order and activation energy for various hydroprocessing reactions were then determined. The absolute average deviations (AAD) of the kinetics values obtained for inert materials are less than 10%. 25 refs., 7 figs., 4 tabs.

  15. Recent developments in research on catalytic reaction networks

    Directory of Open Access Journals (Sweden)

    Roberto Serra

    2013-09-01

    Full Text Available Over the last years, analyses performed on a stochastic model of catalytic reaction networks have provided some indications about the reasons why wet-lab experiments hardly ever comply with the phase transition typically predicted by theoretical models with regard to the emergence of collectively self-replicating sets of molecule (also defined as autocatalytic sets, ACSs, a phenomenon that is often observed in nature and that is supposed to have played a major role in the emergence of the primitive forms of life. The model at issue has allowed to reveal that the emerging ACSs are characterized by a general dynamical fragility, which might explain the difficulty to observe them in lab experiments. In this work, the main results of the various analyses are reviewed, with particular regard to the factors able to affect the generic properties of catalytic reactions network, for what concerns, not only the probability of ACSs to be observed, but also the overall activity of the system, in terms of production of new species, reactions and matter.

  16. Kinetics of catalytic reactions solutions manual

    CERN Document Server

    Vannice, M Albert

    2005-01-01

    Including countless exercises and worked examples, this advanced reference work and textbook will be extremely useful for the work of many industrial scientists. It teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations.

  17. Catalytic activation of molecular hydrogen in alkyne hydrogenation reactions by lanthanide metal vapor reaction products

    International Nuclear Information System (INIS)

    Evans, W.J.; Bloom, I.; Engerer, S.C.

    1983-01-01

    A rotary metal vapor was used in the synthesis of Lu, Er, Nd, Sm, Yb, and La alkyne, diene, and phosphine complexes. A typical catalytic hydrogenation experiment is described. The lanthanide metal vapor product is dissolved in tetrahydrofuran or toluene and placed in a pressure reaction vessel 3-hexyne (or another substrate) is added, the chamber attached to a high vacuum line, cooled to -196 0 C, evacuated, warmed to ambient temperature and hydrogen is added. The solution is stirred magnetically while the pressure in monitored. The reaction products were analyzed by gas chromatography. Rates and products of various systems are listed. This preliminary survey indicates that catalytic reaction chemistry is available to these metals in a wide range of coordination environments. Attempts to characterize these compounds are hampered by their paramagnetic nature and their tendency to polymerize

  18. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.

    2006-01-01

    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  19. 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...... of the applied exchange–correlation functional on the reaction energies rather than on errors versus the experimental data. As a result, improved energy corrections can now be determined for both gas phase and adsorbed reaction species, particularly interesting within heterogeneous catalysis. We show...... that for the CO2 reduction reactions, the main source of error is associated with the C[double bond, length as m-dash]O bonds and not the typically energy corrected OCO backbone....

  20. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  1. Heterogeneous-catalytic redox reactions in nitrate - formate systems

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

    2000-01-01

    It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

  2. Triangular Diagrams Teach Steady and Dynamic Behaviour of Catalytic Reactions.

    Science.gov (United States)

    Klusacek, K.; And Others

    1989-01-01

    Illustrates how triangular diagrams can aid in presenting some of the rather complex transient interactions that occur among gas and surface species during heterogeneous catalytic reactions. The basic equations and numerical examples are described. Classroom use of the triangular diagram is discussed. Several diagrams and graphs are provided. (YP)

  3. 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.

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

    Science.gov (United States)

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

    1987-01-01

    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.

  5. Scale-up of heterogeneous catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Heggs, P; Sunderland, P

    1979-12-01

    This report on the Institution of Chemical Engineers ''Problems in Applied Catalysis'' Meeting (Bath, U.K. 1/4-5/78) covers papers on the nature of the catalyst surface, including the use of IR spectroscopy, electron energy loss spectroscopy, low-energy electron diffraction, electron spectroscopy, secondary ion mass spectroscopy, and modular-beam scattering for investigating solid surfaces and their relevance to catalysis; study of the reaction mechanisms by which catalysis takes place; use of mechanistic models to determine the true chemical kinetics illustrated for the oxidation of benzene to maleic anhydride over a vanadium pentoxide/molybdenum trioxide catalyst; the study with respect to the importance of transport effects in catalyst pellets on scale-up, falsification of true kinetics, and the design of laboratory reactors; full-scale reactor design of packed-bed reactors; and practical scale-up problems illustrated for methanol synthesis over a copper catalyst, ammonia oxidation over a cobalt oxide catalyst, and the steam reforming of naphtha.

  6. 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…

  7. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

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

    2016-01-01

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

    Science.gov (United States)

    Hashemian, Mohammad Amin

    Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

  10. 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.

  11. Non-universal spreading exponents in a catalytic reaction model

    International Nuclear Information System (INIS)

    De Andrade, Marcelo F; Figueiredo, W

    2011-01-01

    We investigated the dependence of the spreading critical exponents and the ultimate survival probability exponent on the initial configuration of a nonequilibrium catalytic reaction model. The model considers the competitive reactions between two different monomers, A and B, where we take into account the energy couplings between nearest neighbor monomers, and the adsorption energies, as well as the temperature T of the catalyst. For each value of T the model shows distinct absorbing states, with different concentrations of the two monomers. Employing an epidemic analysis, we established the behavior of the spreading exponents as we started the Monte Carlo simulations with different concentrations of the monomers. The exponents were determined as a function of the initial concentration ρ A, ini of A monomers. We have also considered initial configurations with correlations for a fixed concentration of A monomers. From the determination of three spreading exponents, and the ultimate survival probability exponent, we checked the validity of the generalized hyperscaling relation for a continuous set of initial states, random and correlated, which are dependent on the temperature of the catalyst

  12. Catalytic activity of catalysts for steam reforming reaction. Contract research

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Hirofumi; Inagaki, Yoshiyuki [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment

    2003-05-01

    Japan Atomic Energy Research Institute has been developing a hydrogen production system by means of steam reforming of methane (chemical reation: CH{sub 4} + H{sub 2}O = CO + 3H{sub 2}) coupling with High Temperature Engineering Test Reactor (HTTR) to demonstrate effectiveness of high-temperature nuclear heat utilization. Prior to construction of HTTR hydrogen production system, a mock-up test facility with a full-scale reaction tube was constructed to investigate transient behavior of the hydrogen production system an establish system controllability. In order to predict transient behavior and hydrogen productivity of the hydrogen production system, it is important to estimate the reaction characteristics under the same temperature and pressure conditions as those of HTTR hydrogen production system. For the purpose of investigate an apparent activation energy of catalysts, catalytic activity test using small apparatus was carried out under the condition of methane flow rate from 1.18 x 10{sup -3} to 3.19 x 10{sup -3} mol/s, temperature from 500 to 900degC, pressure from 1.1 to 4.1MPa, and mol ratio of steam to methane from 2.5 to 3.5. It was confirmed that apparent activation energies of two kinds of Ni catalysts which are to be used in the mock-up test were 51.7 and 57.4kJ/mol, respectively, and reaction rate constants were propositional to the value from P{sup -0.15} to P{sup -0.33}. (author)

  13. Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

    Science.gov (United States)

    Collins, Gillian; Holmes, Justin D

    2016-07-01

    Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Catalytic EC′ reaction at a thin film modified electrode

    International Nuclear Information System (INIS)

    Gerbino, Leandro; Baruzzi, Ana M.; Iglesias, Rodrigo A.

    2013-01-01

    Numerical simulations of cyclic voltammograms corresponding to a catalytic EC′ reaction taking place at a thin film modified electrode are performed by way of finite difference method. Besides considering the chemical kinetic occurring inside the thin film, the model takes into account the different diffusion coefficients for each species at each of the involved phases, i.e. the thin film layer and bulk solution. The theoretical formulation is given in terms of dimensionless model parameters but a brief discussion of each of these parameters and their relationship to experimental variables is presented. Special emphasis is given to the use of working curve characteristics to quantify diffusion coefficient, homogeneous kinetic constant and thickness of the thin layer in a real system. Validation of the model is made by comparison of experimental results corresponding to the electron charge transfer of Ru(NH 3 ) 6 3+ /Ru(NH 3 ) 6 2+ hemi-couple at a thin film of a cross-linked chitosan film containing an immobilized redox dye

  15. Procedure for the preparation of catalysts for application in catalytic gas phase reactions

    International Nuclear Information System (INIS)

    1976-01-01

    The invention describes the preparation of catalysts to be used in catalytic reactions in the gaseous phase. The catalytic material is disposed at the surface of a ceramic or carbon substrate (av. particle size 0.1 μ - 0.5 cm, surface area smaller than 20 m 2 /g) by bombardment of the catalytic material (Pt, Rh, Pd, Ru, Os, Ir) with energetic ions (Ne, Ar, Kr, Xe) in the vicinity of the substrate in medium vacuum

  16. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

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

    International Nuclear Information System (INIS)

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

    2000-01-01

    Experiments on aqueous TiO 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 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)

  18. 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)

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

    DEFF Research Database (Denmark)

    Petrushina, Irina

    of Fermi level by electrochemical production of promoters, reducing or oxidizing current carriers of the catalyst support (O2-, H+, Na+). This type1 was abbreviated as EEPP. In Capters 4-7, the results of my research are given as examples of use of electrochemistry as a tool for study, promotion...... 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...... states that that there are two types of electrochemical promotion: First type is based on change of the Fermi level through the charge of the electric double layer (EDL) between catalyst and its support without electrochemical reaction. This effect was abbreviated as EDLE. Second type is based on change...

  20. 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.

  1. Time behaviour of the reaction front in the catalytic A + B → B + C reaction-diffusion processes

    International Nuclear Information System (INIS)

    Nicolini, F.G.; Rodriguez, M.A.; Wio, H.S.

    1994-07-01

    The problem of the time evolution of the position and width of a reaction front between initially separated reactants for the catalytic reaction A + B → B + C (C inert) is treated within a recently introduced Galanin-like scheme. (author). 6 refs

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

    KAUST Repository

    Wang, Jianfang; Li, Benxia; Gu, Ting; Ming, Tian; Wang, Junxin; Wang, Peng; Yu, Jimmy C.

    2014-01-01

    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.

  3. (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.

  4. Catalytic activity of metal borides in the reaction of decomposition

    International Nuclear Information System (INIS)

    Labodi, I.; Korablev, L.I.; Tavadyan, L.A.; Blyumberg, Eh.A.

    1982-01-01

    Catalytic effect of CoB, MoB 2 , ZrB 2 and NbB 2 , prepared by the method of self-propagating high-temperature synthesis, on decomposition of tertiary butyl hydroperoxide has been studied. A technigue of determination of action mechanism of heterogeneous catalysts in liquid-phase process is suggested. It is established that CoB in contrast to other metal borides catalyzes only hydroperoxide decomposition into radicals

  5. Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

    1978-09-01

    The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

  6. Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

    Directory of Open Access Journals (Sweden)

    Carmen Moreno-Marrodan

    2017-04-01

    Full Text Available The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible.

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

    OpenAIRE

    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 during hydrotreatment is desirable to reduce the formation of by-products such as char and gaseous components. This paper deals with the catalytic hydrotreatment of representative model components for t...

  8. 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.

  9. 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.

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

    KAUST Repository

    Hisatomi, Takashi; Takanabe, Kazuhiro; Domen, Kazunari

    2014-01-01

    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

  11. Catalytic reaction in a porous solid subject to a boundary layer flow

    Energy Technology Data Exchange (ETDEWEB)

    Mihail, R; Teddorescu, C

    1978-01-01

    A mathematical model of a boundary layer flowing past a catalytic slab was developed which included an analysis of the coupled mass and heat transfer and the heterogeneous chemical reaction. The porous flat plate was used to illustrate the interaction of boundary layer flow with chemical reaction within a porous catalytic body. The model yielded systems of transcendental equations which were solved numerically by means of a superposition integral in connection with a norm reduction procedure. A parametric study was conducted and an analysis of the possible multiplicity of steady states was developed and illustrated for the extreme case of infinite solid thermal conductivity. Tables, diagrams, graphs, and 12 references.

  12. Emergence of traveling wave endothermic reaction in a catalytic fixed bed under microwave heating

    International Nuclear Information System (INIS)

    Gerasev, Alexander P.

    2017-01-01

    This paper presents a new phenomenon in a packed bed catalytic reactor under microwave heating - traveling wave (moving reaction zones) endothermic chemical reaction. A two-phase model is developed to simulate the nonlinear dynamic behavior of the packed bed catalytic reactor with an irreversible first-order chemical reaction. The absorbed microwave power was obtained from Lambert's law. The structure of traveling wave endothermic chemical reaction was explored. The effects of the gas velocity and microwave power on performance of the packed bed catalytic reactor were presented. Finally, the effects of the change in the location of the microwave source at the packed bed reactor was demonstrated. - Highlights: • A new phenomenon - traveling waves of endothermic reaction - is predicted. • The physical and mathematical model of a packed bed catalytic reactor under microwave heating is presented. • The structure of the traveling waves is explored. • The configuration of heating the packed bed reactor via microwave plays a key role.

  13. Expanding P450 catalytic reaction space through evolution and engineering

    Science.gov (United States)

    McIntosh, John A.; Farwell, Christopher C.; Arnold, Frances H.

    2014-01-01

    Advances in protein and metabolic engineering have led to wider use of enzymes to synthesize important molecules. However, many desirable transformations are not catalyzed by any known enzyme, driving interest in understanding how new enzymes can be created. The cytochrome P450 enzyme family, whose members participate in xenobiotic metabolism and natural products biosynthesis, catalyzes an impressive range of difficult chemical reactions that continues to grow as new enzymes are characterized. Recent work has revealed that P450-derived enzymes can also catalyze useful reactions previously accessible only to synthetic chemistry. The evolution and engineering of these enzymes provides an excellent case study for how to genetically encode new chemistry and expand biology’s reaction space. PMID:24658056

  14. Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

    Science.gov (United States)

    Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

    2018-03-01

    This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

  15. Determining two-step control in heterogeneous catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Chakrabarty, T; Silveston, P L; Hudgins, R R

    1979-10-01

    The data by Thaller and Thodos on the sec.-butanol dehydrogenation to methyl ethyl ketone on brass catalyst indicated that a dual site surface reaction was rate-controlling below 575/sup 0/K and hydrogen desorption was rate-controlling above 616/sup 0/K (Vertical BarAIChE J.

  16. 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...

  17. Synergetic mechanism of methanol–steam reforming reaction in a catalytic reactor with electric discharges

    International Nuclear Information System (INIS)

    Kim, Taegyu; Jo, Sungkwon; Song, Young-Hoon; Lee, Dae Hoon

    2014-01-01

    Highlights: • Methanol–steam reforming was performed on Cu catalysts under an electric discharge. • Discharge had a synergetic effect on the catalytic reaction for methanol conversion. • Discharge lowered the temperature for catalyst activation or light off. • Discharge controlled the yield and selectivity of species in a reforming process. • Adsorption triggered by a discharge was a possible mechanism for a synergetic effect. - Abstract: Methanol–steam reforming was performed on Cu/ZnO/Al 2 O 3 catalysts under an electric discharge. The discharge occurred between the electrodes where the catalysts were packed. The electric discharge was characterized by the discharge voltage and electric power to generate the discharge. The existence of a discharge had a synergetic effect on the catalytic reaction for methanol conversion. The electric discharge provided modified reaction paths resulting in a lower temperature for catalyst activation or light off. The discharge partially controlled the yield and selectivity of species in a reforming process. The aspect of control was examined in view of the reaction kinetics. The possible mechanisms for the synergetic effect between the catalytic reaction and electric discharge on methanol–steam reforming were addressed. A discrete reaction path, particularly adsorption triggered by an electric discharge, was suggested to be the most likely mechanism for the synergetic effect. These results are expected to provide a guide for understanding the plasma–catalyst hybrid reaction

  18. Practical approaches to the ESI-MS analysis of catalytic reactions.

    Science.gov (United States)

    Yunker, Lars P E; Stoddard, Rhonda L; McIndoe, J Scott

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) is a soft ionization technique commonly coupled with liquid or gas chromatography for the identification of compounds in a one-time view of a mixture (for example, the resulting mixture generated by a synthesis). Over the past decade, Scott McIndoe and his research group at the University of Victoria have developed various methodologies to enhance the ability of ESI-MS to continuously monitor catalytic reactions as they proceed. The power, sensitivity and large dynamic range of ESI-MS have allowed for the refinement of several homogenous catalytic mechanisms and could potentially be applied to a wide range of reactions (catalytic or otherwise) for the determination of their mechanistic pathways. In this special feature article, some of the key challenges encountered and the adaptations employed to counter them are briefly reviewed. Copyright © 2014 John Wiley & Sons, Ltd.

  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. GC of catalytic reactions products involved in the promising fuel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Zheivot, V.; Sazonova, N. [Russian Academy of Sciences, Novosibirsk (Russian Federation). Boreskov Inst. of Catalysis

    2012-09-15

    Catalytic reactions involved in the synthesis of the promising kinds of novel fuel and products formed in these reactions were systematized according to the resulting fuel type. Generalization of the retention of the substances comprising these products is presented. Chromatograms exhibiting their separation on chromatographic materials with the surface of different chemical properties are summarized. We propose procedures for gas-chromatographic analysis of the catalytic reactions products formed in the synthesis of hydrogen, methanol, dimethyl ether and hydrocarbons as a new generation of fuel alternative to petroleum and coal. For partial oxidation of methane into synthesis gas, on-line determination of the components obtained in the reaction was carried out by gas chromatography and gas analyzer based on different physicochemical methods (IR spectroscopy and electrochemical methods). Similarity of the results obtained using these methods is demonstrated. (orig.)

  1. Enhancing chemical synthesis using catalytic reactions under continuous flow conditions

    OpenAIRE

    Asadi, Mousa

    2017-01-01

    Many advantages have been demonstrated for continuous flow chemistry in comparison with batch chemistry; such as easy automation, high level of reproducibility, improved safety, and process reliability. Indeed, with continuous flow processes constant reaction parameters such as temperature, time, amount of reagents, catalyst, solvents, efficient mixing etc. can easily be assured. The research detailed in this PhD thesis takes advantages of flow chemistry applying it to the Fukuyama ...

  2. 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.

  3. Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions.

    Science.gov (United States)

    Bandini, Marco; Tragni, Michele

    2009-04-21

    The direct functionalization of aromatic compounds, via Friedel-Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of pi-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.

  4. 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

  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

  6. Stereoselectivity in catalytic reactions: CO oxidation on Pd(100) by rotationally aligned O2 molecules

    Science.gov (United States)

    Vattuone, L.; Gerbi, A.; Savio, L.; Cappelletti, D.; Pirani, F.; Rocca, M.

    2010-05-01

    We report on stereodynamical effects in heterogeneous catalytic reactions as measured by molecular beam-surface experiments. Specifically for CO oxidation on Pd(100) we find that the rotational alignment of the incoming O2 at low (Θ = 0.04 ML) and at intermediate (ΘCO = 0.17 ML) CO pre-coverage, causes a higher reactivity of molecules in high and in low helicity states, respectively (corresponding to helicoptering and cartwheeling motion of O2). In first approximation, at low CO pre-coverage the difference in reactivity is determined by the different location of the O atoms generated in the dissociation process by the different parent molecules, while at intermediate CO pre-coverage the reactivity is influenced also by the different ability of cartwheeling and helicoptering O2 to penetrate through the CO adlayer. In accord with this the total amount of CO2 produced is always largest for helicopters which generate supersurface O atoms at least in the low CO pre-coverage limit. A deeper inspection of the data indicates, however, that the dynamics is more complex, two different pathways being present for the reaction with O generated by helicopters and one for O generated by cartwheels. Moreover, cartwheels generated oxygen influences the reactivity of subsequently arriving helicopters.

  7. Lattice Boltzmann simulation of endothermal catalytic reaction in catalyst porous media

    International Nuclear Information System (INIS)

    Li Xunfeng; Cai Jun; Xin Fang; Huai Xiulan; Guo Jiangfeng

    2013-01-01

    Gas catalytic reaction in a fixed bed reactor is a general process in chemical industry. The chemical reaction process involves the complex multi-component flow, heat and mass transfer coupling chemical reaction in the catalyst porous structure. The lattice Boltzmann method is developed to simulate the complex process of the surface catalytic reaction in the catalyst porous media. The non-equilibrium extrapolation method is used to treat the boundaries. The porous media is structured by Sierpinski carpet fractal structure. The velocity correction is adopted on the reaction surface. The flow, temperature and concentration fields calculated by the lattice Boltzmann method are compared with those computed by the CFD software. The effects of the inlet velocity, porosity and inlet components ratio on the conversion are also studied. Highlights: ► LBM is developed to simulate the surface catalytic reaction. ► The Sierpinski carpet structure is used to construct the porous media. ► The LBM results are in agreement with the CFD predictions. ► Velocity, temperature and concentration fields are obtained. ► Effects of the velocity, porosity and concentration on conversion are analyzed.

  8. Influence of phase transition on pattern formation during catalytic reactions

    OpenAIRE

    Andrade, Roberto Fernandes Silva; Lima, D.; Cunha, F. B.

    2000-01-01

    p.434–445 We investigate the influence of the order of surface phase transitions on pattern formation during chemical reaction on mono-crystal catalysts. We use a model consisting of two partial differential equations, one of which describes the dynamics of the surface state with the help of a Ginzburg–Landau potential. Second- or first-order transitions are described by decreasing or increasing the relative value of the third-order coefficient of the potential. We concentrate on the stabi...

  9. 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)

    1997-12-31

    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.)

  10. 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.)

  11. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

    2016-12-05

    Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

  12. Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

    Science.gov (United States)

    Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

    2017-06-14

    It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

  13. Asymmetric Catalytic Aza-Diels-Alder/Ring-Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis.

    Science.gov (United States)

    Li, Yang; Barløse, Casper; Jørgensen, Julie; Carlsen, Bjørn Dreiø; Jørgensen, Karl Anker

    2017-01-01

    An asymmetric catalytic aza-Diels-Alder/ring-closing cascade reaction between acylhydrazones and in situ formed trienamines is presented. The reaction proceeds through a formal aza-Diels-Alder cycloaddition, followed by a ring-closing reaction forming the hemiaminal ring leading to chiral bicyclic azaheterocycles in moderate to good yield (up to 71 %), good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). Furthermore, transformations are presented to show the potential application of the formed product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

    Science.gov (United States)

    Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

    2015-04-07

    The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Generalized hydrodynamic treatment of the interplay between restricted transport and catalytic reactions in nanoporous materials.

    Science.gov (United States)

    Ackerman, David M; Wang, Jing; Evans, James W

    2012-06-01

    Behavior of catalytic reactions in narrow pores is controlled by a delicate interplay between fluctuations in adsorption-desorption at pore openings, restricted diffusion, and reaction. This behavior is captured by a generalized hydrodynamic formulation of appropriate reaction-diffusion equations (RDE). These RDE incorporate an unconventional description of chemical diffusion in mixed-component quasi-single-file systems based on a refined picture of tracer diffusion for finite-length pores. The RDE elucidate the nonexponential decay of the steady-state reactant concentration into the pore and the non-mean-field scaling of the reactant penetration depth.

  16. Catalytic conversion reactions mediated by single-file diffusion in linear nanopores: hydrodynamic versus stochastic behavior.

    Science.gov (United States)

    Ackerman, David M; Wang, Jing; Wendel, Joseph H; Liu, Da-Jiang; Pruski, Marek; Evans, James W

    2011-03-21

    We analyze the spatiotemporal behavior of species concentrations in a diffusion-mediated conversion reaction which occurs at catalytic sites within linear pores of nanometer diameter. Diffusion within the pores is subject to a strict single-file (no passing) constraint. Both transient and steady-state behavior is precisely characterized by kinetic Monte Carlo simulations of a spatially discrete lattice-gas model for this reaction-diffusion process considering various distributions of catalytic sites. Exact hierarchical master equations can also be developed for this model. Their analysis, after application of mean-field type truncation approximations, produces discrete reaction-diffusion type equations (mf-RDE). For slowly varying concentrations, we further develop coarse-grained continuum hydrodynamic reaction-diffusion equations (h-RDE) incorporating a precise treatment of single-file diffusion in this multispecies system. The h-RDE successfully describe nontrivial aspects of transient behavior, in contrast to the mf-RDE, and also correctly capture unreactive steady-state behavior in the pore interior. However, steady-state reactivity, which is localized near the pore ends when those regions are catalytic, is controlled by fluctuations not incorporated into the hydrodynamic treatment. The mf-RDE partly capture these fluctuation effects, but cannot describe scaling behavior of the reactivity.

  17. Studies of Catalytic Properties of Inorganic Rock Matrices in Redox Reactions

    Directory of Open Access Journals (Sweden)

    Nikolay M. Dobrynkin

    2017-09-01

    Full Text Available Intrinsic catalytic properties of mineral matrices of various kinds (basalts, clays, sandstones were studied, which are of interest for in-situ heavy oil upgrading (i.e., underground to create advanced technologies for enhanced oil recovery. The elemental, surface and phase composition and matrix particle morphology, surface and acidic properties were studied using elemental analysis, X-ray diffraction, adsorption and desorption of nitrogen and ammonia. The data on the catalytic activity of inorganic matrices in ammonium nitrate decomposition (reaction with a large gassing, oxidation of hydrocarbons and carbon monoxide, and hydrocracking of asphaltenes into maltenes (the conversion of heavy hydrocarbons into more valuable light hydrocarbons were discussed. In order to check their applicability for the asphaltenes hydrocracking catalytic systems development, basalt and clay matrices were used as supports for iron/basalt, nickel/basalt and iron/clay catalysts. The catalytic activity of the matrices in the reactions of the decomposition of ammonium nitrate, oxidation of hydrocarbons and carbon monoxide, and hydrocracking of asphaltens was observed for the first time.

  18. 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

    For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac...... 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....... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

  19. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  20. Design of a facility for the in situ measurement of catalytic reaction by neutron scattering spectroscopy

    Science.gov (United States)

    Tan, Shuai; Cheng, Yongqiang; Daemen, Luke L.; Lutterman, Daniel A.

    2018-01-01

    Catalysis is a critical enabling science for future energy needs. The next frontier of catalysis is to evolve from catalyst discovery to catalyst design, and for this next step to be realized, we must develop new techniques to better understand reaction mechanisms. To do this, we must connect catalytic reaction rates and selectivities to the kinetics, energetics, and dynamics of individual elementary steps and relate these to the structure and dynamics of the catalytic sites involved. Neutron scattering spectroscopies offer unique capabilities that are difficult or impossible to match by other techniques. The current study presents the development of a compact and portable instrumental design that enables the in situ investigation of catalytic samples by neutron scattering techniques. The developed apparatus was tested at the Spallation Neutron Source (SNS) in Oak Ridge National Laboratory and includes a gas handling panel that allows for computer hookups to control the panel externally and online measurement equipment such as coupled GC-FID/TCD (Gas Chromatography-Flame Ionization Detector/Thermal Conductivity Detector) and MS (Mass Spectrometry) to characterize offgassing while the sample is in the neutron scattering spectrometer. This system is flexible, modular, compact, and portable enabling its use for many types of gas-solid and liquid-solid reactions at the various beamlines housed at the SNS.

  1. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  2. Nanoparticle-triggered in situ catalytic chemical reactions for tumour-specific therapy.

    Science.gov (United States)

    Lin, Han; Chen, Yu; Shi, Jianlin

    2018-03-21

    Tumour chemotherapy employs highly cytotoxic chemodrugs, which kill both cancer and normal cells by cellular apoptosis or necrosis non-selectively. Catalysing/triggering the specific chemical reactions only inside tumour tissues can generate abundant and special chemicals and products locally to initiate a series of unique biological and pathologic effects, which may enable tumour-specific theranostic effects to combat cancer without bringing about significant side effects on normal tissues. Nevertheless, chemical reaction-initiated selective tumour therapy strongly depends on the advances in chemistry, materials science, nanotechnology and biomedicine. This emerging cross-disciplinary research area is substantially different from conventional cancer-theranostic modalities in clinics. In response to the fast developments in cancer theranostics based on intratumoural catalytic chemical reactions, this tutorial review summarizes the very-recent research progress in the design and synthesis of representative nanoplatforms with intriguing nanostructures, compositions, physiochemical properties and biological behaviours for versatile catalytic chemical reaction-enabled cancer treatments, mainly by either endogenous tumour microenvironment (TME) triggering or exogenous physical irradiation. These unique intratumoural chemical reactions can be used in tumour-starving therapy, chemodynamic therapy, gas therapy, alleviation of tumour hypoxia, TME-responsive diagnostic imaging and stimuli-responsive drug release, and even externally triggered versatile therapeutics. In particular, the challenges and future developments of such a novel type of cancer-theranostic modality are discussed in detail to understand the future developments and prospects in this research area as far as possible. It is highly expected that this kind of unique tumour-specific therapeutics by triggering specific in situ catalytic chemical reactions inside tumours would provide a novel but efficient

  3. 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.

  4. Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.

    Science.gov (United States)

    Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun

    2017-02-03

    The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.

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

    International Nuclear Information System (INIS)

    Mohamed, Norani Muti; Ahmad, Pervaiz; Saheed, Mohamed Shuaib Mohamed; Burhanudin, Zainal Arif

    2014-01-01

    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

  6. CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

    Directory of Open Access Journals (Sweden)

    Didik Prasetyoko

    2010-07-01

    Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

  7. 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.

  8. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    Science.gov (United States)

    Habershon, Scott

    2016-04-12

    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

  9. 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

  10. 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.

  11. Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

    Science.gov (United States)

    Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.; Naik, Rajesh R.; Knecht, Marc R.

    2011-05-01

    To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.

  12. Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts.

    Science.gov (United States)

    Pacardo, Dennis B; Slocik, Joseph M; Kirk, Kyle C; Naik, Rajesh R; Knecht, Marc R

    2011-05-01

    To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions. © The Royal Society of Chemistry 2011

  13. An Adaptor Domain-Mediated Auto-Catalytic Interfacial Kinase Reaction

    Science.gov (United States)

    Liao, Xiaoli; Su, Jing; Mrksich, Milan

    2010-01-01

    This paper describes a model system for studying the auto-catalytic phosphorylation of an immobilized substrate by a kinase enzyme. This work uses self-assembled monolayers (SAMs) of alkanethiolates on gold to present the peptide substrate on a planar surface. Treatment of the monolayer with Abl kinase results in phosphorylation of the substrate. The phosphorylated peptide then serves as a ligand for the SH2 adaptor domain of the kinase and thereby directs the kinase activity to nearby peptide substrates. This directed reaction is intramolecular and proceeds with a faster rate than does the initial, intermolecular reaction, making this an auto-catalytic process. The kinetic non-linearity gives rise to properties that have no counterpart in the corresponding homogeneous phase reaction: in one example, the rate for phosphorylation of a mixture of two peptides is faster than the sum of the rates for phosphorylation of each peptide when presented alone. This work highlights the use of an adaptor domain in modulating the activity of a kinase enzyme for an immobilized substrate and offers a new approach for studying biochemical reactions in spatially inhomogeneous settings. PMID:19821459

  14. Characterization of catalytic supports based in mixed oxides for control reactions of NO and N2O

    International Nuclear Information System (INIS)

    Garcia C, M.A.; Perez H, R.; Gomez C, A.; Diaz, G.

    1999-01-01

    The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were prepared by the Precipitation and Coprecipitation techniques. The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 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 2 O. (Author)

  15. Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Chunzhen Yang

    2017-05-01

    Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

  16. Amorphous saturated Cerium-Tungsten-Titanium oxide nanofibers catalysts for NOx selective catalytic reaction

    DEFF Research Database (Denmark)

    Dankeaw, Apiwat; Gualandris, Fabrizio; Silva, Rafael Hubert

    2018-01-01

    experiments at the best working conditions (dry and in absence of SO2) are performed to characterize the intrinsic catalytic behavior of the new catalysts. At temeprature lower than 300 °C, superior NOx conversion properties of the amorphous TiOx nanofibers over the crystallized TiO2 (anatase) nanofibers......Herein for the first time, Ce0.184W0.07Ti0.748O2-δ nanofibers are prepared by electrospinning to serve as catalyst in the selective catalytic reduction (SCR) process. The addition of cerium is proven to inhibit crystallization of TiO2, yielding an amorphous TiOx-based solid solution stable up...... temperatures (catalysts in a wide range...

  17. 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....../Ru)//PBI(H3PO4)/H-2, Ar] fuel cell. It has been shown that the partial methane oxidation to C2H2 and the C-2 selectivity were electrochemically promoted by the negative catalyst polarization. This was also the case in NO reduction with hydrogen for low NO and H-2 partial pressures. In both cases the catalytic...... reactions have been promoted by the electrochemically produced hydrogen. It has been found that the NO reduction with hydrogen on the Pt/PBI strongly depends on NO and hydrogen partial pressures in the working gas mixture. At higher NO and H-2 partial pressures the catalysis is promoted...

  18. 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.

  19. Reactivity of nanoaggregations of platinum on supports of different nature in reactions of catalytic decomposition of hydrazine in acid media

    International Nuclear Information System (INIS)

    Anan'ev, A.V.; Boltoeva, M.Yu.; Grigor'ev, M.S.; Shilov, V.P.; Sharygin, L.M.

    2006-01-01

    Platinized catalysts on the basis of supports of different chemical nature are tested in reactions of catalytic hydrazine decomposition in perchloric and nitric acid solutions. In perchloric acid catalytic activity of catalysts on the basis of ceramic materials of Termoksid brand is higher of activity of catalysts on the basis of amorphous silica gel. In nitric acid solutions opposite dependence is observed. Tendency of ceramic supports to peptization in acid solutions is pointed out. Results obtained are interpreted using conceptions of energetic heterogeneity of surface atoms and hydrazine catalytic decomposition mechanisms in different media [ru

  20. Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

    Science.gov (United States)

    Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

    2013-09-01

    In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

  1. Possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime

    Energy Technology Data Exchange (ETDEWEB)

    Chumakov, G A; Slinko, M G

    1979-05-01

    The possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime was demonstrated by analyzing a kinetic model of hydrogen interaction with oxygen over a metallic catalyst. Within a certain interval of partial pressures of oxygen, the average reaction rate over a period of oscillation may be over five times that of the steady-state reaction.

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

    KAUST Repository

    Al-Khattaf, S.; Odedairo, T.; Balasamy, R. J.

    2012-01-01

    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

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

    OpenAIRE

    Daphna S. Horowitz; René van Eeden

    2015-01-01

    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. Mot...

  4. Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

    Science.gov (United States)

    Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

    2018-05-22

    Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

  5. A microcatalytic flow reactor for the study of heterogeneous catalytic reactions at elevated pressures

    Energy Technology Data Exchange (ETDEWEB)

    Belyi, A S; Fomichev, Yu V; Duplyakin, V K; Alfeev, V S

    1977-07-01

    A microcatalytic flow reactor for the study of heterogeneous catalytic reactions at elevated pressures (i.e., up to 40 atm) and nearly isothermal conditions up to 600/sup 0/C was designed for the conversion of small quantities of petrochemical feeds or feed mixtures at uniform, controllable flow rates of 0.5-5.0 cc/hr, for direct gas-chromatographic analysis of product samples at the reactor outlet, and for continuous monitoring of the degree of conversion in processes that evolve or absorb hydrogen. The device includes a feed injection system with a unique sealing feature that ensures a constant flow of liquid from a feed buret under positive displacement by a counterweight piston at very low rates into a tubular reactor of the perfect mixing type, a highly efficient vaporizer-mixer, and a two-channel sampler leading to the chromatograph. The apparatus has proved reliable, accurate, and convenient in two years of regular use. Diagrams.

  6. Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

    Science.gov (United States)

    Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

    2018-02-20

    The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

  7. Theory of potentiostatic current transients for coupled catalytic reaction at random corrugated fractal electrode

    International Nuclear Information System (INIS)

    Jha, Shailendra K.; Kant, Rama

    2010-01-01

    We developed a mathematical model for the first order homogeneous catalytic chemical reaction coupled with an electron transfer (EC') on a rough working electrode. Results are obtained for the various roughness models of electrode corrugations, viz., (i) roughness as an exact periodic function, (ii) roughness as a random function with known statistical properties, and (iii) roughness as a random function with statistical self-affine fractality over a finite range of length scales. Method of Green's function is used in the formulation to obtain second-order perturbation (in roughness profile) expressions for the concentration, the local current density and the current transients. A general operator structure between these quantities and arbitrary roughness profile is emphasized. The statistically averaged (randomly rough) electrode response is obtained by an ensemble averaging over all possible surface configurations. An elegant mathematical formula between the average electrochemical current transient and surface structure factor or power-spectrum of roughness is obtained. This formula is used to obtain an explicit equation for the current on an approximately self-affine (or realistic) fractal electrode with a limited range of length scales of irregularities. This description of realistic fractal is obtained by cutoff power law power-spectrum of roughness. The realistic fractal power-spectrum consists of four physical characteristics, viz., the fractal dimension (D H ), lower (l) and upper (L) cutoff length scales of fractality and a proportionality factor (μ), which is related to the topothesy or strength of fractality. Numerical calculations are performed on final results to understand the effect of catalytic reaction and fractal morphological characteristics on potentiostatic current transients.

  8. 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.

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

    KAUST Repository

    Yin, S. M.; Duanmu, J. J.; Zhu, Yihan; Yuan, Y. F.; Guo, S. Y.; Yang, J. L.; Ren, Z. H.; Han, G. R.

    2017-01-01

    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.

  10. Pd@[nBu4][Br] as a Simple Catalytic System for N-Alkylation Reactions with Alcohols

    Directory of Open Access Journals (Sweden)

    Bastien Cacciuttolo

    2016-08-01

    Full Text Available Palladium nanoparticles, simply and briefly generated in commercial and cheap onium salts using supercritical carbon dioxide, have been found to be an effective catalytic system for additive free N-alkylation reaction using alcohols via cascade oxidation/condensation/reduction steps.

  11. Pd@[nBu₄][Br] as a Simple Catalytic System for N-Alkylation Reactions with Alcohols.

    Science.gov (United States)

    Cacciuttolo, Bastien; Pascu, Oana; Aymonier, Cyril; Pucheault, Mathieu

    2016-08-10

    Palladium nanoparticles, simply and briefly generated in commercial and cheap onium salts using supercritical carbon dioxide, have been found to be an effective catalytic system for additive free N-alkylation reaction using alcohols via cascade oxidation/condensation/reduction steps.

  12. Selective oxidations in microstructured catalytic reactions - A review and an overview of own work on fuel processing for fuel cells

    NARCIS (Netherlands)

    Hessel, V.; Kolb, G.A.; Cominos, V.; Loewe, H.; Nikolaidis, G.; Zapf, R.; Ziogas, A.; Schouten, J.C.; Delsman, E.R.; Croon, de M.H.J.M.; Santamaria, J.; Iglesia, de la O.; Mallada, R.

    2006-01-01

    This review is concerned about catalytic gas-phase oxidation reactions in microreactors, typically being performed in wall-coated microchannels. Not included are liquid and gas-liquid oxidations which are typically done in reactor designs different from the ones considered here. The first part of

  13. Catalytic isotope exchange reaction between deuterium gas and water pre-adsorbed on platinum/alumina

    International Nuclear Information System (INIS)

    Iida, Itsuo; Kato, Junko; Tamaru, Kenzi.

    1976-01-01

    The catalytic isotope exchange reaction between deuterium gas and the water pre-adsorbed on Pt/Al 2 O 3 was studied. At reaction temperatures above 273 K, the exchange rate was proportional to the deuterium pressure and independent of the amount of adsorbed water, which suggests that the rate determining step is the supply of deuterium from the gas phase. Its apparent activation energy was 38 kJ mol -1 . Below freezing point of water, the kinetic behaviour was different from that above freezing point. At higher deuterium pressures the rate dropped abruptly at 273 K. Below the temperature the apparent activation energy was 54 kJ mol -1 and the exchange rate depended not on the deuterium pressure but on the amount of the pre-adsorbed water. At lower pressures, however, the kinetic behaviour was the same as the above 273 K, till the rate of the supply of deuterium from the gas phase exceeded the supply of hydrogen from adsorbed water to platinum surface. These results suggest that below 273 K the supply of hydrogen is markedly retarded, the state of the adsorbed water differing from that above 273 K. It was also demonstrated that when the adsorbed water is in the state of capillary condensation, the exchange rate becomes very small. (auth.)

  14. 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.

  15. Enantioselective syntheses and biological studies of aeruginosin 298-A and its analogs: application of catalytic asymmetric phase-transfer reaction.

    Science.gov (United States)

    Fukuta, Yuhei; Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Nemoto, Tetsuhiro; Kisugi, Takaya; Okino, Tatsufumi; Shibasaki, Masakatsu

    2004-04-13

    Aeruginosin 298-A was isolated from the freshwater cyanobacterium Microcystis aeruginosa (NIES-298) and is an equipotent thrombin and trypsin inhibitor. A variety of analogs were synthesized to gain insight into the structure-activity relations. We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogs, in which all stereocenters were controlled by catalytic asymmetric phase-transfer reaction promoted by two-center asymmetric catalysts and catalytic asymmetric epoxidation promoted by a lanthanide-BINOL complex. Furthermore, serine protease inhibitory activities of aeruginosin 298-A and its analogs were examined.

  16. 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...

  17. Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions.

    Science.gov (United States)

    Ferrini, Paola; Rinaldi, Roberto

    2014-08-11

    Through catalytic hydrogen transfer reactions, a new biorefining method results in the isolation of depolymerized lignin--a non-pyrolytic lignin bio-oil--in addition to pulps that are amenable to enzymatic hydrolysis. Compared with organosolv lignin, the lignin bio-oil is highly susceptible to further hydrodeoxygenation under low-severity conditions and therefore establishes a unique platform for lignin valorization by heterogeneous catalysis. Overall, the potential of a catalytic biorefining method designed from the perspective of lignin utilization is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. 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

  19. Preparation of Low Molecular Weight Heparin by Microwave Discharge Electrodeless Lamp/TiO2 Photo-Catalytic Reaction.

    Science.gov (United States)

    Lee, Do-Jin; Kim, Byung Hoon; Kim, Sun-Jae; Kim, Jung-Sik; Lee, Heon; Jung, Sang-Chul

    2015-01-01

    An MDEL/TiO2 photo-catalyst hybrid system was applied, for the first time, for the production of low molecular weight heparin. The molecular weight of produed heparin decreased with increasing microwave intensity and treatment time. The abscission of the chemical bonds between the constituents of heparin by photo-catalytic reaction did not alter the characteristics of heparin. Formation of by-products due to side reaction was not observed. It is suggested that heparin was depolymerized by active oxygen radicals produced during the MDEL/TiO2 photo-chemical reaction.

  20. Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

    Science.gov (United States)

    Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

    2018-02-09

    Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

    Directory of Open Access Journals (Sweden)

    Yasuharu Kanda

    2018-04-01

    Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

  2. Exponential growth for self-reproduction in a catalytic reaction network: relevance of a minority molecular species and crowdedness

    Science.gov (United States)

    Kamimura, Atsushi; Kaneko, Kunihiko

    2018-03-01

    Explanation of exponential growth in self-reproduction is an important step toward elucidation of the origins of life because optimization of the growth potential across rounds of selection is necessary for Darwinian evolution. To produce another copy with approximately the same composition, the exponential growth rates for all components have to be equal. How such balanced growth is achieved, however, is not a trivial question, because this kind of growth requires orchestrated replication of the components in stochastic and nonlinear catalytic reactions. By considering a mutually catalyzing reaction in two- and three-dimensional lattices, as represented by a cellular automaton model, we show that self-reproduction with exponential growth is possible only when the replication and degradation of one molecular species is much slower than those of the others, i.e., when there is a minority molecule. Here, the synergetic effect of molecular discreteness and crowding is necessary to produce the exponential growth. Otherwise, the growth curves show superexponential growth because of nonlinearity of the catalytic reactions or subexponential growth due to replication inhibition by overcrowding of molecules. Our study emphasizes that the minority molecular species in a catalytic reaction network is necessary for exponential growth at the primitive stage of life.

  3. 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.

  4. Structural analysis of CuO / CeO2-based catalytic materials intended for PROX reaction: Part I

    International Nuclear Information System (INIS)

    Neiva, L.S.; Simoes, A.N.; Bispo, A.; Ribeiro, M.A.; Gama, L.

    2011-01-01

    This work relates the synthesis process of CuO/CeO 2 catalytic materials by a combustion reaction method as well as it introduces a structural analysis of the developed material, this structural analysis had as main focus to evaluate the influence of the doping substance (CuO) when being incorporated in the hostess matrix structure that is CeO 2 . The CuO/CeO catalytic materials developed in this work are destined to preferential oxidation of CO reaction (PROX). The developed materials were characterized by XRD, SEM and textural complete analysis by the BET method. According to the results, the CuO incorporation changed crystallinity of the structure of the catalytic materials. On the other hand, the morphologic and textural characteristics did not showed significant differences regarding the presence of the doping substance (CuO) in the structure of the developed materials. The porosity of the structures of the developed catalytic materials belongs to the type macroporous. (author)

  5. Dynamic control of chiral space in a catalytic asymmetric reaction using a molecular motor

    NARCIS (Netherlands)

    Wang, Jiaobing; Feringa, B.L.

    2011-01-01

    Enzymes and synthetic chiral catalysts have found widespread application to produce single enantiomers, but in situ switching of the chiral preference of a catalytic system is very difficult to achieve. Here, we report on a light-driven molecular motor with integrated catalytic functions in which

  6. Direct nuclear reaction experiments for stellar nucleosynthesis

    International Nuclear Information System (INIS)

    Cherubini, S.

    2016-01-01

    During the last two decades indirect methods where proposed and used in many experiments in order to measure nuclear cross sections between charged particles at stellar energies. These are among the lowest to be measured in nuclear physics. One of these methods, the Trojan Horse method, is based on the Quasi- Free reaction mechanism and has proved to be particularly flexible and reliable. It allowed for the measurement of the cross sections of various reactions of astrophysical interest using stable beams. The use and reliability of indirect methods become even more important when reactions induced by Radioactive Ion Beams are considered, given the much lower intensity generally available for these beams. The first Trojan Horse measurement of a process involving the use of a Radioactive Ion Beam dealt with the "1"8F(p,α)"1"5O process in Nova conditions. To obtain pieces of information on this process, in particular about its cross section at Nova energies, the Trojan Horse method was applied to the "1"8F(d,α "1"5O)n three body reaction. In order to establish the reliability of the Trojan Horse method approach, the Treiman-Yang criterion is an important test and it will be addressed briefly in this paper.

  7. The study of biodiesel production using CaO as a heterogeneous catalytic reaction

    Directory of Open Access Journals (Sweden)

    Kamila Colombo

    2017-06-01

    Full Text Available With the aim of developing a process of biodiesel production that is environmentally benign much interest has been focused on the use of solid base catalysts, such as calcium oxide, for the transesterification of vegetable oils with methanol. In the study reported herein a recycling reactor was used in bench scale, with the capacity to produce 3 L of biodiesel. The reactor was designed especially for this research study. A full 23 factorial plan was used to evaluate the process parameters related to this study, in particular, the catalyst concentration, the alcohol to oil molar ratio and the reaction time. Using this equipment for the transesterification reaction resulted in the recovery of the excess alcohol. The reaction products were characterized using gas chromatography and liquid analysis to determine the ester and calcium concentrations, respectively. The main conclusions drawn were that the best conversion percentage (100% of biodiesel was reached when the methanol:oil molar ratio was 6:1, the reaction time was 75 min and the catalyst mass was 3% in relation to the oil mass used in this process. The CaO concentration determined exceeded the limit of concentration defined by legislation and thus a secondary operation was carried out to purify the reaction products obtained. The results of this study showed a high performance, and the proposed experiment could be used as a new and innovative way to produce biodiesel in the future.

  8. Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

    Science.gov (United States)

    Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

    2003-09-17

    We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

  9. 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.

  10. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

    Science.gov (United States)

    Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F; Lyth, Stephen Mathew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric

    2017-10-16

    Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN 4 C 12 , CoN 3 C 10,porp and CoN 2 C 5 . The O 2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O 2 -adsorption strength, we conclude that cobalt-based moieties bind O 2 too weakly for efficient O 2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopalan, S., E-mail: rajagopalan78@hotmail.com [Indira Gandhi Centre for Atomic Research, Materials Science Group (India); Asthalter, T., E-mail: t.asthalter@web.de [Universität Stuttgart, Institute of Physical Chemistry (Germany); Rabe, V.; Laschat, S. [Universität Stuttgart, Institute of Organic Chemistry (Germany)

    2016-12-15

    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 Fe{sub 3}(μ{sub 3}-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe{sub 3}(μ{sub 3}-O) in pyridine solution, Fe{sub 3}(μ{sub 3}-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe{sub 3}(μ{sub 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{sup (III)}(C{sub 5}H{sub 5}N){sub 2}(O{sub 2}CCH{sub 3}){sub 2}]{sup +} and Fe{sup (II)}(C{sub 5}H{sub 5}N){sub 4}(O{sub 2}CCH{sub 3}){sub 2}, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.

  12. On-line Analysis of Catalytic Reaction Products Using a High-Pressure Tandem Micro-reactor GC/MS.

    Science.gov (United States)

    Watanabe, Atsushi; Kim, Young-Min; Hosaka, Akihiko; Watanabe, Chuichi; Teramae, Norio; Ohtani, Hajime; Kim, Seungdo; Park, Young-Kwon; Wang, Kaige; Freeman, Robert R

    2017-01-01

    When a GC/MS system is coupled with a pressurized reactor, the separation efficiency and the retention time are directly affected by the reactor pressure. To keep the GC column flow rate constant irrespective of the reaction pressure, a restrictor capillary tube and an open split interface are attached between the GC injection port and the head of a GC separation column. The capability of the attached modules is demonstrated for the on-line GC/MS analysis of catalytic reaction products of a bio-oil model sample (guaiacol), produced under a pressure of 1 to 3 MPa.

  13. alpha,beta-unsaturated 2-acyl imidazoles as a practical class of dienophiles for the DNA-Based catalytic asymmetric diels-alder reaction in water

    NARCIS (Netherlands)

    Boersma, A.J.; Feringa, B.L.; Roelfes, G.

    2007-01-01

    alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic

  14. 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; Zhu, Yihan; Lin, Ming; Wang, Qingxiao; Zhao, Lan; Yang, Yang; Yao, Kexin; Han, Yu

    2013-01-01

    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

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

    Directory of Open Access Journals (Sweden)

    Daphna S. Horowitz

    2015-06-01

    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.

  16. Photo catalytic reduction of benzophenone on TiO2: Effect of preparation method and reaction conditions

    International Nuclear Information System (INIS)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I.

    2010-01-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO 2 was synthesized by means of a hydrothermal technique. TiO 2 (Degussa TiO 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 (λ= 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 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 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 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 2 -P25. (Author)

  17. 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.

  18. Enhancement in the catalytic activity of Pd/USY in the heck reaction induced by H2 bubbling.

    Science.gov (United States)

    Okumura, Kazu; Tomiyama, Takuya; Moriyama, Sayaka; Nakamichi, Ayaka; Niwa, Miki

    2010-12-24

    Pd was loaded on ultra stable Y (USY) zeolites prepared by steaming NH(4)-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(OAc)₂. 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 (OH(strong)) generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  19. 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)

  20. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yaping [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States); Liu, Zhimin [School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States); Xue, Wenhua [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States); Crossley, Steven P.; Jentoft, Friederike C. [School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States); Wang, Sanwu, E-mail: sanwu-wang@utulsa.edu [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States)

    2017-01-30

    Highlights: • Hydrogenation of o-cresol over Pt results in formation of two products. • Dissociation of hydrogen from the −OH group involves a low activation energy. • Following hydrogenation of the aromatic ring forms 2-methyl-cyclohexanone. • Further hydrogenation produces the final product, 2-methyl-cyclohexanol. - Abstract: 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 −OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.

  2. 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.

  3. 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.

  4. Redox non-innocent ligands: versatile new tools to control catalytic reactions

    NARCIS (Netherlands)

    Lyaskovskyy, V.; de Bruin, B.

    2012-01-01

    In this (tutorial overview) perspective we highlight the use of "redox non-innocent" ligands in catalysis. Two main types of reactivity in which the redox non-innocent ligand is involved can be specified: (A) The redox active ligand participates in the catalytic cycle only by accepting/donating

  5. Catalytic Tandem Reaction for the Production of Jet and Diesel Fuel Range Alkanes

    DEFF Research Database (Denmark)

    Li, Hu; Gui, Zhenyou; Yang, Song

    2018-01-01

    Jet and diesel fuels are typically composed of C9-C14 and C12-C20 hydrocarbons, respectively, but the carbon-chain length of sugar-derived aldehydes and furanic compounds is no longer than C6. Here, a cascade catalytic process involving alkylation and hydrodeoxygenation (HDO) of 2-methylfuran (2-MF...

  6. Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

    International Nuclear Information System (INIS)

    Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

    1980-01-01

    Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

  7. Molecular weight control in emulsion polymerization by catalytic chain transfer : a reaction engineering approach

    NARCIS (Netherlands)

    Smeets, N.M.B.; Meda, U.S.; Heuts, J.P.A.; Keurentjes, J.T.F.; Herk, van A.M.; Meuldijk, J.

    2007-01-01

    For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on

  8. Basic research for nuclear energy : a study on photo-catalytic decomposition reactions of organics dissolved in water

    Energy Technology Data Exchange (ETDEWEB)

    Sung, K. W.; Na, J. W.; Cho, Y. H.; Kim, K. R

    1999-01-01

    In an experiment on TiO{sub 2} photo-catalysis of five nitrogen-containing organic compounds, the changes of pH and total carbon contents were measured, and the dependence of their photo-catalytic characteristic upon their chemical structures were investigated. -- calculation of the effect of ionic carbon species in an aqueous solution on thermodynamic equilibrium, pH and conductivity showed a small quantity of organics could lead conductivity increase and pH reduction. -- Based on the results of photo-catalytic experiment of ethylamine, phenylhydrazine, pyridine, urea or EDTA, irradiated for 180 minutes after adsorption onto titanium dioxide for 60 minutes, relationship between nitrogen atomic charge and the first-order rate constant was as the following: R (1st - order rate constant) = {delta} ({epsilon} - a ){sup 1/3} + b where, {epsilon} : atomic charge of nitrogen in a molecular, {delta}, a and b : corrective coefficients.

  9. Spectrophotometric determination of nitrite based on its catalytic effect on the reaction of nuclear fast red and potassium bromate

    Directory of Open Access Journals (Sweden)

    HASSAN ZAVVAR MOUSAVI

    2009-08-01

    Full Text Available A highly selective and sensitive catalytic spectrophotometric method was developed for the determination of nitrite in water samples. The method is based on its catalytic effect on the nuclear fast red–potassium bromate redox reaction in acidic medium. The reaction was followed spectrophotometrically by measuring the change in the absorbance at 518 nm of nuclear fast red 5 min after initiation of the reaction. In this study, the experimental parameters were optimized and the effects of other cations and anions on the determination of nitrite were examined. The calibration graph was linear in the range 2.0–45 µg mL-1 of nitrite. The relative standard deviations for the determination of 15 and 30 µg mL-1 of nitrite were 3.1 and 1.75 %, respectively (n = 8. The detection limit calculated from three times the standard deviation of the blank 3Sb was 0.7 µg mL-1. The method was successfully applied to the determination of nitrite in spiked tap, natural and wastewater samples.

  10. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    International Nuclear Information System (INIS)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

    2012-01-01

    The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

  11. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    Energy Technology Data Exchange (ETDEWEB)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

    2012-01-15

    The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

  12. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  13. Experiment and modeling of low-concentration methane catalytic combustion in a fluidized bed reactor

    International Nuclear Information System (INIS)

    Yang, Zhongqing; Yang, Peng; Zhang, Li; Guo, Mingnv; Ran, Jingyu

    2016-01-01

    Highlights: • The catalytic combustion of 0.15~3 vol. % low concentration methane in a fluidized bed was studied. • A mathematical model was proposed on the basis of gas–solid flow theory. • A comparative analysis of the established model with plug flow, mixed flow and K-L models was carried out. • The axial methane profile along fluidized bed was predicted by using the mathematical model. • The bed temperature has greater impact on methane conversion than fluidized velocity. - Abstract: This study undertakes a theoretical analysis and an experimental investigation into the characteristics of low-concentration methane catalytic combustion in a bubbling fluidized bed reactor using 0.5 wt.% Pd/Al_2O_3 as catalytic particles. A mathematical model is established based on gas–solid flow theory and is used to study the effects of bed temperature and fluidized velocity on methane catalytic combustion, and predict the dimensionless methane concentration axial profile in reactor. It is shown that methane conversion increases with bed temperature, but decreases with increasing fluidized velocity. These theoretical results are found to correlate well with the experimental measurement, with a deviation within 5%. A comparative analysis of the developed model with plug flow, mixed flow and K-L models is also carried out, and this further verifies that the established model better reflects the characteristics of low-concentration methane catalytic combustion in a bubbling fluidized bed. Using this reaction model, it was found that the difference in methane conversion between dense and freeboard zones gradually increases with bed temperature; the dense zone reaction levels off at 650 °C, thereby minimizing the difference between the dense and freeboard regions to around 15%. With an increase in bed temperature, the dimensionless methane concentration in the dense zone decreases exponentially, while in the splash zone, it varies from an exponential decay to a slow

  14. Evaluation of catalytic ferrispinel MFe_2O_4 (M = Cu, Co, Mn and Ni) in transesterification reaction

    International Nuclear Information System (INIS)

    Pereira, Kleberson Ricardo de Oliveira; Dantas, Joelda; Costa, Ana Cristina Figueiredo de Melo; Silva, Adriano Sant'Ana; Cornejo, Daniel Reinaldo

    2014-01-01

    Among the existing biofuels, biodiesel has achieved great economic and technological, for its potential to replace petroleum diesel and being biodegradable, have low emission of gaseous and be from renewable sources highlighted. In this context we propose to evaluate the performance of ferrispinel type MFe_2O_4, where M represents divalent metals (Cu, Co, Ni and Mn) in methyl transesterification reaction of soybean oil. The ferrispinel were synthesized by combustion reaction and characterized by XRD, FTIR and magnetic measurements. The results indicate that the synthesis is conducive to the production of ferrispinel with magnetization values ranging from 11.0 to 58.0 emu/g. The conversion values were 53; 55; 57 and 52 %, respectively, concluding that the type of divalent metal affects the morphology and hence the catalytic conversion. (author)

  15. Effect of Drying Conditions on the Catalytic Performance, Structure, and Reaction Rates over the Fe-Co-Mn/MgO Catalyst for Production of Light Olefins

    Directory of Open Access Journals (Sweden)

    Majid Abdouss

    2018-01-01

    How to Cite: Abdouss, M., Arsalanfar, M., Mirzaei, N., Zamani, Y. (2018. Effect of Drying Conditions on the Catalytic Performance, Structure, and Reaction Rates over the Fe-Co-Mn/MgO Catalyst for Production of Light Olefins. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 97-112 (doi:10.9767/bcrec.13.1.1222.97-112

  16. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

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

    Science.gov (United States)

    Almonacid, Daniel E; Yera, Emmanuel R; Mitchell, John B O; Babbitt, Patricia C

    2010-03-12

    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 refine

  18. 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

  19. Fast and quantitative differentiation of single-base mismatched DNA by initial reaction rate of catalytic hairpin assembly.

    Science.gov (United States)

    Li, Chenxi; Li, Yixin; Xu, Xiao; Wang, Xinyi; Chen, Yang; Yang, Xiaoda; Liu, Feng; Li, Na

    2014-10-15

    The widely used catalytic hairpin assembly (CHA) amplification strategy generally needs several hours to accomplish one measurement based on the prevailingly used maximum intensity detection mode, making it less practical for assays where high throughput or speed is desired. To make the best use of the kinetic specificity of toehold domain for circuit reaction initiation, we developed a mathematical model and proposed an initial reaction rate detection mode to quantitatively differentiate the single-base mismatch. Using the kinetic mode, assay time can be reduced substantially to 10 min for one measurement with the comparable sensitivity and single-base mismatch differentiating ability as were obtained by the maximum intensity detection mode. This initial reaction rate based approach not only provided a fast and quantitative differentiation of single-base mismatch, but also helped in-depth understanding of the CHA system, which will be beneficial to the design of highly sensitive and specific toehold-mediated hybridization reactions. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Reaction phenomena of catalytic partial oxidation of methane under the impact of carbon dioxide addition and heat recirculation

    International Nuclear Information System (INIS)

    Chen, Wei-Hsin; Lin, Shih-Cheng

    2015-01-01

    The reaction phenomena of CPOM (catalytic partial oxidation of methane) in a Swiss-roll reactor are studied numerically where a rhodium-based catalyst bed is embedded at the center of the reactor. CO 2 is added into the feed gas and excess enthalpy recovery is performed to evaluate their influences on CPOM performance. In the study, the mole ratio of O 2 to CH 4 (O 2 /CH 4 ratio) is fixed at 0.5 and the mole ratio of CO 2 to O 2 (CO 2 /O 2 ratio) is in the range of 0–2. The results reveal that CO 2 addition into the influent has a slight effect on methane combustion, but significantly enhances dry reforming and suppresses steam reforming. The reaction extents of steam reforming and dry reforming in CPOM without heat recovery and CO 2 addition are in a comparable state. Once CO 2 is added into the feed gas, the dry reforming is enhanced, thereby dominating CH 4 consumption. Compared to the reactor without excess enthalpy recovery, heat recirculation drastically increases the maximum reaction temperature and CH 4 conversion in the catalyst bed; it also intensifies the H 2 selectivity, H 2 yield, CO 2 conversion, and syngas production rate. The predictions indicate that the heat recirculation is able to improve the syngas formation up to 45%. - Highlights: • Catalytic partial oxidation of methane with CO 2 addition and heat recovery is studied. • CO 2 addition has a slight effect on methane combustion. • CO 2 addition significantly enhances dry reforming and suppresses steam reforming. • Dry reforming dominates CH 4 consumption when CO 2 addition is large. • Heat recirculation can improve the syngas formation up to 45%

  1. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

    International Nuclear Information System (INIS)

    Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

    2017-01-01

    Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

  2. Eco-friendly synthesis of silver nanoparticles using green algae (Caulerpa serrulata): reaction optimization, catalytic and antibacterial activities.

    Science.gov (United States)

    Aboelfetoh, Eman F; El-Shenody, Rania A; Ghobara, Mohamed M

    2017-07-01

    Stable colloidal silver nanoparticles (AgNPs) were synthesized using Caulerpa serrulata (green marine algae) aqueous extract as an efficient reducing and stabilizing agent. This method is considered to be a sustainable alternate to the more complicated chemical procedures. To achieve the optimization synthesis of AgNPs, several effects such as extract concentration, contact time, pH values, and temperature were examined. The synthesized AgNPs were characterized by UV-Vis spectroscopy, FT-IR, XRD, and HR-TEM. The synthesized AgNPs showed an intense surface plasmon resonance band at 412 nm at the optimal conditions (20% (v/v) extract and 95 °C). TEM reveal that higher extract concentration and higher temperature leading to the formation of spherical AgNPs with an average particle size of 10 ± 2 nm. The synthesized AgNPs showed excellent catalytic reduction activity of Congo red (CR) dye from aqueous solutions. The degradation percentage of CR with AgNPs accelerated by increasing either NaBH 4 concentration or catalytic dosage. The AgNPs synthesized at higher temperature (e.g., 10Ag-95) exhibited the highest catalytic activity. The reaction kinetics was found to be pseudo first order with respect to the dye concentration. Moreover, the AgNPs displayed antibacterial activity at lower concentration against Staphylococcus aureus, Pseudomonas aeruginosa, Shigella sp., Salmonella typhi, and Escherichia coli and may be a good alternative therapeutic approach. The outcomes of the current study confirmed that the synthesized AgNPs had an awesome guarantee for application in catalysis and wastewater treatment.

  3. Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol: Influence of Reaction Temperature and Feedstock.

    Science.gov (United States)

    Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

    2017-11-06

    The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (>380 °C). At preferred intermediate temperatures (300-340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin.

  4. 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.

  5. New porphyrin-polyoxometalate hybrid materials: synthesis, characterization and investigation of catalytic activity in acetylation reactions.

    Science.gov (United States)

    Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

    2012-10-14

    New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(II) and 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) chloride, and a Lindqvist-type polyoxometalate, Mo(6)O(19)(2-), were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by (1)H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(IV)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.

  6. Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

    Science.gov (United States)

    Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

    2017-07-01

    We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

  7. Project of CO{sub 2} fixation and utilization using catalytic hydrogenation reaction for coping with the global environment issues

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Discussions were given on a carbon dioxide fixing and utilizing project utilizing hydrogenating reaction by means of a catalytic method. In the discussions, development was made on such foundation technologies as CO2 separation by using Cardo type CO2 membrane, a technology to synthesize methanol through hydrogen addition by means of the catalytic method, and an electrolytic technology of membrane-electrode mixed type, as well as a methanol synthesis bench test of 50 kg/d scale. In order to develop this result into specific applications, demonstration tests are required that use methanol synthesizing pilot plants of 4 t/d and 80 t/d capacities. In addition, for the electric power to produce a huge amount of hydrogen, development is necessary on a solar energy utilizing technology of large scale and low cost. Furthermore, from the economic and social viewpoints, the achievements of this project are regarded to depend on understanding of the necessity of a policy of putting a large number of methanol fuel cell automobiles into use, and dealing with the global warming problem. Energy required to change CO2 into useful chemical substance requires five times as much energy as has been produced, hence prevention of the global warming through this channel is difficult. (NEDO)

  8. The catalytic potency of ß-glucosidase from Pyroccus furiosus in the direct glucosylation reaction

    NARCIS (Netherlands)

    Roode, de B.M.; Meer, van der T.D.; Kaper, T.; Franssen, M.C.R.; Padt, van der A.; Oost, van der J.; Boom, R.M.

    2001-01-01

    Enzymes from extremophiles operate at conditions that are different from their `normal' counterparts, and are therefore a useful extension of the enzyme toolbox. In this paper, the direct glucosylation reaction mediated by a hyperthermophilic -glucosidase from Pyrocuccus furiosus was investigated.

  9. 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…

  10. Redox and Lewis acid relay catalysis: a titanocene/zinc catalytic platform in the development of multicomponent coupling reactions.

    Science.gov (United States)

    Gianino, Joseph B; Campos, Catherine A; Lepore, Antonio J; Pinkerton, David M; Ashfeld, Brandon L

    2014-12-19

    A titanocene-catalyzed multicomponent coupling is described herein. Using catalytic titanocene, phosphine, and zinc dust, zinc acetylides can be generated from the corresponding iodoalkynes to affect sequential nucleophilic additions to aromatic aldehydes. The intermediate propargylic alkoxides are trapped in situ with acetic anhydride, which are susceptible to a second nucleophilic displacement upon treatment with a variety of electron-rich species, including acetylides, allyl silanes, electron-rich aromatics, silyl enol ethers, and silyl ketene acetals. Additionally, employing cyclopropane carboxaldehydes led to ring-opened products resulting from iodine incorporation. Taken together, these results form the basis for a new mode of three-component coupling reactions, which allows for rapid access to value added products in a single synthetic operation.

  11. 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.

  12. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    Science.gov (United States)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  13. 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.)

  14. Characterization and reaction studies of dimeric molybdenum(III) complexes with bridging dithiolate ligands. Catalytic reduction of acetylene to ethylene

    International Nuclear Information System (INIS)

    DuBois, M.R.; Haltiwanger, R.C.; Miller, D.J.; Glatzmaier, G.

    1979-01-01

    The complexes [C 5 H 5 MoSC/sub n/H/sub 2n/S] 2 (where n = 2 and 3) have been prepared by the reaction of ethylene sulfide and propylene sulfide, respectively, with C 5 H 5 MoH(CO) 3 or with [C 5 H 5 Mo(CO) 3 ] 2 . Cyclic voltammetry shows that each complex undergoes two reversible oxidations at 0.13 and 0.79 V vs. SCE (in acetonitrile with 0.1 M Bu 4 NBF 4 ). Both the one-electron and two-electron oxidation products have been synthesized and characterized by spectral and magnetic data. Electrochemical data for the oxidized complexes support the conclusion that the complexes have the same gross structural features in all three oxidation states. A single crystal of the monocation [C 5 H 5 MoSC 3 H 6 S] 2 BF 4 has been characterized by an x-ray diffraction study. The compound crystallizes in the space group C2/c with a = 18.266 (1) A, b = 9.206 (4) A, c = 12.911 (5) A, β = 100.83 (3) 0 , and V = 2128 A 3 . The metal ions of the cation are bridged by two 1,2-propanedithiolate ligands. The four sulfur atoms of these ligands form a plane which bisects the metal-metal distance. The neutral dimeric complexes undergo a unique reaction with alkenes and alkynes in which the hydrocarbon portion of the bridging dithiolate ligands is exchanged. The reaction has been characterized with olefinswith both electron-withdrawing and electron-donating substituents. When [C 5 H 5 MoSC 2 H 4 S] 2 (1) is reacted with acetylene at 25 0 C, ethene is produced and the complex [C 5 H 5 MoSC 2 H 2 S] 2 is isolated. The latter complex is reduced by hydrogen (2 atm) at 60 0 C to re-form 1. The utility of these reactions in the catalytic reduction of acetylene to ethylene has been investigated. The role of the sulfur ligands in this catalytic cycle is discussed. 50 references, 2 figures, 5 tables

  15. Development of catalytic materials for the synthesis of valuable chemical products via multifunctional and multisite reactions

    International Nuclear Information System (INIS)

    Apesteguia, C.R; Padro, C.L; Diez, V.K; Di Cosimo, J.I; Trasarti, A.F; Marchi, A.J

    2004-01-01

    This work reports on the successful development of solid catalytic materials carried out by our working group to obtain fine high yield chemical products. Specifically, a report is made of i) the development of metal/acid bi-functional catalysts to obtain racemic menthol from citral in a one step liquid phase process. This menthol is one of the most important chemical flavouring compounds in industry; ii) The use of acid zeolites containing a balanced concentration of Bronsted and Lewis heavy acid sites, which allow the selective synthesis of o-hydroxy acetophenone from the gas phase acylation of phenol with acetic acid. The o-hydroxy acetophenone is an intermediate compound in the production of 4-hydroxy coumarin and warfarin that are used as anticoagulants drugs; iii) The use of mixed MgAl x O y oxides containing dual acid-basic sites (Mg 2- O 2- and Al 3+ -O 2- ) to synthesize isoforone from acetone in gas phase. The isoforone is an intermediate key in the synthesis of vitamin E (CW)

  16. Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions.

    Science.gov (United States)

    Denmark, Scott E; Kalyani, Dipannita; Collins, William R

    2010-11-10

    A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

  17. Green synthesis of silver nanoparticles using Prosopis juliflora bark extract: reaction optimization, antimicrobial and catalytic activities.

    Science.gov (United States)

    Arya, Geeta; Kumari, R Mankamna; Gupta, Nidhi; Kumar, Ajeet; Chandra, Ramesh; Nimesh, Surendra

    2017-07-18

    In the present study, silver nanoparticles (PJB-AgNPs) have been biosynthesized employing Prosopis juliflora bark extract. The biosynthesis of silver nanoparticles was monitored on UV-vis spectrophotometer. The size, charge and polydispersity index (PDI) of PJB-AgNPs were determined using dynamic light scattering (DLS). Different parameters dictating the size of PJB-AgNPs were explored. Nanoparticles biosynthesis optimization studies suggested efficient synthesis of highly dispersed PJB-AgNPs at 25 °C when 9.5 ml of 1 mM AgNO 3 was reduced with 0.5 ml of bark extract for 40 min. Characterization of PJB-AgNPs by SEM showed spherical-shaped nanoparticles with a size range ∼10-50 nm along with a hydrodynamic diameter of ∼55 nm as evaluated by DLS. Further, characterizations were done by FTIR and EDS to evaluate the functional groups and purity of PJB-AgNPs. The antibacterial potential of PJB-AgNPs was tested against E. coli and P. aeruginosa. The PJB-AgNPs remarkably exhibited anticancer activity against A549 cell line as evidenced by Alamar blue assay. The dye degradation activity was also evaluated against 4-nitrophenol that has carcinogenic effect. The results thus obtained suggest application of PJB-AgNPs as antimicrobial, anticancer and catalytic agents.

  18. Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol : Influence of Reaction Temperature and Feedstock

    NARCIS (Netherlands)

    Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

    2017-01-01

    The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while

  19. Effect of foam stirrer design on the catalytic performance of rotating foam stirrer reactions

    NARCIS (Netherlands)

    Leon Matheus, M.A.; Geers, P.; Nijhuis, T.A.; Schaaf, van der J.; Schouten, J.C.

    2012-01-01

    The liquid–solid mass transfer rate in a rotating foam stirrer reactor and in a slurry reactor is studied using the hydrogenation of styrene as a model reaction. The rotating foam stirrer reactor is a novel type of multi-phase reactor where highly open-celled materials, solid foams, are used as a

  20. DNA-based catalytic enantioselective intermolecular oxa-Michael addition reactions

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2012-01-01

    Using the DNA-based catalysis concept, a novel Cu(II) catalyzed enantioselective oxa-Michael addition of alcohols to enones is reported. Enantioselectivities of up to 86% were obtained. The presence of water is important for the reactivity, possibly by reverting unwanted side reactions such as

  1. A Self-Assembled Trigonal Prismatic Molecular Vessel for Catalytic Dehydration Reactions in Water.

    Science.gov (United States)

    Das, Paramita; Kumar, Atul; Howlader, Prodip; Mukherjee, Partha Sarathi

    2017-09-12

    A water-soluble Pd 6 trigonal prism (A) was synthesized by two-component coordination-driven self-assembly of a Pd II 90° acceptor with a tetraimidazole donor. The walls of the prism are constructed by three conjugated aromatic building blocks, which means that the confined pocket of the prism is hydrophobic. In addition to the hydrophobic cavity, large product egress windows make A an ideal molecular vessel to catalyze otherwise challenging pseudo-multicomponent dehydration reactions in its confined nanospace in aqueous medium. This study is an attempt at selective generation of the intermediate tetraketones and xanthenes by fine-tuning the reaction conditions employing a supramolecular molecular vessel. Moreover, either poor or no yield of the dehydrated products in the absence of A under similar reaction conditions supports the ability of the confined space of the barrel to promote such reactions in water. Furthermore, we focused on the rigidification of the tetraphenylethylene-based tetraimidazole unit anchored within the Pd II coordination architecture; enabling counter-anion dependent aggregation induced emission in the presence of water. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. Catalytic performance of Metal-Organic-Frameworks vs.extra-large porezeolite UTL in condensation reactions

    Czech Academy of Sciences Publication Activity Database

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, O. V.; Čejka, Jiří

    2013-01-01

    Roč. 1, AUG 2013 (2013), s. 1-11 ISSN 2296-2646 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : condensation reactions * MOFs * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry http://www.frontiersin.org/Journal/10.3389/fchem.2013.00011/abstract

  4. Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

    Science.gov (United States)

    Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

    2018-05-01

    It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

  5. Catalytic reactions of synthesis gas. Part 2. Methanol carbonylation and homologation

    Energy Technology Data Exchange (ETDEWEB)

    Niemelae, M.

    1993-01-01

    The aim of the review is to evaluate the applicability of methanol hydrocarbonylation as a second test reaction to study the nondissociative activation of CO by heterogeneous rhodium and cobalt catalysts. The main emphasis in methanol (hydro)carbonylation chemistry has been on homogeneous reactions. These systems have been seen advantageous in selectivity, activity and ease of modification. The heterogenization attempts have been carried out to obtain easier separation of the catalyst and the product. The activity of cobalt, rhodium and other metals supported on different materials have been studied in heterogeneous methanol (hydro)carbonylation. The observed activities have been considerably influenced by the support. The most effective catalyst support has been activated carbon. Good carbonylation activities and selectivities have also been observed in conjunction with zeolite supports. The literature study indicates that the typical experimental conditions of methanol (hydro)carbonylation do not exceed the constructional and operational limits of the available reactor system, i.e. 500 C and 50 bar. The reaction is suitable for testing Co and Rh precursors, since both cobalt and rhodium compounds have shown carbonylation activity.

  6. Conversion of KCl into KBH4 by Mechano-Chemical Reaction and its Catalytic Decomposition

    Science.gov (United States)

    Bilen, Murat; Gürü, Metin; Çakanyildirim, Çetin

    2017-07-01

    Production of KBH4, in the presence of KCl, B2O3 and MgH2 by means of a mechanical reaction and a dehydrogenation kinetic, constitute the main parts of this study. Operating time and reactant ratio are considered as two parameters for the mechanical reaction to obtain the maximum yield. The production process was carried out in a ball milling reactor, and the product residue was purified with ethylene diamine (EDA) and subsequently characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and x-ray Diffraction (XRD) analyses. Optimum time for mechano-chemical treatment and reactant ratio (MgH2/KCl) were obtained as 1000 min and 1.0, respectively. Synthesized and commercial KBH4 were compared by hydrolysis tests in the presence of Co1-xNix/Al2O3 heterogeneous catalyst. Hydrogen generation rates, activation energy and order of the KBH4 decomposition reaction were obtained as 1578 {mL}_{{{{H}}2 }} \\min^{ - 1} {g}_{{catalyst}}^{ - 1}, 39.2 kJ mol-1 and zero order, respectively.

  7. Bystanders' Reactions to Witnessing Repetitive Abuse Experiences

    Science.gov (United States)

    Janson, Gregory R.; Carney, JoLynn V.; Hazler, Richard J.; Oh, Insoo

    2009-01-01

    The Impact of Event Scale-Revised (D. S. Weiss & C. R. Marmar, 1997) was used to obtain self-reported trauma levels from 587 young adults recalling childhood or adolescence experiences as witnesses to common forms of repetitive abuse defined as bullying. Mean participant scores were in a range suggesting potential need for clinical assessment…

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

    KAUST Repository

    Yang, Wenguo; Tan, Davin; Lee, Richmond; Li, Lixin; Pan, Yuanhang; Huang, Kuo-Wei; Tan, Choonhong; Jiang, Zhiyong

    2012-01-01

    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

  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. Evaluating the Catalytic Effects of Carbon Materials on the Photocatalytic Reduction and Oxidation Reactions of TiO2

    International Nuclear Information System (INIS)

    Khan, Gulzar; Kim, Young Kwang; Choi, Sung Kyu; Han, Dong Suk; Abdelwahab, Ahmed; Park, Hyunwoong

    2013-01-01

    TiO 2 composites with seven different carbon materials (activated carbons, graphite, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene oxides, and reduced graphene oxides) that are virgin or treated with nitric acid are prepared through an evaporation method. The photocatalytic activities of the as-prepared samples are evaluated in terms of H 2 production from aqueous methanol solution (photo-catalytic reduction: PCR) and degradation of aqueous pollutants (phenol, methylene blue, and rhodamine B) (photocatalytic oxidation: PCO) under AM 1.5-light irradiation. Despite varying effects depending on the kinds of carbon materials and their surface treatment, composites typically show enhanced PCR activity with maximum 50 times higher H 2 production as compared to bare TiO 2 . Conversely, the carbon-induced synergy effects on PCO activities are insignificant for all three substrates. Colorimetric quantification of hydroxyl radicals supports the absence of carbon effects. However, platinum deposition on the binary composites displays the enhanced effect on both PCR and PCO reactions. These differing effects of carbon materials on PCR and PCO reactions of TiO 2 are discussed in terms of physicochemical properties of carbon materials, coupling states of TiO 2 /carbon composites, interfacial charge transfers. Various surface characterizations of composites (UV-Vis diffuse reflectance, SEM, FTIR, surface area, electrical conductivity, and photoluminescence) are performed to gain insight on their photocatalytic redox behaviors

  11. On the Catalytic Effect of Water in the Intramolecular Diels–Alder Reaction of Quinone Systems: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Renato Contreras

    2012-11-01

    Full Text Available The mechanism of the intramolecular Diels–Alder (IMDA reaction of benzoquinone 1, in the absence and in the presence of three water molecules, 1w, has been studied by means of density functional theory (DFT methods, using the M05-2X and B3LYP functionals for exploration of the potential energy surface (PES. The energy and geometrical results obtained are complemented with a population analysis using the NBO method, and an analysis based on the global, local and group electrophilicity and nucleophilicity indices. Both implicit and explicit solvation emphasize the increase of the polarity of the reaction and the reduction of activation free energies associated with the transition states (TSs of this IMDA process. These results are reinforced by the analysis of the reactivity indices derived from the conceptual DFT, which show that the increase of the electrophilicity of the quinone framework by the hydrogen-bond formation correctly explains the high polar character of this intramolecular process. Large polarization at the TSs promoted by hydrogen-bonds and implicit solvation by water together with a high electrophilicity-nucleophilicity difference consistently explains the catalytic effects of water molecules.

  12. 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.

  13. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik [Dept. of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, Seoul (Korea, Republic of); Hong, Jongki; Lee, Won Woong [College of Pharmacy, Kyung Hee University, Seoul (Korea, Republic of); Ryu, Jung Bok [R and D Center, Chuncheon (Korea, Republic of)

    2017-02-15

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li{sub a} X{sub a+1}]{sup −} are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl{sup −} are non-corrosive under the carboxylation condition.

  14. 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

  15. Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions.

    Science.gov (United States)

    Leckie, Stuart M; Harkness, Gavin J; Clarke, Matthew L

    2014-10-09

    As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian, E-mail: anjx@163.com; Shen, Yuhua, E-mail: s_yuhua@163.com

    2017-01-30

    Graphical abstract: This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass simultaneously for environment clean. And the typical sample exhibits excellent catalytic performance toward ORR, which is similar to that of commercial Pt/C. - Highlights: • This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass. • The HPC/RGO composite not only prevents the aggregation of RGO, but also takes advantage of the synergy between them. • This method was accessible, without using any activator, which is an effective strategy for the large scale application of FCs. - Abstract: 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 m{sup 2}/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

  17. Mitoxantrone removal by electrochemical method: A comparison of homogenous and heterogenous catalytic reactions

    Directory of Open Access Journals (Sweden)

    Abbas Jafarizad

    2017-08-01

    Full Text Available Background: Mitoxantrone (MXT is a drug for cancer therapy and a hazardous pharmaceutical to the environment which must be removed from contaminated waste streams. In this work, the removal of MXT by the electro-Fenton process over heterogeneous and homogenous catalysts is reported. Methods: The effects of the operational conditions (reaction medium pH, catalyst concentration and utilized current intensity were studied. The applied electrodes were carbon cloth (CC without any processing (homogenous process, graphene oxide (GO coated carbon cloth (GO/CC (homogenous process and Fe3O4@GO nanocomposite coated carbon cloth (Fe3O4@GO/CC (heterogeneous process. The characteristic properties of the electrodes were determined by atomic force microscopy (AFM, field emission scanning electron microscopy (FE-SEM and cathode polarization. MXT concentrations were determined by using ultraviolet-visible (UV-Vis spectrophotometer. Results: In a homogenous reaction, the high concentration of Fe catalyst (>0.2 mM decreased the MXT degradation rate. The results showed that the Fe3O4@GO/CC electrode included the most contact surface. The optimum operational conditions were pH 3.0 and current intensity of 450 mA which resulted in the highest removal efficiency (96.9% over Fe3O4@GO/CC electrode in the heterogeneous process compared with the other two electrodes in a homogenous process. The kinetics of the MXT degradation was obtained as a pseudo-first order reaction. Conclusion: The results confirmed the high potential of the developed method to purify contaminated wastewaters by MXT.

  18. 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.

  19. Regularities of catalytic reactions of hydrogen, ethane and ethylene with elementary sulfur

    International Nuclear Information System (INIS)

    Zazhigalov, V.A.

    1978-01-01

    Shown is the decisive role of metal-sulfur bond stability for activity determination of metal sulfides (WS 2 , MoS 2 , CdS) in interaction reactions of elementary sulfur and hydrogen, ethane and ethylene. Found is the regularity of changing the relative reactiveness of the given substances and a conclusion is made about uniformity of the investigated catalyst processes. The results of hydrogen, ethane and ethylene oxidation by oxygen and sulfur are compared, the semilarity of these processes being pointed out

  20. The effect of catalytic reaction conditions on the incorporation of tritium in unsaturated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Shevchenko, V P; Nagayev, I Yu; Myasoedov, N F [AN SSSR, Moscow (USSR). Inst. Molekulyarnoj Genetiki

    1989-10-01

    We have obtained multiple-tritium-labelled 5-{alpha}-androstan-3-one, dihydropicrotoxin, dimethyl-propyl-3-chloro-butyl-ammonium chloride, 2,2-di(trifluoromethyl)-3,3-dicyanobicyclohept(2,2,1)ane, dihydroalprenolol, undecanoic acid, dihydro-m,m'-di-tert.-butyl-p-coumaric acid and dihydrofusicoccin. By varying the conditions for the hydrogenation of terminal double bonds, one can considerably increase the molar radioactivity of such compounds through isotopic exchange. We discuss some tentative explanations of the effect of the labelling reaction conditions upon the synthesis of compounds with desired properties. (author).

  1. The effect of catalytic reaction conditions on the incorporation of tritium in unsaturated compounds

    International Nuclear Information System (INIS)

    Shevchenko, V.P.; Nagayev, I.Yu.; Myasoedov, N.F.

    1989-01-01

    We have obtained multiple-tritium-labelled 5-α-androstan-3-one, dihydropicrotoxin, dimethyl-propyl-3-chloro-butyl-ammonium chloride, 2,2-di(trifluoromethyl)-3,3-dicyanobicyclohept[2,2,1]ane, dihydroalprenolol, undecanoic acid, dihydro-m,m'-di-tert.-butyl-p-coumaric acid and dihydrofusicoccin. By varying the conditions for the hydrogenation of terminal double bonds, one can considerably increase the molar radioactivity of such compounds through isotopic exchange. We discuss some tentative explanations of the effect of the labelling reaction conditions upon the synthesis of compounds with desired properties. (author)

  2. Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.

    1997-01-01

    Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

  3. 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.

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

    International Nuclear Information System (INIS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-01-01

    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.

  5. Catalytic activity of calcium-based mixed metal oxides nanocatalysts in transesterification reaction of palm oil

    Science.gov (United States)

    Hassan, Noraakinah; Ismail, Kamariah Noor; Hamid, Ku Halim Ku; Hadi, Abdul

    2017-12-01

    Nowadays, biodiesel has become the forefront development as an alternative diesel fuel derived from biological sources such as oils of plant and fats. Presently, the conventional transesterification of vegetable oil to biodiesel gives rise to some technological problem. In this sense, heterogeneous nanocatalysts of calcium-based mixed metal oxides were synthesized through sol-gel method. It was found that significant increase of biodiesel yield, 91.75 % was obtained catalyzed by CaO-NbO2 from palm oil compared to pure CaO of 53.99 % under transesterification conditions (methanol/oil ratio 10:1, reaction time 3 h, catalyst concentration 4 wt%, reaction temperature 60 °C, and mixing speed of 600 rpm). The phase structure and crystallinity as well as the texture properties of the prepared catalysts were characterized by X-ray Diffraction (XRD) and the textural properties were characterized by N2 adsorption-desorption analysis. Sol-gel method has been known as versatile method in controlling the structural and chemical properties of the catalyst. Calcium-based mixed oxide synthesized from sol-gel method was found to exist as smaller crystallite size with high surface area.

  6. Zeolite synthesis from the pyrrolidine containing system and their catalytic properties in the methanol conversion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Kunio; Kiyozumi, Yoshimichi; Shin, Shigemitsu; Ogawa, Kiyoshi; Yamazaki, Yasuyoshi; Watanabe, Hideo

    1987-12-18

    Systhesis of zeolite from a system containing cheaper pyrrolidine as a crystallization regulator than quaternary ammonium ion was carried out and the methanol conversion reaction was studied over the systhesized zeolite to get C/sub 2/ and C/sub 3/ olefins. Hydrous gels were prepared by adding and agitating pyrrolidine, water glass and sulfuric acid to aluminum sulfate solution; and aluminum nitrate, colloidal silica and pyrrolidine to NaOH solution. Five zeolite, that is, ZSM-5, ZSM-35, ZSM-39, ZSM-48 and KZ-1 were synthesized by changing gel components. X-ray powder diffraction, BET specific surface areas, micropore diameters, micropore volumes, oxygen contents by scanning electron photomicrographs and infra-red spectra were examined. The organic base in hydrous gels influenced greatly on the zeolite composition and structure. The ZSM-5 zeolite exhibited the superior performance as to a high selectivity of light olefins over the target of development. (12 figs, 1 tab, 20 refs)

  7. General Tritium Labelling of Gentamicin C by catalytic hydrogen exchange Reaction with Tritiated Water

    International Nuclear Information System (INIS)

    Suarez, C.; Diaz, D.; Paz, D.

    1991-01-01

    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

  8. General Tritium labelling of gentamicin C by catalytic hydrogen exchange reaction with tritiated water

    International Nuclear Information System (INIS)

    Suarez, C.; Diaz, D.

    1991-01-01

    Gentamicin C was labelled with tritium by means of a PtO 2 catalized hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H 2 O- 3 H, and 50 mg of prereduced PtO 2 ) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 o C, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accoumplished 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

  9. High Zn/Al ratios enhance dehydrogenation vs hydrogen transfer reactions of Zn-ZSM-5 catalytic systems in methanol conversion to aromatics

    DEFF Research Database (Denmark)

    Pinilla-Herrero, Irene; Borfecchia, Elisa; Holzinger, Julian

    2018-01-01

    suggest that catalytic activity is associated with [Zn(H2O)n(OH)]+ species located in the exchange positions of the materials with little or no contribution of ZnO or metallic Zn. The effect of Zn/Al ratio on their catalytic performance in methanol conversion to aromatics has been investigated. In all...... cases, higher Zn content causes an increase in the yield of aromatics while keeping the production of alkanes low. For similar Zn contents, high densities of Al sites favour the hydrogen transfer reactions and alkane formation whereas in samples with low Al contents, and thus higher Zn/Al ratio...

  10. MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

  11. From biodiversity to catalytic diversity: how to control the reaction mechanism by the nature of metallophytes.

    Science.gov (United States)

    Escande, Vincent; Olszewski, Tomasz K; Grison, Claude

    2015-04-01

    Phytoextraction is widely used for the reclamation of degraded sites, particularly to remove trace metals from contaminated soils. Whereas this technique demonstrates several advantages, the biomass resulting from phytoextraction processes is highly enriched in metallic elements and constitutes therefore a problematic waste. We show here that this biomass can be used for the preparation of novel polymetallic extracts, with high potential as catalysts or reagents in organic synthesis. This new concept of ecocatalysis constitutes an innovative recycling of metallic elements whose current known reserves could be exhausted in the coming decades. The ecocatalysts Eco-Zn and Eco-Ni prepared respectively from Zn and Ni hyperaccumulating plants display two distinct chemical reactivities, starting from the same substrates. Eco-Zn led to the formation of esters of commercial interest for the fragrance industry, following a hydro-acyloxy-addition reaction pathway. In contrast, Eco-Ni afforded chlorinated products thank to the hydrochlorination of alkenes. Both ecocatalysts allowed the synthesis of valuable products in high yields through methodologies in line with the spirit of sustainable chemistry.

  12. Improving the catalytic activity of amorphous molybdenum sulfide for hydrogen evolution reaction using polydihydroxyphenylalanine modified MWCNTs

    Science.gov (United States)

    Li, Maoguo; Yu, Muping; Li, Xiang

    2018-05-01

    Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

  13. Fundamental mechanisms and reactions in non-catalytic subcritical hydrothermal processes: A review.

    Science.gov (United States)

    Yousefifar, Azadeh; Baroutian, Saeid; Farid, Mohammed M; Gapes, Daniel J; Young, Brent R

    2017-10-15

    The management and disposal of solid waste is of increasing concern across the globe. Hydrothermal processing of sludge has been suggested as a promising solution to deal with the considerable amounts of sludge produced worldwide. Such a process not only degrades organic compounds and reduces waste volume, but also provides an opportunity to recover valuable substances. Hydrothermal processing comprises two main sub-processes: wet oxidation (WO) and thermal hydrolysis (TH), in which the formation of various free radicals results in the production of different intermediates. Volatile fatty acids (VFAs), especially acetic acid, are usually the main intermediates which remain as a by-product of the process. This paper aims to review the fundamental mechanism for hydrothermal processing of sludge, and the formation of different free radicals and intermediates therein. In addition, the proposed kinetic models for the two processes (WO and TH) from the literature are reviewed and the advantages and disadvantages of each model are outlined. The effect of mass transfer as a critical component of the design and development of the processes, which has been neglected in most of these proposed models, is also reviewed, and the effect of influencing parameters on the processes' controlling step (reaction or mass transfer) is discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2014-01-01

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  15. Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

    Science.gov (United States)

    Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

    2018-03-01

    Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

  16. 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.

  17. 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.

  18. Modelling of catalytic recombiners. Comparison of REKO-DIREKT calculations with REKO-3 experiments

    International Nuclear Information System (INIS)

    Reinecke, E.-A.; Boehm, J.; Drinovac, P.; Struth, S.; Tragsdorf, I.M.

    2005-01-01

    Numerous containments of European light water reactors (LWR) are equipped with passive autocatalytic recombiners (PAR). PARs make use of the fact that hydrogen and oxygen react exothermally on catalytic surfaces generating steam and heat even below conventional concentration limits and ignition temperatures. These devices are designed for the removal of hydrogen generated during a severe accident in order to limit the impact of a possible hydrogen combustion. Alongside many experimental programmes performed at different institutions in the past which demonstrated the technical feasibility of this approach, investigations also revealed that there is still research needed in order to optimise and to enhance existing systems. The knowledge of the processes inside recombiners is still limited. The numerical code REKO-DIREKT has been developed in order to analyse the processes inside a PAR. The code calculates the local catalyst and gas temperatures and the concentration regression along the catalyst plates dependent on the inlet hydrogen concentration, the inlet gas temperature, and the flow rate. Numerous experiments have been performed in the REKO-3 facility taking into account different hydrogen concentrations, different flow rates, the presence of steam, the lack of oxygen, and different arrangements of the catalyst elements. The experimental results are used for the validation of the code providing also data specific for sub-models, e.g. the heat radiation model. The first basic calculations fit well with the experimental results indicating a proper understanding of the fundamental processes. The paper presents model calculations performed and the comparison with experimental results. (author)

  19. 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

  20. Random catalytic reaction networks

    Science.gov (United States)

    Stadler, Peter F.; Fontana, Walter; Miller, John H.

    1993-03-01

    We study networks that are a generalization of replicator (or Lotka-Volterra) equations. They model the dynamics of a population of object types whose binary interactions determine the specific type of interaction product. Such a system always reduces its dimension to a subset that contains production pathways for all of its members. The network equation can be rewritten at a level of collectives in terms of two basic interaction patterns: replicator sets and cyclic transformation pathways among sets. Although the system contains well-known cases that exhibit very complicated dynamics, the generic behavior of randomly generated systems is found (numerically) to be extremely robust: convergence to a globally stable rest point. It is easy to tailor networks that display replicator interactions where the replicators are entire self-sustaining subsystems, rather than structureless units. A numerical scan of random systems highlights the special properties of elementary replicators: they reduce the effective interconnectedness of the system, resulting in enhanced competition, and strong correlations between the concentrations.

  1. 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.

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

    KAUST Repository

    Zhang, Tao; Croue, Jean-Philippe

    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

  3. High Pressure Scanning Tunneling Microscopy Studies of Adsorbate Structure and Mobility during Catalytic Reactions. Novel Design of an Ultra High Pressure, High Temperature Scanning Tunneling Microscope System for Probing Catalytic Conversions

    International Nuclear Information System (INIS)

    Tang, David Chi-Wai

    2005-01-01

    The aim of the work presented therein is to take advantage of scanning tunneling microscope's (STM) capability for operation under a variety of environments under real time and at atomic resolution to monitor adsorbate structures and mobility under high pressures, as well as to design a new generation of STM systems that allow imaging in situ at both higher pressures (35 atm) and temperatures (350 C). The design of a high pressure, high temperature scanning tunneling microscope system, that is capable of monitoring reactions in situ at conditions from UHV and ambient temperature up to 1 atm and 250 C, is briefly presented along with vibrational and thermal analysis, as this system serves as a template to improve upon during the design of the new ultra high pressure, high temperature STM. Using this existing high pressure scanning tunneling microscope we monitored the co-adsorption of hydrogen, ethylene and carbon dioxide on platinum (111) and rhodium (111) crystal faces in the mTorr pressure range at 300 K in equilibrium with the gas phase. During the catalytic hydrogenation of ethylene to ethane in the absence of CO the metal surfaces are covered by an adsorbate layer that is very mobile on the time scale of STM imaging. We found that the addition of CO poisons the hydrogenation reaction and induces ordered structures on the single crystal surfaces. Several ordered structures were observed upon CO addition to the surfaces pre-covered with hydrogen and ethylene: a rotated (√19 x √19)R23.4 o on Pt(111), and domains of c(4 x 2)-CO+C 2 H 3 , previously unobserved (4 x 2)-CO+3C 2 H 3 , and (2 x 2)-3CO on Rh(111). A mechanism for CO poisoning of ethylene hydrogenation on the metal single crystals was proposed, in which CO blocks surface metal sites and reduces adsorbate mobility to limit adsorption and reaction rate of ethylene and hydrogen. In order to observe heterogeneous catalytic reactions that occur well above ambient pressure and temperature that more closely

  4. Influence of the milling process on the structure and morphology of ZnAl_2O_4 and catalytic performance in the methyl transesterification reaction of soybean oil

    International Nuclear Information System (INIS)

    Feitosa, A.C.; Dantas, B.B.; Santana, A.; Costa, A.C.M.F.; Costa, D.B.

    2012-01-01

    This work aimed to evaluate the effect of milling time over the structure and morphology of ZnAl_2O_4, synthesized by combustion reaction, and study the effect of milled samples over the methyl transesterification reaction of soy bean oil. ZnAl_2O_4 was synthesizing, by means combustion reaction, using a electrical resistance plate. The powder was milled over 15, 30, 45 and 60 minutes and the samples were characterized by X-ray diffraction, scanning electron micrograph, particle size distribution and N_2 adsorption isotherms. Milling process promoted changes over the agglomerate size and textural characteristics of the samples. Catalytic tests were conducted at 160 deg C, with 1% of catalyst, with molar ratio oil:methanol of 1:6 and reaction time of 1 hour. According the results, the sample milled over 30 minutes showed the highest conversion. (author)

  5. 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.

  6. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    Science.gov (United States)

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  7. Anodically-grown TiO_2 nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Sacco, Adriano; Garino, Nadia; Lamberti, Andrea; Pirri, Candido Fabrizio; Quaglio, Marzia

    2017-01-01

    Highlights: • Anodically-grown TiO_2 nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO_2 nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO_2 NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  8. Anodically-grown TiO{sub 2} nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sacco, Adriano, E-mail: adriano.sacco@iit.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Garino, Nadia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Lamberti, Andrea, E-mail: andrea.lamberti@polito.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Pirri, Candido Fabrizio [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Quaglio, Marzia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy)

    2017-08-01

    Highlights: • Anodically-grown TiO{sub 2} nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO{sub 2} nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO{sub 2} NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  9. Fabrication and characterisation of gold nano-particle modified polymer monoliths for flow-through catalytic reactions and their application in the reduction of hexacyanoferrate

    International Nuclear Information System (INIS)

    Floris, Patrick; Twamley, Brendan; Nesterenko, Pavel N.; Paull, Brett; Connolly, Damian

    2014-01-01

    Polymer monoliths in capillary (100 μm i.d.) and polypropylene pipette tip formats (vol: 20 μL) were modified with gold nano-particles (AuNP) and subsequently used for flow-through catalytic reactions. Specifically, methacrylate monoliths were modified with amine-reactive monomers using a two-step photografting method and then reacted with ethylenediamine to provide amine attachment sites for the subsequent immobilisation of 4 nm, 7 nm or 16 nm AuNP. This was achieved by flushing colloidal suspensions of gold nano-particles through each aminated polymer monolith which resulted in a multi-point covalent attachment of gold via the lone pair of electrons on the nitrogen of the free amine groups. Field emission scanning electron microscopy and scanning capacitively coupled conductivity detection was used to characterise the surface coverage of AuNP on the monoliths. The catalytic activity of AuNP immobilised on the polymer monoliths in both formats was then demonstrated using the reduction of Fe(III) to Fe(II) by sodium borohydride as a model reaction by monitoring the reduction in absorbance of the hexacyanoferrate (III) complex at 420 nm. Catalytic activity was significantly enhanced on monoliths modified with smaller AuNP with almost complete reduction (95 %) observed when using monoliths agglomerated with 7 nm AuNPs. (author)

  10. Steam reformer with catalytic combustor

    Science.gov (United States)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  11. 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.

  12. N2O Catalytic Decomposition – from Laboratory Experiment to Industry Reactor

    Czech Academy of Sciences Publication Activity Database

    Obalová, L.; Jirátová, Květa; Karásková, K.; Chromčáková, Ž.

    2012-01-01

    Roč. 191, č. 1 (2012), s. 116-120 ISSN 0920-5861 R&D Projects: GA TA ČR TA01020336 Institutional support: RVO:67985858 Keywords : N2O * catalytic decomposition * fixed bed reactor Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.980, year: 2012

  13. 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.

  14. Iron-catalysed fluoroaromatic coupling reactions under catalytic modulation with 1,2-bis(diphenylphosphino)benzene.

    Science.gov (United States)

    Hatakeyama, Takuji; Kondo, Yoshiyuki; Fujiwara, Yu-Ichi; Takaya, Hikaru; Ito, Shingo; Nakamura, Eiichi; Nakamura, Masaharu

    2009-03-14

    A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.

  15. Efficient Catalytic Conversion of Ethanol to 1-Butanol via the Guerbet Reaction over Copper- and Nickel-Doped Porous

    NARCIS (Netherlands)

    Sun, Zhuohua; Vasconcelos, Anais Couto; Bottari, Giovanni; Stuart, Marc C. A.; Bonura, Giuseppe; Cannilla, Catia; Frusteri, Francesco; Barta, Katalin

    The direct conversion of ethanol to higher value 1-butanol is a catalytic transformation of great interest in light of the expected wide availability of bioethanol originating from the fermentation of renewable resources. In this contribution we describe several novel compositions of porous metal

  16. Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Horiuchi, Yoshihiro; Gnanadesikan, Vijay; Ohshima, Takashi; Masu, Hyuma; Katagiri, Kosuke; Sei, Yoshihisa; Yamaguchi, Kentaro; Shibasaki, Masakatsu

    2005-09-05

    The development of a direct catalytic asymmetric aldol-Tishchenko reaction and the nature of its catalyst are described. An aldol-Tishchenko reaction of various propiophenone derivatives with aromatic aldehydes was promoted by [LaLi3(binol)3] (LLB), and reactivity and enantioselectivity were dramatically enhanced by the addition of lithium trifluoromethanesulfonate (LiOTf). First, we observed a dynamic structural change of LLB by the addition of LiOTf using 13C NMR spectroscopy, electronspray ionization mass spectrometry (ESI-MS), and cold-spray ionization mass spectrometry (CSI-MS). X-ray crystallography revealed that the structure of the newly generated self-assembled complex was a binuclear [La2Li4(binaphthoxide)5] complex 6. A reverse structural change of complex 6 to LLB by the addition of one equivalent of Li2(binol) was also confirmed by ESI-MS and experimental results. The drastic concentration effects on the direct catalytic asymmetric aldol-Tishchenko reaction suggested that the addition of LiOTf to LLB generated an active oligomeric catalyst species.

  17. 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. © The Author(s) 2016.

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

    International Nuclear Information System (INIS)

    Xu, Ling; Wang, Chunhua; Guan, Jingqi

    2014-01-01

    Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH 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 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 2 with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH 2 within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH 2 shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction

  19. 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.

  20. The reaction of fish to light (laboratory experiments)

    International Nuclear Information System (INIS)

    De Potter, M.R.

    1993-01-01

    The results of the study on the title subject can contribute to the realization of decreasing the damage to sea trout, caused by cooling water input of thermal power plants and turbines of hydroelectric power plants. Trout can be diverted from the cooling water inlets by means of light screens. Bench-scale experiments were executed to analyze the impact of the rate of the water flow to the reaction of young sea trout (smolts) to light. Also the effectiveness of light bulbs and fluorescence lamps are compared. The smolts show a clear aversion to a small amount of light. For a high water flow and in standing water the aversion reaction to light is considerably smaller or absent

  1. SHORT COMMUNICATION CATALYTIC KINETIC ...

    African Journals Online (AJOL)

    IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...

  2. Memorable Experiences with Sad Music—Reasons, Reactions and Mechanisms of Three Types of Experiences

    Science.gov (United States)

    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. PMID:27300268

  3. Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

    Science.gov (United States)

    Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

    2018-03-01

    Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

  4. 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.

  5. High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

    Energy Technology Data Exchange (ETDEWEB)

    Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C6H11) and π-allyl C6H9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C6H9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C6H9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E2u mode of free benzene, which leads to catalysis. Linear C6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    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 −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

  7. 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.

  8. Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

    KAUST Repository

    Nolan, Steven Patrick

    2017-09-06

    The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After determining electronic and steric properties of these ligands, their properties were compared to those of [Pd(IPr)(cin)Cl]. The three palladium complexes were studied using DFT calculations to delineate their behaviour in the activation step leading to the putative 12-electron active catalyst. Experimentally, their catalytic activity in the Suzuki-Miyaura reaction involving a wide range of coupling partners (30 entries) at low catalyst loading was studied.

  9. 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)

  10. Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction.

    Science.gov (United States)

    Gönül, İlyas; Ay, Burak; Karaca, Serkan; Saribiyik, Oguz Yunus; Yildiz, Emel; Serin, Selahattin

    2017-01-01

    In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl 2 ]·2H 2 O (1) , [Co(L)Cl 2 (H 2 O) 2 ] (2) and [Ni(L)Cl 2 (H 2 O) 2 ] (3) , having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1 . The esterification of butanol gave butyl acetate with 100% selectivity.

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

    International Nuclear Information System (INIS)

    Fajardo, Humberto Vieira; Longo, Elson; Leite, Edson Roberto; Libanori, Rafael; Probst, Luiz Fernando Dias; Carreno, Neftali Lenin Villarreal

    2012-01-01

    In the present study, TiO 2 nano powder was partially coated with Y 2 O 3 precursors generated by a sol-gel modified route. The system of nanocoated particles formed an ultra thin structure on the TiO 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 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)

  12. 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.

  13. 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.

  14. 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. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Experimental and modeling study of high performance direct carbon solid oxide fuel cell with in situ catalytic steam-carbon gasification reaction

    Science.gov (United States)

    Xu, Haoran; Chen, Bin; Zhang, Houcheng; Tan, Peng; Yang, Guangming; Irvine, John T. S.; Ni, Meng

    2018-04-01

    In this paper, 2D models for direct carbon solid oxide fuel cells (DC-SOFCs) with in situ catalytic steam-carbon gasification reaction are developed. The simulation results are found to be in good agreement with experimental data. The performance of DC-SOFCs with and without catalyst are compared at different operating potential, anode inlet gas flow rate and operating temperature. It is found that adding suitable catalyst can significantly speed up the in situ steam-carbon gasification reaction and improve the performance of DC-SOFC with H2O as gasification agent. The potential of syngas and electricity co-generation from the fuel cell is also evaluated, where the composition of H2 and CO in syngas can be adjusted by controlling the anode inlet gas flow rate. In addition, the performance DC-SOFCs and the percentage of fuel in the outlet gas are both increased with increasing operating temperature. At a reduced temperature (below 800 °C), good performance of DC-SOFC can still be obtained with in-situ catalytic carbon gasification by steam. The results of this study form a solid foundation to understand the important effect of catalyst and related operating conditions on H2O-assisted DC-SOFCs.

  16. 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.

  17. Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO.

    Science.gov (United States)

    Raghunath, P; Lee, Yuan-Pern; Lin, M C

    2017-05-25

    The kinetics and mechanisms for the reaction of the Criegee intermediate CH 2 OO with HNO 3 and the unimolecular decomposition of its reaction product CH 2 (O)NO 3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO 3 CH 2 OOH* with internal energy ∼44 kcal mol -1 . A fragmentation of this excited intermediate produces CH 2 (O)NO 3 + OH with its transition state located 5.0 kcal mol -1 below that of the reactants. Further decomposition of CH 2 (O)NO 3 produces HCO + HNO 3 , forming a catalytic cycle for destruction of CH 2 OO by HNO 3 . The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N 2 ) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH 2 OO + HNO 3 at 295 K, 5.1 × 10 -10 cm 3 molecule -1 s -1 , agrees satisfactorily with the experimental value, (5.4 ± 1.0) × 10 -10 cm 3 molecule -1 s -1 . The predicted branching ratios at 295 K are 0.21 for the formation of NO 3 CH 2 OOH and 0.79 for CH 2 (O)NO 3 + OH at a pressure of 40 Torr (N 2 ), and 0.79 for the formation of NO 3 CH 2 OOH and 0.21 for CH 2 (O)NO 3 + OH at 760 Torr (N 2 ). This new catalytic conversion of CH 2 OO to HCO + OH by HNO 3 might have significant impact on atmospheric chemistry.

  18. Synthesis and Characterization of Benzimidazolium Salts as Novel Ionic Liquids and their Catalytic Behavior in the Reaction of Alkylation

    Institute of Scientific and Technical Information of China (English)

    Wei Guo HUANG; Bo CHEN; Yuan Yuan WANG; Li Yi DAI; Yong Kui SHAN

    2005-01-01

    A new series of ionic liquids have been prepared containing benzimidazolium cation (abbreviated as Bim). These salts were characterized by DSC, NMR, elemental analysis and thermogravimetric analysis. They showed different properties compared to imidazolium cation due to the introduction of benzene ring. The alkylation of benzene/diphenyl ether with 1-dodecene was carried in C4eBimBr-AlCl3 ionic liquids showing high catalytic activity when the mole ratio of C4eBimB:AlCl3 was 1:2.

  19. Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

    Science.gov (United States)

    Zhou, Tian

    Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

  20. Hydrodynamics and propulsion mechanism of self-propelled catalytic micromotors: model and experiment.

    Science.gov (United States)

    Li, Longqiu; Wang, Jiyuan; Li, Tianlong; Song, Wenping; Zhang, Guangyu

    2014-10-14

    The hydrodynamic behavior and propulsion mechanism of self-propelled micromotors are studied theoretically and experimentally. A hydrodynamic model to describe bubble growth and detachment is proposed to investigate the mechanism of a self-propelled conical tubular catalytic micromotor considering bubble geometric asymmetry and buoyancy force. The growth force caused by the growth of the bubble surface against the fluid is the driving force for micromotor motion. Also, the buoyancy force plays a primary role in bubble detachment. The effect of geometrical parameters on the micromotor velocity and drag force is presented. The bubble radius ratio is investigated for different micromotor radii to determine its hydrodynamic behavior during bubble ejection. The average micromotor velocity is found to be strongly dependent on the semi-cone angle, expelling frequency and bubble radius ratio. The semi-cone angle has a significant effect on the expelling frequency for conical tubular micromotors. The predicted results are compared to already existing experimental data for cylindrical micromotors (semi-cone angle δ = 0°) and conical micromotors. A good agreement is found between the theoretical calculation and experimental results. This model provides a profound explanation for the propulsion mechanism of a catalytic micromotor and can be used to optimize the micromotor design for its biomedical and environmental applications.

  1. Catalytic activity of hydrophobic Pt/C/PTFE catalysts of different PTFE content for hydrogen-water liquid exchange reaction

    International Nuclear Information System (INIS)

    Hu Sheng; Xiao Chengjian; Zhu Zuliang; Luo Shunzhong; Wang Heyi; Luo Yangming; Wang Changbin

    2007-01-01

    10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of Pt/C/PTFE catalysts decreases when the mass ratio of PTFE and Pt/C is 0.5:1, and their activity decreases when the mass ratio is 1:1. (authors)

  2. Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

    Science.gov (United States)

    Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

    2017-10-24

    Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

  3. 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.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jisu [Inje University, College of Pharmacy (Korea, Republic of); Cha, Song-Hyun; Cho, Seonho [Seoul National University, Department of Naval Architecture and Ocean Engineering (Korea, Republic of); Park, Youmie, E-mail: youmiep@inje.ac.kr [Inje University, College of Pharmacy (Korea, Republic of)

    2016-06-15

    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.

  6. A Ligand Structure-Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels-Alder Reactions

    NARCIS (Netherlands)

    Rosati, F.; Roelfes, J.G.

    A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder

  7. First catalytic hetero-Diels-Alder reaction of imidazole-2-thiones and in silico biological evaluation of the cycloadducts

    NARCIS (Netherlands)

    Eleftheriadis, Nikolaos; Samatidou, Evanthia; Neochoritis, Constantinos G.

    The Lewis acid-catalyzed Diels-Alder reactions of suitably substituted imidazole-2-thiones with dienes were studied. It was found that the electron density of the imidazole core influenced the reaction, since electron withdrawing groups led to the novel spiro-derivatives 2 whereas electron donating

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

    KAUST Repository

    Chaparala, Sree Vidya; Raj, Abhijeet; Chung, Suk-Ho

    2015-01-01

    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

  9. The reaction of fish to light (laboratory experiments)

    International Nuclear Information System (INIS)

    De Potter, M.R.

    1993-01-01

    The results of the study on the title subject can contribute to the realization of decreasing the damage to eel, caused by cooling water input of thermal power plants and turbines of hydroelectric power plants. Eel can be diverted from the cooling water inlets by means of light screens. Bench-scale experiments were executed to analyze the impact of the rate of the water flow to the reaction of eel to light. Also the effectiveness of light bulbs and fluorescence lamps are compared. Eel shows a clear aversion to a small amount of light. The diversion percentage decreases with a higher velocity of the water flow. Application of energy-efficient fluorescent lamps is considered to be a good option for diversion light systems

  10. Reactions on catalytic probe surface during oxygen plasma treatment of polyether sulphone: Reakcije na površini katalitične sonde med plazemsko obdelavo polieter sulfona:

    OpenAIRE

    Mozetič, Miran

    1998-01-01

    Experiments on the behavior of a nickel catalytic probe during activation of the surface of polyether sulphone in oxygen plasma are described. The temperature of the probe mounted 30 cm apart from inductively coupled RF oxygen plasma was measured for the case of empty dischaarge vessel and the case a sample with the dimensions of 8 cm x 1.2 cm x 0.4 cm was mounted in the middle of the discharge coil. It was found that both the maximum temperature and the first time derivative of the probe was...

  11. 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.

  12. 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.)

  13. Bifunctional Ag@Pd-Ag Nanocubes for Highly Sensitive Monitoring of Catalytic Reactions by Surface-Enhanced Raman Spectroscopy.

    Science.gov (United States)

    Li, Jumei; Liu, Jingyue; Yang, Yin; Qin, Dong

    2015-06-10

    We report a route to the facile synthesis of Ag@Pd-Ag nanocubes by cotitrating Na2PdCl4 and AgNO3 into an aqueous suspension of Ag nanocubes at room temperature in the presence of ascorbic acid and poly(vinylpyrrolidone). With an increase in the total titration volume, we observed the codeposition of Pd and Ag atoms onto the edges, corners, and side faces of the Ag nanocubes in a site-by-site fashion. By maneuvering the Pd/Ag ratio, we could optimize the SERS and catalytic activities of the Ag@Pd-Ag nanocubes for in situ SERS monitoring of the Pd-catalyzed reduction of 4-nitrothiophenol by NaBH4.

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

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jé ré mie D. A.; El Eter, Mohamad; Chen, Yin; Abou-Hamad, Edy; Basset, Jean-Marie

    2015-01-01

    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.

  15. A conserved residue of l-alanine dehydrogenase from Bacillus pseudofirmus, Lys-73, participates in the catalytic reaction through hydrogen bonding.

    Science.gov (United States)

    He, Guangzheng; Xu, Shujing; Wang, Shanshan; Zhang, Qing; Liu, Dong; Chen, Yuling; Ju, Jiansong; Zhao, Baohua

    2018-03-01

    A multiple protein sequence alignment of l-alanine dehydrogenases from different bacterial species revealed that five highly conserved amino acid residues Arg-15, Lys-73, Lys-75, His-96 and Asp-269 are potential catalytic residues of l-alanine dehydrogenase from Bacillus pseudofirmus OF4. In this study, recombinant OF4Ald and its mutants of five conserved residues were constructed, expressed in Escherichia coli, purified by His 6 -tag affinity column and gel filtration chromatography, structure homology modeling, and characterized. The purified protein OF4Ald displayed high specificity to l-alanine (15Umg -1 ) with an optimal temperature and pH of 40°C and 10.5, respectively. Enzymatic assay and activity staining in native gels showed that mutations at four conserved residue Arg-15, Lys-75, His-96 and Asp-269 (except residue Lys-73) resulted in a complete loss in enzymatic activity, which signified that these predicted active sites are indispensable for OF4Ald activity. In contrast, the mutant K73A resulted in 6-fold improvement in k cat /K m towards l-alanine as compared to the wild type protein. Further research of the residue Lys-73 substituted by various amino acids and structural modeling revealed that residue Lys-73 might be involved in the catalytic reaction of the enzyme by influencing the enzyme-substrate binding through the hydrogen-bonding interaction with conserved residue Lys-75. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.

    Science.gov (United States)

    Simlandy, Amit Kumar; Mukherjee, Santanu

    2017-05-05

    A highly enantioselective cascade sulfa-Michael/Julia-Kocienski olefination reaction between 2-mercaptobenzaldehydes and β-substituted vinyl PT-sulfones has been realized for the synthesis of 3,4-unsubstituted 2H-thiochromenes. This reaction, catalyzed by diphenylprolinol TMS ether, proceeds through an aromatic iminium intermediate and furnishes a wide range of 2-substiuted 2H-thiochromenes with excellent enantioselectivities (up to 99:1 er).

  17. The effect of defects on the catalytic activity of single Au atom supported carbon nanotubes and reaction mechanism for CO oxidation.

    Science.gov (United States)

    Ali, Sajjad; Fu Liu, Tian; Lian, Zan; Li, Bo; Sheng Su, Dang

    2017-08-23

    The mechanism of CO oxidation by O 2 on a single Au atom supported on pristine, mono atom vacancy (m), di atom vacancy (di) and the Stone Wales defect (SW) on single walled carbon nanotube (SWCNT) surface is systematically investigated theoretically using density functional theory. We determine that single Au atoms can be trapped effectively by the defects on SWCNTs. The defects on SWCNTs can enhance both the binding strength and catalytic activity of the supported single Au atom. Fundamental aspects such as adsorption energy and charge transfer are elucidated to analyze the adsorption properties of CO and O 2 and co-adsorption of CO and O 2 molecules. It is found that CO binds stronger than O 2 on Au supported SWCNT. We clearly demonstrate that the defected SWCNT surface promotes electron transfer from the supported single Au atom to O 2 molecules. On the other hand, this effect is weaker for pristine SWCNTs. It is observed that the high density of spin-polarized states are localized in the region of the Fermi level due to the strong interactions between Au (5d orbital) and the adjacent carbon (2p orbital) atoms, which influence the catalytic performance. In addition, we elucidate both the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms of CO oxidation by O 2 . For the LH pathway, the barriers of the rate-limiting step are calculated to be 0.02 eV and 0.05 eV for Au/m-SWCNT and Au/di-SWCNT, respectively. To regenerate the active sites, an ER-like reaction occurs to form a second CO 2 molecule. The ER pathway is observed on Au/m-SWCNT, Au/SW-SWCNT and Au/SWCNT in which the Au/m-SWCNT has a smaller barrier. The comparison with a previous study (Lu et al., J. Phys. Chem. C, 2009, 113, 20156-20160.) indicates that the curvature effect of SWCNTs is important for the catalytic property of the supported single Au. Overall, Au/m-SWCNT is identified as the most active catalyst for CO oxidation compared to pristine SWCNT, SW-SWCNT and di-SWCNT. Our findings give a

  18. 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.

  19. 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.

  20. Pd-bound functionalized mesoporous silica as active catalyst for Suzuki coupling reaction: Effect of OAcˉ, PPh3 and Clˉ ligands on catalytic activity

    Science.gov (United States)

    Das, Trisha; Uyama, Hiroshi; Nandi, Mahasweta

    2018-04-01

    Three new palladium catalysts, PdCat-I, PdCat-II and PdCat-III, immobilized over heterogeneous silica support have been synthesized using different ligands attached to the palladium precursor. The ligands that have been used in this study are acetate, triphenylphosphine and chloride in PdCat-I, PdCat-II and PdCat-III, respectively. The ligands have different effect on stability of the compounds and impart different oxidation states to the metal center. The materials have been characterized by powder X-ray diffraction, nitrogen adsorption-desorption studies, transmission electron microscopy, thermal analysis, and different spectroscopic techniques. The Pd-content of the samples have been determined by ICP-AES analysis. The materials have been used as catalysts for Suzuki coupling reaction of aryl halides with phenylboronic acid under mild conditions. A comparative study has been carried out to ascertain the effect of the nature of different ligands on the outcome of the catalytic reactions. Products have been identified and estimated by 1H NMR and gas chromatography. The results show that the best yields are obtained with the catalyst containing triphenylphosphine as the ligand in methanol. Such type of work to study the effect of ligand on Suzuki coupling reaction over functionalized mesoporous silica heterogeneous catalysts have not been carried out so far.

  1. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  2. A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

    Science.gov (United States)

    Silvestri, Michael G.; Dills, Charles E.

    1989-01-01

    Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

  3. Verification experiment of EPR paradox by (d, 2He) reaction

    International Nuclear Information System (INIS)

    Sakai, Hideyuki

    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 1 S 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 [ 1 S 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 [ 1 S 0 ] state of two protons by (d, 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 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 2 He decay are made selecting the subject events from very many background events. Monte Carlo simulation predicts the possibility to verify the

  4. 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

  5. Model Experiment of Thermal Runaway Reactions Using the Aluminum-Hydrochloric Acid Reaction

    Science.gov (United States)

    Kitabayashi, Suguru; Nakano, Masayoshi; Nishikawa, Kazuyuki; Koga, Nobuyoshi

    2016-01-01

    A laboratory exercise for the education of students about thermal runaway reactions based on the reaction between aluminum and hydrochloric acid as a model reaction is proposed. In the introductory part of the exercise, the induction period and subsequent thermal runaway behavior are evaluated via a simple observation of hydrogen gas evolution and…

  6. Tritium Labeled Gentamicin C: II.- Bioradiactive Degradation Products of Gentamicin by Catalytic H2O-3H Exchange Reaction

    International Nuclear Information System (INIS)

    Suarez, C.; Diaz, A.; Paz, D.; Jimeno, M. L.

    1992-01-01

    The main bio radioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + Cla) in basic form, are generated by N-demethylation in 3 - N and 6-N positions. Their structures were confirmed by 1HNMR and 13CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicin are in basic form. In contrast with gentamicin sulfate, hydrolytic sub products as gramine, genta mines, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1> Cla. Because of 6'-N-demethyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H2O-3H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicin were studied by strong and mild hydrolysis, and by methanolysis. (Author) 18 refs

  7. Tritium labeled Gentamicin C : II.- Bioradioactive products of Gentamicin by Catalytic H2O-3H exchange reaction

    International Nuclear Information System (INIS)

    Suarez, C.; Diaz, A.; Paz, D.; Jimeno, M.L.

    1992-01-01

    The main bioradioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + C1a) in basic form, are generated by N-dimethylations in 3 - N and 6'-N positions. Their structures were confirmed by HNMR and 13 CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicina are in basic form. In contrast with gentamicin sulfate, hydrolytic subproducts as garamine, gentamicine, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1 > C1a. Because of 6' -N-dimenthyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H 2 O- 3 H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicins were studied by stron and mild hydrolysis, and by methanolysis. (author)

  8. Stereoselective Synthesis of Highly Functionalized α-Diazo-β-ketoalkanoates via Catalytic Onepot Mukaiyama-Aldol Reactions

    Science.gov (United States)

    Zhou, Lei; Doyle, Michael P.

    2010-01-01

    Methyl diazoacetoacetate undergoes zinc triflate catalyzed condensation with a broad selection of aldehydes to produce δ-siloxy-α-diazo-β-ketoalkanoates in good yield, and δ-hydroxy-α-diazo-β-ketoalkanoates are formed with high diastereoselectivity in reactions with α-diazo-β-ketopentanoate promoted by dibutylboron triflate. PMID:20102172

  9. Catalytic depolymerization of lignin and woody biomass in supercritical Ethanol: influence of reaction temperature and feedstock : Influence of reaction temperature and feedstock

    NARCIS (Netherlands)

    Huang, X.; Atay, C.; Zhu, J.; Palstra, S.W.L.; Korányi, T.I.; Boot, M.D.; Hensen, E.J.M.

    2017-01-01

    The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while

  10. 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)

  11. Thermal and non-thermal lattice gas models for a dimer-trimer surface catalytic reaction: a Monte-Carlo simulation study

    International Nuclear Information System (INIS)

    Iqbal, K.; Khand, P.A.

    2012-01-01

    The kinetics of an irreversible dimer-trimer reaction of the type 2 A/sub 3/ +3 B/sub 2/ -- 6 AB by considering the precursor motion of the dimer (B/sub 2) on a square, as well as on a hexagonal surface, by using a Monte Carlo simulation have been studied. When the movement of precursors is limited to the first nearest neighborhood, the model gives reactive window widths of the order of 0.22 and 0.29 for the square and the hexagonal lattices, respectively, which are quite large compared to those predicted by the LH model. In our model, the reactive window width for a square lattice increases significantly as compared to that for the LH models of the same system on square and hexagonal lattices. The width of the reactive region increases when the precursor motion is extended to the second and the third nearest neighborhood. The continuous transition disappears when the precursor motion is extended to the third nearest neighborhood. The diffusion of B atoms does not change the situation qualitatively for both the precursor and the LH models. However, desorption of the dimer changes the situation significantly; i.e., the width of the reactive window shows an exponential growth with respect to the desorption probability of the dimer for both the precursor and the LH models. In our opinion, the inclusion of precursors in the LH model of the dimer-trimer reactions leads to a better and more realistic description of the heterogeneous catalytic reactions. Consequently, further numerical and theoretical activity in this field will be very useful for understanding complex heterogeneous reactions. (orig./A.B.)

  12. Reaction mechanisms and evaluation of effective process operation for catalytic oxidation and coagulation by ferrous solution and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Moon, H.J.; Kim, Y.M. [Dept. of Environmental Engineering, Sangmyung Univ., Cheonan (Korea); Bae, W.K. [Dept. of Civil and Environmental Engineering, Hanyang Univ., Ansan, Kyounggi (Korea)

    2003-07-01

    This research was carried out to evaluate the removal efficiencies of COD{sub cr} and colour for the dyeing wastewater by ferrous solution and the different dosage of H{sub 2}O{sub 2} in Fenton process. In the case of H{sub 2}O{sub 2} divided dosage, 7:3 was more effective than 3:7 to remove COD{sub cr} and colour. The results showed that COD was mainly removed by Fenton coagulation, where the ferric ions are formed in the initial step of Fenton reaction. On the other hand colour was removed by Fenton oxidation rather than Fenton coagulation. This paper also aims at pursuing to investigate the effective removal mechanisms using ferrous ion coagulation, ferric ion coagulation and Fenton oxidation process. The removal mechanism of COD{sub cr} and colour was mainly coagulation by ferrous ion, ferric ion and Fenton oxidation. The removal efficiencies were dependent on the ferric ion amount at the beginning of the reaction. However the final removal efficiency of COD and colour was in the order of Fenton oxidation, ferric ion coagulation and ferrous ion coagulation. The reason of the highest removal efficiency by Fenton oxidation can be explained by the chain reactions with ferrous solution, ferric ion and hydrogen peroxide. (orig.)

  13. 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.

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

    International Nuclear Information System (INIS)

    Lee, Minjae; Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B.

    2014-01-01

    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 2 and O 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

  15. Session 4: Study of alkyl-aromatics hydrodealkylation reaction to orient the production of benzene from the catalytic reforming process

    Energy Technology Data Exchange (ETDEWEB)

    Toppi, S.; Thomas, C.; Sayag, C.; Brodzki, D.; Djega-Mariadassou, G. [Universite Pierre et Marie Curie, Lab. de Reactivite de Surface, UMR CNRS 7609, 75 - Paris (France); Toppi, S.; Travers, C.; Le Peltier, F. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France)

    2004-07-01

    Due to more stringent environmental constraints, the benzene content in the gasoline decreases regularly and has been fixed to 1% since January 2001. In the same time, the demand in aromatics, benzene, toluene, and xylenes, for the petrochemistry continuously increases. The aim of this work is to study the hydrodealkylation reactions and particularly the benzene formation under reforming operating conditions, with the bifunctional industrial catalyst. It is, therefore, of great importance to determine the role of each function of the catalyst involved in the benzene production in order to orient the reaction by modification of the catalyst. n-propylbenzene transformation was investigated on each family of model catalysts and allowed us to propose a detailed scheme for the reaction on acidic and metallic sites. The identified reactions are: - on metallic sites: dehydrogenation, cyclisation and hydrogenolysis A detailed reaction scheme for this transformation has already been proposed involving the formation of cyclisation products and the existence of a common reactive adsorbate for the indene compounds and ethylbenzene; - on acidic sites: dehydrogenation, isomerization and cracking. The study of the cracking reactions coupled with measurements of the acidity of the catalyst, shows that benzene is the preferentially formed cracking product, on the Broensted sites of the catalyst, through a carbo-cationic mechanism. Conversely, ethylbenzene and toluene are formed through a 'radical' mechanism over the Lewis acid sites of alumina. As far as the cracking reaction leading to benzene is concerned, two compulsory steps were pointed out: the first one is the isomerization of n-propylbenzene to iso-propylbenzene, and the second one is the cracking of iso-propylbenzene into benzene. The increase of strong Broensted acidity over model acidic catalysts, has been correlated with a strong increase of the benzene formation rate, emphasizing the role of strong Broensted

  16. Leprosy reactions in postelimination stage: the Bangladesh experience.

    Science.gov (United States)

    Mowla, M R; Ara, S; Mizanur Rahman, A F M; Tripura, S P; Paul, S

    2017-04-01

    Leprosy reactions are immunologically mediated conditions and a major cause of disability before, during and after multidrug therapy (MDT). Little data have been published on the epidemiology of leprosy reactions in Bangladesh. To describe the pattern and prevalence of leprosy reactions in the postelimination stage. A descriptive retrospective cross-sectional study was carried out in Chittagong Medical College Hospital using the registered records of patients in the period between 2004 and 2013. Of the 670 patients with leprosy, 488 (73.38%) were males and 182 (27.37%) were females. The prevalence of reaction was in 300 (44.78%) patients with a male:female ratio of 3.55 : 1. The age-specific cumulative reaction cases at >40 years were 115 (38.33%) among all age groups. The prevalence of reaction was found to be in 166 (55.33%) patients for the reversal reaction, 49 (16.57%) for the erythema nodosum leprosum (ENL) and 85 (28.33%) for the neuritis. Borderline tuberculoid was most common (106, 35.33%)in the reversal reaction group, while lepromatous leprosy was most common (37, 12.33%) in ENL group. More than half of the patients (169, 56.33%) had reactions at the time of presentations, while 85 (28.33%) and 46 (15.33%) patients developed reaction during and after MDT, respectively. The reversal reaction group presented with ≥six skin lesions in 96 (57.83%) patients and ≥two nerve function impairments (NFIs) in 107 (64.46%) patients. The ENL was present chiefly as papulo-nodular lesions in 45 (91.84%) patients followed by pustule-necrotic lesions in four (8.16%), neuritis in 33 (67.35%), fever in 24 (48.98%), lymphadenitis in six (12.24%), arthritis in five (10.20%) and iritis in two (4.08%). Bacterial index ≥3 had been demonstrated in 34 (60.71%) patients in ENL group. The incidence of leprosy reaction seemed to be more than three times common in borderline tuberculoid (52.33%) group than in lepromatous leprosy (14%) group. Reactions with NFI and disability

  17. Aromatic residues located close to the active center are essential for the catalytic reaction of flap endonuclease-1 from hyperthermophilic archaeon Pyrococcus horikoshii.

    Science.gov (United States)

    Matsui, Eriko; Abe, Junko; Yokoyama, Hideshi; Matsui, Ikuo

    2004-04-16

    Flap endonuclease-1 (FEN-1) possessing 5'-flap endonuclease and 5'-->3' exonuclease activity plays important roles in DNA replication and repair. In this study, the kinetic parameters of mutants at highly conserved aromatic residues, Tyr33, Phe35, Phe79, and Phe278-Phe279, in the vicinity of the catalytic centers of FEN-1 were examined. The substitution of these aromatic residues with alanine led to a large reduction in kcat values, although these mutants retained Km values similar to that of the wild-type enzyme. Notably, the kcat of Y33A and F79A decreased 333-fold and 71-fold, respectively, compared with that of the wild-type enzyme. The aromatic residues Tyr33 and Phe79, and the aromatic cluster Phe278-Phe279 mainly contributed to the recognition of the substrates without the 3' projection of the upstream strand (the nick, 5'-recess-end, single-flap, and pseudo-Y substrates) for the both exo- and endo-activities, but played minor roles in recognizing the substrates with the 3' projection (the double flap substrate and the nick substrate with the 3' projection). The replacement of Tyr33, Phe79, and Phe278-Phe279, with non-charged aromatic residues, but not with aliphatic hydrophobic residues, recovered the kcat values almost fully for the substrates without the 3' projection of the upstream strand, suggesting that the aromatic groups of Tyr33, Phe79, and Phe278-Phe279 might be involved in the catalytic reaction, probably via multiple stacking interactions with nucleotide bases. The stacking interactions of Tyr33 and Phe79 might play important roles in fixing the template strand and the downstream strand, respectively, in close proximity to the active center to achieve the productive transient state leading to the hydrolysis.

  18. Tritium-tracer study of catalytic hydrogenation reaction of ethylene on Ni, Pt and Ni-Pt

    International Nuclear Information System (INIS)

    Matsuyama, M.; Yasuda, Y.; Takeuchi, T.

    1978-01-01

    The influence of the pressure of tritiated hydrogen on the rate of the formation of tritiated ethylene, X, and that of tritiated ethane, Z, in the hydrogenation reaction of ethylene on Ni, Pt and Ni-Pt (1:1) alloy catalysts was investigated. The ratio of the rate of the exchange to that of the hydrogenation, selectivity X/Z, decreased markedly with the increase in the pressure of the tritiated hydrogen and the order of X/Z was Ni>Ni-Pt>Pt. These results were interpreted in terms of the difference in the amount of chemisorbed tritium on each metal catalyst. (orig.) [de

  19. Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system.

    Science.gov (United States)

    Huang, Xiaoqiang; Luo, Shipeng; Burghaus, Olaf; Webster, Richard D; Harms, Klaus; Meggers, Eric

    2017-10-01

    We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.

  20. 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.

  1. Direct synthesis of acid-base bifunctionalized hexagonal mesoporous silica and its catalytic activity in cascade reactions.

    Science.gov (United States)

    Shang, Fanpeng; Sun, Jianrui; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-03-01

    A series of efficient acid-base bifunctionalized hexagonal mesoporous silica (HMS) catalysts contained aminopropyl and propanesulfonic acid have been synthesized through a simple co-condensation by protection of amino group. The results of small-angle XRD, TEM, and N(2) adsorption-desorption measurements show that the resultant materials have mesoscopic structures. X-ray photoelectron spectroscopies, elemental analysis (EA), back titration, (29)Si NMR and (13)C NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The resultant catalysts exhibit excellent acid-basic properties, which make them possess high activity for one-pot deacetalization-Knoevenagel and deacetalization-nitroaldol (Henry) reactions. Copyright © 2010 Elsevier Inc. All rights reserved.

  2. Catalytic activity in reactions of isotopic exchange of carbon monoxide and adsorption properties of catalysts on zinc oxide base

    International Nuclear Information System (INIS)

    Mikheeva, T.M.; Kasatkina, L.A.; Volynkina, A.Ya.

    1987-01-01

    Activity of different zinc oxide samples in reaction of CO homomolecular isotopic exchnge (HMIE) ( 13 C 18 O+ 12 C 16 O= 13 C 16 O+ 12 C 18 O), CO adsorption on ZnO and isotopic exchange between adsorbed and gaseous CO are investigated. The most active is ZnO sample prepared from ZnCO 3 . Quantitative ratio between different with respect to surface strength molecules of adsorbed CO are experimentally determined. It is shown that by increase of ZnO time contact with CO the quantity of adsorbed CO(N σ/0 ), capable of fast exchange with a gaseous phase, is reduced and the quantity of slowly exchanged adsorbed CO is increased. Correlation between decrease of N σ/0 and decrease of CO HMIE with the catalyst holding time in CO medium is stated

  3. Multinational experience with hypersensitivity drug reactions in Latin America.

    Science.gov (United States)

    Jares, Edgardo José; Sánchez-Borges, Mario; Cardona-Villa, Ricardo; Ensina, Luis Felipe; Arias-Cruz, Alfredo; Gómez, Maximiliano; Barayazarra, Susana; Bernstein, Jonathan A; Serrano, Carlos D; Cuello, Mabel Noemi; Morfin-Maciel, Blanca María; De Falco, Alicia; Cherrez-Ojeda, Iván

    2014-09-01

    Epidemiologic drug allergy data from Latin America are scarce, and there are no studies on specific procedures focusing on this topic in Latin America. To assess the clinical characteristics and management of hypersensitivity drug reactions in different Latin American countries. An European Network of Drug Allergy questionnaire survey was implemented in 22 allergy units in 11 Latin American countries to report on consecutive patients who presented with a suspected hypersensitivity drug reaction. Each unit used its own protocols to investigate patients. Included were 868 hypersensitivity drug reactions in 862 patients (71% of adults and elderly patients were women and 51% of children were girls, P = .0001). Children presented with less severe reactions than adults and elderly patients (P Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

  4. Roles of the redox-active disulfide and histidine residues forming a catalytic dyad in reactions catalyzed by 2-ketopropyl coenzyme M oxidoreductase/carboxylase.

    Science.gov (United States)

    Kofoed, Melissa A; Wampler, David A; Pandey, Arti S; Peters, John W; Ensign, Scott A

    2011-09-01

    NADPH:2-ketopropyl-coenzyme M oxidoreductase/carboxylase (2-KPCC), an atypical member of the disulfide oxidoreductase (DSOR) family of enzymes, catalyzes the reductive cleavage and carboxylation of 2-ketopropyl-coenzyme M [2-(2-ketopropylthio)ethanesulfonate; 2-KPC] to form acetoacetate and coenzyme M (CoM) in the bacterial pathway of propylene metabolism. Structural studies of 2-KPCC from Xanthobacter autotrophicus strain Py2 have revealed a distinctive active-site architecture that includes a putative catalytic triad consisting of two histidine residues that are hydrogen bonded to an ordered water molecule proposed to stabilize enolacetone formed from dithiol-mediated 2-KPC thioether bond cleavage. Site-directed mutants of 2-KPCC were constructed to test the tenets of the mechanism proposed from studies of the native enzyme. Mutagenesis of the interchange thiol of 2-KPCC (C82A) abolished all redox-dependent reactions of 2-KPCC (2-KPC carboxylation or protonation). The air-oxidized C82A mutant, as well as wild-type 2-KPCC, exhibited the characteristic charge transfer absorbance seen in site-directed variants of other DSOR enzymes but with a pK(a) value for C87 (8.8) four units higher (i.e., four orders of magnitude less acidic) than that for the flavin thiol of canonical DSOR enzymes. The same higher pK(a) value was observed in native 2-KPCC when the interchange thiol was alkylated by the CoM analog 2-bromoethanesulfonate. Mutagenesis of the flavin thiol (C87A) also resulted in an inactive enzyme for steady-state redox-dependent reactions, but this variant catalyzed a single-turnover reaction producing a 0.8:1 ratio of product to enzyme. Mutagenesis of the histidine proximal to the ordered water (H137A) led to nearly complete loss of redox-dependent 2-KPCC reactions, while mutagenesis of the distal histidine (H84A) reduced these activities by 58 to 76%. A redox-independent reaction of 2-KPCC (acetoacetate decarboxylation) was not decreased for any of the

  5. Flow injection determination of hydrogen peroxide using catalytic effect of cobalt(II) ion on a dye formation reaction.

    Science.gov (United States)

    Kurihara, Makoto; Muramatsu, Miyuki; Yamada, Mari; Kitamura, Naoya

    2012-07-15

    A novel flow injection photometric method was developed for the determination of hydrogen peroxide in rainwater. This method is based on a cobalt(II)-catalyzed oxidative coupling of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3,5-dimethoxyaniline (DAOS) as a modified Trinder's reagent to produce intensely colored dye (λ(max)=530nm) in the presence of hydrogen peroxide at pH 8.4. In this method, 1,2-dihydroxy-3,5-benzenedisulfonic acid (Tiron) acted as an activator for the cobalt(II)-catalyzed reaction and effectively increased the peak height for hydrogen peroxide. The linear calibration graphs were obtained in the hydrogen peroxide concentration range 5×10(-8) to 2.2×10(-6)mol dm(-3) at a sampling rate of 20h(-1). The relative standard deviations for ten determinations of 2.2×10(-6) and 2×10(-7)mol dm(-3) hydrogen peroxide were 1.1% and 3.7%, respectively. The proposed method was successfully applied to the determination of hydrogen peroxide in rainwater samples and the analytical results agreed fairly well with the results obtained by different two reference methods; peroxidase method and hydrogen peroxide electrode method. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Synthesis of ACNT on quartz substrate with catalytic decomposition reaction from Cinnamomum camphora by using FC-CVD method

    Science.gov (United States)

    Wulan, Praswasti P. D. K.; Silaen, Toni Partogi Johannes

    2017-05-01

    Camphor is a renewable carbon source that can be used as raw material for synthesizing Carbon Nanotube (CNT). Camphor is a substance that can be found on the Cinnamomum camphora tree. In this research, the method used to synthesize Aligned Carbon Nanotube (ACNT) from camphor is Floating Catalyst Chemical Vapor Deposition (FC-CVD) with Ferrocene as catalyst at temperature of 800°C, hydrogen gas as the co-reactant and argon gas as carrier gas. This method is the most popular method of synthesizing ACNT which oriented and have a high density. Camphor decomposes into benzene, toluene, and xylene at a temperature of 800°C. By using GC-FID for characterization test, the results showed decomposition at a temperature of 800°C camphor dominated by benzene with a concentration of 92.422 to 97.656%. The research was conducted by varying the flow rate of carrier gas such as argon at 40, 55, 70, 85 and 100 mL / min at a temperature of 800°C for 60 minutes of reaction time. Argon carrier gas flow rate of 70 mL / min producing CNT with the highest yield, but this is not followed by best quality of CNT. CNT with best quality is obtained at a flow rate of argon carrier gas at 55 mL / min based on test results characterization by using SEM, EDX, Mapping, and RAMAN Spectroscopy. This research have not obtained CNT with aligned structured.

  7. Efficient Construction of Energetic Materials via Nonmetallic Catalytic Carbon-Carbon Cleavage/Oxime-Release-Coupling Reactions.

    Science.gov (United States)

    Zhao, Gang; He, Chunlin; Yin, Ping; Imler, Gregory H; Parrish, Damon A; Shreeve, Jean'ne M

    2018-03-14

    The exploitation of C-C activation to facilitate chemical reactions is well-known in organic chemistry. Traditional strategies in homogeneous media rely upon catalyst-activated or metal-mediated C-C bonds leading to the design of new processes for applications in organic chemistry. However, activation of a C-C bond, compared with C-H bond activation, is a more challenging process and an underdeveloped area because thermodynamics does not favor insertion into a C-C bond in solution. Carbon-carbon bond cleavage through loss of an oxime moiety has not been reported. In this paper, a new observation of self-coupling via C-C bond cleavage with concomitant loss of oxime in the absence of metals (either metal-complex mediation or catalysis) results in dihydroxylammonium 5,5-bistetrazole-1,10-diolate (TKX-50) as well as N, N'-([3,3'-bi(1,2,4-oxadiazole)]-5,5'-diyl)dinitramine, a potential candidate for a new generation of energetic materials.

  8. Sub-4 nm PtZn Intermetallic Nanoparticles for Enhanced Mass and Specific Activities in Catalytic Electrooxidation Reaction

    International Nuclear Information System (INIS)

    Qi, Zhiyuan

    2017-01-01

    Atomically ordered intermetallic nanoparticles (iNPs) have sparked considerable interest in fuel cell applications by virtue of their exceptional electronic and structural properties. However, the synthesis of small iNPs in a controllable manner remains a formidable challenge because of the high temperature generally required in the formation of intermetallic phases. Here in this paper we report a general method for the synthesis of PtZn iNPs (3.2 ± 0.4 nm) on multiwalled carbon nanotubes (MWNT) via a facile and capping agent free strategy using a sacrificial mesoporous silica (mSiO 2 ) shell. The as-prepared PtZn iNPs exhibited ca. 10 times higher mass activity in both acidic and basic solution toward the methanol oxidation reaction (MOR) compared to larger PtZn iNPs synthesized on MWNT without the mSiO 2 shell. Density functional theory (DFT) calculations predict that PtZn systems go through a “non-CO” pathway for MOR because of the stabilization of the OH* intermediate by Zn atoms, while a pure Pt system forms highly stable COH* and CO* intermediates, leading to catalyst deactivation. Experimental studies on the origin of the backward oxidation peak of MOR coincide well with DFT predictions. Moreover, the calculations demonstrate that MOR on smaller PtZn iNPs is energetically more favorable than larger iNPs, due to their high density of corner sites and lower-lying energetic pathway. Therefore, smaller PtZn iNPs not only increase the number but also enhance the activity of the active sites in MOR compared with larger ones. This work opens a new avenue for the synthesis of small iNPs with more undercoordinated and enhanced active sites for fuel cell applications.

  9. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces

    Science.gov (United States)

    Liu, Da-Jiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental

  10. Visible-light promoted catalytic activity of dumbbell-like Au nanorods supported on graphene/TiO2 sheets towards hydrogenation reaction

    Science.gov (United States)

    Dai, Yunqian; Zhu, Mingyun; Wang, Xiaotian; Wu, Yanan; Huang, Chengqian; Fu, Wanlin; Meng, Xiangyu; Sun, Yueming

    2018-06-01

    In this work, the rationally-designed sharp corners on Au nanorods tremendously improved the catalytic activity, particularly in the presence of visible light irradiation, towards the hydrogenation of 4-nitrophenol to 4-aminophenol. A strikingly increased rate constant of 50.6 g‑1 s‑1 L was achieved in M-Au-3, which was 41.8 times higher than that of parent Au nanorods under dark conditions. The enhanced activities were proportional to the extent of the protruding sharp corners. Furthermore, remarkably enhanced activities were achieved in novel ternary Au/RGO/TiO2 sheets, which were endowed with a 52.0 times higher rate constant than that of straight Au nanorods. These remarkably enhanced activities were even higher than those of previously reported 3–5 nm Au and 3 nm Pt nanoparticles. It was systematically observed that there are three aspects to the synergistic effects between Au and RGO sheets: (i) electron transfer from RGO to Au, (ii) a high concentration of p-nitrophenol close to dumbbell-like Au nanorods on RGO sheets, and (iii) increased local reaction temperature from the photothermal effect of both dumbbell-like Au nanorods and RGO sheets.

  11. Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies

    Directory of Open Access Journals (Sweden)

    Qingwen Wang

    2013-03-01

    Full Text Available Catalytic refining of bio-oil by reacting with olefin/alcohol over solid acids can convert bio-oil to oxygen-containing fuels. Reactivities of groups of compounds typically present in bio-oil with 1-octene (or 1-butanol were studied at 120 °C/3 h over Dowex50WX2, Amberlyst15, Amberlyst36, silica sulfuric acid (SSA and Cs2.5H0.5PW12O40 supported on K10 clay (Cs2.5/K10, 30 wt. %. These compounds include phenol, water, acetic acid, acetaldehyde, hydroxyacetone, d-glucose and 2-hydroxymethylfuran. Mechanisms for the overall conversions were proposed. Other olefins (1,7-octadiene, cyclohexene, and 2,4,4-trimethylpentene and alcohols (iso-butanol with different activities were also investigated. All the olefins and alcohols used were effective but produced varying product selectivities. A complex model bio-oil, synthesized by mixing all the above-stated model compounds, was refined under similar conditions to test the catalyst’s activity. SSA shows the highest hydrothermal stability. Cs2.5/K10 lost most of its activity. A global reaction pathway is outlined. Simultaneous and competing esterification, etherfication, acetal formation, hydration, isomerization and other equilibria were involved. Synergistic interactions among reactants and products were determined. Acid-catalyzed olefin hydration removed water and drove the esterification and acetal formation equilibria toward ester and acetal products.

  12. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed; Merzougui, Belabbes A.; Akinpelu, Akeem; Laoui, Tahar; Hedhili, Mohamed N.; Swain, Greg M.; Shao, Minhua

    2014-01-01

    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.

  13. 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.

  14. Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

    Science.gov (United States)

    Plaga, W; Frank, R; Knappe, J

    1988-12-15

    Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

  15. Adverse reactions in voluntary whole blood donors: Experience at ...

    African Journals Online (AJOL)

    Background: Whole blood donation, generally considered as a safe procedure, may be sometimes associated with adverse reactions and injuries of variable severity during or after the blood donation process. There are few reports of adverse events related to blood donation in the Democratic Republic of Congo.

  16. 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. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. First Nuclear Reaction Experiment with Stored Radioactive 56Ni Beam and Internal Hydrogen and Helium Targets

    NARCIS (Netherlands)

    Egelhof, P.; Bagchi, Soumya; Csatlós, M.; Dillmann, I.; Dimopoulou, C.; Furuno, T; Geissel, H.; Gernhauser, R.; Kalantar-Nayestanaki, Nasser; Kuilman, M.; Mahjour-Shafiei, M.; Najafi, M.A.; Rigollet, C.; Streicher, B.

    2014-01-01

    The investigation of light-ion induced direct reactions using stored and cooled radioactive beams, interacting with internal targets of storage rings, can lead to substantial advantages over external target experiments, in particular for direct reaction experiments in inverse kinematics at very low

  18. 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

  19. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  20. The ReactorSTM: Atomically resolved scanning tunneling microscopy under high-pressure, high-temperature catalytic reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Herbschleb, C. T.; Tuijn, P. C. van der; Roobol, S. B.; Navarro, V.; Bakker, J. W.; Liu, Q.; Stoltz, D.; Cañas-Ventura, M. E.; Verdoes, G.; Spronsen, M. A. van; Bergman, M.; Crama, L.; Taminiau, I.; Frenken, J. W. M., E-mail: frenken@physics.leidenuniv.nl [Huygens-Kamerlingh Onnes Laboratory, Leiden University, P.O. box 9504, 2300 RA Leiden (Netherlands); Ofitserov, A.; Baarle, G. J. C. van [Leiden Probe Microscopy B.V., J.H. Oortweg 21, 2333 CH Leiden (Netherlands)

    2014-08-15

    To enable atomic-scale observations of model catalysts under conditions approaching those used by the chemical industry, we have developed a second generation, high-pressure, high-temperature scanning tunneling microscope (STM): the ReactorSTM. It consists of a compact STM scanner, of which the tip extends into a 0.5 ml reactor flow-cell, that is housed in a ultra-high vacuum (UHV) system. The STM can be operated from UHV to 6 bars and from room temperature up to 600 K. A gas mixing and analysis system optimized for fast response times allows us to directly correlate the surface structure observed by STM with reactivity measurements from a mass spectrometer. The in situ STM experiments can be combined with ex situ UHV sample preparation and analysis techniques, including ion bombardment, thin film deposition, low-energy electron diffraction and x-ray photoelectron spectroscopy. The performance of the instrument is demonstrated by atomically resolved images of Au(111) and atom-row resolution on Pt(110), both under high-pressure and high-temperature conditions.

  1. Women's Experiences of Social Reactions From Informal and Formal Supports: Using a Modified Administration of the Social Reactions Questionnaire.

    Science.gov (United States)

    DePrince, Anne P; Dmitrieva, Julia; Gagnon, Kerry L; Srinivas, Tejaswinhi

    2017-11-01

    A growing literature links social reactions to disclosures of intimate violence to posttraumatic outcomes. The Social Reactions Questionnaire (SRQ), a widely used measure developed to assess social reactions, asks about reactions received from people generally. The ability to examine the impact of social reactions from specific groups of people-such as criminal justice personnel versus community-based providers-has become increasingly more important from both research and practice perspectives. For example, as sexual assault responses nationally have relied on community-coordinated models that involve both criminal justice and community-based systems, tools are lacking to systematically assess the impact of social reactions from criminal justice personnel and community-based providers on survivors. Using the SRQ, the current study asked women to report separately on reactions received from criminal justice personnel, community-based providers, and informal supports. We recruited a diverse community sample of women ( N = 228, ages 18-63, 19% lesbian/bisexual, 44% ethnic minority) who experienced a sexual assault in the previous year and disclosed to the criminal justice system and/or a community-based provider. Multilevel analyses revealed considerable variability in the social reactions reported by women across criminal justice personnel, community-based providers, and informal supports. Analyses supported a seven-factor structure for the SRQ when the measure is yoked to particular experiences of disclosure, in this case to criminal justice personnel, community-based providers, or informal supports. The utility of this modified administration and scoring of the SRQ and the importance of considering reactions across different groups are described.

  2. Neutral current induced reactions in the Gargamelle experiment

    International Nuclear Information System (INIS)

    Doninck, W. van

    1976-07-01

    In the heavy liquid bubble chamber Gargamelle at CERN, 3 candidates are found for the pure leptonic neutral current process anti upsilonsub(μ)e - → anti upsilon sub(μ)e - . For the inclusive semileptonic reactions upsilon N → μ - X and anti upsilon N → μ + X the ratios of the neutral current to the charged current cross sections are measured to be Rsub(upsilon) = 0.25 +- 0.04 and Rsub(anti upsilon) = 0.56 +- 0.09. These inclusive results differ from the prediction of parity conserving models by more than 3 standard deviations. All three reactions are compatible with the Weinberg-Salam-model and a value of sin 2 THETAsub(ω) near 0.3. (BJ) [de

  3. Notable light-free catalytic activity for pollutant destruction over flower-like BiOI microspheres by a dual-reaction-center Fenton-like process.

    Science.gov (United States)

    Wang, Liang; Yan, Dengbiao; Lyu, Lai; Hu, Chun; Jiang, Ning; Zhang, Lili

    2018-10-01

    BiOI is widely used as photocatalysts for pollutant removal, water splitting, CO 2 reduction and organic transformation due to its excellent photoelectric properties. Here, we report for the first time that a light-free catalyst consisting of the flower-like BiOI microspheres (f-BiOI MSs) exposing (1 0 1) and (1 1 0) crystal planes prepared by a hydrothermal method in ethylene glycol environment can rapidly eliminate the refractory BPA within only ∼3 min through a Fenton-like process. The reaction activity is ∼190 times higher than that of the conventional Fenton catalyst Fe 2 O 3 . A series of characterizations and experiments reveal the formation of the dual reaction centers on f-BiOI MSs. The electron-rich O centers efficiently reduce H 2 O 2 to OH, while the electron-poor oxygen vacancies capture electrons from the adsorbed pollutants and divert them to the electron-rich area during the Fenton-like reactions. By these processes, pollutants are degraded and mineralized quickly in a wide pH range. Our findings address the problems of the classical Fenton reaction and are useful for the development of efficient Fenton-like catalysts through constructing dual reaction centers. Copyright © 2018 Elsevier Inc. All rights reserved.

  4. The Enhancement of the Selectivity of Complex Reactions by a Catalytic Membrane Reactor -Ethylene Oxidation Over a Ag Catalyst Supported in a Ceramic Membrane-

    OpenAIRE

    馮, 臨; 小林, 正義; Lin, FENG; Masayoshi, KOBAYASHI

    1991-01-01

    This research demonstrated that, using a membrane reactor consisting of a tubular, microporous, glass-ceramic membrane, it is possible to achieve selective oxidation of ethylene to ethylene oxide with an Ag catalyst. In experiments which a reaction temperature range of 115 to 300℃ and a contact time of 1.5 to 5 seconds, resulting data illustrated the following characteristics of this membrane reactor : 1) compared with a classic tubular reactor, the selectivity of ethylene oxide is increased ...

  5. Comparative study on catalytic behavior of polynuclear Mg-Mo-complex and FeMo-co-factor of nitrogenase in reactions with C2H2, N2 and CO

    International Nuclear Information System (INIS)

    Bardina, N.V.; Bazhenova, T.A.; Petrova, G.N.; Shilova, A.K.; Shilov, A.E.

    2006-01-01

    Catalytic reduction kinetics of C 2 H 2 in the presence of the Mg-Mo-cluster {[Mg 2 Mo 8 O 22 (MeO) 6 (MeOH) 4 ] 2- [Mg(MeOH) 6 ] 2+ }·6MeOH 1 is studied. Several interdependent coordinating centers are active in reference to substrates and inhibitors in the polynuclear Mg-Mo-complex, as in the reduced by europium amalgam (μ 6 -N)MoFe 7 S 9 ·homocitrate (FeMoco, 2). Comparison of regularities in reduction mechanism of C 2 H 2 , N 2 and CO with the participation of synthetic polynuclear complex 1 and natural cluster 2 is conducted. Regularities of the studied reactions in the systems involving natural catalytic cluster FeMoco and the synthetic Mg-Mo-complex modelling of its effect are noted to be similar. The main variations the systems show as regards to the reaction with molecular nitrogen [ru

  6. Benchmark experiments at ASTRA facility on definition of space distribution of 235U fission reaction rate

    International Nuclear Information System (INIS)

    Bobrov, A. A.; Boyarinov, V. F.; Glushkov, A. E.; Glushkov, E. S.; Kompaniets, G. V.; Moroz, N. P.; Nevinitsa, V. A.; Nosov, V. I.; Smirnov, O. N.; Fomichenko, P. A.; Zimin, A. A.

    2012-01-01

    Results of critical experiments performed at five ASTRA facility configurations modeling the high-temperature helium-cooled graphite-moderated reactors are presented. Results of experiments on definition of space distribution of 235 U fission reaction rate performed at four from these five configurations are presented more detail. Analysis of available information showed that all experiments on criticality at these five configurations are acceptable for use them as critical benchmark experiments. All experiments on definition of space distribution of 235 U fission reaction rate are acceptable for use them as physical benchmark experiments. (authors)

  7. High catalytic activity and stability of Ni/CexZr1-xO2/MSU-H for CH4/CO2 reforming reaction

    Science.gov (United States)

    Chang, Xiaoqian; Liu, Bingsi; Xia, Hong; Amin, Roohul

    2018-06-01

    How to reduce emission of CO2 as greenhouse gases, which resulted in global warming, is of very important significance. A series of Ni/CexZr1-xO2/MSU-H catalysts was prepared by means of hexagonally ordered mesoporous MSU-H with thermal and hydrothermal stabilities, which is cheap and can be synthesized in the large scale. The 10%Ni/Ce0.75Zr0.25O2/MSU-H catalyst presents high catalytic activity, stability and the ability of coke-resistance for CH4/CO2 reforming reaction due to high SBET (428 m2/g) and smaller Nio nanoparticle size (3.14 nm). The high dispersed Nio nanoparticles over MSU-H promoted the decomposition of CH4 and the carbon species accumulated on active Nio sites reacting with crystal lattice oxygen in Ce0.75Zr0.25O2 to form CO molecules. In the meantime, the remained oxygen vacancies on the interface between Nio and Ce0.75Zr0.25O2 could be supplemented via CO2. HRTEM images and XRD results of Ni/Ce0.75Zr0.25O2/MSU-H verified that high dispersion of Ni nanoparticles over Ni/Ce0.75Zr0.25O2/MSU-H correlated closely with the synergistic action between Ce0.75Zr0.25O2 and MSU-H as well as hexagonally ordered structure of MSU-H, which can provide effectively the oxygen storage capacity and inhibit the formation of coke.

  8. 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.

  9. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman

    2018-02-09

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  10. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman; Krach, Patricia E.; Cavallo, Luigi; Falivene, Laura; Rueping, Magnus

    2018-01-01

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  11. Nitric Oxide Reduction by Carbon Monoxide over Supported Hexaruthenium Cluster Catalysts. 1. The Active Site Structure That Depends on Supporting Metal Oxide and Catalytic Reaction Conditions.

    Science.gov (United States)

    Minato, Taketoshi; Izumi, Yasuo; Aika, Ken-Ichi; Ishiguro, Atsushi; Nakajima, Takayuki; Wakatsuki, Yasuo

    2003-08-28

    Ruthenium site structures supported on metal oxide surfaces were designed by reacting organometallic Ru cluster [Ru6C(CO)16](2-) or [Ru6(CO)18](2-) with various metal oxides, TiO2, Al2O3, MgO, and SiO2. The surface Ru site structure, formed under various catalyst preparation and reaction conditions, was investigated by the Ru K-edge extended X-ray absorption fine structure (EXAFS). Samples of [Ru6C(CO)16](2-)/TiO2(anatase) and [Ru6C(CO)16](2-)/TiO2(rutile) were found to retain the original Ru6C framework when heated in the presence of NO (2.0 kPa) or NO (2.0 kPa) + CO (2.0 kPa) at 423 K, i.e., catalytic reaction conditions for NO decomposition. At 523 K, the Ru-Ru bonds of the Ru6C framework were cleaved by the attack of NO. In contrast, the Ru site became spontaneously dispersed over TiO2 (anatase). When being supported over TiO2 (mesoporous), MgO, or Al2O3, the Ru6C framework split into fragments in gaseous NO or NO + CO even at 423 K. The Ru6 framework of [Ru6(CO)18](2-) was found to break easily into smaller ensembles in the presence of NO and/or CO at 423 K on support. Taking into consideration the realistic environments in which these catalysts will be used, we also examined the effect of water and oxygen. When water was introduced to the sample [Ru6C(CO)16](2-)/TiO2(anatase) at 423 K, it did not have any effects on the stabilized Ru6C framework structure. In the presence of oxygen gas, however, the Ru hexanuclear structure decomposed into isolated Ru cations bound to surface oxygen atoms of TiO2 (anatase).

  12. Deiodination reactions using tributyltin hydride for potential labelling experiments

    International Nuclear Information System (INIS)

    Zippi, E.M.; Plourde, G.W. II; Satyamurthy, N.

    1995-01-01

    2,6-Dinitro-1-iodobenzene and 2,4-dinitro-1-iodobenzene were deiodinated with tributylin hydride at different temperatures using various addition modes. The product ratios of 1,3-dinitrobenzene and the corresponding tributylstannyldinitrobenzene compounds were determined by NMR in order to evaluate the optimum conditions for impending tritiation experiments. (Author)

  13. Application of Box-Behnken design in the optimization of catalytic behavior of a new mixed chelate of copper (II) complex in chemiluminescence reaction of luminol

    International Nuclear Information System (INIS)

    Khajvand, Tahereh; Chaichi, Mohammad Javad; Nazari, OmLeila; Golchoubian, Hamid

    2011-01-01

    In this work, we observed an enhancement of chemiluminescence (CL) emission of luminol when a new mixed chelate of copper complex (N-(2-(2-aminoethylamino)ethyl)-1H-pyrrole-2-carboxamide-Cu(II)) was mixed with a solution containing luminol in methanol/water. The Box-Behnken design matrix and response surface methodology (RSM) have been applied to design the experiments to evaluate the interactive effects of the three most important operating variables-luminol (10 -4 -10 -2 M), fluorescein (10 -5 -10 -3 M) and hydrogen peroxide (1-3 M) concentrations on the CL emission of luminol. The total 15 experiments were conducted in the present study towards the construction of a quadratic model. Independent variables luminol and hydrogen peroxide have significant value P F less than 0.0500 indicate that model terms are significant for the CL emission of luminol. The regression equation coefficients were calculated and the data fitted to a second-order polynomial equation for CL emission of luminol. The new introduced inorganic catalyst of luminol CL reaction can be effect more than that of the common ones such as potassium hexacyanoferrate (III) and copper (II) acetate. - Research highlights: → In this study we introduce a new mixed chelate of copper complex as a catalyst of luminol chemiluminescence (CL) reaction. → The copper complex (N-(2-(2-aminoethylamino)ethyl)-1H-pyrrole-2-carboxamide-Cu(II)) catalyst luminol reaction more than that of copper acetate and potassium hexacyanoferrate (III). → The Box-Behnken design matrix and response surface methodology are used for prediction of CL intensity of luminol. → There are good correlation between experimental and expected CL intensity that predicted by the theoretical model. → Fluorescein used as a fluorescer in the luminol CL reaction in presence of the new catalyst.

  14. Solvent-Free Wittig Reaction: A Green Organic Chemistry Laboratory Experiment

    Science.gov (United States)

    Leung, Sam H.; Angel, Stephen A.

    2004-01-01

    Some Wittig reactions can be carried out by grinding the reactants in a mortar with a pestle for about 20 minutes, as per investigation. A laboratory experiment involving a solvent-free Wittig reaction that can be completed in a three-hour sophomore organic chemistry laboratory class period, are developed.

  15. Conservatives Anticipate and Experience Stronger Emotional Reactions to Negative Outcomes.

    Science.gov (United States)

    Joel, Samantha; Burton, Caitlin M; Plaks, Jason E

    2014-02-01

    The present work examined whether conservatives and liberals differ in their anticipation of their own emotional reactions to negative events. In two studies, participants imagined experiencing positive or negative outcomes in domains that do not directly concern politics. In Study 1, 190 American participants recruited online (64 male, Mage  = 32 years) anticipated their emotional responses to romantic relationship outcomes. In Study 2, 97 Canadian undergraduate students (26 male, Mage  = 21 years) reported on their anticipated and experienced emotional responses to academic outcomes. In both studies, more conservative participants predicted they would feel stronger negative emotions following negative outcomes than did more liberal participants. Furthermore, a longitudinal follow-up of Study 2 participants revealed that more conservative participants actually felt worse than more liberal participants after receiving a lower-than-desired exam grade. These effects remained even when controlling for the Big Five traits, prevention focus, and attachment style (Study 1), and optimism (Study 2). We discuss how the relationship between political orientation and anticipated affect likely contributes to differences between conservatives and liberals in styles of decision and policy choices. © 2013 Wiley Periodicals, Inc.

  16. Sodium-concrete reactions experiments and code development

    International Nuclear Information System (INIS)

    Casselman, C.; Malet, J.C.; Dufresne, J.; Bolvin, M.

    1988-01-01

    Hypothesis of hot sodium leak in a fast breeder reactor implies, for the safety organism to consider spillage of sodium on concrete. This safety analysis involves the understanding of sodium-concrete reactions, the knowledge of their consequences and to test the choiced preventive solutions. In association with EDF, the nuclear safety department had carried out an extensive experimental program, the different parts of which are connected with each aspect of this problem: - firstly, interaction between sodium and bare surface of usual concrete; - secondly, the case of a sodium spillage on a concrete surface covered with a defected liner; - thirdly, special concrete tests for a comparison with usual concrete behavior, in direct contact with hot sodium; - at last, a test which concerns a new design with a layer of the selected concrete protected with a defected liner. On the same time, theoretical work leads to elaborate a physical model to describe temporal evolution of thermal and chemical decomposition of a concrete slab under hot sodium action. SORBET-REBUS system will use quoted above test results to its validation

  17. QRTEngine: An easy solution for running online reaction time experiments using Qualtrics

    NARCIS (Netherlands)

    Barnhoorn, Jonathan Sebastiaan; Haasnoot, Erwin; Bocanegra, Bruno R.; van Steenbergen, Henk

    2015-01-01

    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

  18. The Barium Hydroxide-Ammonium Thiocyanate Reaction: A Titrimetric Continuous Variations Experiment.

    Science.gov (United States)

    Harris, Arlo D.

    1979-01-01

    Presents an experiment for inorganic, organic, or physical chemistry students utilizing acid-base titrimetry to study the stoichiometric of a solid state reaction. Time involved ranges from one to three, three-hour lab periods. (Author/SA)

  19. Catalytic nanoporous membranes

    Science.gov (United States)

    Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

    2013-08-27

    A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

  20. 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.

  1. 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.)

  2. 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.

  3. 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.

  4. Understanding and Improvement of an Experiment Measuring Chemical Reaction Rates by Monitoring Volume Change of a Gas: On the Reaction between HCl(aq) and Mg(s)

    International Nuclear Information System (INIS)

    Bang, Jeong Ah; Yoon, Hee Sook; Jeong, Dae Hong; Choi, Won Ho

    2006-01-01

    In this study we analyzed and improved an experiment measuring chemical reaction rates introduced in the high school science textbooks through an understanding of the phenomena observed in carrying out the experiment. For this purpose, the contents of textbooks related to the experiment were analyzed, and the problems observed in carrying out the experiment were addressed through experimental analysis. When the experiment was carried out by the method of aquatic transposition presented in textbooks, the observed volume change of H 2 gas was delayed and chemical reaction rate was increased in the early stage of reaction period. To resolve these problems, an improved method for measuring the reaction rates was suggested. In the improved experiment the reaction rate was measured to be constant on time, which was interpreted in terms of the concentration of H + and the surface area of magnesium

  5. Nuclear bremsstrahlung in proton induced reactions at 190 MeV (first experiments at AGOR)

    NARCIS (Netherlands)

    Wilschut, HW

    1998-01-01

    An overview is given of the first experiments with the new KVI cyclotron AGOR. First experiments have focused on nuclear bremsstrahlung in few-and many-body reactions. A classical introduction to nuclear bremsstrahlung is given. First results on coherent bremsstrahlung are discussed.

  6. Catalytic treatment

    Energy Technology Data Exchange (ETDEWEB)

    Bindley, W T.R.

    1931-04-18

    An apparatus is described for the catalytic treatment of liquids, semi-liquids, and gases comprising a vessel into which the liquid, semi-liquid, or gas to be treated is introduced through a common inlet to a chamber within the vessel whence it passes to contact with a catalyst through radially arranged channels or passages to a common outlet chamber.

  7. Design, construction and implementation of a packed reactor system to study the production of hydrogen by the catalytic reaction of reforming of oxygenated hydrocarbons

    International Nuclear Information System (INIS)

    Salas Aguilar, Cesar Augusto

    2014-01-01

    The Laboratorio de Quimica Inorganica of the Universidad de Costa Rica has evaluated the performance of several types of catalysts and supports in steam reforming reactions, using different conditions for synthesis of the same. The construction of a reaction system at laboratory scale is described to improve the conditions of the reforming process compared to previous projects. Catalysts synthesized and characterized are used but providing better disposal through a packed bed reactor. The system has had the necessary instrumentation for proper measurement of the temperature at the entrance and inside the reactor, proper feeding of reactants, flow measurement and sampling and measurement system. The conceptual design of the reactions system presented has taken into account the income of reactants through a peristaltic pump, preheating or vaporization of reagents, income and measurement of carrier gas sampling, take of sampling, flow measurement product, reactor packed and cooler product. The order of each stage is defined and positioning in the entire system. The design of a preheater and a tubular reactor is detailed, taking into account the dimensions and construction materials of each of the pieces. The design is presented in a series of diagrams and then the result of the construction is illustrated by photographs, all work done also has been described. The implementation of the system has described by the coupling of all parties and the respective tests. A basic experimental plan is presented to evaluate the performance of the reaction system, using glycerin as a reactant, demonstrating ability to react and take effective data. Four experiments are performed: vacuum reactor, packed reactor with two types of filling and reactor with an exposed surface cobalt oxide (II) reduced, the gases produced in the reaction are analyzed by gas chromatography. The results are discussed and analyzed, focusing on the overall selectivity of hydrogen relative to methane, and the

  8. "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.

  9. 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

  10. "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; Thivolle-Cazat, Jean; Taoufik, Mostafa; Stoffelbach, Franç ois; Norsic, Sé bastien; Basset, Jean-Marie

    2011-01-01

    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.

  11. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  12. 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.

  13. Medical students' experience of and reaction to stress: the role of depression and anxiety.

    Science.gov (United States)

    Saravanan, Coumaravelou; Wilks, Ray

    2014-01-01

    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. 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. 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. Overall, depressed and anxious students were found to experience more stress and react differently to stressors compared to nondepressed and nonanxious students.

  14. Catalytic burners in larger boiler appliances

    Energy Technology Data Exchange (ETDEWEB)

    Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))

    2009-02-15

    This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

  15. Catalytic pyrolysis of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Vail' eva, N A; Buyanov, R A

    1979-01-01

    Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

  16. On fusion/fission chain reactions in the Fleischmann-Pons cold fusion experiment

    International Nuclear Information System (INIS)

    Anghaie, S.; Froelich, P.; Monkhorst, H.J.

    1990-01-01

    In this paper the possibility of fusion/fission chain reactions following d-d source reactions in electrochemical cold fusion experiments have been investigated. The recycling factors for the charged particles in fusion reactions with consumable nuclei deuteron, 6 Li nd 7 Li, are estimated. It is concluded that, based on the established nuclear fusion cross sections and electronic stopping power, the recycling factor is four to five orders of magnitude less than required for close to critical conditions. It is argued that the cross generation of charged particles by neutrons does not play a significant role in this process, even if increased densities at the surface of electrodes do occur

  17. Catalytic effects of silver plasmonic nanoparticles on the redox reaction leading to ABTS˙+ formation studied using UV-visible and Raman spectroscopy.

    Science.gov (United States)

    Garcia-Leis, A; Jancura, D; Antalik, M; Garcia-Ramos, J V; Sanchez-Cortes, S; Jurasekova, Z

    2016-09-29

    ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) is a compound extensively employed to evaluate the free radical trapping capacity of antioxidant agents and complex mixtures such as biological fluids or foods. This evaluation is usually performed by using a colourimetric experiment, where preformed ABTS radical cation (ABTS˙ + ) molecules are reduced in the presence of an antioxidant causing an intensity decrease of the specific ABTS˙ + UV-visible absorption bands. In this work we report a strong effect of silver plasmonic nanoparticles (Ag NPs) on ABTS leading to the formation of ABTS˙ + . The reaction of ABTS with Ag NPs has been found to be dependent on the interfacial and plasmonic properties of NPs. Specifically, this reaction is pronounced in the presence of spherical nanoparticles prepared by the reduction of silver nitrate with hydroxylamine (AgH) and in the case of star-shaped silver nanoparticles (AgNS). On the other hand, spherical nanoparticles prepared by the reduction of silver nitrate with citrate apparently do not react with ABTS. Additionally, the formation of ABTS˙ + is investigated by surface-enhanced Raman scattering (SERS) and the assignment of the most intense vibrational bands of this compound is performed. The SERS technique enables us to detect this radical cation at very low concentrations of ABTS (∼2 μM). Altogether, these findings allow us to suggest the use of ABTS/Ag NPs-systems as reliable and easy going substrates to test the antioxidant capacity of various compounds, even at concentrations much lower than those usually used in the spectrophotometric assays. Moreover, we have suggested that ABTS could be employed as a suitable agent to investigate the interfacial and plasmonic properties of the metal nanoparticles and, thus, to characterize the nanoparticle metal systems employed for various purposes.

  18. Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction.

    Science.gov (United States)

    Yang, Dong; Ortuño, Manuel A; Bernales, Varinia; Cramer, Christopher J; Gagliardi, Laura; Gates, Bruce C

    2018-03-14

    Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr 6 O 8 . Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr 6 O 8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an S N 2 mechanism.

  19. Catalytic Antibodies

    Indian Academy of Sciences (India)

    biological processes and is intended to catalyze a reaction for which no real enzyme is ... the reaction. In order to enhance the rates of chemical reactions, enzymes, ..... of such antibodies has already been exploited in the production of a biosensor. ..... tant to the pharmaceutical and fine chemical industries for the synthesis ...

  20. 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.

  1. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2013-01-01

    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.

  2. Study on the reactive transient α-λ3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed α-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Wang, Hao-Yang; Zhou, Juan; Guo, Yin-Long

    2012-03-30

    Hypervalent iodine compounds are important and widely used oxidants in organic chemistry. In 2005, Ochiai reported the PhI-catalyzed α-acetoxylation reaction of acetophenone by the oxidation of PhI with m-chloroperbenzoic acid (m-CPBA) in acetic acid. However, until now, the most critical reactive α-λ(3)-iodine alkyl acetophenone intermediate (3) had not been isolated or directly detected. Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to intercept and characterize the transient reactive α-λ(3)-iodine alkyl acetophenone intermediate in the reaction solution. The trivalent iodine species was detected when PhI and m-CPBA in acetic acid were mixed, which indicated the facile oxidation of a catalytic amount of PhI(I) to the iodine(III) species by m-CPBA. Most importantly, 3·H(+) was observed at m/z 383 from the reaction solution and this ion gave the protonated α-acetoxylation product 4·H(+) at m/z 179 in MS/MS by an intramolecular reductive elimination of PhI. These ESI-MS/MS studies showed the existence of the reactive α-λ(3)-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3·H(+) was consistent with the proposed solution-phase reactivity of the α-λ(3)-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai. Copyright © 2012 John Wiley & Sons, Ltd.

  3. A Simple Experiment for Teaching Process Intensification by Static Mixing in Chemical Reaction Engineering

    Science.gov (United States)

    Baz-Rodríguez, Sergio; Herrera-Soberanis, Natali; Rodríguez-Novelo, Miguel; Guillén-Francisc, Juana; Rocha-Uribe, José

    2016-01-01

    An experiment for teaching mixing intensification in reaction engineering is described. For this, a simple tubular reactor was constructed; helical static mixer elements were fabricated from stainless steel strips and inserted into the reactor. With and without the internals, the equipment operates as a static mixer reactor or a laminar flow…

  4. A Laboratory Experiment, Based on the Maillard Reaction, Conducted as a Project in Introductory Statistics

    Science.gov (United States)

    Kravchuk, Olena; Elliott, Antony; Bhandari, Bhesh

    2005-01-01

    A simple laboratory experiment, based on the Maillard reaction, served as a project in Introductory Statistics for undergraduates in Food Science and Technology. By using the principles of randomization and replication and reflecting on the sources of variation in the experimental data, students reinforced the statistical concepts and techniques…

  5. Pop-It Beads to Introduce Catalysis of Reaction Rate and Substrate Depletion Effects

    Science.gov (United States)

    Gehret, Austin U.

    2017-01-01

    A kinesthetic classroom activity was designed to help students understand enzyme activity and catalysis of reaction rate. Students served the role of enzymes by manipulating Pop-It Beads as the catalytic event. This activity illuminates the relationship between reaction rate and reaction progress by allowing students to experience first-hand the…

  6. Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

    and the oxidative coupling of methane. These two reactions have tremendous technological significance for practical application in industry. An understanding of the fundamental aspects and reaction mechanisms of the catalytic reactions reviewed in this study would

  7. Thermal desorption (TD) study of heterogeneous catalytic reactions--4. Nonuniformity of Pt/. gamma. -Al/sub 2/O/sub 3/ catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rozanov, V V [Inst. Chem. Phys. Acad. Sci. U.S.S.R.; Sklyarov, A V; Gland, J

    1979-10-01

    Programed TD of n-heptane adsorbed on 0.6-3% by wt Pt/..gamma..-Al/sub 2/O/sub 3/ laboratory catalysts with different dispersities of the metallic phase showed the formation of toluene at 160/sup 0/-260/sup 0/C with spectral maxima at about 200/sup 0/ and 230/sup 0/C and a benzene desorption maxima at 300/sup 0/C. The desorption of both benzene and the high-temperature form of toluene decreased with decreased dispersity of the catalyst and was not observed with the catalyst characterized by an average Pt particle size of 1000 A. Toluene adsorbed on the same catalysts showed a TD peak of benzene at 300/sup 0/C. With commercial Pt/Al/sub 2/O/sub 3/ reforming catalysts, up to five toluene desorption peaks were observed at 200/sup 0/-360/sup 0/C, suggesting the presence of active sites with different activities and concentrations on the catalyst surface. Experiments on TD of deuterated n-heptane suggested different reaction mechanisms associated with different types of active sites and the formation of low- and high-temperature forms of toluene. Only the latter had a maximum coinciding with a TD peak of D/sub 2/ (240/sup 0/C), probably formed by dehydrogenation of adsorbed diene or olefin intermediates.

  8. Study on solar chemical heat pump system. Basic experiment on falling film reaction for dehydrogenation of 2-propanol; Solar chemical heat pump no kenkyu. 2-propanol bunkai hanno ni okeru ryuka ekimakushiki hanno jikken

    Energy Technology Data Exchange (ETDEWEB)

    Doi, T; Ando, Y; Tanaka, T; Takashima, T [Electrochemical Laboratory, Tsukuba (Japan); Nomura, T; Kamoshida, J [Shibaura Institute of Technology, Tokyo (Japan)

    1996-10-27

    An experiment and the examination were carried out in order to elucidate the optimum conditions in the falling liquid film reaction method, in the conversion of solar energy using the decomposition reaction of 2-propanol. The device for the experiment was constituted of a reaction container, tubular pump, cooling pipe, sampling container for effluent from the upper and lower part of the reaction container, and gas burette. Examined in the experiment were various factors such as a fibrous activated carbon (catalyst support), ratio for carrying catalyst, catalytic composition and heating temperature. In the experiment, with the temperature inside the reaction container fully stabilized under prescribed conditions, measurement was done for the hydrogen generation by the gas burette for 10 minutes as well as for the sampling of effluent. The experiment revealed that the heat utilization ratio reached the maximum of about 27% when the heating temperature was 90{degree}C using a catalyst with the ratio of RU and Pt 1 to 1 and the ratio for carrying catalyst 10wt%, so that a great improvement was obtained in the heat utilization ratio at a low temperature. Also obtained was a large inversion ratio of about 15%. 4 refs., 6 figs., 5 tabs.

  9. Differences in male and female subjective experience and physiological reactions to emotional stimuli.

    Science.gov (United States)

    Poláčková Šolcová, Iva; Lačev, Alek

    2017-07-01

    Research based on self-reported data often indicates that women are the more emotional sex. The present study examined differences in emotion between the sexes across two components of the emotional process: subjective experience and physiological reactions to emotional stimuli. During the experimental study, participants (N=124; 22.5±2.88; 51 males) subjectively rated their emotional experience (valence and intensity) towards presented positive and negative affective stimuli, while physiological reactions (facial electromyography, heart rate, skin conductance, and finger skin temperature) were measured during expositions. Results from self-reports suggest that women declared more intensive emotional experiences for positive and negative stimuli and rated negative stimuli as more negative in comparison to men. Physiological measurements showed differences between the sexes in the physiological baseline measurements (facial electromyography, skin conductance and finger skin temperature). However, physiological responses towards positive or negative emotional stimuli did not prove to be different between men and women, except for finger skin temperature. Relations between self-reported subjective experiences and physiological changes were weak and insignificant. Collectively, our findings suggest certain emotional differences experienced between men and women. These differences can be found specifically in self-reported subjective experiences, while significant differences were not predominantly present in recorded physiological reactions. Copyright © 2017. Published by Elsevier B.V.

  10. 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....

  11. Ultrahigh-sensitive detection of molecules produced in catalytic reactions by uni-atomic-composition bi-element clusters supported on solid substrate

    International Nuclear Information System (INIS)

    Yasumatsu, H; Fukui, N

    2013-01-01

    An apparatus has been developed for measuring catalytic activities of uni-atomic-composition bi-element clusters supported on a solid substrate. The cluster sample is prepared by irradiating a cluster-ion beam having the uni-atomic composition onto the substrate on a soft-landing condition in an ultra-high vacuum. The catalytic activity is measured by temperature-programmed desorption (TPD) mass analysis. Molecules at a density as low as 3 cm −3 have been detected with an ultrahigh-sensitive TPD mass spectrometer consisting of a cylindrical electron gun, a quadrupole mass filter and a micro-channel-plate ion-detector. The high reproducibility has been achieved by careful calibration of the TPD mass spectrometer. As a benchmark example, thermal oxidation of CO catalysed on Pt 30 disks supported on a silicon surface was studied. The CO 2 products have been successfully observed at the Pt 30 density as low as 3 × 10 12 clusters in a circular area of 8 mm in diameter at the ramping rate of the sample temperature as low as 0.3 K s −1 .

  12. One-pot synthesis of reduced graphene oxide supported PtCuy catalysts with enhanced electro-catalytic activity for the methanol oxidation reaction

    International Nuclear Information System (INIS)

    Peng, Xinglan; Zhao, Yanchun; Chen, Duhong; Fan, Yanfang; Wang, Xiao; Wang, Weili; Tian, Jianniao

    2014-01-01

    The outstanding performance PtCu y (y = 1,2,3) alloy nanoparticles supported on reduced graphene oxide (rGO) have been synthesized by a facile, efficient, one-pot hydrothermal synthesis approach. The as-prepared PtCu y /rGO catalysts are comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy. Cyclic voltammetry, CO-stripping voltammetry and chronoamperometry results reveal that the PtCu y /rGO catalysts have higher electro-catalytic activity, more negative onset oxidative potential, more excellent tolerance ability for CO poisoning and enhanced stability for the electro-oxidation of methanol compared to pure Pt/rGO. As far as the as-made PtCu y /rGO catalysts are concerned, the PtCu 2 /rGO exhibits the highest electro-catalytic activity. The mechanism of the promoting effect of Cu on Pt is explained based on the electronic modification effect. The nature of interfacial interactions between the Pt-Cu active metal phase and the rGO supporting materials is crucial to achieving high performance

  13. Do Victimization Experiences Accentuate Reactions to Ostracism? An Experiment Using Cyberball

    Science.gov (United States)

    Ruggieri, Sabrina; Bendixen, Mons; Gabriel, Ute; Alsaker, Françoise

    2013-01-01

    Based on the notion that the history of victimization has an impact on the sensitivity to current victimization situations this study investigated whether victims of bullying show more pronounced responses to single episodes of social exclusion. We examined whether victimization experiences in school are associated with responses to ostracism in a…

  14. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.

    1983-04-01

    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author) [pt

  15. Directional Track Selection Technique in CR39 SSNTD for lowyield reaction experiments

    Science.gov (United States)

    Ingenito, Francesco; Andreoli, Pierluigi; Batani, Dimitri; Bonasera, Aldo; Boutoux, Guillaume; Burgy, Frederic; Cipriani, Mattia; Consoli, Fabrizio; Cristofari, Giuseppe; De Angelis, Riccardo; Di Giorgio, Giorgio; Ducret, Jean Eric; Giulietti, Danilo; Jakubowska, Katarzyna

    2018-01-01

    There is a great interest in the study of p-11B aneutronic nuclear fusion reactions, both for energy production and for determination of fusion cross-sections at low energies. In this context we performed experiments at CELIA in which energetic protons, accelerated by the laser ECLIPSE, were directed toward a solid Boron target. Because of the small cross-sections at these energies the number of expected reactions is low. CR39 Solid-State Nuclear Track Detectors (SSNTD) were used to detect the alpha particles produced. Because of the low expected yield, it is difficult to discriminate the tracks due to true fusion products from those due to natural background in the CR39. To this purpose we developed a methodology of particle recognition according to their direction with respect to the detector normal, able to determine the position of their source. We applied this to the specific experiment geometry, so to select from all the tracks those due to particles coming from the region of interaction between accelerated protons and solid boron target. This technique can be of great help on the analysis of SSNTD in experiments with low yield reactions, but can be also generally applied to any experiment where particles reach the track detector with known directions, and for example to improve the detection limit of particle spectrometers using CR39.

  16. Chemistry and engineering of catalytic hydrodesulfurization

    NARCIS (Netherlands)

    Schuit, G.C.A.; Gates, B.C.

    1973-01-01

    A review with 74 refs. on catalytic hydrodesulfurization of pure compds. and petroleum feedstocks, with emphasis on reaction intermediates and structures of Al2O3-supported Ni-W and Co-Mo catalysts. [on SciFinder (R)

  17. Mannich reactions of alkynes: the role of sub-stoichiometric amounts of stable polymeric alkynylcopper (I) compounds in the catalytic cycle (abstract)

    International Nuclear Information System (INIS)

    Khan, A.N.; Buckley, B.R.; Heaney, H.

    2011-01-01

    The rapid development of the use of organocopper reagents and catalysts in organic synthesis since the middle of the last century has been comprehensively documented. The advantages of using heterogeneous catalysts include ease of work-up and purification, reduction in waste disposal, and the ability to recycle catalysts. Reactions of terminal alkynes that involve copper(I) catalysts have been widely studied, in particular as a result of the search for atom efficiency. Ligand associated alkynylcopper(I) derivatives have been reported many times, for example in copper(I) catalysed alkyne-azide cycloaddition (CuAAC) reactions. Our interest in Mannich reactions, and also in alkynylcopper(I) pre-catalysts, prompted this study of reactions of alkynes with secondary amines with aldehydes. Early studies of Mannich reactions involving alkynes almost always involved formaldehyde, exceptions included imines and derivatives of glyoxylic esters. An efficient one-pot three-component coupling of an aldehyde, alkyne, and amine to generate propargyl amines has been effected by microwave heating in water using a polymeric alkynylcopper(I) complex as catalyst (Scheme 1). This reaction utilizes water as a solvent which provides a green-approach for such reactions. This method has proved to be applicable to a wide range of substrates. (author)

  18. 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.

  19. 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.

  20. Background studies of high energy γ rays from (n,γ) reactions in the CANDLES experiment

    Science.gov (United States)

    Nakajima, K.; Iida, T.; Akutagawa, K.; Batpurev, T.; Chan, W. M.; Dokaku, F.; Fushimi, K.; Kakubata, H.; Kanagawa, K.; Katagiri, S.; Kawasaki, K.; Khai, B. T.; Kino, H.; Kinoshita, E.; Kishimoto, T.; Hazama, R.; Hiraoka, H.; Hiyama, T.; Ishikawa, M.; Li, X.; Maeda, T.; Matsuoka, K.; Moser, M.; Nomachi, M.; Ogawa, I.; Ohata, T.; Sato, H.; Shamoto, K.; Shimada, M.; Shokati, M.; Takahashi, N.; Takemoto, Y.; Takihira, Y.; Tamagawa, Y.; Tozawa, M.; Teranishi, K.; Tetsuno, K.; Trang, V. T. T.; Tsuzuki, M.; Umehara, S.; Wang, W.; Yoshida, S.; Yotsunaga, N.

    2018-07-01

    High energy γ rays with several MeV produced by (n,γ) reactions can be a trouble for low background measurements in the underground laboratories such as double beta decay experiments. In the CANDLES project, which aimed to observe the neutrino-less double beta decay from 48Ca, γ rays caused by (n,γ) reactions were found to be the most significant background. The profile of the background was studied by measurements with a neutron source and a simulation with a validity check of neutron processes in Geant4. The observed spectrum of γ rays from (n,γ) reactions was well reproduced by the simulated spectra, which were originated from the surrounding rock and a detector tank made of stainless steel. The environmental neutron flux was derived by the observed event rate of γ rays from (n,γ) reactions using the simulation. The thermal and non-thermal neutron flux were found to be (1.3 ± 0.6) ×10-6 cm-2s-1 and (1.1 ± 0.5) ×10-5 cm-2s-1 , respectively. It is necessary to install an additional shield to reduce the background from (n,γ) reaction to the required level.

  1. Catalytic Aminohalogenation of Alkenes and Alkynes.

    Science.gov (United States)

    Chemler, Sherry R; Bovino, Michael T

    2013-06-07

    Catalytic aminohalogenation methods enable the regio- and stereoselective vicinal difunctionalization of alkynes, allenes and alkenes with amine and halogen moieties. A range of protocols and reaction mechanisms including organometallic, Lewis base, Lewis acid and Brønsted acid catalysis have been disclosed, enabling the regio- and stereoselective synthesis of halogen-functionalized acyclic amines and nitrogen heterocycles. Recent advances including aminofluorination and catalytic enantioselective aminohalogenation reactions are summarized in this review.

  2. Kinetic catalytic studies of scorpion's hemocyanin

    International Nuclear Information System (INIS)

    Queinnec, E.; Vuillaume, M.; Gardes-Albert, M.; Ferradini, C.; Ducancel, F.

    1991-01-01

    Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 10 7 mol -1 .l.s -1 [fr

  3. Adverse allergic reactions to linear ionic gadolinium-based contrast agents: experience with 194, 400 injections

    International Nuclear Information System (INIS)

    Aran, S.; Shaqdan, K.W.; Abujudeh, H.H.

    2015-01-01

    Aim: To report the authors' experience with the administration of four gadolinium-based contrast agents (GBCA; gadopentetate dimeglumine, gadofosveset trisodium, gadoxetate disodium and gadobenate dimeglumine) in a large study population at a single, large academic medical centre. Materials and methods: The institutional review board approved this retrospective study in which data in the electronic incident reporting system were searched. A total of 194, 400 intravenous administrations of linear ionic GBCAs were assessed for the incidence of adverse reactions and risk factors from 1 January 2007 to 14 January 2014. The severity of reactions (mild, moderate, and severe), patient type (outpatients, inpatients, and emergency), examination type, and treatment options were also investigated. Results: In total, 204/194400 (0.1%) patients (mean age 45.7 ± 14.9) showed adverse reactions, consisting of 6/746 (0.80%), 10/3200 (0.31%), 14/6236 (0.22%) and 174/184218 (0.09%), for gadofosveset trisodium, gadoxetate disodium, gadobenate dimeglumine, and gadopentetate dimeglumine, respectively. An overall significant difference was found between different GBCAs regarding the total number of reactions (p < 0.0001). When comparing the GBCAs together, significant differences were found between gadofosveset trisodium versus gadopentetate dimeglumine (p < 0.0001), gadofosveset trisodium versus gadobenate dimeglumine (p = 0.0051), gadoxetate disodium versus gadopentetate dimeglumine (p < 0.0001) and gadopentetate dimeglumine versus gadobenate dimeglumine (p = 0.0013). Rate of reaction was higher in females (F: 146/113187, 0.13%/M: 58/81213, 0.07%; p < 0.0001). Rate of reactions was higher in outpatient (180/158885, 0.11%), emergency (10/10413, 0.10%), and inpatients (14/25102, 0.05%), respectively (p < 0.0001). Most of the patients had mild symptoms 171/204 (83.8%). Abdomen–pelvis, liver, and thoracic examinations had highest rates of reactions (0.17 versus 0

  4. Experiences on removal of sodium-water reaction products in SWAT-3

    International Nuclear Information System (INIS)

    Tanabe, H.; Hiroi, H.; Sato, M.; Otaka, J.

    2002-01-01

    This report summarizes experiences and information concerning the removal of sodium water reaction products (SMRP) obtained through large leak tests of the Steam Generator Safety Test Facility (SWAT-3) at PNC/OEC, which were conducted to validate the safety design of steam generators of a prototype LMFBR Monju. The following three problems are discussed here: (1) drainability of SWRP, (2) removal of SWRP by using a cold trap, and (3) steam cleaning of SWRP. (author)

  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. COMPARISON OF CATALYTIC ACTIVITIES BOTH FOR SELECTIVE OXIDATION AND DECOMPOSITION OF AMMONIA OVER Fe/HZβ CATALYST

    Directory of Open Access Journals (Sweden)

    YELİZ ÇETİN

    2016-11-01

    Full Text Available Ammonia is one of the syngas contaminants that must be removed before using the syngas downstream applications. The most promising hot-gas clean-up techniques of ammonia are selective catalytic oxidation (SCO and catalytic decomposition. In this study, the catalytic activities over Zeolite Hβ supported iron catalyst (Fe/HZβ were compared both for the two catalytic routes. For SCO experiments; temperature (300-550 °C, O2 (2000-6000 ppmv and (0-10% H2 concentrations were investigated with the presence of 800 ppm NH3 in each of the final gas mixture. In the second route, catalytic ammonia decomposition experiments were carried out with H2 in balance N2 (0-30% containing 800 ppm NH3 at 700°C and 800°C. In the SCO, NH3 conversions were increased with increasing reaction temperatures with the absence of H2 in the reaction mixture. With 10% H2, it was shown that NH3 conversions increased with decreasing the reaction temperature. This was interpreted as the competing H2 and NH3 oxidations over the catalyst. On the other hand, in the catalytic decomposition, thermodynamic equilibrium conversion of almost 100% was attained at both 700 and 800 °C. Upon H2 addition, all conversions decreased. The decrease in conversion seemed to be linear with inlet hydrogen concentration. Hydrogen was seen to inhibit ammonia decomposition reaction. It was shown that Fe/HZβ catalyst is better to use for catalytic decomposition of NH3 in syngas rather than SCO of NH3 in spite of higher reaction temperatures needed in the decomposition reaction.

  7. Method of fabricating a catalytic structure

    Science.gov (United States)

    Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

    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.

  8. N-BUTYL SUBSTITUTED N-HETEROCYCLIC CARBENE-PD(II-PYRIDINE (PEPPSI COMPLEXES: SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTIVITY IN THE SUZUKI-MIYAURA REACTION

    Directory of Open Access Journals (Sweden)

    Rukiye Fırıncı

    2016-08-01

    Full Text Available A series of N-butyl substituted imidazolium salts, (1a-c and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI themed palladium N-heterocyclic carbene complexes (2a-c were synthesized and characterized. Pd-NHC complexes were fully determined by elemental analysis and spectroscopic. The synthesized complexes were tested in Suzuki-Miyaura cross-coupling reaction. These complexes were found to be efficient catalysts for the Suzuki-Miyaura reaction of phenylboronic acid with aryl bromides.

  9. Review of the sodium fire experiments including sodium-concrete-reactions and summary of the results

    International Nuclear Information System (INIS)

    Cherdron, W.

    1996-01-01

    In the technical and design concept of containment systems of sodium cooled breeder reactors it has to be considered, that leakages in sodium pipes lead to sodium fires. The temperature and pressure rise caused by sodium fires makes it indispensable to analyse these accidents to be able to assess the safety of the whole system. Generally sodium leakages may lead to three different types of fires with different consequences. The main influences are the geometry of the leakage, shape, size, location, and the sodium conditions, such as temperature, flow rate and velocity. It must be also considered the reaction of sodium with surfaces like concrete. The paper gives an overview over all the sodium fire experiments performed in the FAUNA-facility (220 m 3 ) of the Forschungszentrum Karlsruhe in the years 1979 to 1993. The experimental program started with the investigation of pool fires on burning areas between 2 and 12 m 2 with up to 500 kg of Sodium. The experiments had been continued with 3 combined fires and 40 experiments on spray fires. 7 experiments on sodium-concrete reactions completed the program. (author)

  10. Neutron-induced reactions relevant for Inertial-Cofinement Fusion Experiments

    Science.gov (United States)

    Boswell, Melissa; Devlin, Mathew; Fotiadis, Nikolaos; Merrill, Frank; Nelson, Ronald; Tonchev, Anton

    2014-09-01

    The typical ignition experiment at the National Ignition Facility ablatively implodes a plastic capsule filled with DT fuel, generating a high flux of 14-MeV neutrons from the d(t,n) α reaction. There is some spread in the energy of these primary 14-MeV neutrons, which is mainly attributable to Doppler shifting from the relative thermal motion of the burning DT fuel. Neutrons created during this reaction have 5--10% chance of scattering before escaping the fuel assembly, losing some fraction of their energy in the scattering process. Neutrons emerging with an energy greater than the reaction energy are generated by a two-step process where neutrons first transfer momentum to a deuteron or tritium ion, these enhanced energy ions then fuse in flight to produce higher energy neutrons; some of these neutrons have energies in excess of 30 MeV. Measuring the fluencies of both the low- and high-energy neutrons is a powerful mechanism for studying the properties of the fuel assembly, and the various parameters important to 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 o.

  11. Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction-Diffusion Approach.

    Science.gov (United States)

    Dóka, Éva; Lente, Gábor

    2017-04-13

    This work presents a rigorous mathematical study of the effect of unavoidable inhomogeneities in laser flash photolysis experiments. There are two different kinds of inhomegenities: the first arises from diffusion, whereas the second one has geometric origins (the shapes of the excitation and detection light beams). Both of these are taken into account in our reported model, which gives rise to a set of reaction-diffusion type partial differential equations. These equations are solved by a specially developed finite volume method. As an example, the aqueous reaction between the sulfate ion radical and iodide ion is used, for which sufficiently detailed experimental data are available from an earlier publication. The results showed that diffusion itself is in general too slow to influence the kinetic curves on the usual time scales of laser flash photolysis experiments. However, the use of the absorbances measured (e.g., to calculate the molar absorption coefficients of transient species) requires very detailed mathematical consideration and full knowledge of the geometrical shapes of the excitation laser beam and the separate detection light beam. It is also noted that the usual pseudo-first-order approach to evaluating the kinetic traces can be used successfully even if the usual large excess condition is not rigorously met in the reaction cell locally.

  12. 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.

  13. Flowthrough Reductive Catalytic Fractionation of Biomass

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Eric M.; Stone, Michael L.; Katahira, Rui; Reed, Michelle; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2017-11-01

    Reductive catalytic fractionation (RCF) has emerged as a leading biomass fractionation and lignin valorization strategy. Here, flowthrough reactors were used to investigate RCF of poplar. Most RCF studies to date have been conducted in batch, but a flow-based process enables the acquisition of intrinsic kinetic and mechanistic data essential to accelerate the design, optimization, and scale-up of RCF processes. Time-resolved product distributions and yields obtained from experiments with different catalyst loadings were used to identify and deconvolute events during solvolysis and hydrogenolysis. Multi-bed RCF experiments provided unique insights into catalyst deactivation, showing that leaching, sintering, and surface poisoning are causes for decreased catalyst performance. The onset of catalyst deactivation resulted in higher concentrations of unsaturated lignin intermediates and increased occurrence of repolymerization reactions, producing high-molecular-weight species. Overall, this study demonstrates the concept of flowthrough RCF, which will be vital for realistic scale-up of this promising approach.

  14. Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

    KAUST Repository

    Nolan, Steven Patrick; Izquierdo, Frederic; Zinser, Caroline; Minenkov, Yury; Cordes, David; Slawin, Alexandra; Cavallo, Luigi; Nahra, Fady; Cazin, Catherine

    2017-01-01

    The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After

  15. 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.

  16. Study of the water-gas shift reaction on Mo2C/Mo catalytic coatings for application in microstructured fuel processors

    NARCIS (Netherlands)

    Rebrov, E.V.; Kuznetsov, S.A.; Croon, de M.H.J.M.; Schouten, J.C.

    2007-01-01

    The activity and stability of two types of molybdenum carbide coatings deposited on molybdenum substrates (Mo2C/Mo) were compared in the water-gas shift reaction at 513–631 K. The activity of the Mo2C/Mo coatings obtained by carburization of preoxidized molybdenum substrates in a CH4/H2 mixture at

  17. Unexpected catalytic reactions of silyl-protected enol diazoacetates with nitrile oxides that form 5-arylaminofuran-2(3H)-one-4-carboxylates.

    Science.gov (United States)

    Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y; Doyle, Michael P

    2012-02-03

    Silyl-protected enol diazoacetates undergo dirhodium(II)-catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. © 2012 American Chemical Society

  18. Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

    Science.gov (United States)

    Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

    2016-02-04

    Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.; Rodionov, Valentin; Kü hn, Fritz; Reiser, Oliver

    2012-01-01

    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

  20. 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.

  1. Synthesis, characterization and catalytic performance of mixed nanoferrites submitted to transesterification and esterification reaction using methyl and ethyl route for biodiesel production

    International Nuclear Information System (INIS)

    Dantas, Joelda; Leal, Elvia; Mapossa, Antonio Benjamim; Silva, Adriano Sant'Ana; Costa, Ana Cristina Figueiredo de Melo

    2016-01-01

    The mixed nanoferrites of Ni_0_._5Zn_0_._5Fe_2O_4 and Ni_0_._2Cu_0_._3Zn_0_._5Fe_2O_4 were synthesized by combustion reaction using urea as fuel and a conical reactor as heating source in batches of 10 g, and then tested as heterogeneous nanocatalysts in the transesterification and esterification reaction of soya bean oil using the methyl and ethyl routes to biodiesel production. During the synthesis the time and temperature of the reactions were measured, and the evolved gases and the color of the emitted flames were observed. The samples were characterized by XRD, EDX, FTIR, SEM/EDS, BET and gas chromatography. The reaction tests were carried out with 10 g of oil for 1 h, oil:alcohol molar ratio of 1:12, 2 % (w/w) of catalyst, and conducted at 180 °C. The XRD patterns and the FTIR spectra revealed the presence of the inverse spinel phase type B(AB)_2O_4. The morphology showed the formation of agglomerates with fragile morphology and high surface area. The chromatographic analysis produced excellent results in the esterification reactions for both samples in the tested conditions, with special emphasis on Ni_0_._5Zn_0_._5Fe_2O_4, whose conversions were of 91.4 % in methyl esters and of 77.8 % in ethyl esters, while the Ni_0_._2Cu_0_._3Zn_0_._5Fe_2O_4 sample showed conversion of 75.1 and 65.1 %, respectively. The conversions in the methyl and ethyl transesterification were of 14 and 2 % of the Ni_0_._5Zn_0_._5Fe_2O_4 sample, and of 11 and 3 % for the Ni_0_._2Cu_0_._3Zn_0_._5Fe_2O_4 sample. (author)

  2. Catalytic cracking of hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    1940-09-12

    A process is described for the vapor phase catalytic cracking of hydrocarbon oils boiling substantially in the gas oil range. The reaction takes place in the presence of a solid catalyst between 700 to 900/sup 0/F under pressure between atmospheric and 400 psi. A gas containing between 20 and 90 mol % of free hydrogen is used. The reaction is allowed to proceed until consumption of the free begins. The reaction is discontinued at that point and the catalyst is regenerated for further use.

  3. Performance study of the anisotropic flow and reaction plane reconstruction in the CBM experiment

    International Nuclear Information System (INIS)

    Mikhaylov, V; Kugler, A; Kushpil, V; Tlustý, P; Selyuzhenkov, I

    2016-01-01

    The Projectile Spectator Detector (PSD) is a subsystem of the CBM experiment at the future FAIR facility designed to determine centrality and reaction plane orientation in the heavy-ion collisions. It will be done by measurement of the energy distribution of the heavy nucleons and nuclei fragments emitted close to the beam rapidity in forward direction. For the anticipated beam energies of FAIR SIS100 and SIS300 accelerators, different event generators (iQMD, UrQMD, DCM-QGSM, LA-QGSM and HSD) were used for the study of directed and elliptic proton flow in Au+Au collisions. Produced particles were transported with the GEANT4 Monte-Carlo using the CBM detector geometry. Performance of the reaction plane determination is shown for different PSD setups to demonstrate effects of the detector granularity and magnetic field. Simulation results are compared with the FOPI, AGS E877, E895 and STAR experimental data. (paper)

  4. Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment.

    Science.gov (United States)

    Sementa, L; Wijzenbroek, M; van Kolck, B J; Somers, M F; Al-Halabi, A; Busnengo, H F; Olsen, R A; Kroes, G J; Rutkowski, M; Thewes, C; Kleimeier, N F; Zacharias, H

    2013-01-28

    We present new experimental and theoretical results for reactive scattering of dihydrogen from Cu(100). In the new experiments, the associative desorption of H(2) is studied in a velocity resolved and final rovibrational state selected manner, using time-of-flight techniques in combination with resonance-enhanced multi-photon ionization laser detection. Average desorption energies and rotational quadrupole alignment parameters were obtained in this way for a number of (v = 0, 1) rotational states, v being the vibrational quantum number. Results of quantum dynamics calculations based on a potential energy surface computed with a specific reaction parameter (SRP) density functional, which was derived earlier for dihydrogen interacting with Cu(111), are compared with the results of the new experiments and with the results of previous molecular beam experiments on sticking of H(2) and on rovibrationally elastic and inelastic scattering of H(2) and D(2) from Cu(100). The calculations use the Born-Oppenheimer and static surface approximations. With the functional derived semi-empirically for dihydrogen + Cu(111), a chemically accurate description is obtained of the molecular beam experiments on sticking of H(2) on Cu(100), and a highly accurate description is obtained of rovibrationally elastic and inelastic scattering of D(2) from Cu(100) and of the orientational dependence of the reaction of (v = 1, j = 2 - 4) H(2) on Cu(100). This suggests that a SRP density functional derived for H(2) interacting with a specific low index face of a metal will yield accurate results for H(2) reactively scattering from another low index face of the same metal, and that it may also yield accurate results for H(2) interacting with a defected (e.g., stepped) surface of that same metal, in a system of catalytic interest. However, the description that was obtained of the average desorption energies, of rovibrationally elastic and inelastic scattering of H(2) from Cu(100), and of the

  5. Homogeneous conversion of methane to methanol. 2. Catalytic activation of methane by cis- and trans-platin: A density functional study of the Shilov type reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mylvaganam, K.; Bacskay, G.B.; Hush, N.S.

    2000-03-08

    The C-H activation of methane catalyzed by cis- and trans-platin in aqueous solution has been studied by density functional based computational methods. By analogy with the Shilov reaction, the initial step is the replacement of an ammonia ligand by methane, followed by the formation of a methyl complex and the elimination o a proton. The computations utilize the B3LYP hybrid functionals, effective core potentials, and double-{zeta} to polarized double-{zeta} basis sets and include solvation effects by a dielectric continuum method. In contrast with the Shilov reaction studied by Seigbahn and Crabtree (J.Am.Chem.Soc. 1996, 118, 4443), in the platins the replacement of an ammonia ligand by methane is found to be effectively rate determining, in that the energy barriers to C-H activation are comparable with those of the initial substitution reaction, viz. {approximately} 34 and 44 kcal/mol for cis- and trans-platin, respectively. Several reaction pathways for C-H activation and subsequent proton elimination were identified. For cis-platin the energy barriers associated with the oxidative addition and {sigma}-bond metathesis type mechanisms were found to be comparable, while for trans-platin oxidative addition is predicted to be strongly preferred over {sigma}-bond metathesis, which, interestingly, also proceeds through a Pt(IV) methyl hydrido complex as reaction intermediate. In line with accepted ideas on trans influence, the methyl and hydride ligands in the Pt(IV) complexes that arise in the oxidative addition reactions were always found to be cis to each other. On the basis of the population analyses on the Pt(IV) complexes it is suggested that the Pt-H and Pt-CH{sub 3} bonds are best described as covalent bonds and, further, that the preference of the hydride and methyl anions to be cis to each other is a consequence of such covalent bonding. In light of these findings, the energies of several methyl Pt(IV) hydrido bisulfate complexes were also recalculated

  6. Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson-Nernst-Planck equations involving ionization in a weak electrolyte

    Science.gov (United States)

    Suzuki, Yohichi; Seki, Kazuhiko

    2018-03-01

    We studied ion concentration profiles and the charge density gradient caused by electrode reactions in weak electrolytes by using the Poisson-Nernst-Planck equations without assuming charge neutrality. In weak electrolytes, only a small fraction of molecules is ionized in bulk. Ion concentration profiles depend on not only ion transport but also the ionization of molecules. We considered the ionization of molecules and ion association in weak electrolytes and obtained analytical expressions for ion densities, electrostatic potential profiles, and ion currents. We found the case that the total ion density gradient was given by the Kuramoto length which characterized the distance over which an ion diffuses before association. The charge density gradient is characterized by the Debye length for 1:1 weak electrolytes. We discuss the role of these length scales for efficient water splitting reactions using photo-electrocatalytic electrodes.

  7. Chain-growth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction and its application to one-shot spontaneous block copolymerization.

    Science.gov (United States)

    Sugiyama, Yu-ki; Kato, Rei; Sakurada, Tetsuya; Okamoto, Sentaro

    2011-06-29

    A cobalt-catalyzed alkyne [2 + 2 + 2] cycloaddition reaction has been applied to polymerizations yielding linear polymers via selective cross-cyclotrimerization of yne-diyne monomers, which occurs in a chain-growth manner. Additionally, through control of the alkyne reactivity of the two monomers, this method was efficiently applied to the spontaneous block copolymerization of their mixture. Here we present the proposed mechanism of the catalyst transfer process of this cycloaddition polymerization.

  8. 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.

  9. Quantitation of movement of the phosphoryl group during catalytic transfer in the arginine kinase reaction: {sup 31}P relaxation measurements on enzyme-bound equilibrium mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Bruce D. [Indiana University, Purdue University at Indianapolis (IUPUI), Department of Physics (United States); Jarori, Gotam K. [Tata Institute of Fundamental Research (India); Nageswara Rao, B.D. [Indiana University, Purdue University at Indianapolis (IUPUI), Department of Physics (United States)], E-mail: brao@iupui.edu

    2002-05-15

    {sup 31}P nuclear spin relaxation measurements have been made on enzyme-bound equilibrium mixtures of lobster-muscle arginine kinase in the presence of substituent activating paramagnetic cation Co(II) (in place of Mg(II)), i.e., on samples in which the reaction, E{center_dot}CoATP{center_dot}arginine {r_reversible} E{center_dot}CoADP{center_dot}P-arginine, is in progress. The results have been analyzed on the basis of a previously published theory (Nageswara Rao, B.D. (1995) J. Magn. Reson., B108, 289-293) to determine the structural changes in the reaction complex accompanying phosphoryl transfer. The analysis enables the determination of the change in the Co(II)-{sup 31}P ({gamma}-P(ATP)) vector as the transferable phosphoryl group moves over and attaches to arginine to form P-arginine. It is shown that the Co(II)-{sup 31}P distance of {approx}3.0 A, representing direct coordination of Co(II) to {gamma}-P(ATP), changes to {approx}4.0 A when P-arginine is formed in the enzyme-bound reaction complex. This elongation of the Co(II)-{sup 31}P vector implies an excursion of at least 1.0 A for the itinerant phosphoryl group on the surface of the enzyme.

  10. Quantitation of movement of the phosphoryl group during catalytic transfer in the arginine kinase reaction: 31P relaxation measurements on enzyme-bound equilibrium mixtures

    International Nuclear Information System (INIS)

    Ray, Bruce D.; Jarori, Gotam K.; Nageswara Rao, B.D.

    2002-01-01

    31 P nuclear spin relaxation measurements have been made on enzyme-bound equilibrium mixtures of lobster-muscle arginine kinase in the presence of substituent activating paramagnetic cation Co(II) (in place of Mg(II)), i.e., on samples in which the reaction, E·CoATP·arginine ↔ E·CoADP·P-arginine, is in progress. The results have been analyzed on the basis of a previously published theory (Nageswara Rao, B.D. (1995) J. Magn. Reson., B108, 289-293) to determine the structural changes in the reaction complex accompanying phosphoryl transfer. The analysis enables the determination of the change in the Co(II)- 31 P (γ-P(ATP)) vector as the transferable phosphoryl group moves over and attaches to arginine to form P-arginine. It is shown that the Co(II)- 31 P distance of ∼3.0 A, representing direct coordination of Co(II) to γ-P(ATP), changes to ∼4.0 A when P-arginine is formed in the enzyme-bound reaction complex. This elongation of the Co(II)- 31 P vector implies an excursion of at least 1.0 A for the itinerant phosphoryl group on the surface of the enzyme

  11. Oxidative C-H/C-H Cross-Coupling Reactions between N-Acylanilines and Benzamides Enabled by a Cp*-Free RhCl3/TFA Catalytic System.

    Science.gov (United States)

    You, Jingsong; Shi, Yang; Zhang, Luoqiang; Lan, Jingbo; Zhang, Min; Zhou, Fulin; Wei, Wenlong

    2018-06-03

    Using the dual chelation-assisted strategy, a completely regiocontrolled oxidative C-H/C-H cross-coupling reaction between an N-acylaniline and a benzamide has been accomplished for the first time, which enables a step-economical and highly efficient pathway to 2-amino-2'-carboxybiaryl scaffolds from readily available substrates. A Cp*-free RhCl3/TFA catalytic system has been developed to replace the generally used [Cp*RhCl2]2/AgSbF6 (Cp* = pentamethyl cyclopentadienyl) in oxidative C-H/C-H cross-coupling reactions between two (hetero)arenes. The RhCl3/TFA system avoids the use of expensive Cp* ligand and AgSbF6. As an illustrative example, the protocol developed herein greatly streamlines access to naturally occurring benzo[c]phenanthridine alkaloid oxynitidine in an excellent overall yield. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Computer assisted optimization of sensitivity of the catalytic polarography wave of uranly/nitrate system

    International Nuclear Information System (INIS)

    Betteridge, D.; Wade, A.P.; Neves, E.A.; Gutz, I.

    1982-01-01

    The utilization of 'Simplex' optimization program, writes in Basic language, used to the study of catalytic polarographic wave procedure the reaction of uranium (III) with nitrate in acidic medium at the mercury electrode/solution interface is described. This 'Simplex' optimization requires a much smaller number of experiments to reach an improved condition without increase of the number of trial and error experiments. (C.G.C.) [pt

  13. Interfacial reactions in the Sb–Sn/(Cu, Ni) systems: Wetting experiments

    International Nuclear Information System (INIS)

    Novakovic, R.; Lanata, T.; Delsante, S.; Borzone, G.

    2012-01-01

    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 2.5 Sn 97.5 and Sb 14.5 Sn 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: ► Sb–Sn alloys are used as high temperature lead-free solders. ► Sb–Sn alloys have good wetting properties on Cu and Ni substrates. ► Interfacial reactions and products are important for joint properties. ► Interfacial reactions/products data can be used to study the phase diagrams.

  14. 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.

  15. Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

    Energy Technology Data Exchange (ETDEWEB)

    Aghamohammadi, Sogand [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Charghand, Mojtaba [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of)

    2014-02-01

    Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH{sub 3}-TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH{sub 3}-TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive

  16. Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

    International Nuclear Information System (INIS)

    Aghamohammadi, Sogand; Haghighi, Mohammad; Charghand, Mojtaba

    2014-01-01

    Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH 3 -TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH 3 -TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive thermodynamic

  17. 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.

  18. A reaction time experiment on adult attachment: The development of a measure for neurophysiological settings

    Directory of Open Access Journals (Sweden)

    Theresia Wichmann

    2016-11-01

    Full Text Available In the last decades, there has been an increase of experimental research on automatic unconscious processes concerning the evaluation of the self and others. Previous research investigated implicit aspects of romantic attachment using self-report measures as explicit instruments for assessing attachment style. There is a lack of experimental procedures feasible for neurobiological settings. We developed a reaction time experiment (RT using a narrative attachment measure with an implicit nature and were interested to capture automatic processes, when the individuals’ attachment system is activated. We aimed to combine attachment methodology with knowledge from implicit measures by using a decision reaction time paradigm. This should serve as a means to capture implicit aspects of attachment. This experiment evaluated participants’ response to prototypic attachment sentences in association with their own attachment classification, measured with the Adult Attachment Projective Picture System (AAP.First the AAP was administered as the standardized interview procedure to 30 healthy participants, which were classified into a secure or insecure group. In the following experimental session, both experimenter and participants were blind with respect to classifications. 128 prototypically secure or insecure sentences related to the 8 pictures of the AAP were presented to the participants. Their response and reaction times were recorded. Based on the response (accept, reject a continuous security scale was defined. Both the AAP classification and security scale were related to the reaction times. Differentiated study hypotheses were confirmed for insecure sentences, which were accepted faster by participants from the insecure attachment group (or with lower security scale, and rejected faster by participants form secure attachment group (or with higher security scale. The elaborating unconscious processes were more activated by insecure sentences with

  19. Impact of transamination reactions and protein turnover on labeling dynamics in C-13-labeling experiments

    DEFF Research Database (Denmark)

    Grotkjær, Thomas; Åkesson, M.; Christensen, Bjarke

    2004-01-01

    A dynamic model describing carbon atom transitions in the central metabolism of Saccharomyces cerevisiae is used to investigate the influence of transamination reactions and protein turnover on the transient behavior of C-13-labeling chemostat experiments. The simulations performed suggest...... that carbon exchange due to transamination and protein turnover can significantly increase the required time needed for metabolites in the TCA cycle to reach isotopic steady state, which is in agreement with published experimental observations. On the other hand, transamination and protein turnover will speed...... behavior until after three residence times. These observations suggest that greater caution should be used while also pointing to new opportunities in the design and interpretation of C-13-labeling experiments....

  20. Analyses for experiment on sodium-water reaction temperature by the CHAMPAGNE code

    International Nuclear Information System (INIS)

    Yoshioka, Naoki; Kishida, Masako; Yamada, Yumi

    2000-03-01

    In this work, analyses on sodium-water reaction temperature in the new SWAT-1(SWAT-1R) test were completed by the CHAMPAGNE code in order to understand void and velocity distribution in sodium system, which was difficult to be measured in experiments. The application method of the RELAP5/Mod2 code was investigated to LMFBR steam generator (SG) blow down analysis, too. The following results were obtained. (1) Analyses on sodium-water reaction temperature in the SWAT-1R test. 1) Analyses were carried out for the SWAT-1R test under the condition water leak rate 600 g/s by treating the pressure loss coefficient, the interface friction coefficient and the coefficient related to reaction rate as parameters. The effect and mechanism of each parameter on the shape of reaction zone were well understood by these analyses. 2) The void and velocity distribution in sodium system were estimated by use of the most suitable parameters. These analytical results are expected to be useful for planning of the SWAT-1R test and evaluation of test result. (2) Investigation of the RELAP5/Mod2 code. 1) The items to be improved in the RELAP5/Mod2 code were clarified to apply this code to the FBR SG blow down analysis. 2) One of these items was an addition of the shell-side (sodium-side) model. A sodium-side model was designed and added to the RELAP5/Mod2 code. Test calculations were carried out by this improved code and the basic function of this code was confirmed. (author)

  1. 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.

  2. Overview of Battelle-Europe experiments and model development on H2-deflagrations, igniter and catalytic device verifications

    International Nuclear Information System (INIS)

    Wolf, L.; Kanzleiter, T.; Behrens, U.; Langer, G.; Fischer, K.; Holzbauer, H.; Seidler, M.; Wolff, U.

    1991-01-01

    The design and implementation of an optimal mitigation strategy against the potential threat by H 2 -deflagrations/detonations in the aftermath of least probable severe accidents necessitates a knowledge base about these phenomena for representative conditions and realistic geometries. In order to extend existing know-how into the area of multi-compartment geometries connected by vents, the German Ministry of Research and Technology (BMFT) initiated in 1987 and fully sponsored since 1988 a multi-faceted experimental research program on H 2 -deflagrations and related issues in multi-compartment geometries in the Battelle Model Containment (BMC). The following test groups constitute the Battelle-program: Test Group H: basic tests in H 2 -air and H 2 -steam air-mixtures; Test Group I: (sponsored by industry): supplemental tests in H 2 -air and H 2 -steam-air atmospheres; Test Group G: efficiency of H 2 -mitigative measures such as igniters, catalyst modules and combinations thereof. Thus far, a total of 70 experiments have been performed and evaluated. The paper gives an overview of the Battelle-program by reviewing the examined geometries, bandwidths of tested H 2 -concentrations, steam concentrations, ignition locations, specific atmospheric conditions (homogeneous, stratified) and other important parameters varied during and among the different test groups H, G, and I. Some experimental findings are reported

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

    Science.gov (United States)

    A groundwater treatment technology based on catalytic reductive dehalogenation has been developed to efficiently destroy chlorinated hydrocarbons in situ using a reactive well approach. The treatment process utilizes dissolved H2 as an electron donor, in...

  9. 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.

  10. FAST GC-FID METHOD FOR MONITORING ACIDIC AND BASIC CATALYTIC TRANSESTERIFICATION REACTIONS IN VEGETABLE OILS TO METHYL ESTER BIODIESEL PREPARATION

    Directory of Open Access Journals (Sweden)

    Renata Takabayashi Sato

    2016-04-01

    Full Text Available A fast gas chromatography with a flame ionisation detector (GC-FID method for the simultaneous analysis of methyl palmitate (C16:0, stearate (C18:0, oleate (C18:1, linoleate (C18:2 and linolenate (C18:3 in biodiesel samples was proposed. The analysis was conducted in a customised ionic-liquid stationary-phase capillary, SLB-IL 111, with a length of 14 m, an internal diameter of 0.10 mm, a film thickness of 0.08 µm and operated isothermally at 160 °C using hydrogen as the carrier gas at a rate of 50 cm s-1 in run time about 3 min. Once methyl myristate (C14:0 is present lower than 0.5% m/m in real samples it was used as an internal standard. The method was successful applied to monitoring basic and acidic catalysis transesterification reactions of vegetable oils such as soybean, canola, corn, sunflower and those used in frying process.

  11. Photonuclear reactions in astrophysical p-process: Theoretical calculations and experiment simulation based on ELI-NP

    Science.gov (United States)

    Xu, Yi; Luo, Wen; Balabanski, Dimiter; Goriely, Stephane; Matei, Catalin; Tesileanu, Ovidiu

    2017-09-01

    The astrophysical p-process is an important way of nucleosynthesis to produce the stable and proton-rich nuclei beyond Fe which can not be reached by the s- and r-processes. In the present study, the astrophysical reaction rates of (γ,n), (γ,p), and (γ,α) reactions are computed within the modern reaction code TALYS for about 3000 stable and proton-rich nuclei with 12 Infrastructure-Nuclear Physics (ELI-NP) facility is being developed, which will provide the great opportunity to experimentally study the photonuclear reactions in p-process. Simulations of the experimental setup for the measurements of the photonuclear reactions 96Ru(γ,p) and 96Ru(γ,α) are performed. It is shown that the experiments of photonuclear reactions in p-process based on ELI-NP are quite promising.

  12. Rapid and facile preparation of zinc ferrite (ZnFe{sub 2}O{sub 4}) oxide by microwave-solvothermal technique and its catalytic activity in heterogeneous photo-Fenton reaction

    Energy Technology Data Exchange (ETDEWEB)

    Anchieta, Chayene G.; Severo, Eric C.; Rigo, Caroline; Mazutti, Marcio A. [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Kuhn, Raquel C., E-mail: raquelckuhn@yahoo.com.br [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Muller, Edson I.; Flores, Erico M.M. [Department of Chemistry, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Moreira, Regina F.P.M. [Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, 88040-970, Florianópolis (Brazil); Foletto, Edson L. [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil)

    2015-06-15

    In this work zinc ferrite (ZnFe{sub 2}O{sub 4}) oxide was rapidly and easily prepared by microwave-solvothermal route and its catalytic property in photo-Fenton reaction was evaluated. The effects of microwave heating time and power on the properties of produced particles were investigated. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and nitrogen adsorption–desorption isotherms were the techniques used for characterizing the solid products. The synthesized material was tested as a catalyst in the degradation of the textile dye molecule by the heterogeneous photo-Fenton process. Characterization results showed that the microwave heating time and power have significant influences on the formation of the phase spinel as well as on its physical properties. The reaction results showed that the ZnFe{sub 2}O{sub 4} oxide has good photocatalytic activity, which can be attributed to high surface area and pore volume, and large pore size. The ZnFe{sub 2}O{sub 4} oxide produced by the microwave irradiation exhibited promising photocatalytic activity for the removal of textile dye, reaching nearly 100% of decolorization at 40 min and 60% of mineralization at 240 min. Therefore, ZnFe{sub 2}O{sub 4} particles rapidly prepared by the microwave route have the potential for use in treatment of textile wastewater by the heterogeneous photo-Fenton process. - Highlights: • ZnFe{sub 2}O{sub 4} was synthesized by microwave-solvothermal method. • ZnFe{sub 2}O{sub 4} was prepared by different microwave heating times and powers. • ZnFe{sub 2}O{sub 4} was used as heterogeneous photo-Fenton catalyst. • Degradation of Procion red dye using heterogeneous photo-Fenton process. • ZnFe{sub 2}O{sub 4} was highly efficient to degrade textile dye under visible light.

  13. Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.

    Science.gov (United States)

    Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua

    2016-03-03

    The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error.

  14. Structural analysis of CuO / CeO{sub 2}-based catalytic materials intended for PROX reaction: Part I; Analise estrutural de materiais cataliticos a base de CuO/CeO{sub 2} destinados a reacao de PROX: parte I

    Energy Technology Data Exchange (ETDEWEB)

    Neiva, L.S.; Simoes, A.N.; Bispo, A.; Ribeiro, M.A.; Gama, L., E-mail: lsoutoneiva@yahoo.com.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Aademica de Engenharia de Materiais

    2011-07-01

    This work relates the synthesis process of CuO/CeO{sub 2} catalytic materials by a combustion reaction method as well as it introduces a structural analysis of the developed material, this structural analysis had as main focus to evaluate the influence of the doping substance (CuO) when being incorporated in the hostess matrix structure that is CeO{sub 2}. The CuO/CeO catalytic materials developed in this work are destined to preferential oxidation of CO reaction (PROX). The developed materials were characterized by XRD, SEM and textural complete analysis by the BET method. According to the results, the CuO incorporation changed crystallinity of the structure of the catalytic materials. On the other hand, the morphologic and textural characteristics did not showed significant differences regarding the presence of the doping substance (CuO) in the structure of the developed materials. The porosity of the structures of the developed catalytic materials belongs to the type macroporous. (author)

  15. 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

  16. Radiation chemical effects in experiments to study the reaction of glass in an environment of gamma-irradiated air, groundwater, and tuff

    International Nuclear Information System (INIS)

    Van Konynenburg, R.A.

    1986-01-01

    The results of experiments performed by John K. Bates et al. on the reaction of nuclear waste glass with a gamma-irradiated 90 0 C aqueous solution were analyzed using theory developed from past research in radiation chemistry. The aqueous solution they used is similar to what would be expected in a water-saturated environment in a nuclear waste repository in tuff. The purpose of our study was to develop an understanding of the radiation-chemical processes that occurred in the Bates et al. experiments so the results could be applied to the design and performance analysis of a proposed repository in unsaturated tuff in Nevada. For the Bates et al. experiments at the highest dose (269 Mrad), which originally contained about 16 ml of ''equilibrated'' water taken from Nevada Test Site Well J-13 and 5.4 ml of air, we predicted that water decomposition to H 2 and O 2 would produce a pressure increase of at least 1.0 MPa at 20 0 C. We also predicted that nitrogen fixation from the air would occur, producing an increase of 1.6 x 10 -4 M in total fixed nitrogen concentration in solution. In addition, an equimolar production of H + would occur, which would be buffered by the HCO 3 - in the water. The fixed nitrogen in solution was predicted to be present as NO 2 - and NO 3 - with the ratio influenced by the presence of materials catalytic to the decomposition of H 2 O 2 . We found reasonable agreement between our predictions and the observations of Bates et al., where comparisons were possible. We apply the results to the proposed Nevada repository to the degree possible, given the different expected conditions

  17. 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.

  18. Cross Sections for Neutron-induced Reactions on Actinide Targets Extracted from Surrogate Experiments: A Status Report

    International Nuclear Information System (INIS)

    Escher, J.E.; Burke, J.T.; Dietrich, F.S.; Lesher, S.R.; Scielzo, N.D.; Thompson, I.J.; Younes, W.

    2009-01-01

    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,γ) 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.

  19. Reaction Rate Benchmark Experiments with Miniature Fission Chambers at the Slovenian TRIGA Mark II Reactor

    Science.gov (United States)

    Štancar, Žiga; Kaiba, Tanja; Snoj, Luka; Barbot, Loïc; Destouches, Christophe; Fourmentel, Damien; Villard, Jean-François AD(; )

    2018-01-01

    A series of fission rate profile measurements with miniature fission chambers, developed by the Commisariat á l'énergie atomique et auxénergies alternatives, were performed at the Jožef Stefan Institute's TRIGA research reactor. Two types of fission chambers with different fissionable coating (235U and 238U) were used to perform axial fission rate profile measurements at various radial positions and several control rod configurations. The experimental campaign was supported by an extensive set of computations, based on a validated Monte Carlo computational model of the TRIGA reactor. The computing effort included neutron transport calculations to support the planning and design of the experiments as well as calculations to aid the evaluation of experimental and computational uncertainties and major biases. The evaluation of uncertainties was performed by employing various types of sensitivity analyses such as experimental parameter perturbation and core reaction rate gradient calculations. It has been found that the experimental uncertainty of the measurements is sufficiently low, i.e. the total relative fission rate uncertainty being approximately 5 %, in order for the experiments to serve as benchmark experiments for validation of fission rate profiles. The effect of the neutron flux redistribution due to the control rod movement was studied by performing measurements and calculations of fission rates and fission chamber responses in different axial and radial positions at different control rod configurations. It was confirmed that the control rod movement affects the position of the maximum in the axial fission rate distribution, as well as the height of the local maxima. The optimal detector position, in which the redistributions would have minimum effect on its signal, was determined.

  20. 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.

  1. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

    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 15bar of oxygen partial pressure (P{sub O{sub 2}}) and at 180, 200 and 220deg. 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{sub O{sub 2}} were 140-160deg. C and 2-9bar, 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 160deg. C and 2 bar of P{sub O{sub 2}}, 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{sub 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.

  2. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    International Nuclear Information System (INIS)

    Suarez-Ojeda, Maria Eugenia; Kim, Jungkwon; Carrera, Julian; Metcalfe, Ian S.; Font, Josep

    2007-01-01

    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 15bar of oxygen partial pressure (P O 2 ) and at 180, 200 and 220deg. 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 O 2 were 140-160deg. C and 2-9bar, 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 160deg. C and 2 bar of P O 2 , 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

  3. Self-propagating exothermic reaction analysis in Ti/Al reactive films using experiments and computational fluid dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Seema, E-mail: seema.sen@tu-ilmenau.de [Technical University of Ilmenau, Department of Materials for Electronics, Gustav-Kirchhoff-Str. 5, 98693 Ilmenau (Germany); Niederrhein University of Applied Science, Department of Mechanical and Process Engineering, Reinarzstraße 49, 47805 Krefeld (Germany); Lake, Markus; Kroppen, Norman; Farber, Peter; Wilden, Johannes [Niederrhein University of Applied Science, Department of Mechanical and Process Engineering, Reinarzstraße 49, 47805 Krefeld (Germany); Schaaf, Peter [Technical University of Ilmenau, Department of Materials for Electronics, Gustav-Kirchhoff-Str. 5, 98693 Ilmenau (Germany)

    2017-02-28

    Highlights: • Development of nanoscale Ti/Al multilayer films with 1:1, 1:2 and 1:3 molar ratios. • Characterization of exothermic reaction propagation by experiments and simulation. • The reaction velocity depends on the ignition potentials and molar ratios of the films. • Only 1Ti/3Al films exhibit the unsteady reaction propagation with ripple formation. • CFD simulation shows the time dependent atom mixing and temperature flow during exothermic reaction. - Abstract: 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. 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. On the Structural Context and Identification of Enzyme Catalytic Residues

    Directory of Open Access Journals (Sweden)

    Yu-Tung Chien

    2013-01-01

    Full Text Available Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.

  6. Catalytic modification of cellulose and hemicellulose - Sugarefine

    Energy Technology Data Exchange (ETDEWEB)

    Repo, T. [Helsinki Univ. (Finland),Laboratory of Inorganic Chemistry], email: timo.repo@helsinki.fi

    2012-07-01

    The main goal of the project is to develop catalytic methods for the modification of lignocellulose-based saccharides in the biorefineries. The products of these reactions could be used for example as biofuel components, raw materials for the chemical industry, solvents and precursors for biopolymers. The catalyst development aims at creating efficient, selective and green catalytic methods for profitable use in biorefineries. The project is divided in three work packages: In WP1 (Catalytic dehydration of cellulose) the aim is at developing non-toxic, efficient methods for the catalytic dehydration of cellulose the target molecule being here 5-hydroxymethylfurfural (5-HMF). 5-HMF is an interesting platform chemical for the production of fuel additives, solvents and polymers. In WP2 (Catalytic reduction), the objective of the catalytic reduction studies is to produce commercially interesting monofunctional chemicals, such as 1-butanol or 2-methyltetrahydrofuran (2-MeTHF). In WP3 (Catalytic oxidation), the research focuses on developing a green and efficient oxidation method for producing acids. Whereas acetic and formic acids are bulk chemicals, diacids such as glucaric and xylaric acids are valuable specialty chemicals for detergent, polymer and food production.

  7. Cold-cap reactions in vitrification of nuclear waste glass: experiments and modeling

    International Nuclear Information System (INIS)

    Chun, Jaehun; Pierce, David A.; Pokorny, Richard; Hrma, Pavel R.

    2013-01-01

    Cold-cap reactions are multiple overlapping reactions that occur in the waste-glass melter during the vitrification process when the melter feed is being converted to molten glass. In this study, we used differential scanning calorimetry (DSC) to investigate cold-cap reactions in a high-alumina high-level waste melter feed. To separate the reaction heat from both sensible heat and experimental instability, we employed the run/rerun method, which enabled us to define the degree of conversion based on the reaction heat and to estimate the heat capacity of the reacting feed. Assuming that the reactions are nearly independent and can be approximated by the nth order kinetics, we obtained the kinetic parameters using the Kissinger method combined with least squares analysis. The resulting mathematical simulation of the cold-cap reactions provides a key element for the development of an advanced cold-cap model

  8. A study on naphtha catalytic reforming reactor simulation and analysis.

    Science.gov (United States)

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-06-01

    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.

  9. A study on naphtha catalytic reforming reactor simulation and analysis

    OpenAIRE

    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 uni...

  10. Effect of the method of introduction of Ca/sup 2 +/ and La/sup 3 +/ cations into the HNA''U'' zeolite on its catalytic properties in the reaction of isobutane alkylation with n-butenes

    Energy Technology Data Exchange (ETDEWEB)

    Razali, B.; Kuznetsov, O.I.; Panchenkov, G.M.

    1981-11-01

    The catalytic activity, selectivity, and stability of the operation of zeolites, synthesized by different methods, in the indicated reaction is investigated. It is shown that the most effective catalysts are specimens synthesized by alternating the ion exchange of Na/sup +/ for La/sup 3+/ or jointly under hydrothermal conditions. It is found that a particular specimen is characterized by the highest efficiency and stability in operation.

  11. 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

  12. Catalytic hydrogenation of carbon monoxide

    International Nuclear Information System (INIS)

    Wayland, B.B.

    1993-12-01

    Focus of this project is on developing new approaches for hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. The strategies to accomplish CO reduction are based on favorable thermodynamics manifested by rhodium macrocycles for producing a series of intermediates implicated in the catalytic hydrogenation of CO. Metalloformyl complexes from reactions of H 2 and CO, and CO reductive coupling to form metallo α-diketone species provide alternate routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics are promising candidates for future development

  13. Clinical experience of adverse drug reaction in gadolinium-DTPA enhancement of MRI

    International Nuclear Information System (INIS)

    Kim, Mi Hyae; Hong, Ju Hee; Lee, Yeon Su; Cha, Kyung Soo; Chang, Suk Il; Lee, Young Chul; Kim, Yeong Soo

    1992-01-01

    Gadopentetate dimenglumine(Gd-DTPA) has low toxicity and good tolerance and it is said that the observed adverse drug reaction of Gd-DTPA is compatible to those of iodinated nonionic contrast media. The overall incidence of adverse drug reaction of Gd-DTPA is even lower than those of iodinated nonionic contrast media. Then, the possibility of potential adverse drug reaction of these contrast media is not fully known and recently, many authors have a growing interest in this point. We have taken 2501 cases of MRI and executed 1467 case of Gd-DTPA enhancement scanning(58.7%) and experienced 12 cases of adverse drug reaction(11 cases: mild reaction, 1 case: severs anaphylactic shock) and the overall incidence of our adverse drug reaction of Gd-DTPA was 0.8%. In conclusion, the adverse drug reaction of Gd-DTPA is not rare and the severe adverse drug reaction of Gd-DTPA may occur. So, the possibility of adverse drug reaction after Gd-DTPA injection should always be kept in mind, especially when the patient has a history of reaction to contrast material, allergy(particularly asthma) and cardiac disease. For the safe use of Gd-DTPA, well trained personnel and nearby emergent care facilities should be available

  14. 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.

  15. Enhancing communication about paediatric medicines: lessons from a qualitative study of parents' experiences of their child's suspected adverse drug reaction.

    Science.gov (United States)

    Arnott, Janine; Hesselgreaves, Hannah; Nunn, Anthony J; Peak, Matthew; Pirmohamed, Munir; Smyth, Rosalind L; Turner, Mark A; Young, Bridget

    2012-01-01

    There is little research on parents' experiences of suspected adverse drug reactions in their children and hence little evidence to guide clinicians when communicating with families about problems associated with medicines. To identify any unmet information and communication needs described by parents whose child had a suspected adverse drug reaction. Semi-structured qualitative interviews with parents of 44 children who had a suspected adverse drug reaction identified on hospital admission, during in-patient treatment or reported by parents using the Yellow Card Scheme (the UK system for collecting spontaneous reports of adverse drug reactions). Interviews were conducted face-to-face or by telephone; most interviews were audiorecorded and transcribed. Analysis was informed by the principles of the constant comparative method. Many parents described being dissatisfied with how clinicians communicated about adverse drug reactions and unclear about the implications for their child's future use of medicines. A few parents felt that clinicians had abandoned their child and reported refusing the use of further medicines because they feared a repeated adverse drug reaction. The accounts of parents of children with cancer were different. They emphasised their confidence in clinicians' management of adverse drug reactions and described how clinicians prospectively explained the risks associated with medicines. Parents linked symptoms to medicines in ways that resembled the established reasoning that clinicians use to evaluate the possibility that a medicine has caused an adverse drug reaction. Clinicians' communication about adverse drug reactions was poor from the perspective of parents, indicating that improvements are needed. The accounts of parents of children with cancer indicate that prospective explanation about adverse drug reactions at the time of prescription can be effective. Convergence between parents and clinicians in their reasoning for linking children

  16. Enhancing communication about paediatric medicines: lessons from a qualitative study of parents' experiences of their child's suspected adverse drug reaction.

    Directory of Open Access Journals (Sweden)

    Janine Arnott

    Full Text Available There is little research on parents' experiences of suspected adverse drug reactions in their children and hence little evidence to guide clinicians when communicating with families about problems associated with medicines.To identify any unmet information and communication needs described by parents whose child had a suspected adverse drug reaction.Semi-structured qualitative interviews with parents of 44 children who had a suspected adverse drug reaction identified on hospital admission, during in-patient treatment or reported by parents using the Yellow Card Scheme (the UK system for collecting spontaneous reports of adverse drug reactions. Interviews were conducted face-to-face or by telephone; most interviews were audiorecorded and transcribed. Analysis was informed by the principles of the constant comparative method.Many parents described being dissatisfied with how clinicians communicated about adverse drug reactions and unclear about the implications for their child's future use of medicines. A few parents felt that clinicians had abandoned their child and reported refusing the use of further medicines because they feared a repeated adverse drug reaction. The accounts of parents of children with cancer were different. They emphasised their confidence in clinicians' management of adverse drug reactions and described how clinicians prospectively explained the risks associated with medicines. Parents linked symptoms to medicines in ways that resembled the established reasoning that clinicians use to evaluate the possibility that a medicine has caused an adverse drug reaction.Clinicians' communication about adverse drug reactions was poor from the perspective of parents, indicating that improvements are needed. The accounts of parents of children with cancer indicate that prospective explanation about adverse drug reactions at the time of prescription can be effective. Convergence between parents and clinicians in their reasoning for

  17. Enhancing Communication about Paediatric Medicines: Lessons from a Qualitative Study of Parents' Experiences of Their Child's Suspected Adverse Drug Reaction

    Science.gov (United States)

    Arnott, Janine; Hesselgreaves, Hannah; Nunn, Anthony J.; Peak, Matthew; Pirmohamed, Munir; Smyth, Rosalind L.

    2012-01-01

    Background There is little research on parents' experiences of suspected adverse drug reactions in their children and hence little evidence to guide clinicians when communicating with families about problems associated with medicines. Objective To identify any unmet information and communication needs described by parents whose child had a suspected adverse drug reaction. Methods Semi-structured qualitative interviews with parents of 44 children who had a suspected adverse drug reaction identified on hospital admission, during in-patient treatment or reported by parents using the Yellow Card Scheme (the UK system for collecting spontaneous reports of adverse drug reactions). Interviews were conducted face-to-face or by telephone; most interviews were audiorecorded and transcribed. Analysis was informed by the principles of the constant comparative method. Results Many parents described being dissatisfied with how clinicians communicated about adverse drug reactions and unclear about the implications for their child's future use of medicines. A few parents felt that clinicians had abandoned their child and reported refusing the use of further medicines because they feared a repeated adverse drug reaction. The accounts of parents of children with cancer were different. They emphasised their confidence in clinicians' management of adverse drug reactions and described how clinicians prospectively explained the risks associated with medicines. Parents linked symptoms to medicines in ways that resembled the established reasoning that clinicians use to evaluate the possibility that a medicine has caused an adverse drug reaction. Conclusion Clinicians' communication about adverse drug reactions was poor from the perspective of parents, indicating that improvements are needed. The accounts of parents of children with cancer indicate that prospective explanation about adverse drug reactions at the time of prescription can be effective. Convergence between parents and

  18. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  19. synthesis, characterization, electrical and catalytic studies of some

    African Journals Online (AJOL)

    B. S. Chandravanshi

    catalytic activity of the VO(IV) and Mn(III) complexes have been tested in the epoxidation reaction of styrene ... Vanadyl sulfate pentahydrate, chromium chloride hexahydrate, anhydrous ferric ..... The catalytic oxidation of styrene gives the products styrene oxide, benzaldehyde, benzoic acid, ... bond via a radical mechanism.

  20. Reaction to the Special Issue on Centralizing the Experiences of LGB People of Color in Counseling Psychology

    Science.gov (United States)

    Zea, Maria Cecilia

    2010-01-01

    This reaction article comments on the Major Contribution "Centralizing the Experiences of LGB People of Color in Counseling Psychology." The content analysis of the published literature on lesbian, gay, and bisexual (LGB) people of color from 1998 to 2007 provides much-needed information that will help psychologists set future research agendas and…

  1. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    The objective of this thesis is to report the development of a new, alternative process for the flexible production of nitrile compounds in continuous flow. Nitriles are an important class of compounds that find applications as solvents, chemical intermediates and pharmaceutical compounds......, 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...

  2. Prehospital treatment of burns: a qualitative study of experiences, perceptions and reactions of victims.

    Science.gov (United States)

    Sadeghi Bazargani, H; Fouladi, N; Alimohammadi, H; Sadeghieh Ahari, S; Agamohammadi, M; Mohamadi, R

    2013-08-01

    The manner in which burns are initially managed, at an incident scene, can affect the extent and depth of burn wounds and their final prognosis. The aim of this study was to understand people's experiences, perceptions and reactions towards the initial management of burns and fire accidents in Ardabil Province, Iran. In a qualitative study, 48 burn victims accompanied by their caregivers were enrolled. Focus group discussion (FGD) was used to collect data. All the interviews were recorded, transcribed and analysed using content analysis method. Four categories of information were retrieved in this study, including fire control, scald and burn wound management, seeking medical consultation and severity indicators. Uncertainty regarding what to do when someone catches fire was an evident finding that was explored through the discussions. The results revealed that transferring the patient to the hospital most often takes place after initial treatments administered at home. People believed that cooling a burn wound for a time longer than a few seconds may harm the wound. A strong belief in the efficacy of traditional remedies was disclosed when the statements of participants revealed that traditional or home-made remedies were widely used either to control pain immediately after burn and later during the wound repair process to accelerate the repair or to control the infection and prevent oedema and scar. Among these remedies, pennyroyal and grated potatoes seemed to be the most popular ones. Pennyroyal was thought to prevent infection and potatoes were used to relieve pain. People doubted the capability of health-care workers who work in rural health houses. People considered electrical burns and burns on the chest to be the most severe types of burns. Inappropriate perceptions regarding initial management of burns existed among the participants that should be addressed in future quantitative research or through developing programmes on secondary prevention of burns

  3. Influence of the milling process on the structure and morphology of ZnAl{sub 2}O{sub 4} and catalytic performance in the methyl transesterification reaction of soybean oil; Influencia do processo de moagem na estrutura e morfologia de ZnAl{sub 2}O{sub 4} e no desempenho catalitico na reacao de transesterificacao metilica do oleo de soja

    Energy Technology Data Exchange (ETDEWEB)

    Feitosa, A.C.; Dantas, B.B.; Santana, A.; Costa, A.C.M.F., E-mail: alexcaval2@hotmail.com [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia de Materiais; Costa, D.B. [Universidade Federal de Alagoas (UFAL), Maceio, AL (Brazil). Departamento de Quimica

    2012-07-01

    This work aimed to evaluate the effect of milling time over the structure and morphology of ZnAl{sub 2}O{sub 4}, synthesized by combustion reaction, and study the effect of milled samples over the methyl transesterification reaction of soy bean oil. ZnAl{sub 2}O{sub 4} was synthesizing, by means combustion reaction, using a electrical resistance plate. The powder was milled over 15, 30, 45 and 60 minutes and the samples were characterized by X-ray diffraction, scanning electron micrograph, particle size distribution and N{sub 2} adsorption isotherms. Milling process promoted changes over the agglomerate size and textural characteristics of the samples. Catalytic tests were conducted at 160 deg C, with 1% of catalyst, with molar ratio oil:methanol of 1:6 and reaction time of 1 hour. According the results, the sample milled over 30 minutes showed the highest conversion. (author)

  4. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii

    1979-12-01

    A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.

  5. Toward a catalytic site in DNA

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Vogel, Stefan

    2007-01-01

    A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented....

  6. Catalytic asymmetric synthesis of the alkaloid (+)-myrtine

    NARCIS (Netherlands)

    Pizzuti, Maria Gabriefla; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    A new protocol for the asymmetric synthesis of trans-2,6-disubstituted-4-piperidones has been developed using a catalytic enantioselective conjugate addition reaction in combination with a diastereoselective lithiation-substitution sequence; an efficient synthesis of (+)-myrtine has been achieved

  7. Catalytic oxidation of cyclohexane to cyclohexanone

    Indian Academy of Sciences (India)

    ... a precursor and characterized by chemical analysis using the ICP–AES method, XRD, TEM, FTIR and BET surface area determination. The oxidation reaction was carried out at 70°C under atmospheric pressure. The results showed the catalytic performance of Pt/Al2O3 as being very high in terms of turnover frequency.

  8. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank

    2014-01-01

    45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal...

  9. Catalytic conversion of 11C-labeled methanol over Cs-ZSM-5 zeolite

    International Nuclear Information System (INIS)

    Sarkadi-Priboczki, E.; Kovacs, Z.; Kumar, N.; Salmi, T.; Murzin, D.Yu.

    2004-01-01

    Reaction mechanism of the conversion of 11 C labeled methanol over basic Cs-ZSM-5 zeolite catalyst was investigated and the reaction products obtained were compared with that of H-ZSM-5 acidic catalyst. The catalytic experiments were carried out by passing 11 C-labeled methanol with He as a carrier gas over Cs-ZSM-5 packed in a micro reactor. After adsorption of the radio methanol, the catalyst was heated up to 330 deg C. The products of the catalytic conversion of the 11 C-labeled methanol were analyzed by radio-gas chromatography (gas chromatograph with thermal conductivity detector on-line coupled with a radioactivity detector). (N.T.)

  10. Catalytic Transformation of Ethylbenzene over Y-Zeolite-based Catalysts

    KAUST Repository

    Al-Khattaf, Sulaiman

    2008-01-01

    Catalytic transformation of ethylbenzene (EB) has been investigated over ultrastable Y (USY)-zeolite-based catalysts in a novel riser simulator at different operating conditions. The effect of reaction conditions on EB conversion is reported

  11. The Catalytic Enantioselective Total Synthesis of (+)‐Liphagal

    DEFF Research Database (Denmark)

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.

    2011-01-01

    Ring a ding: The first catalytic enantioselective total synthesis of the meroterpenoid natural product (+)-liphagal is disclosed. The approach showcases a variety of technology including enantioselective enolate alkylation, a photochemical alkyne-alkene [2+2] reaction, microwaveassisted metal...

  12. Quantum catalysis : the modelling of catalytic transition states

    NARCIS (Netherlands)

    Hall, M.B.; Margl, P.; Naray-Szabo, G.; Schramm, Vern; Truhlar, D.G.; Santen, van R.A.; Warshel, A.; Whitten, J.L.; Truhlar, D.G.; Morokuma, K.

    1999-01-01

    A review with 101 refs.; we present an introduction to the computational modeling of transition states for catalytic reactions. We consider both homogeneous catalysis and heterogeneous catalysis, including organometallic catalysts, enzymes, zeolites and metal oxides, and metal surfaces. We summarize

  13. Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

    Science.gov (United States)

    Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

    2005-12-09

    In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

  14. Proton-gamma coincidence experiment on medium mass nuclei at 400MeV and study of reaction mechanisms

    International Nuclear Information System (INIS)

    Baldit, Alain.

    1981-01-01

    Previous γ ray production experiments produced by proton on nuclei show important cross sections for residual nuclei corresponding to a four nucleon (2p + 2n) removal. With our (p - γ) coincidence experiment the forward emitted proton reflects the primary interaction and the γ spectra characterizes the final state of the reaction. Protons are detected with a magnetic spectrometer and γ rays are selected with a Ge(Li) diode. Angular and momentum analysis of scattered protons demonstrate a primary quasi free process on nucleons. No indication of knock out reactions on clusters has been seen. The residual nuclei are mainly produced by evaporation processes. A theoretical calculation involving intranuclear cascades and evaporation processes has been performed. The nucleus model is based upon a Fermi gas and nuclear density agrees with diffusion electron experiments. Residual nuclei far from target are well described with a such model. Residual nuclei near the target are sensitive to the nuclear structure [fr

  15. The H2 + + He proton transfer reaction: quantum reactive differential cross sections to be linked with future velocity mapping experiments

    Science.gov (United States)

    Hernández Vera, Mario; Wester, Roland; Gianturco, Francesco Antonio

    2018-01-01

    We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ion {{{H}}}2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

  16. Preparation of a Strong Thin Polonium Source And Preliminary Experiments on the Yield of (α,n) Reactions

    International Nuclear Information System (INIS)

    Broda, E.

    1945-01-01

    This report was written by E. Broda and P. K. Wright at the Cavendish Laboratory (Cambridge) in July 1945 and is about the preparation of a strong thin polonium source and preliminary experiments on the yield of (alpha,n) reactions. This report includes the experiment description, the discussion of the results and consist of 4 parts: (1) the electrode position of polonium under different conditions (2) a standard procedure for preparation of strong thin Po sources (3) a simple method for the recovery of RaD from complex mixtures (4) some preliminary experiments with a Po source. (nowak)

  17. Preparation of a Strong Thin Polonium Source And Preliminary Experiments on the Yield of (α,n) Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Broda, E.

    1945-07-01

    This report was written by E. Broda and P. K. Wright at the Cavendish Laboratory (Cambridge) in July 1945 and is about the preparation of a strong thin polonium source and preliminary experiments on the yield of (alpha,n) reactions. This report includes the experiment description, the discussion of the results and consist of 4 parts: (1) the electrode position of polonium under different conditions (2) a standard procedure for preparation of strong thin Po sources (3) a simple method for the recovery of RaD from complex mixtures (4) some preliminary experiments with a Po source. (nowak)

  18. 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.

  19. Dynamics of ion–molecule reactions from beam experiments: A historical survey

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk; Futrell, J. H.

    2015-01-01

    Roč. 377, FEB 2015 (2015), s. 84-92 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Ion–molecule reactions * Dynamics * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  20. 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.

  1. Some experiments on the primary electron acceptor in reaction centres from Rhodopseudomanas sphaeroides

    Energy Technology Data Exchange (ETDEWEB)

    Wraight, C A; Cogdell, R J; Clayton, R K

    1975-01-01

    The bacterial reaction center absorbance change at 450 nm (A-450), assigned to an anionic semiquinone, has been suggested as a candidate for the reduced form of the primary electron acceptor in bacterial photosynthesis. In reaction centers of Rhodopseudomonas sphaeroides we have found kinetic discrepancies between the decay of A-450 and the recovery of photochemical competence. In addition, no proton uptake is measurable on the first turnover, although subsequent ones elicit one proton bound per electron. These results are taken to indicate that the acceptor reaction after a long dark period may be different for the first turnover than for subsequent ones. It is suggested that A-450 is still a likely candidate for the acceptor function but that in reaction centers, additional quinone may act as an adventitious primary acceptor when the ''true'' primary acceptor is reduced. Alternatively, the primary acceptor may act in a ''ping-pong'' fashion with respect to subsequent photoelectrons.

  2. Adverse Reactions in Allogeneic Blood Donors: A Tertiary Care Experience from a Developing Country

    OpenAIRE

    Sultan, Sadia; Baig, Mohammad Amjad; Irfan, Syed Mohammed; Ahmed, Syed Ijlal; Hasan, Syeda Faiza

    2016-01-01

    Objectives: Fragmented blood transfusion services along with an unmotivated blood donation culture often leads to blood shortage. Donor retention is crucial to meet the increasing blood demand, and adverse donor reactions have a negative impact on donor return. The aim of this study was to estimate adverse donor reactions and identify any demographic association.   Methods: We conducted a prospective study between January 2011 and December 2013. A total of 41,759 healthy donors were enrol...

  3. 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

    2012-01-01

    The O(3P) + C2H4 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 + CH2CHO, H + CH3CO, H2 + CH2CO, CH3 + HCO, CH2 + CH2O) 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, CH3 + HCO and H + CH2CHO. The agreement between experimental and theoretical functions is excellent, implying that theory has reached the capability of describing complex multichannel nonadiabatic reactions. PMID:22665777

  4. Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tu, Yuting [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Xiong, Ya; Tian, Shuanghong [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275 (China); Kong, Lingjun [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Descorme, Claude, E-mail: claude.descorme@ircelyon.univ-lyon1.fr [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2014-07-15

    Highlights: • A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared. • FeSC exhibited high catalytic activity in the wet air oxidation of 2-chlorophenol. • A strong correlation was observed between the 2-CP conversion, the iron leaching and the pH. • Using an acetate buffer, the iron leaching was suppressed while keeping some catalytic activity. • A simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst. - Abstract: A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pH{sub PZC}, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120 °C under 0.9 MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5 h and 90% Total Organic Carbon (TOC) was removed after 24 h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

  5. Determination of transport and reaction swarm coefficients from the analysis of complex transient pulses from the pulsed Townsend experiment

    International Nuclear Information System (INIS)

    Bekstein, A; De Urquijo, J; Rodríguez-Luna, J C; Juárez, A M; Ducasse, O

    2012-01-01

    We present in this paper the interpretation and analysis of transient pulses from a pulsed Townsend experiment by solving the continuity equations of the charged carriers (electrons and ions) involved in the avalanche. The set of second order partial differential equations is solved by SIMAV, a simulator designed specifically for the pulsed Townsend avalanche. Complex situations involving processes such as electron detachment, ion-molecule reactions, Penning ionization and secondary electron emission from ion impact at the cathode, virtually impossible to solve analytically, are discussed here to illustrate the capability of the simulator to help explain the various reaction processes involved in the avalanche, and also to derive some of the transport and reaction coefficients.

  6. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  7. Catalytic reduction of hexaminecobalt(III) by pitch-based spherical activated carbon (PBSAC)

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu; Mao, Yan-Peng; Zhu, Hai-Song; Cheng, Jing-Yi; Long, Xiang-Li; Yuan, Wei-Kang [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China)

    2010-07-15

    The wet ammonia (NH{sub 3}) desulfurization process can be retrofitted to remove nitric oxide (NO) and sulfur dioxide (SO{sub 2}) simultaneously by adding soluble cobalt(II) salt into the aqueous ammonia solution. Activated carbon is used as a catalyst to regenerate hexaminecobalt(II), Co(NH{sub 3}){sub 6}{sup 2+}, so that NO removal efficiency can be maintained at a high level for a long time. In this study, the catalytic performance of pitch-based spherical activated carbon (PBSAC) in the simultaneous removal of NO and SO{sub 2} with this wet ammonia scrubbing process has been studied systematically. Experiments have been performed in a batch stirred cell to test the catalytic characteristics of PBSAC in the catalytic reduction of hexaminecobalt(III), Co(NH{sub 3}){sub 6}{sup 3+}. The experimental results show that PBSAC is a much better catalyst in the catalytic reduction of Co(NH{sub 3}){sub 6}{sup 3+} than palm shell activated carbon (PSAC). The Co(NH{sub 3}){sub 6}{sup 3+} reduction reaction rate increases with PBSAC when the PBSAC dose is below 7.5 g/L. The Co(NH{sub 3}){sub 6}{sup 3+} reduction rate increases with its initial concentration. Best Co(NH{sub 3}){sub 6}{sup 3+} conversion is gained at a pH range of 2.0-6.0. A high temperature is favorable to such reaction. The intrinsic activation energy of 51.00 kJ/mol for the Co(NH{sub 3}){sub 6}{sup 3+} reduction catalyzed by PBSAC has been obtained. The experiments manifest that the simultaneous elimination of NO and SO{sub 2} by the hexaminecobalt solution coupled with catalytic regeneration of hexaminecobalt(II) can maintain a NO removal efficiency of 90% for a long time. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  8. Diagnostic technique for measuring fusion reaction rate for inertial confinement fusion experiments at Shen Guang-III prototype laser facility

    International Nuclear Information System (INIS)

    Wang Feng; Peng Xiao-Shi; Liu Shen-Ye; Xu Tao; Kang Dong-Guo

    2013-01-01

    A study is conducted using a two-dimensional simulation program (Lared-s) with the goal of developing a technique to evaluate the effect of Rayleigh-Taylor growth in a neutron fusion reaction region. Two peaks of fusion reaction rate are simulated by using a two-dimensional simulation program (Lared-s) and confirmed by the experimental results. A neutron temporal diagnostic (NTD) system is developed with a high temporal resolution of ∼ 30 ps at the Shen Guang-III (SG-III) prototype laser facility in China, to measure the fusion reaction rate history. With the shape of neutron reaction rate curve and the spherical harmonic function in this paper, the degree of Rayleigh-Taylor growth and the main source of the neutron yield in our experiment can be estimated qualitatively. This technique, including the diagnostic system and the simulation program, may provide important information for obtaining a higher neutron yield in implosion experiments of inertial confinement fusion

  9. Adverse Reactions in Allogeneic Blood Donors: A Tertiary Care Experience from a Developing Country

    Directory of Open Access Journals (Sweden)

    Sadia Sultan

    2016-03-01

    Full Text Available Objectives: Fragmented blood transfusion services along with an unmotivated blood donation culture often leads to blood shortage. Donor retention is crucial to meet the increasing blood demand, and adverse donor reactions have a negative impact on donor return. The aim of this study was to estimate adverse donor reactions and identify any demographic association.   Methods: We conducted a prospective study between January 2011 and December 2013. A total of 41,759 healthy donors were enrolled. Professionally trained donor attendants drew blood and all donors were observed during and following donation for possible adverse events for 20 minutes. Blood donors were asked to report if they suffered from any delayed adverse consequences.   Results: Out of 41,759 blood donors, 537 (1.3% experienced adverse reactions. The incidence was one in every 78 donations. The mean age of donors who experienced adverse events was 26.0±6.8 years, and all were male. Out of 537 donors, 429 (80% developed vasovagal reaction (VVR, 133 (25% had nausea, 63 (12% fainted, 35 (6% developed hyperventilation, 9 (2% had delayed syncope, and 9 (2% developed hematoma. Arterial prick, nerve injury, cardiac arrest, and seizures were not observed. Donors aged less than < 30 years and weighing < 70 kg were significantly associated with VVR, hyperventilation, and nausea (p < 0.005. Undergraduates and Urdu speaking donors also had a significant association with fainting and nausea, respectively (p < 0.05.   Conclusion: The prevalence of adverse events was low at our tertiary center. A VVR was the predominant adverse reaction and was associated with age and weight. Our study highlights the importance of these parameters in the donation process. A well-trained and experienced phlebotomist and pre-evaluation counseling of blood donors could further minimize the adverse reactions.

  10. Adverse Reactions in Allogeneic Blood Donors: A Tertiary Care Experience from a Developing Country.

    Science.gov (United States)

    Sultan, Sadia; Baig, Mohammad Amjad; Irfan, Syed Mohammed; Ahmed, Syed Ijlal; Hasan, Syeda Faiza

    2016-03-01

    Fragmented blood transfusion services along with an unmotivated blood donation culture often leads to blood shortage. Donor retention is crucial to meet the increasing blood demand, and adverse donor reactions have a negative impact on donor return. The aim of this study was to estimate adverse donor reactions and identify any demographic association.  . We conducted a prospective study between January 2011 and December 2013. A total of 41,759 healthy donors were enrolled. Professionally trained donor attendants drew blood and all donors were observed during and following donation for possible adverse events for 20 minutes. Blood donors were asked to report if they suffered from any delayed adverse consequences.  . Out of 41,759 blood donors, 537 (1.3%) experienced adverse reactions. The incidence was one in every 78 donations. The mean age of donors who experienced adverse events was 26.0±6.8 years, and all were male. Out of 537 donors, 429 (80%) developed vasovagal reaction (VVR), 133 (25%) had nausea, 63 (12%) fainted, 35 (6%) developed hyperventilation, 9 (2%) had delayed syncope, and 9 (2%) developed hematoma. Arterial prick, nerve injury, cardiac arrest, and seizures were not observed. Donors aged less than donors also had a significant association with fainting and nausea, respectively (p adverse events was low at our tertiary center. A VVR was the predominant adverse reaction and was associated with age and weight. Our study highlights the importance of these parameters in the donation process. A well-trained and experienced phlebotomist and pre-evaluation counseling of blood donors could further minimize the adverse reactions.

  11. Catalytic combustion in gas stoves - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

    2003-06-01

    Several independent studies show that gas stoves to some degree contribute to the indoor emissions of NO{sub x} especially in situations were the ventilation flow is poor. The peak-NO{sub x} concentrations can reach several hundred ppb but the integral concentration seldom exceeds about 20 - 50 ppb, which corresponds to an indoor-outdoor ratio of about 1 - 2.5. Epidemiological studies indicate increasing problems with respiratory symptoms in sensitive people at concentrations as low as 15 ppb of NO{sub 2}. Consequently, the NO{sub x}-concentration in homes where gas stoves are used is high enough to cause health effects. However, in situations where the ventilation flow is high (utilisation of ventilation hoods) the NO{sub x}-emissions are not likely to cause any health problems. This study has been aimed at investigating the possibilities to reduce the NO{sub x} emissions from gas stoves by replacing the conventional flame combustion with catalytic combustion. The investigation is requested by Swedish Gas Center, and is a following-up work of an earlier conducted feasibility study presented in April-2002. The present investigation reports on the possibility to use cheap and simple retro-fit catalytic design suggestions for traditional gas stoves. Experiments have been conducted with both natural and town gas, and parameters such as emissions of NO{sub x}, CO and unburned fuel gas and thermal efficiency, etc, have been examined and are discussed. The results show that it is possible to reduce the NO{sub x} emissions up to 80% by a simple retro-fit installation, without decreasing the thermal efficiency of the cooking plate. The measured source strengths correspond to indoor NO{sub x} concentrations that are below or equal to the average outdoor concentration, implying that no additional detrimental health effects are probable. The drawback of the suggested installations is that the concentration of CO and in some cases also CH{sub 4} are increased in the flue gases

  12. From thermometric to spectrophotometric kinetic-catalytic methods of analysis. A review.

    Science.gov (United States)

    Cerdà, Víctor; González, Alba; Danchana, Kaewta

    2017-05-15

    Kinetic-catalytic analytical methods have proved to be very easy and highly sensitive strategies for chemical analysis, that rely on simple instrumentation [1,2]. Molecular absorption spectrophotometry is commonly used as the detection technique. However, other detection systems, like electrochemical or thermometric ones, offer some interesting possibilities since they are not affected by the color or turbidity of the samples. In this review some initial experience with thermometric kinetic-catalytic methods is described, up to our current experience exploiting spectrophotometric flow techniques to automate this kind of reactions, including the use of integrated chips. Procedures for determination of inorganic and organic species in organic and inorganic matrices are presented. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Basic visualization experiments on eutectic reaction of boron carbide and stainless steel under sodium-cooled fast reactor conditions

    International Nuclear Information System (INIS)

    Yamano, Hidemasa; Suzuki, Tohru; Kamiyama, Kenji; Kudo, Isamu

    2016-01-01

    This paper describes basic visualization experiments on eutectic reaction and relocation of boron carbide (B 4 C) and stainless steel (SS) under a high temperature condition exceeding 1500degC as well as the importance of such behaviors in molten core during a core disruptive accident in a Generation-IV sodium-cooled fast reactor (750 MWe class) designed in Japan. At first, a reactivity history was calculated using an exact perturbation calculation tool taking into account expected behaviors. This calculation indicated the importance of a relocation behavior of the B 4 C-SS eutectic because its behavior has a large uncertainty in the reactivity history. To clarify this behavior, basic experiments were carried out by visualizing the reaction of a B 4 C pellet contacted with molten SS in a high temperature-heating furnace. The experiments have shown the eutectic reaction visualization as well as freezing and relocation of the B 4 C-SS eutectic in upper part of the solidified test piece due to the density separation. (author)

  14. 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

  15. Dynamics of chemical reactions of multiply-charged cations: Information from beam scattering experiments

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk

    2015-01-01

    Roč. 378, FEB 2015 (2015), s. 113-126 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Multiply-charged ions * Dynamics of chemical reactions * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  16. 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…

  17. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15.

    Science.gov (United States)

    Sun, Qiangqiang; Wang, Yu; Li, Laisheng; Bing, Jishuai; Wang, Yingxin; Yan, Huihua

    2015-04-09

    Comparative experiments were conducted to investigate the catalytic ability of MnO(x)/SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O3/MnO(x)/SBA-15). Adsorption of CA and its intermediates by MnO(x)/SBA-15 was proved unimportant in O3/MnO(x)/SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO3) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO(x)/SBA-15 facilitated the generation of hydroxyl radicals (OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO(x) on SBA-15 were believed to be the main active component in MnO(x)/SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more OH. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. A study on the photocatalytic reaction of the metals and organics

    Energy Technology Data Exchange (ETDEWEB)

    Nah, Jung Won; Cho, Yung Hyun; Sung, Ki Woong; Kim, Yong Ik; Hong, Kwang Bum; Kang, Heui Suk; Koo, Je Hyoo; Kim, Kwang Lak; Paek, Seung Woo; Lee, Han Soo; Chung, Heung Suk [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of); Chung, Yong Won [In Hah Univ., Inchun (Korea, Republic of)

    1994-12-01

    Lead metal ion was selected as the model one in the experiment for photo catalytic reaction containing EDTA. Disappearance rate of lead ion in solution was analyzed with control variables of initial pH value, concentration of chelating agent, and concentration ratio of metal ion and chelating agent. 31 figs, 6 tabs, 67 refs. (Author).

  19. A study on the photocatalytic reaction of the metals and organics

    International Nuclear Information System (INIS)

    Nah, Jung Won; Cho, Yung Hyun; Sung, Ki Woong; Kim, Yong Ik; Hong, Kwang Bum; Kang, Heui Suk; Koo, Je Hyoo; Kim, Kwang Lak; Paek, Seung Woo; Lee, Han Soo; Chung, Heung Suk; Chung, Yong Won

    1994-12-01

    Lead metal ion was selected as the model one in the experiment for photo catalytic reaction containing EDTA. Disappearance rate of lead ion in solution was analyzed with control variables of initial pH value, concentration of chelating agent, and concentration ratio of metal ion and chelating agent. 31 figs, 6 tabs, 67 refs. (Author)

  20. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh M; Bragin, O V

    1978-01-01

    A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.