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Sample records for catalytic reaction studies

  1. An experimental study of catalytic and non-catalytic reaction in heat recirculating reactors and applications to power generation

    NASA Astrophysics Data System (ADS)

    Ahn, Jeongmin

    An experimental study of the performance of a Swiss roll heat exchanger and reactor was conducted, with emphasis on the extinction limits and comparison of results with and without Pt catalyst. At Re<40, the catalyst was required to sustain reaction; with the catalyst self-sustaining reaction could be obtained at Re less than 1. Both lean and rich extinction limits were extended with the catalyst, though rich limits were extended much further. At low Re, the lean extinction limit was rich of stoichiometric and rich limit had equivalence ratios 80 in some cases. Non-catalytic reaction generally occurred in a flameless mode near the center of the reactor. With or without catalyst, for sufficiently robust conditions, a visible flame would propagate out of the center, but this flame could only be re-centered with catalyst. Gas chromatography indicated that at low Re, CO and non-C3 H8 hydrocarbons did not form. For higher Re, catalytic limits were slightly broader but had much lower limit temperatures. At sufficiently high Re, catalytic and gas-phase limits merged. Experiments with titanium Swiss rolls have demonstrated reducing wall thermal conductivity and thickness leads to lower heat losses and therefore increases operating temperatures and extends flammability limits. By use of Pt catalysts, reaction of propane-air mixtures at temperatures 54°C was sustained. Such low temperatures suggest that polymers may be employed as a reactor material. A polyimide reactor was built and survived prolonged testing at temperatures up to 500°C. Polymer reactors may prove more practical for microscale devices due to their lower thermal conductivity and ease of manufacturing. Since the ultimate goal of current efforts is to develop combustion driven power generation devices at MEMS like scales, a thermally self-sustaining miniature power generation device was developed utilizing a single-chamber solid-oxide-fuel-cell (SOFC) placed in a Swiss roll. With the single-chamber design

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

    SciTech Connect

    McCrea, Keith R.

    2001-09-07

    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

  3. Ultrahigh-vacuum chamber equipped with a reaction cell for studying liquid-phase catalytic reactions

    NASA Astrophysics Data System (ADS)

    Gardin, Denis E.; Somorjai, Gabor A.

    1993-05-01

    We describe the construction and operation of a liquid-phase reaction cell designed in our laboratory that is attached to an ultrahigh-vacuum (UHV) chamber equipped with the traditional surface science techniques for structure and composition analysis. The sample surface can be prepared and characterized in the UHV chamber prior to transfer in the liquid-phase reaction cell. The transfer has been designed so that there is no loss of the UHV chamber vacuum integrity, as few parts as possible come into contact with the liquid, the surface stays clean during the transfer. The liquid-phase reaction cell itself is designed to study liquid-phase hydrogenation reactions at pressures up to 2 atm and temperatures up to 70 °C. A 1-mm-diam liquid jet with a velocity up to 6 m/s is produced by a gear pump that is incident on the sample surface to allow good mass transfer at the liquid-solid interface. The progress of the reaction is followed by gas chromatography. We report the reaction rate data for the hydrogenation of cyclohexene on a platinum foil.

  4. Active Site, Catalytic Cycle, and Iodination Reactions of Vanadium Iodoperoxidase: A Computational Study.

    PubMed

    Pacios, Luis F; Gálvez, Oscar

    2010-05-11

    A combined computational study using molecular surfaces and Poisson-Boltzmann electrostatic potentials for proteins and quantum calculations on complexes representing the vanadate cofactor throughout the catalytic cycle is employed to study the activity of vanadium iodoperoxidase (VIPO) from alga Laminaria digitata . A model structure of VIPO is compared with available crystal structures of chloroperoxidases (VClPOs) and bromoperoxidases (VBrPOs) focusing on properties of the active site that concern halogen specificity. It is found that VIPO displays distinctive features regarding electrostatic potentials at the site cavity and the local topography of the cavity entrance. Quantum calculations on cofactor stages throughout the catalytic cycle reveal that, while steps involving binding of hydrogen peroxide and halide oxidization agree with available data on VBrPO, final formation and subsequent release of hypohalous acid could follow a different pathway consisting of His476-assisted protonation of bonded hypoiodite and further displacement by a water molecule. Ab initio free energies of reaction computed to explore iodination of organic substrates predict strongly exoergonic reactions with HOI, whereas other possible iodination reagents give thermodynamically disfavored reactions.

  5. Catalytic diastereoselective petasis reactions.

    PubMed

    Muncipinto, Giovanni; Moquist, Philip N; Schreiber, Stuart L; Schaus, Scott E

    2011-08-22

    Multicomponent Petasis reactions: the first diastereoselective Petasis reaction catalyzed by chiral biphenols that enables the synthesis of syn and anti β-amino alcohols in pure form has been developed. The reaction exploits a multicomponent approach that involves boronates, α-hydroxy aldehydes, and amines. PMID:21751322

  6. Adsorbate structures and catalytic reactions studied in the torrpressure range by scanning tunneling microscopy

    SciTech Connect

    Hwang, Kevin Shao-Lin

    2003-05-23

    High-pressure, high-temperature scanning tunneling microscopy (HPHTSTM) was used to study adsorbate structures and reactions on single crystal model catalytic systems. Studies of the automobile catalytic converter reaction [CO + NO {yields} 1/2 N{sub 2} + CO{sub 2}] on Rh(111) and ethylene hydrogenation [C{sub 2}H{sub 4} + H{sub 2} {yields} C{sub 2}H{sub 6}] on Rh(111) and Pt(111) elucidated information on adsorbate structures in equilibrium with high-pressure gas and the relationship of atomic and molecular mobility to chemistry. STM studies of NO on Rh(111) showed that adsorbed NO forms two high-pressure structures, with the phase transformation from the (2 x 2) structure to the (3 x 3) structure occurring at 0.03 Torr. The (3 x 3) structure only exists when the surface is in equilibrium with the gas phase. The heat of adsorption of this new structure was determined by measuring the pressures and temperatures at which both (2 x 2) and (3 x 3) structures coexisted. The energy barrier between the two structures was calculated by observing the time necessary for the phase transformation to take place. High-pressure STM studies of the coadsorption of CO and NO on Rh(111) showed that CO and NO form a mixed (2 x 2) structure at low NO partial pressures. By comparing surface and gas compositions, the adsorption energy difference between topsite CO and NO was calculated. Occasionally there is exchange between top-site CO and NO, for which we have described a mechanism for. At high NO partial pressures, NO segregates into islands, where the phase transformation to the (3 x 3) structure occurs. The reaction of CO and NO on Rh(111) was monitored by mass spectrometry (MS) and HPHTSTM. From MS studies the apparent activation energy of the catalytic converter reaction was calculated and compared to theory. STM showed that under high-temperature reaction conditions, surface metal atoms become mobile. Ethylene hydrogenation and its poisoning by CO was also studied by STM on Rh

  7. Catalytic Organometallic Reactions of Ammonia

    PubMed Central

    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

  8. A Pt-cluster-based heterogeneous catalyst for homogeneous catalytic reactions: X-ray absorption spectroscopy and reaction kinetic studies of their activity and stability against leaching.

    PubMed

    Li, Yimin; Liu, Jack Hung-Chang; Witham, Cole A; Huang, Wenyu; Marcus, Matthew A; Fakra, Sirine C; Alayoglu, Pinar; Zhu, Zhongwei; Thompson, Christopher M; Arjun, Arpana; Lee, Kihong; Gross, Elad; Toste, F Dean; Somorjai, Gabor A

    2011-08-31

    The design and development of metal-cluster-based heterogeneous catalysts with high activity, selectivity, and stability under solution-phase reaction conditions will enable their applications as recyclable catalysts in large-scale fine chemicals production. To achieve these required catalytic properties, a heterogeneous catalyst must contain specific catalytically active species in high concentration, and the active species must be stabilized on a solid catalyst support under solution-phase reaction conditions. These requirements pose a great challenge for catalysis research to design metal-cluster-based catalysts for solution-phase catalytic processes. Here, we focus on a silica-supported, polymer-encapsulated Pt catalyst for an electrophilic hydroalkoxylation reaction in toluene, which exhibits superior selectivity and stability against leaching under mild reaction conditions. We unveil the key factors leading to the observed superior catalytic performance by combining X-ray absorption spectroscopy (XAS) and reaction kinetic studies. On the basis of the mechanistic understandings obtained in this work, we also provide useful guidelines for designing metal-cluster-based catalyst for a broader range of reactions in the solution phase. PMID:21721543

  9. Advanced Solution Methods for Microkinetic Models of Catalytic Reactions: A Methanol Synthesis Case Study

    SciTech Connect

    Rubert-Nason, Patricia; Mavrikakis, Manos; Maravelias, Christos T.; Grabow, Lars C.; Biegler, Lorenz T.

    2014-04-01

    Microkinetic models, combined with experimentally measured reaction rates and orders, play a key role in elucidating detailed reaction mechanisms in heterogeneous catalysis and have typically been solved as systems of ordinary differential equations. In this work, we demonstrate a new approach to fitting those models to experimental data. For the specific example treated here, by reformulating a typical microkinetic model for a continuous stirred tank reactor to a system of nonlinear equations, we achieved a 1000-fold increase in solution speed. The reduced computational cost allows a more systematic search of the parameter space, leading to better fits to the available experimental data. We applied this approach to the problem of methanol synthesis by CO/CO2 hydrogenation over a supported-Cu catalyst, an important catalytic reaction with a large industrial interest and potential for large-scale CO2 chemical fixation.

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

    PubMed

    Somorjai, Gabor A; Aliaga, Cesar

    2010-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  12. Study on Reaction Products in Plasma-Assisted Selective Catalytic Reduction of NOx

    NASA Astrophysics Data System (ADS)

    Yoshizawa, Hayato; Tochikubo, Fumiyoshi; Uchida, Satoshi; Watanabe, Tsuneo

    Since the gas discharge plasma easily converts NO to NO2, which can be reduced more actively in selective catalytic reduction with hydrocarbons (HC-SCR), the plasma-assisted HC-SCR is an effective method for NOx reduction from diesel engine exhaust gases. In this work, the relation between NOx removal and reaction products is investigated in plasma-assisted HC-SCR in simulated flue gas as parameters of gas composition, plasma specific energy and catalyst temperature. C2H4 is used as a hydrocarbon and commercially available Al2O3 is used as a catalyst. After the plasma treatment of simulated flue gas, HCHO and HCOOH were generated as by-products, while NO was effectively converted to NO2. These by-products were confirmed to be reactive at lower catalyst temperature than C2H4 in HC-SCR. The relation between NOx removal and reaction products suggests that HCHO and HCOOH contribute the effective NOx reduction at low catalyst temperature in plasma-assisted HC-SCR.

  13. Theoretical Study of Plasmon-Enhanced Surface Catalytic Coupling Reactions of Aromatic Amines and Nitro Compounds.

    PubMed

    Zhao, Liu-Bin; Zhang, Meng; Huang, Yi-Fan; Williams, Christopher T; Wu, De-Yin; Ren, Bin; Tian, Zhong-Qun

    2014-04-01

    Taking advantage of the unique capacity of surface plasmon resonance, plasmon-enhanced heterogeneous catalysis has recently come into focus as a promising technique for high performance light-energy conversion. This work performs a theoretical study on the reaction mechanism for conversions of p-aminothiophenol (PATP) and p-nitrothiophenol (PNTP) to aromatic azo species, p,p'-dimercaptoazobenzene (DMAB). In the absence of O2 or H2, the plasmon-driven photocatalysis mechanism (hot electron-hole reactions) is the major reaction channel. In the presence of O2 or H2, the plasmon-assisted surface catalysis mechanism (activated oxygen/hydrogen reactions) is the major reaction channel. The present results show that the coupling reactions of PATP and PNTP strongly depend on the solution pH, the irradiation wavelength, the irradiation power, and the nature of metal substrates as well as the surrounding atmosphere. The present study has drawn a fundamental physical picture for understanding plasmon-enhanced heterogeneous catalysis.

  14. Catalytic reaction in confined flow channel

    DOEpatents

    Van Hassel, Bart A.

    2016-03-29

    A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flow channel.

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

    SciTech Connect

    Rioux, Robert M.

    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.

  16. The Direct Catalytic Asymmetric Aldol Reaction

    PubMed Central

    Brindle, Cheyenne S.

    2013-01-01

    Asymmetric aldol reactions are a powerful method for the construction of carbon-carbon bonds in an enantioselective fashion. Historically this reaction has been performed in a stoichiometric fashion to control the various aspects of chemo-, diastereo-, regio- and enantioselectivity, however, a more atom economical approach would unite high selectivity with the use of only a catalytic amount of a chiral promoter. This critical review documents the development of direct catalytic asymmetric aldol methodologies, including organocatalytic and metal-based strategies. New methods have improved the reactivity, selectivity and substrate scope of the direct aldol reaction and enabled the synthesis of complex molecular targets PMID:20419212

  17. Catalytic Radical Domino Reactions in Organic Synthesis

    PubMed Central

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

    2014-01-01

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

  18. Computational Study of Catalytic Reaction of Quercetin 2,4-Dioxygenase.

    PubMed

    Saito, Toru; Kawakami, Takashi; Yamanaka, Shusuke; Okumura, Mitsutaka

    2015-06-11

    We present a quantum mechanics/molecular mechanics (QM/MM) and QM-only study on the oxidative ring-cleaving reaction of quercetin catalyzed by quercetin 2,4-dioxygenase (2,4-QD). 2,4-QD has a mononuclear type 2 copper center and incorporates two oxygen atoms at C2 and C4 positions of the substrate. It has not been clear whether dioxygen reacts with a copper ion or a substrate radical as the first step. We have found that dioxygen is more likely to bind to a Cu(2+) ion, involving the dissociation of the substrate from the copper ion. Then a Cu(2+)-alkylperoxo complex can be generated. Comparison of geometry and stability between QM-only and QM/MM results strongly indicates that steric effects of the protein environment contribute to maintain the orientation of the substrate dissociated from the copper center. The present QM/MM results also highlight that a prior rearrangement of the Cu(2+)-alkylperoxo complex and a subsequent hydrogen bond switching assisted by the movement of Glu73 can facilitate formation of an endoperoxide intermediate selectively. PMID:25990020

  19. Computational Study of Catalytic Reaction of Quercetin 2,4-Dioxygenase.

    PubMed

    Saito, Toru; Kawakami, Takashi; Yamanaka, Shusuke; Okumura, Mitsutaka

    2015-06-11

    We present a quantum mechanics/molecular mechanics (QM/MM) and QM-only study on the oxidative ring-cleaving reaction of quercetin catalyzed by quercetin 2,4-dioxygenase (2,4-QD). 2,4-QD has a mononuclear type 2 copper center and incorporates two oxygen atoms at C2 and C4 positions of the substrate. It has not been clear whether dioxygen reacts with a copper ion or a substrate radical as the first step. We have found that dioxygen is more likely to bind to a Cu(2+) ion, involving the dissociation of the substrate from the copper ion. Then a Cu(2+)-alkylperoxo complex can be generated. Comparison of geometry and stability between QM-only and QM/MM results strongly indicates that steric effects of the protein environment contribute to maintain the orientation of the substrate dissociated from the copper center. The present QM/MM results also highlight that a prior rearrangement of the Cu(2+)-alkylperoxo complex and a subsequent hydrogen bond switching assisted by the movement of Glu73 can facilitate formation of an endoperoxide intermediate selectively.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    Liu, Cong; Evans, Tabitha J.; Cheng, Lei; Nimlos, Mark R.; Mukarakate, Calvin; Robichaud, David J.; Assary, Rajeev S.; Curtiss, Larry A.

    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.

  2. Crystallographic and catalytic studies of the peroxide-shunt reaction in a diiron hydroxylase.

    PubMed

    Bailey, Lucas J; Fox, Brian G

    2009-09-29

    A diiron hydroxylase reaction typically begins by combination of O2 with a diferrous center to form reactive intermediates capable of hydrocarbon hydroxylation. In this natural cycle, reducing equivalents are provided by specific interactions with electron transfer proteins. The biological process can be bypassed by combining H2O2 with a diferric center, i.e., peroxide-shunt catalysis. Here we show that toluene 4-monooxygenase has a peroxide-shunt reaction that is approximately 600-fold slower than catalysis driven by biological electron transfer. However, the toluene 4-monooxygenase hydroxylase-effector protein complex was stable in the presence of 300 mM H2O2, suggesting overall benign effects of the exogenous oxidant on active site structure and function. The X-ray structure of the toluene 4-monooxygenase hydroxylase-effector protein complex determined from crystals soaked in H2O2 revealed a bound diatomic molecule, assigned to a cis-mu-1,2-peroxo bridge. This peroxo species resides in an active site position adjacent to the hydrogen-bonding substructure established by effector protein binding and faces into the distal cavity where substrate must bind during regiospecific aromatic ring hydroxylation catalysis. These results provide a new structural benchmark for how activated intermediates may be formed and dispatched during diiron hydroxylase catalysis. PMID:19705873

  3. The reduction of carbon dioxide in iron biocatalyst catalytic hydrogenation reaction: a theoretical study.

    PubMed

    Yang, Longhua; Wang, Hongming; Zhang, Ning; Hong, Sanguo

    2013-08-21

    The reaction mechanism of CO₂ hydrogenation catalyzed by [FeH(PP₃)]BF₄ (PP₃ = P(CH₂CH₂PPh₂)₃) had been investigated by DFT calculations. Our calculations indicated that the reduction of carbon dioxide could be carried out via two spin states, the high-spin (HS) triplet state and the low-spin (LS) singlet state. The minimum energy crossing points (MECPs) on the seam of two intersecting PESs (potential energy surfaces) were searched out. Some interesting phenomena, such as the open-loop phenomenon, and the O-rebound process, were demonstrated to be the important causes of the spin crossover. All these calculations gave us insight into the essence of the related experiment from the macro point of view, and helped to verify which spin states the related complexes pertinent were in. All of these researches would help advance the development of efficient and structurally tailorable CO₂ hydrogenation catalysts.

  4. Cage-like copper(II) silsesquioxanes: transmetalation reactions and structural, quantum chemical, and catalytic studies.

    PubMed

    Bilyachenko, Alexey N; Dronova, Marina S; Yalymov, Alexey I; Lamaty, Frédéric; Bantreil, Xavier; Martinez, Jean; Bizet, Christelle; Shul'pina, Lidia S; Korlyukov, Alexander A; Arkhipov, Dmitry E; Levitsky, Mikhail M; Shubina, Elena S; Kirillov, Alexander M; Shul'pin, Georgiy B

    2015-06-01

    The transmetalation of bimetallic copper-sodium silsesquioxane cages, namely, [(PhSiO1.5 )10 (CuO)2 (NaO0.5 )2 ] ("Cooling Tower"; 1), [(PhSiO1.5 )12 (CuO)4 (NaO0.5 )4 ] ("Globule"; 2), and [(PhSiO1.5 )6 (CuO)4 (NaO0.5 )4 (PhSiO1.5 )6 ] ("Sandwich"; 3), resulted in the generation of three types of hexanuclear cylinder-like copper silsesqui- oxanes, [(PhSiO1.5 )12 (CuO)6 (C4 H9 OH)2 (C2 H5 OH)6 ] (4), [(PhSiO1.5 )12 (CuO)6 (C4 H8 O2 )4 (PhCN)2 (MeOH)4 ] (5), and [(PhSiO1.5 )12 (CuO)6 (NaCl)(C4 H8 O2 )12 (H2 O)2 ] (6). The products show a prominent "solvating system-structure" dependency, as determined by X-ray diffraction. Topological analysis of cages 1-6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1, 2, and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols. PMID:25950426

  5. Catalytic Conia-ene and related reactions.

    PubMed

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-01

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years. PMID:26031492

  6. Catalytic Conia-ene and related reactions.

    PubMed

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-01

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

  7. Process for catalytic reaction of heavy oils

    SciTech Connect

    Ushio, M.; Ishii, T.; Morita, T.; Oishi, Y.

    1984-11-13

    A process for catalytic reaction of heavy oils and a particulate solid medium, which comprises withdrawing a part or the whole of the used medium from the reactor, separating the withdrawn particles into the particles which have been rendered magnetic by the deposition thereon of nickel, vanadium, iron and copper originally contained in the heavy oils, and non-magnetic particles, using a high gradient magnetic separator which is so designed that a ferromagnetic matrix is placed in a uniform high magnetic field, and returning the non-magnetic particles of the medium into the reactor for re-use.

  8. An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations

    PubMed Central

    Nakagawa, Masaki; Togashi, Yuichi

    2016-01-01

    Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed. PMID:27047384

  9. An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations.

    PubMed

    Nakagawa, Masaki; Togashi, Yuichi

    2016-01-01

    Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed.

  10. Asymmetric catalytic hydrogenation reactions in supercritical carbon dioxide

    SciTech Connect

    Burk, M.J.; Gross, M.F.; Feng, S.; Tumas, W.

    1995-08-09

    We demonstrate that asymmetric catalytic hydrogenation reactions can be conducted in supercritical CO{sub 2} and that, in some cases, higher enantioselectivities can be achieved in this solvent relative to conventional solvents. These preliminary studies effectively demonstrate the feasibility of conducting highly enantioselective hydrogenation reactions in supercritical CO{sub 2}. Importantly, we have shown that higher enantioselectivities may be achieved in supercritical CO{sub 2} relative to conventional solvents. 16 refs., 2 tabs.

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

    NASA Technical Reports Server (NTRS)

    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.

  12. New model catalysts (platinum nanoparticles) and new techniques (SFG and STM) for studies of reaction intermediates and surface restructuring at high pressures during catalytic reactions

    NASA Astrophysics Data System (ADS)

    Somorjai, G. A.

    1997-11-01

    Single-crystal surfaces have long served us well as model catalysts; however, a new type of model catalyst has been prepared using electron beam lithography. Ordered arrays of platinum nano-particles in the 2.5-50 nm size range are deposited on oxide substrates (silica, alumina, and titania) of 1 cm 2 surface area, and are used in catalyzed surface reactions at high pressures (atmospheres). Their preparation, cleaning, and reactivity is discussed. Scanning tunneling microscopy (STM) and vibrational spectroscopy by sum frequency generation (SFG) can be utilized to monitor the substrate and adsorbate structure, respectively, over a fourteen order of magnitude pressure range (10 -10-10 4 Torr). As a consequence, we can monitor the surface structure and reaction intermediates during high pressure catalytic reactions. An STM that operates at both high pressure (atmosphere) and high temperature has been constructed and utilized to monitor platinum (111) and (110) surface structure during chemisorption of H 2, O 2 and CO, and during catalytic reactions of olefin hydrogenation and hydrogenolysis. Changes of surface structure upon chemisorption and during reactions have been monitored. Catalysis by the platinum tip was also detected in the presence of H 2 or O 2 at high pressures and 300 K, leading to hydrogenation or oxidation of carbonaceous deposits with nanometer spatial resolution. Vibrational spectroscopy using SFG has been used to monitor pressure dependent changes in the chemisorption of CO and NO over Pt(111). Bonding — which is similar to that in Pt m(CO) n (where n/m > 1 ) clusters and for an incommensurate CO overlayer — is observed above 100 Torr. Reaction intermediates that form during ethylene, propylene, and isobutene hydrogenation, as well as CO oxidation, at atmospheric pressures and 300 K were monitored by SFG. The dominant reacting species that hydrogenate are the weakly π-bonded olefins, while the strongly chemisorbed alkylidyne and di-σ bonded

  13. Visible Light Mediated Photoredox Catalytic Arylation Reactions.

    PubMed

    Ghosh, Indrajit; Marzo, Leyre; Das, Amrita; Shaikh, Rizwan; König, Burkhard

    2016-08-16

    anion of the organic dye perylenediimide is excited by a second photon allowing the one electron reduction of acceptor substituted aryl chlorides. The radical anion of the aryl halide fragments under the loss of a halide ion and the aryl radical undergoes C-H arylation with biologically important pyrrole derivatives or adds to a double bond. Rhodamine 6G as an organic photocatalyst allows an even higher degree of control of the reaction. The dye is photoreduced in the presence of an amine donor under irradiation with green light (e.g., 530 nm), yielding its radical anion, which is a mild reducing reagent. The hypsochromic shift of the absorption of the rhodamine 6G radical anion toward blue region of the visible light spectrum allows its selective excitation using blue light (e.g., 455 nm). The excited radical anion is highly reducing and able to activate even bromoanisole for C-H arylation reactions, although only in moderate yield. Photoredox catalytic C-H arylation reactions are valuable alternatives to metal catalyzed reactions. They have an excellent functional group tolerance, could potentially avoid metal containing catalysts, and use visible light as a traceless reagent for the activation of arylating reagents.

  14. Visible Light Mediated Photoredox Catalytic Arylation Reactions.

    PubMed

    Ghosh, Indrajit; Marzo, Leyre; Das, Amrita; Shaikh, Rizwan; König, Burkhard

    2016-08-16

    anion of the organic dye perylenediimide is excited by a second photon allowing the one electron reduction of acceptor substituted aryl chlorides. The radical anion of the aryl halide fragments under the loss of a halide ion and the aryl radical undergoes C-H arylation with biologically important pyrrole derivatives or adds to a double bond. Rhodamine 6G as an organic photocatalyst allows an even higher degree of control of the reaction. The dye is photoreduced in the presence of an amine donor under irradiation with green light (e.g., 530 nm), yielding its radical anion, which is a mild reducing reagent. The hypsochromic shift of the absorption of the rhodamine 6G radical anion toward blue region of the visible light spectrum allows its selective excitation using blue light (e.g., 455 nm). The excited radical anion is highly reducing and able to activate even bromoanisole for C-H arylation reactions, although only in moderate yield. Photoredox catalytic C-H arylation reactions are valuable alternatives to metal catalyzed reactions. They have an excellent functional group tolerance, could potentially avoid metal containing catalysts, and use visible light as a traceless reagent for the activation of arylating reagents. PMID:27482835

  15. Quantum mechanical/molecular mechanical study of catalytic mechanism and role of key residues in methylation reactions catalyzed by dimethylxanthine methyltransferase in caffeine biosynthesis.

    PubMed

    Yue, Yufei; Guo, Hong

    2014-02-24

    The caffeine biosynthetic pathway is of considerable importance for the beverage and pharmaceutical industries which produces two blockbuster products: theobromine and caffeine. The major biochemistry in caffeine biosynthesis starts from the initial substrate of xanthosine and ends with the final product caffeine, with theobromine serving as an intermediate. The key enzyme, S-adenosyl-l-methionine (SAM) dependent 3,7-dimethyl-xanthine methyltransferase (DXMT), catalyzes two important methyl transfer steps in caffeine biosynthesis: (1) methylation of N3 of 7-methylxanthine (7mX) to form theobromine (Tb); (2) methylation of N1 of theobromine to form caffeine (Cf). Although DXMT has been structurally characterized recently, our understanding of the detailed catalytic mechanism and role of key catalytic residues is still lacking. In this work, the quantum mechanical/molecular mechanical (QM/MM) MD and free energy simulations are performed to elucidate the catalytic mechanism of the enzyme-catalyzed reactions and to explain experimental observations concerning the activity of this enzyme. The roles of certain active-site residues are studied, and the results of computer simulation seem to suggest that a histidine residue (His160) at the active site of DXMT may act as a general base/acid catalyst during the methyl transfer process.

  16. Theory and Modeling of Asymmetric Catalytic Reactions.

    PubMed

    Lam, Yu-Hong; Grayson, Matthew N; Holland, Mareike C; Simon, Adam; Houk, K N

    2016-04-19

    Modern density functional theory and powerful contemporary computers have made it possible to explore complex reactions of value in organic synthesis. We describe recent explorations of mechanisms and origins of stereoselectivities with density functional theory calculations. The specific functionals and basis sets that are routinely used in computational studies of stereoselectivities of organic and organometallic reactions in our group are described, followed by our recent studies that uncovered the origins of stereocontrol in reactions catalyzed by (1) vicinal diamines, including cinchona alkaloid-derived primary amines, (2) vicinal amidophosphines, and (3) organo-transition-metal complexes. Two common cyclic models account for the stereoselectivity of aldol reactions of metal enolates (Zimmerman-Traxler) or those catalyzed by the organocatalyst proline (Houk-List). Three other models were derived from computational studies described in this Account. Cinchona alkaloid-derived primary amines and other vicinal diamines are venerable asymmetric organocatalysts. For α-fluorinations and a variety of aldol reactions, vicinal diamines form enamines at one terminal amine and activate electrophilically with NH(+) or NF(+) at the other. We found that the stereocontrolling transition states are cyclic and that their conformational preferences are responsible for the observed stereoselectivity. In fluorinations, the chair seven-membered cyclic transition states is highly favored, just as the Zimmerman-Traxler chair six-membered aldol transition state controls stereoselectivity. In aldol reactions with vicinal diamine catalysts, the crown transition states are favored, both in the prototype and in an experimental example, shown in the graphic. We found that low-energy conformations of cyclic transition states occur and control stereoselectivities in these reactions. Another class of bifunctional organocatalysts, the vicinal amidophosphines, catalyzes the (3 + 2) annulation

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

    ERIC Educational Resources Information Center

    Fraga, E. R.; And Others

    1975-01-01

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

  18. Catalytic Asymmetric 1,4-Addition Reactions of Simple Alkylnitriles.

    PubMed

    Yamashita, Yasuhiro; Sato, Io; Suzuki, Hirotsugu; Kobayashi, Shū

    2015-10-01

    The development of catalytic asymmetric carbon-carbon bond-forming reactions of alkylnitriles that do not have an activating group at the α-position, under proton-transfer conditions, is a challenging research topic. Here, we report catalytic asymmetric direct-type 1,4-addition reactions of alkylnitriles with α,β-unsaturated amides by using a catalytic amount of potassium hexamethyldisilazide (KHMDS) with a chiral macro crown ether. The desired reactions proceeded in high yields with good diastereo- and enantioselectivities. To our knowledge, this is the first example of catalytic asymmetric direct-type 1,4-addition reaction of alkylnitriles without any activating group at the α-position.

  19. Catalytical Conversion of Carbohydrates into Lactic Acid via Hydrothermal Reaction

    NASA Astrophysics Data System (ADS)

    Wei, Zhen; Jin, Fangming; Zhang, Guangyi; Zhang, Shiping; Yao, Guodong

    2010-11-01

    This paper focuses on catalytical conversion of carbohydrates into lactic acid, under the hydrothermal conditions, which may have a promising future for its high speediness and effectiveness. The catalysis of ZnO was investigated to improve the lactic acid yields. The results showed that the lactic acid yields increased immensely by the addition of ZnO. The effects of the reaction time and the addition amount of ZnO on the conversion of carbohydrates to lactic acid were studied. The highest lactic acid yields reached up to 28% starting from glucose after the reaction time of 60 s under the conditions of 0.2 mmol ZnO, 300° C, the filling rate of 35%, and over 30% starting from fructose at the same temperature and filling rate when the reaction time of 40 s and 2.0 mmol ZnO were employed. The collaborative effects of ZnO and NaOH used as the catalysts together at the same time were also studied. Furthermore, the catalytic mechanism of ZnO in the hydrothermal conversion of carbohydrates into lactic acid was discussed.

  20. Fundamental studies of catalytic gasification

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.

    1990-06-01

    Previous work has shown that chars and coal can be gasified with steam in the presence of alkali-transition metal oxide catalysts or alkali-earth alkali catalysts at relatively low temperatures. These studies are to be extended to the investigation of the amounts of catalysts required and whether a throw away catalyst can be used. Fresh versus stored char will be gasified to determine the role of oxidation of the char on gasification rates. Less expensive catalyst materials such as sodium instead of potassium and iron instead of nickel will be explored. Reaction rates will be determined in the presence of nitrogen, Co and CO{sub 2}. Reactions of methane and carbon solids in the presence of an oxidizing agent such as water, oxygen, and/or carbon dioxide will be explored in the presence of similar catalyst. This quarter, additional experiments on catalytic gasification of coal were carried out. Major emphasis, however, was on the production of C{sub 2} and higher hydrocarbons from methane at very high selectivities. Catalysts studied include KCaNiO. 6 figs., 1 tab.

  1. Direct Catalytic Enantio- and Diastereoselective Ketone Aldol Reactions of Isocyanoacetates**

    PubMed Central

    delaCampa, Raquel; Ortín, Irene; Dixon, Darren J

    2015-01-01

    A catalytic asymmetric aldol addition/cyclization reaction of unactivated ketones with isocyanoacetate pronucleophiles has been developed. A quinine-derived aminophosphine precatalyst and silver oxide were found to be an effective binary catalyst system and promoted the reaction to afford chiral oxazolines possessing a fully substituted stereocenter with good diastereoselectivities and excellent enantioselectivities. PMID:25735645

  2. Catalytic enantioselective intramolecular aza-diels-alder reactions.

    PubMed

    Min, Chang; Lin, Chih-Tsung; Seidel, Daniel

    2015-05-26

    A readily available chiral Brønsted acid was identified as an efficient catalyst for intramolecular Povarov reactions. Polycyclic amines containing three contiguous stereogenic centers were obtained with excellent stereocontrol in a single step from secondary anilines and aldehydes possessing a pendent dienophile. These transformations constitute the first examples of catalytic enantioselective intramolecular aza-Diels-Alder reactions.

  3. Apparatus for fluid-bed catalytic reactions

    SciTech Connect

    Harandi, M.; Owen, H.

    1991-09-17

    This patent describes an apparatus for the conversion of hydrocarbons. It comprises a reactor vessel for containing a fluid bed reaction zone including finely divided catalyst, the reactor vessel further comprising a feed distributor positioned in a lower portion of the reactor vessel, a heat exchange conduit within the reactor vessel in direct contact with the fluid bed reaction zone for transferring heat from a hot circulating fluid to the fluid bed reaction zone, and a catalyst separator positioned in an upper section of the reactor vessel for segregating reaction products from entrained spent catalyst; a first conduit for withdrawing spent catalyst from the fluid bed reaction zone; a feed preheater vessel operatively connected to the first conduit for contacting an aliphatic feedstream with a fluidized bed of the spent catalyst, the feed preheater vessel being sized to provide spent catalyst circulation through the preheater vessel of from about 0.1 to about 100 volumes of spent catalyst per hour.

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

    NASA Astrophysics Data System (ADS)

    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

  5. Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms.

    PubMed

    Cho, Hee Yeon; Morken, James P

    2014-07-01

    Catalytic reactions have played an indispensable role in organic chemistry for the last several decades. In particular, catalytic multicomponent reactions have attracted significant attention due to their efficiency and expediency towards complex molecule synthesis. The presence of bismetallic reagents (e.g. B-B, Si-Si, B-Si, Si-Sn, etc.) in this process renders the products enriched with various functional groups and multiple stereocenters. For this reason, catalytic bismetallative coupling is considered an effective method to generate the functional and stereochemical complexity of simple hydrocarbon substrates. This review highlights key developments of transition-metal catalyzed bismetallative reactions involving multiple π components. Specifically, it will highlight the scope, synthetic applications, and proposed mechanistic pathways of this process.

  6. Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms

    PubMed Central

    Cho, Hee Yeon

    2014-01-01

    Catalytic reactions have played an indispensable role in organic chemistry for the last several decades. In particular, catalytic multicomponent reactions have attracted a lot of attention due to their efficiency and expediency towards complex molecule synthesis. The presence of bismetallic reagents (e.g. B–B, Si–Si, B–Si, Si–Sn, etc.) in this process renders the products enriched with various functional groups and multiple stereocenters. For this reason, catalytic bismetallative coupling is considered an effective method to generate the functional and stereochemical complexity of simple hydrocarbon substrates. This review highlights key developments of transition-metal catalyzed bismetallative reactions involving multiple π components. Specifically, it will highlight the scope, synthetic applications, and proposed mechanistic pathways of this process. PMID:24736839

  7. Catalytic Friedel-Crafts reaction of aminocyclopropanes.

    PubMed

    de Nanteuil, Florian; Loup, Joachim; Waser, Jérôme

    2013-07-19

    A Lewis acid catalyzed Friedel-Crafts reaction between donor-acceptor aminocyclopropanes and indoles and other electron-rich aromatic compounds is reported. Indole alkylation at the C3 position was generally obtained for a broad range of functional groups and substitution patterns. In the case of C3-substituted indoles, C2 alkylation was observed. The reaction gives a rapid access to gamma amino acid derivatives present in numerous bioactive molecules. PMID:23815365

  8. New insights in understanding plasma-catalysis reaction pathways: study of the catalytic ozonation of an acetaldehyde saturated Ag/TiO2/SiO2 catalyst

    NASA Astrophysics Data System (ADS)

    Sauce, Sonia; Vega-González, Arlette; Jia, Zixian; Touchard, Sylvain; Hassouni, Khaled; Kanaev, Andrei; Duten, Xavier

    2015-07-01

    This paper is a preliminary study intended to straighten out the role of reactive oxygen species in the activation mechanisms occurring in a plasma driven catalysis process for acetaldehyde decomposition. For this purpose, the interaction between the surface, the pollutant and one of the main oxidative species generated by non-thermal plasma, namely ozone, was studied. Acetaldehyde catalytic ozonation over a nanostructured Ag/TiO2/SiO2 catalyst is carried out at room temperature and atmospheric pressure, and followed by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS). For this, the catalyst is firstly saturated with acetaldehyde. At the end of the saturation, acetaldehyde and crotonaldehyde, its condensation product, are identified as the major adsorbed species. In a second step, the surface ozonation is carried out and three additional intermediates are identified, namely, acetone, formic acid and acetic acid. Gaseous CO, CO2, methyl formate and methyl acetate are detected at the DRIFTS outlet, evidencing the partial mineralization of the adsorbed species. A global reaction scheme is proposed for explaining the formation of those adsorbed intermediates and gaseous products. This proposed heterogeneous ozone induced chemistry has to be taken into account when associating non-thermal plasma in air to a catalyst. Contribution to the topical issue "The 14th International Symposium on High Pressure Low Temperature Plasma Chemistry (HAKONE XIV)", edited by Nicolas Gherardi, Ronny Brandenburg and Lars Stollenwark

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

    PubMed

    Bezborodov, A M; Zagustina, N A

    2014-01-01

    Aspects of enzymatic catalysis in lipase-catalyzed reactions of organic synthesis are discussed in the review. The data on modern methods of protein engineering and enzyme modification allowing a broader range of used substrates are briefly summarized. The application of lipase in the preparation of pharmaceuticals and agrochemicals containing no inactive enantiomers and in the synthesis of secondary alcohol enantiomers and optically active amides is demonstrated. The subject of lipase involvement in the C-C bond formation in the Michael reaction is discussed. Data on the enzymatic synthesis of construction materials--polyesters, siloxanes, etc.--are presented. Examples demonstrating the application of lipase enzymatic catalysis in industry are given. PMID:25707112

  10. Fe/N/C composite in Li-O2 battery: studies of catalytic structure and activity toward oxygen evolution reaction.

    PubMed

    Shui, Jiang-Lan; Karan, Naba K; Balasubramanian, Mahalingam; Li, Shu-You; Liu, Di-Jia

    2012-10-10

    Atomically dispersed Fe/N/C composite was synthesized and its role in controlling the oxygen evolution reaction during Li-O(2) battery charging was studied by use of a tetra(ethylene glycol) dimethyl ether-based electrolyte. Li-O(2) cells using Fe/N/C as the cathode catalyst showed lower overpotentials than α-MnO(2)/carbon catalyst and carbon-only material. Gases evolved during the charge step contained only oxygen for Fe/N/C cathode catalyst, whereas CO(2) was also detected in the case of α-MnO(2)/C or carbon-only material; this CO(2) was presumably generated from electrolyte decomposition. Our results reiterate the catalytic effect in reducing overpotentials, which not only enhances battery efficiency but also improves its lifespan by reducing or eliminating electrolyte decomposition. The structure of the Fe/N/C catalyst was characterized by transmission electron microscopy, scanning transmission electron microscopy, inductively coupled plasma optical emission spectroscopy, and X-ray absorption spectroscopy. Iron was found to be uniformly distributed within the carbon matrix, and on average, Fe was coordinated by 3.3 ± 0.6 and 2.2 ± 0.3 low Z elements (C/N/O) at bond distances of ~1.92 and ~2.09 Å, respectively. PMID:22998563

  11. Fe/N/C composite in Li-O2 battery: studies of catalytic structure and activity toward oxygen evolution reaction.

    PubMed

    Shui, Jiang-Lan; Karan, Naba K; Balasubramanian, Mahalingam; Li, Shu-You; Liu, Di-Jia

    2012-10-10

    Atomically dispersed Fe/N/C composite was synthesized and its role in controlling the oxygen evolution reaction during Li-O(2) battery charging was studied by use of a tetra(ethylene glycol) dimethyl ether-based electrolyte. Li-O(2) cells using Fe/N/C as the cathode catalyst showed lower overpotentials than α-MnO(2)/carbon catalyst and carbon-only material. Gases evolved during the charge step contained only oxygen for Fe/N/C cathode catalyst, whereas CO(2) was also detected in the case of α-MnO(2)/C or carbon-only material; this CO(2) was presumably generated from electrolyte decomposition. Our results reiterate the catalytic effect in reducing overpotentials, which not only enhances battery efficiency but also improves its lifespan by reducing or eliminating electrolyte decomposition. The structure of the Fe/N/C catalyst was characterized by transmission electron microscopy, scanning transmission electron microscopy, inductively coupled plasma optical emission spectroscopy, and X-ray absorption spectroscopy. Iron was found to be uniformly distributed within the carbon matrix, and on average, Fe was coordinated by 3.3 ± 0.6 and 2.2 ± 0.3 low Z elements (C/N/O) at bond distances of ~1.92 and ~2.09 Å, respectively.

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

    PubMed

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

    2013-12-14

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

  13. Catalytic ignition model in a monolithic reactor with in-depth reaction

    NASA Technical Reports Server (NTRS)

    Tien, Ta-Ching; Tien, James S.

    1990-01-01

    Two transient models have been developed to study the catalytic ignition in a monolithic catalytic reactor. The special feature in these models is the inclusion of thermal and species structures in the porous catalytic layer. There are many time scales involved in the catalytic ignition problem, and these two models are developed with different time scales. In the full transient model, the equations are non-dimensionalized by the shortest time scale (mass diffusion across the catalytic layer). It is therefore accurate but is computationally costly. In the energy-integral model, only the slowest process (solid heat-up) is taken as nonsteady. It is approximate but computationally efficient. In the computations performed, the catalyst is platinum and the reactants are rich mixtures of hydrogen and oxygen. One-step global chemical reaction rates are used for both gas-phase homogeneous reaction and catalytic heterogeneous reaction. The computed results reveal the transient ignition processes in detail, including the structure variation with time in the reactive catalytic layer. An ignition map using reactor length and catalyst loading is constructed. The comparison of computed results between the two transient models verifies the applicability of the energy-integral model when the time is greater than the second largest time scale of the system. It also suggests that a proper combined use of the two models can catch all the transient phenomena while minimizing the computational cost.

  14. Manual control of catalytic reactions: Reactions by an apoenzyme gel and a cofactor gel

    NASA Astrophysics Data System (ADS)

    Kobayashi, Yuichiro; Takashima, Yoshinori; Hashidzume, Akihito; Yamaguchi, Hiroyasu; Harada, Akira

    2015-11-01

    Enzymes play a vital role in catalysing almost all chemical reactions that occur in biological systems. Some enzymes must form complexes with non-protein molecules called cofactors to express catalytic activities. Although the control of catalytic reactions via apoenzyme-cofactor complexes has attracted significant attention, the reports have been limited to the microscale. Here, we report a system to express catalytic activity by adhesion of an apoenzyme gel and a cofactor gel. The apoenzyme and cofactor gels act as catalysts when they form a gel assembly, but they lose catalytic ability upon manual dissociation. We successfully construct a system with switchable catalytic activity via adhesion and separation of the apoenzyme gel with the cofactor gel. We expect that this methodology can be applied to regulate the functional activities of enzymes that bear cofactors in their active sites, such as the oxygen transport of haemoglobin or myoglobin and the electron transport of cytochromes.

  15. Manual control of catalytic reactions: Reactions by an apoenzyme gel and a cofactor gel.

    PubMed

    Kobayashi, Yuichiro; Takashima, Yoshinori; Hashidzume, Akihito; Yamaguchi, Hiroyasu; Harada, Akira

    2015-11-05

    Enzymes play a vital role in catalysing almost all chemical reactions that occur in biological systems. Some enzymes must form complexes with non-protein molecules called cofactors to express catalytic activities. Although the control of catalytic reactions via apoenzyme-cofactor complexes has attracted significant attention, the reports have been limited to the microscale. Here, we report a system to express catalytic activity by adhesion of an apoenzyme gel and a cofactor gel. The apoenzyme and cofactor gels act as catalysts when they form a gel assembly, but they lose catalytic ability upon manual dissociation. We successfully construct a system with switchable catalytic activity via adhesion and separation of the apoenzyme gel with the cofactor gel. We expect that this methodology can be applied to regulate the functional activities of enzymes that bear cofactors in their active sites, such as the oxygen transport of haemoglobin or myoglobin and the electron transport of cytochromes.

  16. Catalytic Ignition and Upstream Reaction Propagation in Monolith Reactors

    NASA Technical Reports Server (NTRS)

    Struk, Peter M.; Dietrich, Daniel L.; Miller, Fletcher J.; T'ien, James S.

    2007-01-01

    Using numerical simulations, this work demonstrates a concept called back-end ignition for lighting-off and pre-heating a catalytic monolith in a power generation system. In this concept, a downstream heat source (e.g. a flame) or resistive heating in the downstream portion of the monolith initiates a localized catalytic reaction which subsequently propagates upstream and heats the entire monolith. The simulations used a transient numerical model of a single catalytic channel which characterizes the behavior of the entire monolith. The model treats both the gas and solid phases and includes detailed homogeneous and heterogeneous reactions. An important parameter in the model for back-end ignition is upstream heat conduction along the solid. The simulations used both dry and wet CO chemistry as a model fuel for the proof-of-concept calculations; the presence of water vapor can trigger homogenous reactions, provided that gas-phase temperatures are adequately high and there is sufficient fuel remaining after surface reactions. With sufficiently high inlet equivalence ratio, back-end ignition occurs using the thermophysical properties of both a ceramic and metal monolith (coated with platinum in both cases), with the heat-up times significantly faster for the metal monolith. For lower equivalence ratios, back-end ignition occurs without upstream propagation. Once light-off and propagation occur, the inlet equivalence ratio could be reduced significantly while still maintaining an ignited monolith as demonstrated by calculations using complete monolith heating.

  17. Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts.

    PubMed

    Cao, Shaowen; Tao, Franklin Feng; Tang, Yu; Li, Yuting; Yu, Jiaguo

    2016-08-22

    Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liquid interfaces with a purpose of establishing correlations of size- and shape-dependent chemical and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a molecular level.

  18. Fluorogenic, catalytic, photochemical reaction for amplified detection of nucleic acids.

    PubMed

    Dutta, Subrata; Fülöp, Annabelle; Mokhir, Andriy

    2013-09-18

    Photochemical, nucleic acid-induced reactions, which are controlled by nontoxic red light, are well-suited for detection of nucleic acids in live cells, since they do not require any additives and can be spatially and temporally regulated. We have recently described the first reaction of this type, in which a phenylselenyl derivative of thymidine (5'-PhSeT-ODNa) is cleaved in the presence of singlet oxygen (Fülöp, A., Peng, X., Greenberg, M. M., Mokhir, A. (2010) A nucleic acid directed, red light-induced chemical reaction. Chem. Commun. 46, 5659-5661). The latter reagent is produced upon exposure of a photosensitizer 3'-PS-ODNb (PS = Indium(III)-pyropheophorbide-a-chloride: InPPa) to >630 nm light. In 2012 we reported on a fluorogenic version of this reaction (Dutta, S., Flottmann, B., Heilemann, M., Mokhir, A. (2012) Hybridization and reaction-based, fluorogenic nucleic acid probes. Chem. Commun. 47, 9664-9666), which is potentially applicable for the detection of nucleic acids in cells. Unfortunately, its yield does not exceed 25% and no catalytic turnover could be observed in the presence of substrate excess. This problem occurs due to the efficient, competing oxidation of the substrate containing an electron rich carbon-carbon double bonds (SCH═CHS) in the presence of singlet oxygen with formation of a noncleavable product (SCH═CHSO). Herein we describe a related, but substantially improved photochemical, catalytic transformation of a fluorogenic, organic substrate, which consists of 9,10-dialkoxyanthracene linked to fluorescein, with formation of a bright fluorescent dye. In highly dilute solution this reaction occurs only in the presence of a nucleic acid template. We developed three types of such a reaction and demonstrated that they are high yielding and generate over 7.7 catalytic turnovers, are sensitive to single mismatches in nucleic acid targets, and can be applied for determination of both the amount of nucleic acids and potentially their

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

    PubMed

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

    2016-04-01

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

  20. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, 1 January--31 March 1994

    SciTech Connect

    Iglesia, E.; Heinemann, H.; Perry, D.L.

    1994-03-01

    This report describes work in progress on three tasks: (1) Catalytic steam gasification of coals and cokes; (2) Oxidative coupling of methane; and (3) Synthesis and characterization of catalysts. Since Task 1 is complete, a final report has been written. This report describes membrane reactors, cyclic methane conversion reactors, theoretical descriptions of reaction-separation schemes, and time-space relationships in cyclic and membrane reactors, all subtasks of Task 2. Initial studies under Task 3 are briefly described.

  1. Elementary steps of the catalytic NOx reduction with NH3: Cluster studies on reaction paths and energetics at vanadium oxide substrate

    NASA Astrophysics Data System (ADS)

    Gruber, M.; Hermann, K.

    2013-12-01

    We consider different reaction scenarios of the selective catalytic reduction (SCR) of NO in the presence of ammonia at perfect as well as reduced vanadium oxide surfaces modeled by V2O5(010) without and with oxygen vacancies. Geometric and energetic details as well as reaction paths are evaluated using extended cluster models together with density-functional theory. Based on earlier work of adsorption, diffusion, and reaction of the different surface species participating in the SCR we confirm that at Brønsted acid sites (i.e., OH groups) of the perfect oxide surface nitrosamide, NH2NO, forms a stable intermediate. Here adsorption of NH3 results in NH4 surface species which reacts with gas phase NO to produce the intermediate. Nitrosamide is also found as intermediate of the SCR near Lewis acid sites of the reduced oxide surface (i.e., near oxygen vacancies). However, here the adsorbed NH3 species is dehydrogenated to surface NH2 before it reacts with gas phase NO to produce the intermediate. The calculations suggest that reaction barriers for the SCR are overall higher near Brønsted acid sites of the perfect surface compared with Lewis acid sites of the reduced surface, examined for the first time in this work. The theoretical results are consistent with experimental findings and confirm the importance of surface reduction for the SCR process.

  2. Elementary steps of the catalytic NO{sub x} reduction with NH{sub 3}: Cluster studies on reaction paths and energetics at vanadium oxide substrate

    SciTech Connect

    Gruber, M.; Hermann, K.

    2013-12-28

    We consider different reaction scenarios of the selective catalytic reduction (SCR) of NO in the presence of ammonia at perfect as well as reduced vanadium oxide surfaces modeled by V{sub 2}O{sub 5}(010) without and with oxygen vacancies. Geometric and energetic details as well as reaction paths are evaluated using extended cluster models together with density-functional theory. Based on earlier work of adsorption, diffusion, and reaction of the different surface species participating in the SCR we confirm that at Brønsted acid sites (i.e., OH groups) of the perfect oxide surface nitrosamide, NH{sub 2}NO, forms a stable intermediate. Here adsorption of NH{sub 3} results in NH{sub 4} surface species which reacts with gas phase NO to produce the intermediate. Nitrosamide is also found as intermediate of the SCR near Lewis acid sites of the reduced oxide surface (i.e., near oxygen vacancies). However, here the adsorbed NH{sub 3} species is dehydrogenated to surface NH{sub 2} before it reacts with gas phase NO to produce the intermediate. The calculations suggest that reaction barriers for the SCR are overall higher near Brønsted acid sites of the perfect surface compared with Lewis acid sites of the reduced surface, examined for the first time in this work. The theoretical results are consistent with experimental findings and confirm the importance of surface reduction for the SCR process.

  3. Catalytic Ignition and Upstream Reaction Propagation in a Platinum Tube

    NASA Technical Reports Server (NTRS)

    Struk, P. M.; Dietrich, D. L.; Mellish, B. P.; Miller, F. J.; T'ien, J. S.

    2007-01-01

    A challenge for catalytic combustion in monolithic reactors at elevated temperatures is the start-up or "light-off" from a cold initial condition. In this work, we demonstrate a concept called "back-end catalytic ignition that potentially can be utilized in the light-off of catalytic monoliths. An external downstream flame or Joule heating raises the temperature of a small portion of the catalyst near the outlet initiating a localized catalytic reaction that propagates upstream heating the entire channel. This work uses a transient numerical model to demonstrate "back-end" ignition within a single channel which can characterize the overall performance of a monolith. The paper presents comparisons to an experiment using a single non-adiabatic channel but the concept can be extended to the adiabatic monolith case. In the model, the time scales associated with solid heat-up are typically several orders of magnitude larger than the gas-phase and chemical kinetic time-scales. Therefore, the model assumes a quasi-steady gas-phase with respect to a transient solid. The gas phase is one-dimensional. Appropriate correlations, however, account for heat and mass transfer in a direction perpendicular to the flow. The thermally-thin solid includes axial conduction. The gas phase, however, does not include axial conduction due to the high Peclet number flows. The model includes both detailed gas-phase and catalytic surface reactions. The experiment utilizes a pure platinum circular channel oriented horizontally though which a CO/O2 mixture (equivalence ratios ranging from 0.6 to 0.9) flows at 2 m/s.

  4. Growth states of catalytic reaction networks exhibiting energy metabolism

    NASA Astrophysics Data System (ADS)

    Kondo, Yohei; Kaneko, Kunihiko

    2011-07-01

    All cells derive nutrition by absorbing some chemical and energy resources from the environment; these resources are used by the cells to reproduce the chemicals within them, which in turn leads to an increase in their volume. In this study we introduce a protocell model exhibiting catalytic reaction dynamics, energy metabolism, and cell growth. Results of extensive simulations of this model show the existence of four phases with regard to the rates of both the influx of resources and cell growth. These phases include an active phase with high influx and high growth rates, an inefficient phase with high influx but low growth rates, a quasistatic phase with low influx and low growth rates, and a death phase with negative growth rate. A mean field model well explains the transition among these phases as bifurcations. The statistical distribution of the active phase is characterized by a power law, and that of the inefficient phase is characterized by a nearly equilibrium distribution. We also discuss the relevance of the results of this study to distinct states in the existing cells.

  5. Growth states of catalytic reaction networks exhibiting energy metabolism.

    PubMed

    Kondo, Yohei; Kaneko, Kunihiko

    2011-07-01

    All cells derive nutrition by absorbing some chemical and energy resources from the environment; these resources are used by the cells to reproduce the chemicals within them, which in turn leads to an increase in their volume. In this study we introduce a protocell model exhibiting catalytic reaction dynamics, energy metabolism, and cell growth. Results of extensive simulations of this model show the existence of four phases with regard to the rates of both the influx of resources and cell growth. These phases include an active phase with high influx and high growth rates, an inefficient phase with high influx but low growth rates, a quasistatic phase with low influx and low growth rates, and a death phase with negative growth rate. A mean field model well explains the transition among these phases as bifurcations. The statistical distribution of the active phase is characterized by a power law, and that of the inefficient phase is characterized by a nearly equilibrium distribution. We also discuss the relevance of the results of this study to distinct states in the existing cells. PMID:21867233

  6. Predicting the Catalytic Reactions using Random Phase Approximation

    NASA Astrophysics Data System (ADS)

    Yan, J.; Olsen, T.; Mortensen, J. J.; Jacobsen, K. W.; Thygesen, K. S.; Abild-Pedersen, F.; Norskov, J. K.

    2012-02-01

    Density functional theory has became the workhorse for simulations of catalytic reactions and computational design of novel catalysis. The generally applied semi-local exchange-correlation functionals have successfully predicted catalytic reaction trends over a variety of surfaces. However, in order to achieve quantitative predictions of reaction rates for molecule-surface systems, in particular where there is weak Van der Waals interactions or strong correlation, it is of vital importance to include non-local correlation effects. The use of random phase approximation (RPA) to construct the correlation energy, combined with the exact, self-interaction free exchange energy, offers a non-empirical way for accurately describe the adsorption energies [1] and dispersion forces [2]. We have recently implemented RPA in the GPAW code [3-4], an electronic structure package using projector augmented wave method and real space grids. In this talk I will present our initial results comparing RPA and generalized gradient functionals for the activation energies and reaction energies for transition metal or metal oxide surfaces. [4pt] [1] L. Schimka, et.al, Nature Mat. 9, 741 (2010) [2] T. Olsen, et.al, Phys. Rev. Lett. 107, 156401 (2011) [3] J. Yan, et.al, Phys. Rev. B 83, 245122 (2011). [4] J. Yan, et.al, Phys. Rev. Lett. 106, 146803 (2011)

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

    PubMed Central

    Yu, Zhiyong; Ely, Robert J.

    2014-01-01

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

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

    PubMed

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

    2014-09-01

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

  9. Catalytic X-H insertion reactions based on carbenoids.

    PubMed

    Gillingham, Dennis; Fei, Na

    2013-06-21

    Catalysed X-H insertion reactions into diazo compounds (where X is any heteroatom) are a powerful yet underutilized class of transformations. The following review will explore the historical development of X-H insertion and give an up-to-date account of the metal catalysts most often employed, including an assessment of their strengths and weaknesses. Despite decades of development, recent work on enantioselective variants, as well as applying catalytic X-H insertion towards problems in chemical biology indicate that this field has ample room for innovation. PMID:23407887

  10. The Influence of Elastic Strain on Catalytic Activity in the Hydrogen Evolution Reaction.

    PubMed

    Yan, Kai; Maark, Tuhina Adit; Khorshidi, Alireza; Sethuraman, Vijay A; Peterson, Andrew A; Guduru, Pradeep R

    2016-05-17

    Understanding the role of elastic strain in modifying catalytic reaction rates is crucial for catalyst design, but experimentally, this effect is often coupled with a ligand effect. To isolate the strain effect, we have investigated the influence of externally applied elastic strain on the catalytic activity of metal films in the hydrogen evolution reaction (HER). We show that elastic strain tunes the catalytic activity in a controlled and predictable way. Both theory and experiment show strain controls reactivity in a controlled manner consistent with the qualitative predictions of the HER volcano plot and the d-band theory: Ni and Pt's activities were accelerated by compression, while Cu's activity was accelerated by tension. By isolating the elastic strain effect from the ligand effect, this study provides a greater insight into the role of elastic strain in controlling electrocatalytic activity. PMID:27079940

  11. On the role of DNA in DNA-based catalytic enantioselective conjugate addition reactions.

    PubMed

    Dijk, Ewold W; Boersma, Arnold J; Feringa, Ben L; Roelfes, Gerard

    2010-09-01

    A kinetic study of DNA-based catalytic enantioselective Friedel-Crafts alkylation and Michael addition reactions showed that DNA affects the rate of these reactions significantly. Whereas in the presence of DNA, a large acceleration was found for the Friedel-Crafts alkylation and a modest acceleration in the Michael addition of dimethyl malonate, a deceleration was observed when using nitromethane as nucleophile. Also, the enantioselectivities proved to be dependent on the DNA sequence. In comparison with the previously reported Diels-Alder reaction, the results presented here suggest that DNA plays a similar role in both cycloaddition and conjugate addition reactions.

  12. Studies of the enzymic mechanism of Candida tenuis xylose reductase (AKR 2B5): X-ray structure and catalytic reaction profile for the H113A mutant.

    PubMed

    Kratzer, Regina; Kavanagh, Kathryn L; Wilson, David K; Nidetzky, Bernd

    2004-05-01

    Xylose reductase from the yeast Candida tenuis (CtXR) is a family 2 member of the aldo-keto reductase (AKR) superfamily of proteins and enzymes. Active site His-113 is conserved among AKRs, but a unified mechanism of how it affects catalytic activity is outstanding. We have replaced His-113 by alanine using site-directed mutagenesis, determined a 2.2 A structure of H113A mutant bound to NADP(+), and compared catalytic reaction profiles of NADH-dependent reduction of different aldehydes catalyzed by the wild type and the mutant. Deuterium kinetic isotope effects (KIEs) on k(cat) and k(cat)/K(m xylose) show that, relative to the wild type, the hydride transfer rate constant (k(7) approximately 0.16 s(-1)) has decreased about 1000-fold in H113A whereas xylose binding was not strongly affected. No solvent isotope effect was seen on k(cat) and k(cat)/K(m xylose) for H113A, suggesting that proton transfer has not become rate-limiting as a result of the mutation. The pH profiles of log(k(cat)/K(m xylose)) for the wild type and H113A decreased above apparent pK(a) values of 8.85 and 7.63, respectively. The DeltapK(a) of -1.2 pH units likely reflects a proximally disruptive character of the mutation, affecting the position of Asp-50. A steady-state kinetic analysis for H113A-catalyzed reduction of a homologous series of meta-substituted benzaldehyde derivatives was carried out, and quantitative structure-reactivity correlations were used to factor the observed kinetic substituent effect on k(cat) and k(cat)/K(m aldehyde) into an electronic effect and bonding effects (which are lacking in the wild type). Using the Hammett sigma scale, electronic parameter coefficients (rho) of +0.64 (k(cat)) and +0.78 (k(cat)/K(m aldehyde)) were calculated and clearly differ from rho(k(cat)/K(aldehyde)) and rho(k(cat)) values of +1.67 and approximately 0.0, respectively, for the wild-type enzyme. Hydride transfer rate constants of H113A, calculated from kinetic parameters and KIE data

  13. Copper nanoparticles generated from aggregates of a hexarylbenzene derivative: a reusable catalytic system for 'click' reactions.

    PubMed

    Kaur, Sharanjeet; Bhalla, Vandana; Kumar, Manoj

    2015-01-11

    Fluorescent aggregates of hexarylbenzene derivative 3 have been utilized as reactors for the preparation of copper nanoparticles in aqueous medium, which serve as effective catalytic system for the alkyl-azide 'click' reaction to synthesize 1,2,3-triazoles in excellent yields under solvent-free conditions. This catalytic system can be recycled and reused five times without significant loss of catalytic activity.

  14. Fundamental studies of catalytic gasification

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.

    1990-09-01

    Our previous work has shown that chars and coal can be gasified with steam in the presence of alkali-transition metal oxide catalysts or alkali-earth catalysts at relatively low temperatures. These studies are to be extended to the investigation of the amounts of catalysts required and whether a throw away catalyst can be used. Fresh versus stored char will be gasified to determine the role of oxidation of the char on gasification rates. Less expensive catalyst materials such as sodium instead of potassium and iron instead of nickel will be explored. Reaction rates will be determined in the presence of nitrogen, CO and CO{sub 2}. Reactions of methane and carbon solids in the presence of an oxidizing agent such as water, oxygen, and/or carbon dioxide will be explored in the presence of similar catalysts. It is expected that hydrocarbon liquids and C{sub 2} plus gases will be produced along with hydrogen. These studies will be performed over a wide range of reaction pressures and reaction temperatures in a flow reactor using a GC-MS detector. Pure paraffinic and cyclic hydrocarbons of high carbon to hydrogen ratio will be designed to have an indication of the ease of gasification of different carbonaceous materials. Results on the performance of Na, Cs, and BaO{sub x} as catalysts are briefly discussed. 3 figs.

  15. Hydrothermal synthesis of vanadium nitride and modulation of its catalytic performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Huang, Taizhong; Mao, Shun; Zhou, Guihua; Wen, Zhenhai; Huang, Xingkang; Ci, Suqin; Chen, Junhong

    2014-07-01

    A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts.A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts. Electronic supplementary information (ESI) available: Experimental methods; SEM characterization of the catalysts; Tafel test of Pt/C catalyst; BET and cyclic performance tests of VN. See DOI: 10.1039/c4nr02646b

  16. [Study on bromate formation of catalytic ozonation process].

    PubMed

    Wu, Lin; Yang, Hong-Wei; Yang, Shao-Xia; Lü, Miao; Cheng, Wen

    2011-08-01

    In a batch reactor, the BrO3(-) formation was investigated in the ozonation and catalytic ozonation of Br(-)-containing Yellow river water, using the different heterogeneous catalysts. The results showed that BrO3(-) minimization was achieved in the catalytic ozonation with NiO, CuO, Fe3O4 and Al2O3 as catalysts and the percent reductions of BrO3(-) were 34.0%, 32.8%, 29.2% and 20.8% respectively. In the reaction R(ct), the ratio of concentration of *OH to O3, decreased with the reaction time, and the range of R(ct) was from 10(-8) to 10(-6). In the ozonation process, one of the main reaction pathways of BrO3(-) formation was the combination oxidation of Br(-) by *OH and then O3, another was the combination oxidation of Br(-) by O3 and then *OH. In the catalytic ozonation with Fe3O4 catalyst, the main pathway was the combination oxidation by *OH and then O3. Moreover, about 60.7% removal for UV254 was obtained after 20 min in the catalytic ozonation reaction. In our study, it was found that the catalytic ozonation process can effectively minimize the formation of BrO3(-) and also oxidize organic compounds. PMID:22619950

  17. Study of the oxidative half-reaction catalyzed by a non-heme ferrous catalytic center by means of structural and computational methodologies

    NASA Astrophysics Data System (ADS)

    Cicero, Giancarlo; Carbonera, Chiara; Valegård, Karin; Hajdu, Janos; Andersson, Inger; Ranghino, Graziella

    Deacetoxycephalosporin C synthase (DAOCS) is a mononuclear ferrous enzyme that catalyzes the expansion of the five-membered thiazolidine ring of the penicillin nucleus into the six-membered dihydrothiazine ring of the cephalosporins. In the first half-reaction with dioxygen and 2-oxoglutarate, a reactive iron-oxygen species is produced that can subsequently react with the penicillin substrate to yield the cephalosporin. We describe quantum mechanical calculations of the first part of the reaction based on the high-resolution structures of the active site of DAOCS and its complexes with ligands. These studies are aimed at understanding how the reactive species can be produced and contained in the active site of the enzyme. The results demonstrate the priming of the active site by the co-substrate for oxygen binding and hint to the presence of a stable iron-peroxo intermediate in equilibrium with a more reactive ferryl species and the formation of CO2 as a leaving group by decarboxylation of 2-oxoglutarate. A conclusion from these studies is that substitution of CO2 by the penicillin substrate triggers the oxidation reaction in a booby-trap-like mechanism.

  18. Graphene-Semiconductor Catalytic Nanodiodes for Quantitative Detection of Hot Electrons Induced by a Chemical Reaction.

    PubMed

    Lee, Hyosun; Nedrygailov, Ievgen I; Lee, Young Keun; Lee, Changhwan; Choi, Hongkyw; Choi, Jin Sik; Choi, Choon-Gi; Park, Jeong Young

    2016-03-01

    Direct detection of hot electrons generated by exothermic surface reactions on nanocatalysts is an effective strategy to obtain insight into electronic excitation during chemical reactions. For this purpose, we fabricated a novel catalytic nanodiode based on a Schottky junction between a single layer of graphene and an n-type TiO2 layer that enables the detection of hot electron flows produced by hydrogen oxidation on Pt nanoparticles. By making a comparative analysis of data obtained from measuring the hot electron current (chemicurrent) and turnover frequency, we demonstrate that graphene's unique electronic structure and extraordinary material properties, including its atomically thin nature and ballistic electron transport, allow improved conductivity at the interface between the catalytic Pt nanoparticles and the support. Thereby, graphene-based nanodiodes offer an effective and facile way to approach the study of chemical energy conversion mechanisms in composite catalysts with carbon-based supports.

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

    SciTech Connect

    Ju, Hua; Li, Zhihu; Xu, Yanhui

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  1. Bench- and Pilot-Scale Studies of Reaction and Regeneration of Ni-Mg-K/Al2O3 for Catalytic Conditioning of Biomass-Derived Syngas

    SciTech Connect

    Magrini-Bair, K. A.; Jablonski, W. S.; Parent, Y. O.; Yung, M. M.

    2012-05-01

    The National Renewable Energy Laboratory (NREL) is collaborating with both industrial and academic partners to develop technologies to help enable commercialization of biofuels produced from lignocellulosic biomass feedstocks. The focus of this paper is to report how various operating processes, utilized in-house and by collaborators, influence the catalytic activity during conditioning of biomass-derived syngas. Efficient cleaning and conditioning of biomass-derived syngas for use in fuel synthesis continues to be a significant technical barrier to commercialization. Multifunctional, fluidizable catalysts are being developed to reform undesired tars and light hydrocarbons, especially methane, to additional syngas, which can improve utilization of biomass carbon. This approach also eliminates both the need for downstream methane reforming and the production of an aqueous waste stream from tar scrubbing. This work was conducted with NiMgK/Al{sub 2}O{sub 3} catalysts. These catalysts were assessed for methane reforming performance in (i) fixed-bed, bench-scale tests with model syngas simulating that produced by oak gasification, and in pilot-scale, (ii) fluidized tests with actual oak-derived syngas, and (iii) recirculating/regenerating tests using model syngas. Bench-scale tests showed that the catalyst could be completely regenerated over several reforming reaction cycles. Pilot-scale tests using raw syngas showed that the catalyst lost activity from cycle to cycle when it was regenerated, though it was shown that bench-scale regeneration by steam oxidation and H{sub 2} reduction did not cause this deactivation. Characterization by TPR indicates that the loss of a low temperature nickel oxide reduction feature is related to the catalyst deactivation, which is ascribed to nickel being incorporated into a spinel nickel aluminate that is not reduced with the given activation protocol. Results for 100 h time-on-stream using a recirculating/regenerating reactor suggest

  2. Effects of copper catalytic reactions on the development of supersonic hydrogen flames

    SciTech Connect

    Chang, S.L.; Lottes, S.A.; Berry, G.F.

    1992-10-01

    Copper species are present in hydrogen flames in arc heated supersonic ramjet testing facilities. Homogeneous and heterogeneous copper catalytic reactions may affect the flame development by enhancing the recombination of hydrogen atoms. Computer simulation is used to investigate the effects of the catalytic reactions on the reaction and ignition times of the flames. The simulation uses a modified general chemical kinetics computer program to simulate the development of copper-contaminated hydrogen flames under scramjet testing conditions. Reaction times of hydrogen flames are found to be reduced due to the copper catalytic effects, but ignition times are much less sensitive to such effects. The reduction of reaction time depends on copper concentration, particle size (if copper is in the condensed phase), and Mach number (or initial temperature and pressure). As copper concentration increases or the particle size decreases, reaction time decreases. As Mach number increases (or pressure and temperature decrease), the copper catalytic effects are greater.

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

    SciTech Connect

    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.

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

    PubMed

    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. PMID:26938837

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

    PubMed

    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.

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

    SciTech Connect

    Ekerdt, J.G.

    1992-02-03

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

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

  8. Reaction of dialkyltin methoxide with carbon dioxide relevant to the mechanism of catalytic carbonate synthesis

    SciTech Connect

    Choi, J.C.; Sakakura, Toshiyasu; Sako, Takeshi

    1999-04-21

    Conversion of carbon dioxide to industrially useful compounds has been a challenge for synthetic chemists and has recently attracted much interest. One of the most attractive synthetic goals starting from CO{sub 2} is dimethyl carbonate (DMC). Indeed, the straightforward reaction of methanol and CO{sub 2} catalyzed by R{sub 2}Sn(OMe){sub 2} leading to DMC has been intensively studied although catalytic performance is still far from satisfactory. The authors have recently enhanced the catalytic efficiency of R{sub 2}Sn(OMe){sub 2} using dehydrated derivatives of methanol (e.g., ortho esters and acetals) as a starting material under supercritical CO{sub 2} conditions.

  9. Catalytic behavior of Group VIII transition metals in the deuterium-acrolein reaction

    SciTech Connect

    Touroude, R.

    1980-09-01

    The catalytic reactions between acrolein and deuterium over all the Group VIII transition metals were studied by microwave spectrometry. A high catalyst selectivity in the exchange reaction, in which hydrogen is replaced by deuterium in acrolein, was found. Over Rh, Pd, Ir, Ru, and Ni, hydrogens situated on the ..beta.. carbon were quasi-selectively exchanged while over Pt, Os, and especially Co, an additional exchange of the aldehydic hydrogen took place. Over Fe, the hydrogen situated on the ..cap alpha.. carbon and the aldehydic hydrogen were exchanged equally. An attempt is made to relate the nature of the exchange to hydrogenation, decarbonylation, and hydrogenolysis and several reaction mechanisms are proposed in addition to the classical Horiuti-Polanyi mechanism, which is restricted to hydrogenation of the C-C double bond.

  10. A general catalytic reaction sequence to access alkaloid-inspired indole polycycles.

    PubMed

    Danda, Adithi; Kumar, Kamal; Waldmann, Herbert

    2015-05-01

    A catalytic two-step reaction sequence was developed to access a range of complex heterocyclic frameworks based on biorelevant indole/oxindole scaffolds. The reaction sequence includes catalytic Pictet-Spengler cyclization followed by Au(I) catalyzed intramolecular hydroamination of acetylenes. A related cascade polycyclization of a designed β-carboline embodying a 1,5-enyne group yields the analogues of the alkaloid harmicine. PMID:25846800

  11. Catalytic reactions of cyclooctane and ethylcyclohexane on HY zeolite

    SciTech Connect

    Abbot, J.; Wojciechowski, B.W.

    1987-10-01

    Few systematic studies of the reactions of cycloparaffins on zeolites have been reported, considering their importance as a component of commercial crude feedstocks. Studies of small ring (C/sub 3/, C/sub 4/) cycloparaffins have shown that the primary reaction product is the corresponding olefin. It has not been established, however, that the corresponding olefin is produced as an initial product of the cracking of medium-sized (C/sub 5/, C/sub 6/) rings. Studies of cycloparaffin cracking on silica-alumina catalysts report that the degree of saturation of low-molecular-weight products is much greater than that observed in comparable n-paraffin cracking. Reactions of methylcyclohexane on HY zeolite at 450/sup 0/C have shown that dehydrogenation, isomerization, and cracking are all primary processes. Here the authors report product distributions in the cracking of ethylcyclohexane and cyclooctane on HY zeolite at 400/sup 0/C and compare product distributions for these cycloparaffins. 19 references.

  12. Catalytic reaction of cytokinin dehydrogenase: preference for quinones as electron acceptors.

    PubMed Central

    Frébortová, Jitka; Fraaije, Marco W; Galuszka, Petr; Sebela, Marek; Pec, Pavel; Hrbác, Jan; Novák, Ondrej; Bilyeu, Kristin D; English, James T; Frébort, Ivo

    2004-01-01

    The catalytic reaction of cytokinin oxidase/dehydrogenase (EC 1.5.99.12) was studied in detail using the recombinant flavoenzyme from maize. Determination of the redox potential of the covalently linked flavin cofactor revealed a relatively high potential dictating the type of electron acceptor that can be used by the enzyme. Using 2,6-dichlorophenol indophenol, 2,3-dimethoxy-5-methyl-1,4-benzoquinone or 1,4-naphthoquinone as electron acceptor, turnover rates with N6-(2-isopentenyl)adenine of approx. 150 s(-1) could be obtained. This suggests that the natural electron acceptor of the enzyme is quite probably a p-quinone or similar compound. By using the stopped-flow technique, it was found that the enzyme is rapidly reduced by N6-(2-isopentenyl)adenine (k(red)=950 s(-1)). Re-oxidation of the reduced enzyme by molecular oxygen is too slow to be of physiological relevance, confirming its classification as a dehydrogenase. Furthermore, it was established for the first time that the enzyme is capable of degrading aromatic cytokinins, although at low reaction rates. As a result, the enzyme displays a dual catalytic mode for oxidative degradation of cytokinins: a low-rate and low-substrate specificity reaction with oxygen as the electron acceptor, and high activity and strict specificity for isopentenyladenine and analogous cytokinins with some specific electron acceptors. PMID:14965342

  13. Catalytic conversion of canola oil over potassium-impregnated HZSM-5 catalysts: C{sub 2}-C{sub 4} olefin production and model reaction studies

    SciTech Connect

    Katikaneni, S.P.R.; Adjaye, J.D.; Idem, R.O.; Bakhshi, N.N.

    1996-10-01

    The influence of catalyst acidity, reaction temperature, and canola oil space velocity on the conversion of canola oil was evaluated using a fixed-bed microreactor at atmospheric pressure at reaction temperatures and space velocities (WHSV) in the ranges 400--500 C and 1.8--3.6 h{sup {minus}1}, respectively, over potassium-impregnated HZSMs-5 catalysts. These catalysts were thoroughly characterized using XRD, N{sub 2} adsorption measurements, {sup 1}H NMR, TPD of NH{sub 3}, FT-IR, C{sub 2}-C{sub 4} olefins from canola oil were determined. The incorporation of potassium into HZSM-5 catalyst resulted in both the dilution and poisoning of Bronsted and total acid sites. These acidity changes only severely affected the acid catalyzed reactions, such as oligomerization and aromatization, and resulted in drastic modifications in product distribution. The maximum C{sub 2}C{sub 4} olefin yield of 25.8 wt % was obtained at 500 C and 1.8 h{sup {minus}1} space velocity with catalyst K1 of relatively low Bronsted and total acidity.

  14. A computational study of detoxification of lewisite warfare agents by British anti-lewisite: catalytic effects of water and ammonia on reaction mechanism and kinetics.

    PubMed

    Sahu, Chandan; Pakhira, Srimanta; Sen, Kaushik; Das, Abhijit K

    2013-04-25

    trans-2-Chlorovinyldichloroarsine (lewisite, L agent, Lew-I) acts as a blistering agents. British anti-lewisite (BAL, 2,3-dimercaptopropanol) has long been used as an L-agent antidote. The main reaction channels for the detoxification proceed via breaking of As-Cl bonds and formation of As-S bonds, producing stable, nontoxic ring product [(2-methyl-1,3,2-dithiarsolan-4-yl)methanol]. M06-2X/GENECP calculations have been carried out to establish the enhanced rate of detoxification mechanism in the presence of NH3 and H2O catalysts in both gas and solvent phases, which has been modeled by use of the polarized continuum model (PCM). In addition, natural bond orbital (NBO) and atoms in molecules (AIM) analysis have been performed to characterize the intermolecular hydrogen bonding in the transition states. Transition-state theory (TST) calculation establishes that the rates of NH3-catalyzed (2.88 × 10(-11) s(-1)) and H2O-catalyzed (2.42 × 10(-11) s(-1)) reactions are reasonably faster than the uncatalyzed detoxification (5.44 × 10(-13) s(-1)). The results obtained by these techniques give new insight into the mechanism of the detoxification process, identification and thermodynamic characterization of the relevant stationary species, the proposal of alternative paths on modeled potential energy surfaces for uncatalyzed reaction, and the rationalization of the mechanistic role played by catalysts and solvents. PMID:23540856

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

    PubMed

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

    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.

  16. Catalytic enantioselective stereoablative reactions: an unexploited approach to enantioselective catalysis.

    PubMed

    Mohr, Justin T; Ebner, David C; Stoltz, Brian M

    2007-11-21

    Approaches to the preparation of enantioenriched materials via catalytic methods that destroy stereogenic elements of a molecule are discussed. Although these processes often decrease overall molecular complexity, there are several notable advantages including material recycling, enantiodivergence and convergence, and increased substrate scope. Examples are accompanied by discussion of the critical design elements required for the success of these methods.

  17. Phosphoryl transfer reaction snapshots in crystals: Insights into the mechanism of protein kinase a catalytic subunit

    SciTech Connect

    Das, Amit; Gerlits, Oksana O.; Heller, William T.; Kovalevskyi, Andrii Y.; Langan, Paul; Tian, Jianhui

    2015-06-19

    To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, the thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. As a result, the present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.

  18. Phosphoryl transfer reaction snapshots in crystals: Insights into the mechanism of protein kinase a catalytic subunit

    DOE PAGESBeta

    Das, Amit; Gerlits, Oksana O.; Heller, William T.; Kovalevskyi, Andrii Y.; Langan, Paul; Tian, Jianhui

    2015-06-19

    To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, themore » thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. As a result, the present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.« less

  19. Fundamental studies of catalytic gasification

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.

    1991-09-01

    In this project a considerable number of important findings have been made. Leads for scale-up have been developed and mechanisms for the reaction have been delineated. A small amount of additional experimental work is necessary and the extensive body of this project must be summarized in a final report. Recently limited experimentation has been carried out on the production of C{sub 2} hydrocarbons from methane in the presence of Ca/K/Ni oxide catalysts and of oxygen, carbon and water. The main finding thus far has been that C{sub 2} yields of 10--13% can be obtained at about 600{degrees}C or 150{degrees} lower temperature than described in the literature for similar yields. Occasionally much higher yields were obtained and reasons for this must be determined. We have recently found that with a modified catalyst and by operating at quite low temperature ({approx}600{degrees}C) CO{sub 2} formation can be almost totally suppressed. Yields of 7--10% C{sub 2} hydrocarbons at 99+% selectivity have been obtained. The presence of water and small amounts of oxygen is essential. Yields of this magnitude may be attractive since there is no loss of methane to valueless by-products, no purification of the recycle steam is required and no oxygen is used to burn methane. Further improvement in yields by catalyst and operating conditions modifications will be investigated. It is also intended to clarify the chemistry which inhibits burning of methane to carbon oxides.

  20. Propagating Surface Plasmon Polaritons: Towards Applications for Remote‐Excitation Surface Catalytic Reactions

    PubMed Central

    Zhang, Zhenglong; Fang, Yurui; Wang, Wenhui; Chen, Li

    2016-01-01

    Plasmonics is a well‐established field, exploiting the interaction of light and metals at the nanoscale; with the help of surface plasmon polaritons, remote‐excitation can also be observed by using silver or gold plasmonic waveguides. Recently, plasmonic catalysis was established as a new exciting platform for heterogeneous catalytic reactions. Recent reports present remote‐excitation surface catalytic reactions as a route to enhance the rate of chemical reactions, and offer a pathway to control surface catalytic reactions. In this review, we focus on recent advanced reports on silver plasmonic waveguide for remote‐excitation surface catalytic reactions. First, the synthesis methods and characterization techniques of sivelr nanowire plasmonic waveguides are summarized, and the properties and physical mechanisms of plasmonic waveguides are presented in detail. Then, the applications of plasmonic waveguides including remote excitation fluorescence and SERS are introduced, and we focus on the field of remote‐excitation surface catalytic reactions. Finally, forecasts are made for possible future applications for the remote‐excitation surface catalysis by plasmonic waveguides in living cells. PMID:27774380

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

    DOE PAGESBeta

    Garcia, Andres; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.

    2016-05-20

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

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

    PubMed

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. In-situ observations of catalytic surface reactions with soft x-rays under working conditions

    NASA Astrophysics Data System (ADS)

    Toyoshima, Ryo; Kondoh, Hiroshi

    2015-03-01

    Catalytic chemical reactions proceeding on solid surfaces are an important topic in fundamental science and industrial technologies such as energy conversion, pollution control and chemical synthesis. Complete understanding of the heterogeneous catalysis and improving its efficiency to an ultimate level are the eventual goals for many surface scientists. Soft x-ray is one of the prime probes to observe electronic and structural information of the target materials. Most studies in surface science using soft x-rays have been performed under ultra-high vacuum conditions due to the technical limitation, though the practical catalytic reactions proceed under ambient pressure conditions. However, recent developments of soft x-ray based techniques operating under ambient pressure conditions have opened a door to the in-situ observation of materials under realistic environments. The near-ambient-pressure x-ray photoelectron spectroscopy (NAP-XPS) using synchrotron radiation enables us to observe the chemical states of surfaces of condensed matters under the presence of gas(es) at elevated pressures, which has been hardly conducted with the conventional XPS technique. Furthermore, not only the NAP-XPS but also ambient-pressure compatible soft x-ray core-level spectroscopies, such as near-edge absorption fine structure (NEXAFS) and x-ray emission spectroscopy (XES), have been significantly contributing to the in-situ observations. In this review, first we introduce recent developments of in-situ observations using soft x-ray techniques and current status. Then we present recent new findings on catalytically active surfaces using soft x-ray techniques, particularly focusing on the NAP-XPS technique. Finally we give a perspective on the future direction of this emerging technique.

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

    SciTech Connect

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

    2009-03-02

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

  6. Process of forming catalytic surfaces for wet oxidation reactions

    NASA Technical Reports Server (NTRS)

    Jagow, R. B. (Inventor)

    1977-01-01

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

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

    DOEpatents

    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.

  8. Catalytic activities enhanced by abundant structural defects and balanced N distribution of N-doped graphene in oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Bai, Xiaogong; Shi, Yantao; Guo, Jiahao; Gao, Liguo; Wang, Kai; Du, Yi; Ma, Tingli

    2016-02-01

    N-doped graphene (NG) is a promising candidate for oxygen reduction reaction (ORR) in the cathode of fuel cells. However, the catalytic activity of NG is lower than that of commercial Pt/C in alkaline and acidic media. In this study, NG samples were obtained using urea as N source. The structural defects and N distribution in the samples were adjusted by regulating the pyrolysis temperature. The new NG type exhibited remarkable catalytic activities for ORR in both alkaline and acidic media.

  9. Catalytic asymmetric direct-type 1,4-addition reactions of simple amides.

    PubMed

    Suzuki, Hirotsugu; Sato, Io; Yamashita, Yasuhiro; Kobayashi, Shū

    2015-04-01

    The development of catalytic asymmetric direct-type reactions of less acidic carbonyl compounds such as amides and esters has been a challenging theme in organic chemistry for decades. Here we describe the asymmetric direct 1,4-addition reactions of simple amides with α,β-unsaturated carbonyl compounds using a catalytic amount of a novel chiral catalyst consisting of a potassium base and a macrocyclic chiral crown ether. The desired 1,5-dicarbonyl compounds were obtained in high yields with excellent diastereo- and enantioselectivities. This is the first example of a highly enantioselective catalytic direct-type reaction of simple amides. In addition, the structure of the chiral potassium catalyst has been investigated by X-ray crystallographic, dynamic (1)H NMR, and MALDI-TOF MS analyses.

  10. Sum frequency generation and catalytic reaction studies of the removal of the organic capping agents from Pt nanoparticles by UV-ozone treatment

    SciTech Connect

    Aliaga, Cesar; Park, Jeong Y.; Yamada, Yusuke; Lee, Hyun Sook; Tsung, Chia-Kuang; Yang, Peidong; Somorjai, Gabor A.

    2009-12-10

    We report the structure of the organic capping layers of platinum colloid nanoparticles and their removal by UV-ozone exposure. Sum frequency generation vibrational spectroscopy (SFGVS) studies identify the carbon-hydrogen stretching modes on poly(vinylpyrrolidone) (PVP) and tetradecyl tributylammonium bromide (TTAB)-capped platinum nanoparticles. We found that the UV-ozone treatment technique effectively removes the capping layer on the basis of several analytical measurements including SFGVS, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The overall shape of the nanoparticles was preserved after the removal of capping layers, as confirmed by transmission electron microscopy (TEM). SFGVS of ethylene hydrogenation on the clean platinum nanoparticles demonstrates the existence of ethylidyne and di-{sigma}-bonded species, indicating the similarity between single-crystal and nanoparticle systems.

  11. Nuclear reaction studies

    SciTech Connect

    Alexander, J.M.; Lacey, R.A.

    1994-11-01

    Research focused on the statistical and dynamical properties of ``hot`` nuclei formed in symmetric heavy-ion reactions. Theses included ``flow`` measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study {sup 40}Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs.

  12. Metal Vinylidenes as Catalytic Species in Organic Reactions

    PubMed Central

    McClory, Andrew

    2008-01-01

    Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis. PMID:18172846

  13. Two-dimensional reaction free energy surfaces of catalytic reaction: effects of protein conformational dynamics on enzyme catalysis.

    PubMed

    Min, Wei; Xie, X Sunney; Bagchi, Biman

    2008-01-17

    We introduce a two-dimensional (2D) multisurface reaction free energy description of the catalytic cycle that explicitly connects the recently observed multi-time-scale conformational dynamics as well as dispersed enzymatic kinetics to the classical Michaelis-Menten equation. A slow conformational motion on a collective enzyme coordinate Q facilitates the catalytic reaction along the intrinsic reaction coordinate X, providing a dynamic realization of Pauling's well-known idea of transition-state stabilization. The catalytic cycle is modeled as transitions between multiple displaced harmonic wells in the XQ space representing different states of the cycle, which is constructed according to the free energy driving force of the cycle. Subsequent to substrate association with the enzyme, the enzyme-substrate complex under strain exhibits a nonequilibrium relaxation toward a new conformation that lowers the activation energy of the reaction, as first proposed by Haldane. The chemical reaction in X is thus enslaved to the down hill slow motion on the Q surface. One consequence of the present theory is that, in spite of the existence of dispersive kinetics, the Michaelis-Menten expression of the catalysis rate remains valid under certain conditions, as observed in recent single-molecule experiments. This dynamic theory builds the relationship between the protein conformational dynamics and the enzymatic reaction kinetics and offers a unified description of enzyme fluctuation-assisted catalysis. PMID:18085768

  14. SpaciMS: spatial and temporal operando resolution of reactions within catalytic monoliths

    SciTech Connect

    Sa, Jacinto; Fernandes, Daniel; Aiouache, Farid; Goguet, Alexandre; Hardacdre, Christopher; Lundie, David; Naeem, Wasif; Partridge Jr, William P; Stere, Cristina

    2010-01-01

    Monolithic catalysts are widely used as structured catalysts, especially in the abatement of pollutants. Probing what happens inside these monoliths during operation is, therefore, vital for modelling and prediction of the catalyst behavior. SpaciMS is a spatially resolved capillary-inlet mass spectroscopy system allowing for the generation of spatially resolved maps of the reactions within monoliths. In this study SpaciMS results combined with 3D CFD modelling demonstrate that SpaciMS is a highly sensitive and minimally invasive technique that can provide reaction maps as well as catalytic temporal behavior. Herein we illustrate this by examining kinetic oscillations during a CO oxidation reaction over a Pt/Rh on alumina catalyst supported on a cordierite monolith. These oscillations were only observed within the monolith by SpaciMS between 30 and 90% CO conversion. Equivalent experiments performed in a plug-flow reactor using this catalyst in a crushed form over a similar range of reaction conditions did not display any oscillations demonstrating the importance of intra monolith analysis. This work demonstrates that the SpaciMS offers an accurate and comprehensive picture of structured catalysts under operation.

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

    PubMed

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

    2013-06-01

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

  16. Facilitating ZnO nanostructure growths by making seeds for self-catalytic reactions

    SciTech Connect

    Yin Liang; Yu, Choongho

    2012-03-15

    Long and straight single-crystalline ZnO nanowires were successfully synthesized on ZnCl{sub 2}-coated Zn foils in oxygen environment by using simple thermal annealing processes. With relatively low reaction temperatures (410 and 700 Degree-Sign C), nanowires whose lengths and diameters are up to {approx}50 {mu}m and 10-100 nm were obtained. We found that ZnO seeds created from ZnCl{sub 2} played an important role in facilitating the ZnO nanowire growth via self-catalytic reactions. Systematic studies by altering critical synthesis factors that determine shape, length, diameter, and density of the nanowires were performed in order to unveil the growth mechanisms. We also compared the nanowires synthesized from Zn foils with tetrapod ZnO nanostructures synthesized from Zn powders at various temperatures. - Graphical abstract: (Left panel) ZnO seeds from ZnCl{sub 2} after thermal annealing at 500 Degree-Sign C for 5 min, (right panel) dense ZnO nanowires grown from Zn foils with ZnCl{sub 2} coating after thermal annealing at 700 Degree-Sign C for 60 min. Highlights: Black-Right-Pointing-Pointer ZnCl{sub 2} facilitated ZnO nanowire growth by creating ZnO seeds. Black-Right-Pointing-Pointer ZnO nanowires were synthesized via self-catalytic reactions. Black-Right-Pointing-Pointer Long and straight single-crystalline ZnO nanowires were synthesized. Black-Right-Pointing-Pointer Key parameters in thermal annealing processes were identified.

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

    PubMed

    Catlow, C Richard A

    2016-08-01

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

  18. Multidimensional steric parameters in the analysis of asymmetric catalytic reactions

    NASA Astrophysics Data System (ADS)

    Harper, Kaid C.; Bess, Elizabeth N.; Sigman, Matthew S.

    2012-05-01

    Although asymmetric catalysis is universally dependent on spatial interactions to impart specific chirality on a given substrate, examination of steric effects in these catalytic systems remains empirical. Previous efforts by our group and others have seen correlation between steric parameters developed by Charton and simple substituents in both substrate and ligand; however, more complex substituents were not found to be correlative. Here, we review and compare the steric parameters common in quantitative structure activity relationships (QSAR), a common method for pharmaceutical function optimization, and how they might be applied in asymmetric catalysis, as the two fields are undeniably similar. We re-evaluate steric/enantioselection relationships, which we previously analysed with Charton steric parameters, using the more sophisticated Sterimol parameters developed by Verloop and co-workers in a QSAR context. Use of these Sterimol parameters led to strong correlations in numerous processes where Charton parameters had previously failed. Sterimol parameterization also allows for greater mechanistic insight into the key elements of asymmetric induction within these systems.

  19. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

    PubMed Central

    Jouffroy, Matthieu; Gramage-Doria, Rafael; Sémeril, David; Oberhauser, Werner; Toupet, Loïc

    2014-01-01

    Summary The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

  20. Catalytic reaction of acrolein and methacrolein with alcohols and glycols

    SciTech Connect

    Paparizos, C.; shout, R. S.; Shaw, W. G.

    1985-02-12

    Disclosed is the reaction acrolein or methacrolein with a mono- or dihydroxyalkane to produce a 3-alkoxypropionaldehyde or a 3-(hydroxyalkoxy)propionaldehyde in the case of acrolein; or to produce a 3-alkoxy-2-methylpropionaldehyde or a 3-(hydroxyalkoxy)-2-methylpropionaldehyde in the case of methacrolein, by contacting a mixture of the recited reactants with a particulate solid metallic catalyst comprising an alloy of palladium and cadmium.

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

    PubMed

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

    2014-12-17

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

  2. Robustness and modularity properties of a non-covalent DNA catalytic reaction

    PubMed Central

    Zhang, David Yu

    2010-01-01

    The biophysics of nucleic acid hybridization and strand displacement have been used for the rational design of a number of nanoscale structures and functions. Recently, molecular amplification methods have been developed in the form of non-covalent DNA catalytic reactions, in which single-stranded DNA (ssDNA) molecules catalyze the release of ssDNA product molecules from multi-stranded complexes. Here, we characterize the robustness and specificity of one such strand displacement-based catalytic reaction. We show that the designed reaction is simultaneously sensitive to sequence mutations in the catalyst and robust to a variety of impurities and molecular noise. These properties facilitate the incorporation of strand displacement-based DNA components in synthetic chemical and biological reaction networks. PMID:20194118

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

    ERIC Educational Resources Information Center

    Paspek, Stephen C.; And Others

    1980-01-01

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

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

    ERIC Educational Resources Information Center

    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…

  5. Nitrated Confined Imidodiphosphates Enable a Catalytic Asymmetric Oxa-Pictet-Spengler Reaction.

    PubMed

    Das, Sayantani; Liu, Luping; Zheng, Yiying; Alachraf, M Wasim; Thiel, Walter; De, Chandra Kanta; List, Benjamin

    2016-08-01

    The development of a highly enantioselective catalytic oxa-Pictet-Spengler reaction has proven a great challenge for chemical synthesis. We now report the first example of such a process, which was realized by utilizing a nitrated confined imidodiphosphoric acid catalyst. Our approach provides substituted isochroman derivatives from both aliphatic and aromatic aldehydes with high yields and excellent enantioselectivities. DFT calculations provide insight into the reaction mechanism. PMID:27457383

  6. [The pH-dependent catalytic reaction of penicillin G acylase and its mutants].

    PubMed

    Chen, Jian-Bo; Yang, Sheng; Wu, Xing-Jia; Li, Shi-Yun; Yuan, Zhong-Yi

    2002-11-01

    The pH-dependence in the catalytic reaction of recombinant penicillin G acylase and its mutants from B.megaterium has been studied by using kinetic methods. pK(1) and pK(2)of the residues of the wild type penicillin G a cylase, involved in the catalyzed reaction, were 5.50-5.87 and 10.73, respectively, from the curves of logV(m) and log(V(m)/K(m)) versus pH. Results showed tha t the pK(1) and pK(2) values of these residues of the mutants were similar to that of the wild type. pK(1) of 5.64-5.86 for mutant A and 5.69-6.96 for mutant B were obtained, while pK(2) was 10.61 and 10.48 for mutant A and B, respectively. At the same time, pK values at different temperatures were investigated. The ionization enthalpies(deltaH) were 44.38-59.03 kJ/mol and 147.37 kJ/mol, respectively, from th e curve of pK versus temperature. It was presumed according to the results mentioned above that the ionizing residues, involved in the reaction, wer e histidine and lysine that are localized around the active site.

  7. A plasmon-driven selective surface catalytic reaction revealed by surface-enhanced Raman scattering in an electrochemical environment.

    PubMed

    Cui, Lin; Wang, Peijie; Fang, Yurui; Li, Yuanzuo; Sun, Mengtao

    2015-07-06

    Plasmonic catalytic reactions of molecules with single amine or nitro groups have been investigated in recent years. However, plasmonic catalysis of molecules with multiple amine and/or nitro groups is still unknown. In this paper, plasmon-driven catalytic reactions of 4,4'-dinitroazobenzene (DNAB), 4,4'-diaminoazobenzene (DAAB) and 4-nitro-4'-aminoazobenzene (NAAB) are investigated using electrochemical surface-enhanced Raman scattering (SERS) spectroscopy. The results reveal that a plasmon-driven reduction reaction occurred for DNAB and NAAB in which the NO2 group was reduced to NH2, while the plasmon-driven oxidation reaction of NH2 did not occur. This result demonstrates that plasmon-driven reduction reactions are much easier than plasmon-driven oxidization reactions in electrochemical environments. The molecular resonance may also play an important role in plasmon-driven catalytic reactions. These findings provide us with a deeper understanding of plasmon-driven catalytic reactions.

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

    PubMed

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

    2016-05-20

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

  9. Revisiting catalytic model reaction p-nitrophenol/NaBH4 using metallic nanoparticles coated on polymeric spheres

    NASA Astrophysics Data System (ADS)

    Li, Maolin; Chen, Guofang

    2013-11-01

    The early reported pseudo-first-order reaction kinetics of the polymer-supported metallic nanocatalysts for the model reaction of p-nitrophenol (p-NP)/NaBH4 were probably oversimplified. Here a detailed study of p-NP reduction by NaBH4 in the presence of the raspberry-like poly(allylamine hydrochloride)-modified polymer poly(glycidyl methacrylate) composite sub-microspheres with tunable gold nanoparticles (PGMA@PAH@AuNPs) was presented. Effects of polyelectrolyte concentration, the ratio of polymer spheres to gold nanoparticles, and the solution pH value for composite synthesis on the induction period, reaction time, average reaction rate and average turnover frequency were systematically investigated. Experimental results in all cases of our study revealed an nth order (n > 1) of the p-NP/NaBH4 catalytic reaction by the prepared polymer composite particles. The apparent order of reaction, n, is dependent on the total surface area of the coated gold nanoparticles on the polymer spheres, which can be closely correlated with the tunable gold nanoparticle surface coverage. The mechanism of the observed catalytic activity enhancement was proposed based on active epoxy groups of the polymer spheres and a large adsorption of p-nitrophenolate anions onto the positively-charged spheres.

  10. Polytopic bis(oxazoline)-based ligands for recoverable catalytic systems applied to the enantioselective Henry reaction.

    PubMed

    Angulo, Beatriz; García, José I; Herrerías, Clara I; Mayoral, José A; Miñana, Ana C

    2015-09-21

    Several kinds of polytopic chiral ligands (including ditopic, tritopic and tetratopic), based on the bis(oxazoline) and azabis(oxazoline) motifs, have been tested in the preparation of recoverable catalytic systems for the Henry reaction. The results obtained with the different ligands are, in general, good, but they point to the existence of a delicate balance between the coordinating ability of the ligand, the catalytic activity and the recovery of the catalyst by formation of the coordination polymer, related to the easiness to form oligomeric species in solution.

  11. Structural effects in the reaction between carbon dioxide and coke doped with various potassium bearing catalytic precursors

    NASA Astrophysics Data System (ADS)

    Alam, M.; Debroy, T.

    1986-09-01

    The rate of reaction between carbon dioxide and coke with and without the additions of KCN, KOCN, and K2CO3 was studied using thermogravimetry. Since both potassium and carbon are lost during the reaction, the concentration of potassium in the coke samples was determined as a function of the extent of the reaction by atomic absorption spectrometry. The changes in the specific surface area due to the reaction were studied by the nitrogen adsorption technique. The changes in the pore structure of coke were investigated by mercury porosimetry and scanning electron microscopy. The distribution of potassium in the coke structure was examined as a function of the reaction time by the energy dispersion X-ray technique. Furthermore, since sulfur is known to influence the rate of the C-CO2 reaction, the sulfur content of the coke samples with or without the addition of catalytic precursors was monitored as a function of the extent of reaction. The influences of the structural parameters and the concentration of potassium on the rate of the coke-CO2 reaction were determined. The rate data were analyzed on the basis of a structural model to examine the contributions of the chemical reaction and the pore diffusion on the overall rate of the coke-CO2 reaction.

  12. Enzyme catalytic efficiency: a function of bio-nano interface reactions.

    PubMed

    Campbell, Alan S; Dong, Chenbo; Meng, Fanke; Hardinger, Jeremy; Perhinschi, Gabriela; Wu, Nianqiang; Dinu, Cerasela Zoica

    2014-04-23

    Biocatalyst immobilization onto carbon-based nanosupports has been implemented in a variety of applications ranging from biosensing to biotransformation and from decontamination to energy storage. However, retaining enzyme functionality at carbon-based nanosupports was challenged by the non-specific attachment of the enzyme as well as by the enzyme-enzyme interactions at this interface shown to lead to loss of enzyme activity. Herein, we present a systematic study of the interplay reactions that take place upon immobilization of three pure enzymes namely soybean peroxidase, chloroperoxidase, and glucose oxidase at carbon-based nanosupport interfaces. The immobilization conditions involved both single and multipoint single-type enzyme attachment onto single and multi-walled carbon nanotubes and graphene oxide nanomaterials with properties determined by Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Our analysis showed that the different surface properties of the enzymes as determined by their molecular mapping and size work synergistically with the carbon-based nanosupports physico-chemical properties (i.e., surface chemistry, charge and aspect ratios) to influence enzyme catalytic behavior and activity at nanointerfaces. Knowledge gained from these studies can be used to optimize enzyme-nanosupport symbiotic reactions to provide robust enzyme-based systems with optimum functionality to be used for fermentation, biosensors, or biofuel applications.

  13. Polyethersulfone hollow fiber modified with poly(styrenesulfonate) and Pd nanoparticles for catalytic reaction

    NASA Astrophysics Data System (ADS)

    Emin, C.; Gu, Y.; Remigy, J.-C.; Lahitte, J.-F.

    2015-07-01

    The aim of this work is the synthesis of polymer-stabilized Pd nanoparticles (PdNP) inside a functionalized polymeric porous membrane in order to develop hybrid catalytic membrane reactors and to test them in model metal-catalyzed organic reactions. For this goal, a polymeric membrane support (Polyethersulfone hollow fiber-shaped) was firstly functionalized with an ionogenic polymer (i.e. poly(styrenesulfonate) capable to retain PdNP precursors using an UV photo-grafting method. PdNP were then generated inside the polymeric matrix by chemical reduction of precursor salts (intermatrix synthesis). The catalytic performance of the PdNP catalytic membranes was evaluated using reduction of nitrophenol by sodium borohydride (NaBH4) in water.

  14. Reaction kinetics, catalytic mechanisms, conformational changes, and inhibitor design for prenyltransferases.

    PubMed

    Liang, Po-Huang

    2009-07-21

    Isoprenoids comprise a family of more than 55000 natural products with great structural variety derived from five-carbon isopentenyl diphosphate (IPP) and its isomer dimethylallyl diphosphate (DMAPP). Allylic diphosphates such as farnesyl diphosphate (FPP) synthesized from DMAPP and IPP serve as outlet points for a great variety of products. A group of prenyltransferases catalyzing chain elongation of FPP to designated lengths by consecutive condensation reactions with specific numbers of IPP are classified as cis and trans types according to the stereochemistry of the double bonds formed by IPP condensation. The complete kinetics of the multistep IPP condensation reactions by both types of enzymes has been determined using steady-state and pre-steady-state approaches. Because their crystal structures were determined in conjunction with biochemical studies, a more thorough understanding of their catalytic mechanisms, protein conformational changes, and product chain-length determination mechanisms has been gained recently. Since these prenyltransferases play important roles, potent inhibitors have been identified and their cocrystal structures have been determined for drug development. In this review, the current knowledge of these prenyltransferases that synthesize prenyl oligomers or polymers is summarized.

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

    PubMed

    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.

  16. [Study on catalytic oxidation of benzene by microwave heating].

    PubMed

    Zhang, Yu-cai; Bo, Long-li; Wang, Xiao-hui; Liu, Hai-nan; Zhang, Hao

    2012-08-01

    The performance in catalytic oxidation of benzene was investigated in two different heating modes, microwave heating and conventional electric furnace heating. The effects of copper (Cu)-manganese (Mn) mass ratio, doping dose of cerium (Ce) and calcination temperature on the catalytic activity of Cu-Mn-Ce/molecular sieve catalyst were also checked in catalytic oxidation of benzene with microwave heating, and the catalysts were subsequently characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that the catalyst had better catalytic activity for the oxidation of benzene under microwave heating than electric furnace heating, and high oxidation efficiency for benzene was reached due to the "local hot spots" and dipole polarization effect of microwave and stable bed reaction temperature. Under the conditions of Cu, Mn and Ce mass ratio 1:1:0.33 and calcination temperature 500 degrees C, the catalyst had the optimal catalytic activity for benzene oxidation, and its light-off temperature and complete combustion temperature were 165 degrees C and 230 degrees C, respectively. It was indicated by characteristics of XRD and SEM that the presence of copper and manganese oxides and Cu1.5Mn1.5O4 with spinel crystal improved the catalytic activity of the catalyst, and the doping of Ce promoted the dispersion and regularization of active components. High calcination temperature led to the sintering of the catalyst surface and agglomeration of active components, which decreased the catalytic activity of the catalyst in the catalytic oxidation

  17. Entropy production of a steady-growth cell with catalytic reactions

    NASA Astrophysics Data System (ADS)

    Himeoka, Yusuke; Kaneko, Kunihiko

    2014-10-01

    Cells generally convert external nutrient resources to support metabolism and growth. Understanding the thermodynamic efficiency of this conversion is essential to determine the general characteristics of cellular growth. Using a simple protocell model with catalytic reaction dynamics to synthesize the necessary enzyme and membrane components from nutrients, the entropy production per unit-cell-volume growth is calculated analytically and numerically based on the rate equation for chemical kinetics and linear nonequilibrium thermodynamics. The minimal entropy production per unit-cell growth is found to be achieved at a nonzero nutrient uptake rate rather than at a quasistatic limit as in the standard Carnot engine. This difference appears because the equilibration mediated by the enzyme exists only within cells that grow through enzyme and membrane synthesis. Optimal nutrient uptake is also confirmed by protocell models with many chemical components synthesized through a catalytic reaction network. The possible relevance of the identified optimal uptake to optimal yield for cellular growth is also discussed.

  18. Nonequilibrium Relaxation of Conformational Dynamics Facilitates Catalytic Reaction in an Elastic Network Model of T7 DNA Polymerase.

    PubMed

    Zhao, Ziqing W; Xie, X Sunney; Ge, Hao

    2016-03-24

    Nucleotide-induced conformational closing of the finger domain of DNA polymerase is crucial for its catalytic action during DNA replication. Such large-amplitude molecular motion is often not fully accessible to either direct experimental monitoring or molecular dynamics simulations. However, a coarse-grained model can offer an informative alternative, especially for probing the relationship between conformational dynamics and catalysis. Here we investigate the dynamics of T7 DNA polymerase catalysis using a Langevin-type elastic network model incorporating detailed structural information on the open conformation without the substrate bound. Such a single-parameter model remarkably captures the induced conformational dynamics of DNA polymerase upon dNTP binding, and reveals its close coupling to the advancement toward transition state along the coordinate of the target reaction, which contributes to significant lowering of the activation energy barrier. Furthermore, analysis of stochastic catalytic rates suggests that when the activation energy barrier has already been significantly lowered and nonequilibrium relaxation toward the closed form dominates the catalytic rate, one must appeal to a picture of two-dimensional free energy surface in order to account for the full spectrum of catalytic modes. Our semiquantitative study illustrates the general role of conformational dynamics in achieving transition-state stabilization, and suggests that such an elastic network model, albeit simplified, possesses the potential to furnish significant mechanistic insights into the functioning of a variety of enzymatic systems.

  19. The Non-innocent Phenalenyl Unit: An Electronic Nest to Modulate the Catalytic Activity in Hydroamination Reaction

    PubMed Central

    Mukherjee, Arup; Sen, Tamal K.; Ghorai, Pradip Kr; Mandal, Swadhin K.

    2013-01-01

    The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, material chemistry to device physics acting as key electronic reservoir which has not only led to the best organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which in turn determines the outcome of the catalysis. PMID:24084653

  20. Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures.

    PubMed

    Christopher, Phillip; Xin, Hongliang; Linic, Suljo

    2011-06-01

    Catalysis plays a critical role in chemical conversion, energy production and pollution mitigation. High activation barriers associated with rate-limiting elementary steps require most commercial heterogeneous catalytic reactions to be run at relatively high temperatures, which compromises energy efficiency and the long-term stability of the catalyst. Here we show that plasmonic nanostructures of silver can concurrently use low-intensity visible light (on the order of solar intensity) and thermal energy to drive catalytic oxidation reactions--such as ethylene epoxidation, CO oxidation, and NH₃ oxidation--at lower temperatures than their conventional counterparts that use only thermal stimulus. Based on kinetic isotope experiments and density functional calculations, we postulate that excited plasmons on the silver surface act to populate O₂ antibonding orbitals and so form a transient negative-ion state, which thereby facilitates the rate-limiting O₂-dissociation reaction. The results could assist the design of catalytic processes that are more energy efficient and robust than current processes.

  1. Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation

    PubMed Central

    Hu, Xiao-Qiang; Qi, Xiaotian; Chen, Jia-Rong; Zhao, Quan-Qing; Wei, Qiang; Lan, Yu; Xiao, Wen-Jing

    2016-01-01

    Compared with the popularity of various C-centred radicals, the N-centred radicals remain largely unexplored in catalytic radical cascade reactions because of a lack of convenient methods for their generation. Known methods for their generation typically require the use of N-functionalized precursors or various toxic, potentially explosive or unstable radical initiators. Recently, visible-light photocatalysis has emerged as an attractive tool for the catalytic formation of N-centred radicals, but the pre-incorporation of a photolabile groups at the nitrogen atom largely limited the reaction scope. Here, we present a visible-light photocatalytic oxidative deprotonation electron transfer/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediation strategy for catalytic N-radical cascade reaction of unsaturated hydrazones. This mild protocol provides a broadly applicable synthesis of 1,6-dihydropyradazines with complete regioselectivity and good yields. The 1,6-dihydropyradazines can be easily transformed into diazinium salts that showed promising in vitro antifungal activities against fungal pathogens. DFT calculations are conducted to explain the mechanism. PMID:27048886

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

    SciTech Connect

    Mohamed, Norani Muti E-mail: pervaiz-pas@yahoo.com E-mail: zainabh@petronas.com.my; Ahmad, Pervaiz E-mail: pervaiz-pas@yahoo.com E-mail: zainabh@petronas.com.my; Saheed, Mohamed Shuaib Mohamed E-mail: pervaiz-pas@yahoo.com E-mail: zainabh@petronas.com.my; Burhanudin, Zainal Arif E-mail: pervaiz-pas@yahoo.com E-mail: zainabh@petronas.com.my

    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.

  3. A palladium-nanoparticle and silicon-nanowire-array hybrid: a platform for catalytic heterogeneous reactions.

    PubMed

    Yamada, Yoichi M A; Yuyama, Yoshinari; Sato, Takuma; Fujikawa, Shigenori; Uozumi, Yasuhiro

    2014-01-01

    We report the development of a silicon nanowire array-stabilized palladium nanoparticle catalyst, SiNA-Pd. Its use in the palladium-catalyzed Mizoroki-Heck reaction, the hydrogenation of an alkene, the hydrogenolysis of nitrobenzene, the hydrosilylation of an α,β-unsaturated ketone, and the C-H bond functionalization reactions of thiophenes and indoles achieved a quantitative production with high reusability. The catalytic activity reached several hundred-mol ppb of palladium, reaching a TON of 2 000 000.

  4. Direct Formation of Oxocarbenium Ions under Weakly Acidic Conditions: Catalytic Enantioselective Oxa-Pictet-Spengler Reactions.

    PubMed

    Zhao, Chenfei; Chen, Shawn B; Seidel, Daniel

    2016-07-27

    Two catalysts, an amine HCl salt and a bisthiourea, work in concert to enable the generation of oxocarbenium ions under mild conditions. The amine catalyst generates an iminium ion of sufficient electrophilicity to enable 1,2-attack by an alcohol. Catalyst turnover is achieved by amine elimination with concomitant formation of an oxocarbenium intermediate. The bisthiourea catalyst accelerates all of the steps of the reaction and controls the stereoselectivity via anion binding/ion pair formation. This new concept was applied to direct catalytic enantioselective oxa-Pictet-Spengler reactions of tryptophol with aldehydes. PMID:27396413

  5. Direct Formation of Oxocarbenium Ions under Weakly Acidic Conditions: Catalytic Enantioselective Oxa-Pictet-Spengler Reactions.

    PubMed

    Zhao, Chenfei; Chen, Shawn B; Seidel, Daniel

    2016-07-27

    Two catalysts, an amine HCl salt and a bisthiourea, work in concert to enable the generation of oxocarbenium ions under mild conditions. The amine catalyst generates an iminium ion of sufficient electrophilicity to enable 1,2-attack by an alcohol. Catalyst turnover is achieved by amine elimination with concomitant formation of an oxocarbenium intermediate. The bisthiourea catalyst accelerates all of the steps of the reaction and controls the stereoselectivity via anion binding/ion pair formation. This new concept was applied to direct catalytic enantioselective oxa-Pictet-Spengler reactions of tryptophol with aldehydes.

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

    SciTech Connect

    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

  7. Plant lipases: biocatalyst aqueous environment in relation to optimal catalytic activity in lipase-catalyzed synthesis reactions.

    PubMed

    Caro, Yanis; Pina, Michel; Turon, Fabrice; Guilbert, Stephane; Mougeot, Estelle; Fetsch, David V; Attwool, Philip; Graille, Jean

    2002-03-20

    Adsorption and desorption isotherms of two commercial enzyme preparations of papain and bromelain were determined with a Dynamic Vapor System. The Guggenheim-Anderson-deBoer (GAB) modeling of the obtained sorption isotherms allowed the definition of different levels of hydration of those samples. Afterward, these enzyme preparations were used as biocatalysts in water and solvent-free esterification and alcoholysis reactions. The evolution of the obtained fatty acid ester level as a function of the initial hydration level of the biocatalyst, i.e., thermodynamic water activity (a(w)) and water content, was studied. The results show an important correlation between the initial hydration level of the biocatalyst and its catalytic activity during the lipase-catalyzed synthesis reactions. Thus, the Carica papaya lipase (crude papain preparation) catalytic activity is highly dependent on the biocatalyst hydration state. The optimized synthesis reaction yield is obtained when the a(w) value of the enzyme preparation is stabilized at 0.22, which corresponds to 2% water content. This optimal level of hydration occurs on the linear part of the biocatalyst's sorption isotherm, where the water molecules can form a mono- or multiple layer with the protein network. The synthesis reaction yield decreases when the a(w) of the preparation is higher than 0.22, because the excess water molecules modify the system equilibrium leading to the reverse and competitive reaction, i.e., hydrolysis. These results show also that an optimal storage condition for the highly hydrophilic crude papain preparation is a relative humidity strictly lower than 70% to avoid an irreversible structural transition leading to a useless biocatalyst. Concerning the bromelain preparation, no effect of the hydration level on the catalytic activity during esterification reactions was observed. This biocatalyst has too weak a catalytic activity which makes it difficult to observe any differences. Furthermore, the

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Catalytic activities of platinum nanotubes: a density functional study

    NASA Astrophysics Data System (ADS)

    Mukherjee, Prajna; Gupta, Bikash C.; Jena, Puru

    2015-10-01

    In this work we investigate the catalytic properties of platinum nanotubes using density functional theory based calculations. In particular, we study the dissociation of hydrogen and oxygen molecules as well as oxidation of CO molecules. The results indicate that platinum nanotubes have good catalytic properties and can be effectively used in converting CO molecule to CO2.

  10. A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

    NASA Astrophysics Data System (ADS)

    Conte, Marco; Wilson, Karen; Chechik, Victor

    2010-10-01

    A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X-band electron paramagnetic resonance spectroscopy.

  11. Catalytic reduction of CN-, CO, and CO2 by nitrogenase cofactors in lanthanide-driven reactions.

    PubMed

    Lee, Chi Chung; Hu, Yilin; Ribbe, Markus W

    2015-01-19

    Nitrogenase cofactors can be extracted into an organic solvent to catalyze the reduction of cyanide (CN(-)), carbon monoxide (CO), and carbon dioxide (CO2) without using adenosine triphosphate (ATP), when samarium(II) iodide (SmI2) and 2,6-lutidinium triflate (Lut-H) are employed as a reductant and a proton source, respectively. Driven by SmI2, the cofactors catalytically reduce CN(-) or CO to C1-C4 hydrocarbons, and CO2 to CO and C1-C3 hydrocarbons. The C-C coupling from CO2 indicates a unique Fischer-Tropsch-like reaction with an atypical carbonaceous substrate, whereas the catalytic turnover of CN(-), CO, and CO2 by isolated cofactors suggests the possibility to develop nitrogenase-based electrocatalysts for the production of hydrocarbons from these carbon-containing compounds.

  12. Detection of DNA with Catalytic Beacons Based on Peroxidase-oxidase Oscillating Reaction.

    PubMed

    Zeng, Jinhong; Liu, Qiong; Xu, Huibi; Wang, Hongmei; Wang, Jun; Cai, Ruxiu

    2005-01-01

    This paper aims at investigating a new method for the detection of DNA with catalytic beacons based on peroxidase-oxidase (PO) oscillation and analytic pulse perturbation technique. Two DNAzymes were constructed by the binding of specific DNA sequence with hemin or by the hybridization of target DNA with the catalytic beacon. Both DNAzymes possessed peroxidase-like activity and perturb the PO oscillator reaction when they were added into the oscillation system. The period and amplitude of oscillation increased significantly by both DNAzymes, which implied the decrease in the average rate of consumption of oxygen in solution, i.e., the decrease of the average rate of NADH oxidation. The results provide a new sensitive method for DNA detection and molecular recognition.

  13. Catalytic reaction of 3-phenyl-2-propyn-1-ol with alcohols

    SciTech Connect

    Grigoryan, S.G.; Avetisyan, K.G.; Matnishyan, A.A.

    1987-01-10

    The cyclic ketal 2,5-dimethyl-2,5-bis(3-phenyl-2-propynyloxy)-1,4-dioxane was obtained by the reaction of 3-phenyl-2-propyn-1=ol with propargyl alcohol in the presence of the HgO-BF/sub 3/ O(C/sub 2/H/sub 5/)/sub 2/ catalytic system. The transformation of 3-phenyl-2-propyn-1-ol and its ethers in methanol and ethanol by the action of the above-mentioned catalytic system leads to 1-phenyl-3-alkoxy-1-propanone, 1-phenyl-1,1,3-trialkoxypropane, and 1-phenyl-2-propen-1-one. The intermediate organomercury compound, which is the product from regioselective addition of mercuric oxide and the saturated alcohol at the triple bond, was isolated. Its protodemercuration led to the above-mentioned linear products. The formation of the cyclic ketal is presumably due to the preferred formation of mercury bis-hydroxypropargylide.

  14. Catalytic Transfer Hydrogenation with a Methandiide-Based Carbene Complex: An Experimental and Computational Study.

    PubMed

    Weismann, Julia; Gessner, Viktoria H

    2015-11-01

    The transfer hydrogenation (TH) reaction of ketones with catalytic systems based on a methandiide-derived ruthenium carbene complex was investigated and optimised. The complex itself makes use of the noninnocent behaviour of the carbene ligand (M=CR2 →MH-C(H)R2 ), but showed only moderate activity, thus requiring long reaction times to achieve sufficient conversion. DFT studies on the reaction mechanism revealed high reaction barriers for both the dehydrogenation of iPrOH and the hydrogen transfer. A considerable improvement of the catalytic activity could be achieved by employing triphenylphosphine as additive. Mechanistic studies on the role of PPh3 in the catalytic cycle revealed the formation of a cyclometalated complex upon phosphine coordination. This ruthenacycle was revealed to be the active species under the reaction conditions. The use of the isolated complex resulted in high catalytic activities in the TH of aromatic as well as aliphatic ketones. The complex was also found to be active under base-free conditions, suggesting that the cyclometalation is crucial for the enhanced activity. PMID:26403918

  15. The influence of Ser-154, Cys-113, and the phosphorylated threonine residue on the catalytic reaction mechanism of Pin1.

    PubMed

    Vöhringer-Martinez, Esteban; Verstraelen, Toon; Ayers, Paul W

    2014-08-21

    Pin1 is an enzyme that specifically catalyzes the cis-trans isomerization of proline amide bonds in peptides that contain a phosphorylated threonine or serine residue in the position preceding proline. In the cell, the isomerization reaction is associated with cellular signaling and has been related to diseases such as Alzheimer and cancer. The catalytic mechanism by which Pin1 accelerates the isomerization reaction, however, is still unknown. In this study, we use molecular dynamics simulation in combination with the QM/MM methodology to disclose the influence of the residues Ser-154 and Cys-113 in the enzyme and the phosphorylated threonine residue in the peptide on the reaction mechanism. To account for the correct electrostatic interaction between the three residues and the reactive center, we derive atomic charges that account for the varying electrostatic field in the catalytic cavity. Different methods based on reproducing the molecular electrostatic potential or an atoms in molecules approach were investigated. Finally, the reaction mechanism is analyzed with the mean reaction force and the influence of the three residues is disclosed. Our results show that Pin1 specifically catalyzes the isomerization of the trans conformer in a jump-rope type of motion, as suggested by us and confirmed experimentally by others. This is accomplished by anchoring the threonine phosphate residue on one end of the peptide through electrostatic interactions with the basic triad of the enzyme and at the other end through specific enzyme-peptide hydrogen bonds. Cys-113 reduces the structural contribution to the activation free energy through the stabilization of the cis conformer, and Ser-154 in combination with Gln-131 assist in the isomerization reaction of the trans isomer. PMID:25059768

  16. TiO2-sludge carbon enhanced catalytic oxidative reaction in environmental wastewaters applications.

    PubMed

    Athalathil, Sunil; Erjavec, Boštjan; Kaplan, Renata; Stüber, Frank; Bengoa, Christophe; Font, Josep; Fortuny, Agusti; Pintar, Albin; Fabregat, Azael

    2015-12-30

    The enhanced oxidative potential of sludge carbon/TiO2 nano composites (SNCs), applied as heterogeneous catalysts in advanced oxidation processes (AOPs), was studied. Fabrification of efficient SNCs using different methods and successful evaluation of their catalytic oxidative activity is reported for the first time. Surface modification processes of hydrothermal deposition, chemical treatment and sol-gel solution resulted in improved catalytic activity and good surface chemistry of the SNCs. The solids obtained after chemical treatment and hydrothermal deposition processes exhibit excellent crystallinity and photocatalytic activity. The highest photocatalytic rate was obtained for the material prepared using hydrothermal deposition technique, compared to other nanocomposites. Further, improved removal of bisphenol A (BPA) from aqueous phase by means of catalytic ozonation and catalytic wet air oxidation processes is achieved over the solid synthesized using chemical treatment method. The present results demonstrate that the addition of TiO2 on the surface of sludge carbon (SC) increases catalytic oxidative activity of SNCs. The latter produced from harmful sludge materials can be therefore used as cost-effective and efficient sludge derived catalysts for the removal of hazardous pollutants.

  17. Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

    PubMed

    Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

    2013-10-14

    Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect. PMID:23990024

  18. Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

    PubMed

    Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

    2013-10-14

    Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect.

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

    PubMed

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

    2014-06-28

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

  20. Synthesis and the thermal and catalytic dehydrogenation reactions of amine-thioboranes.

    PubMed

    Robertson, Alasdair P M; Haddow, Mairi F; Manners, Ian

    2012-08-01

    A series of trimethylamine-thioborane adducts, Me(3)N·BH(2)SR (R = tBu [2a], nBu [2b], iPr [2c], Ph [2d], C(6)F(5) [2e]) have been prepared and characterized. Attempts to access secondary and primary amine adducts of thioboranes via amine-exchange reactions involving these species proved unsuccessful, with the thiolate moiety shown to be vulnerable to displacement by free amine. However, treatment of the arylthioboranes, [BH(2)-SPh](3) (9) and C(6)F(5)SBH(2)·SMe(2) (10) with Me(2)NH and iPr(2)NH successfully yielded the adducts Me(2)NH·BH(2)SR (R = Ph [11a], C(6)F(5) [12a]) and iPr(2)NH·BH(2)SR (R = Ph [11b], C(6)F(5) [12b]) in high yield. These adducts were also shown to be accessible via thermally induced hydrothiolation of the aminoboranes Me(2)N═BH(2), derived from the cyclic dimer [Me(2)N-BH(2)](2) (13), and iPr(2)N═BH(2) (14), respectively. Attempts to prepare the aliphatic thiolate substituted adducts R(2)NH·BH(2)SR' (R = Me, iPr; R' = tBu, nBu, iPr) via this method, however, proved unsuccessful, with the temperatures required to facilitate hydrothiolation also inducing thermal dehydrogenation of the amine-thioborane products to form aminothioboranes, R(2)N═BH(SR'). Thermal and catalytic dehydrogenation of the targeted amine-thioboranes, 11a/11b and 12a/12b were also investigated. Adducts 11b and 12b were cleanly dehydrogenated to yield iPr(2)N═BH(SPh) (22) and iPr(2)N═BH(SC(6)F(5)) (23), respectively, at 100 °C (18 h, toluene), with dehydrogenation also possible at 20 °C (42 h, toluene) with a 2 mol % loading of [Rh(μ-Cl)cod](2) in the case of the former species. Similar studies with adduct 11a evidenced a competitive elimination of H(2) and HSPh upon thermolysis, and other complex reactivity under catalytic conditions, whereas the fluorinated analogue 12a was found to be resistant to dehydrogenation. PMID:22800118

  1. [Study on catalytic oxidation of benzene by microwave heating].

    PubMed

    Zhang, Yu-cai; Bo, Long-li; Wang, Xiao-hui; Liu, Hai-nan; Zhang, Hao

    2012-08-01

    The performance in catalytic oxidation of benzene was investigated in two different heating modes, microwave heating and conventional electric furnace heating. The effects of copper (Cu)-manganese (Mn) mass ratio, doping dose of cerium (Ce) and calcination temperature on the catalytic activity of Cu-Mn-Ce/molecular sieve catalyst were also checked in catalytic oxidation of benzene with microwave heating, and the catalysts were subsequently characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that the catalyst had better catalytic activity for the oxidation of benzene under microwave heating than electric furnace heating, and high oxidation efficiency for benzene was reached due to the "local hot spots" and dipole polarization effect of microwave and stable bed reaction temperature. Under the conditions of Cu, Mn and Ce mass ratio 1:1:0.33 and calcination temperature 500 degrees C, the catalyst had the optimal catalytic activity for benzene oxidation, and its light-off temperature and complete combustion temperature were 165 degrees C and 230 degrees C, respectively. It was indicated by characteristics of XRD and SEM that the presence of copper and manganese oxides and Cu1.5Mn1.5O4 with spinel crystal improved the catalytic activity of the catalyst, and the doping of Ce promoted the dispersion and regularization of active components. High calcination temperature led to the sintering of the catalyst surface and agglomeration of active components, which decreased the catalytic activity of the catalyst in the catalytic oxidation PMID:23213902

  2. A One-Pot Tandem Strategy in Catalytic Asymmetric Vinylogous Aldol Reaction of Homoallylic Alcohols.

    PubMed

    Hou, Xufeng; Jing, Zhenzhong; Bai, Xiangbin; Jiang, Zhiyong

    2016-01-01

    Reported is a rationally-designed one-pot sequential strategy that allows homoallylic alcohols to be employed in a catalytic, asymmetric, direct vinylogous aldol reaction with a series of activated acyclic ketones, including trifluoromethyl ketones, γ-ketoesters, and α-keto phosphonates, in high yields (up to 95%) with excellent regio- and enantio-selectivity (up to 99% ee). This modular combination, including Jones oxidation and asymmetric organocatalysis, has satisfactory compatibility and reliability even at a 20 mmol scale, albeit without intermediary purification. PMID:27355935

  3. Note on the stochastic theory of a self-catalytic chemical reaction. II

    NASA Astrophysics Data System (ADS)

    Dambrine, S.; Moreau, M.

    1981-04-01

    The general results of article I on the stochastic representation of the macroscopic stationary state of a self-catalytic chemical system are applied to a step-by-step chemical reaction. The relaxation times to the quasi-stationary state and to the final stationary state are computed by evaluating the first two non-trivial eigenvalues of the transition matrix. The previous results of Oppenheim, Shuler and Weiss are confirmed, precised and extended. The critical and subcritical cases are treated by the same method.

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

    NASA Technical Reports Server (NTRS)

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

    1971-01-01

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

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

    PubMed

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

    2016-08-01

    An efficient protocol for the synthesis of highly functionalized furans via intramolecular Wittig reaction has been developed using catalytic amounts of phosphine and triethylamine. Silyl chloride served as the initial promoter to activate the phosphine oxide. Reduction of the activated phosphine oxide by hydrosilane resulted in generation of phosphine, while decomposition of Et3N·HCl resulted in regeneration of base, which mediated formation of phosphorus ylide. Remarkably, the in situ generated byproduct, Et3N·HCl, also catalyzes reduction of phosphine oxide. PMID:27434727

  6. Characterization and mechanism insight of accelerated catalytic promiscuity of Sulfolobus tokodaii (ST0779) peptidase for aldol addition reaction.

    PubMed

    Li, Rong; Perez, Bianca; Jian, Hui; Jensen, Mads Mørk; Gao, Renjun; Dong, Mingdong; Glasius, Marianne; Guo, Zheng

    2015-11-01

    A novel peptidase from thermophilic archaea Sulfolobus tokodaii (ST0779) is examined for its catalytic promiscuity of aldol addition, which shows comparable activity as porcine pancreatic lipase (PPL, one of the best enzymes identified for biocatalytic aldol addition) at 30 °C but much accelerated activity at elevated temperature. The molecular catalytic efficiency kcat/Km (M(-1) s(-1)) of this thermostable enzyme at 55 °C adds up to 140 times higher than that of PPL at its optimum temperature 37 °C. The fluorescence quenching analysis depicts that the binding constants of PPL are significantly higher than those of ST0779, and their numbers of binding sites show opposite temperature dependency. Thermodynamic parameters estimated by fluorescence quenching analysis unveil distinctly different substrate-binding modes between PPL and ST0779: the governing binding interaction between PPL and substrates is hydrophobic force, while the dominating substrate-binding forces for ST0779 are van der Waals and H-bonds interactions. A reasonable mechanism for ST0779-catalyzed aldol reaction is proposed based on kinetic study, spectroscopic analysis, and molecular stereostructure simulation. This work represents a successful example to identify a new enzyme for catalytic promiscuity, which demonstrates a huge potential to discover and exploit novel biocatalyst from thermophile microorganism sources. PMID:26169629

  7. Catalytic reactions with bulk-mediated excursions: Mixing fails to restore chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Coppey, M.; Bénichou, O.; Klafter, J.; Moreau, M.; Oshanin, G.

    2004-03-01

    In this paper we analyze the effect of the bulk-mediated excursions (BME) of reactive species on the long-time behavior of the catalytic Langmuir-Hinshelwood-like A+B→0 reactions in systems in which a catalytic plane (CP) is in contact with a liquid phase, containing concentrations of reactive particles. Such BME result from repeated particles desorption from the CP, subsequent diffusion in the liquid phase, and eventual readsorption on the CP away from the initial detachment point. This process leads to an effective superdiffusive transport along the CP. We consider both “batch” reactions, in which all particles of reactive species were initially adsorbed onto the CP, and reactions followed by a steady inflow of particles onto the CP. We show that for batch reactions the BME provide an effective mixing channel and here the mean-field-type behavior emerges. On the contrary, for reaction followed by a steady inflow of particles, we observe essential departures from the mean-field behavior and find that the mixing effect of the BME is insufficient to restore chemical equilibrium. We show that a steady state is established as t→∞, in which the limiting value of the mean coverage of the CP depends on the particles’ diffusion coefficient in the bulk liquid phase, and that the spatial distributions of adsorbed particles are strongly correlated. Moreover, we show that the relaxation to such a steady state is a power-law function of time, in contrast to the exponential time dependence describing the approach to equilibrium in perfectly stirred systems.

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

    PubMed

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

    2015-05-20

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

  9. Catalytic reactions of gas phase zirconium oxide clusters with NO and CO revealed by post heating

    NASA Astrophysics Data System (ADS)

    Miyajima, Ken; Mafuné, Fumitaka

    2016-09-01

    Reactivity of gas phase zirconium oxide clusters (ZrnOm+) toward NO and CO gases was investigated by mass spectrometry in combination with post heating. Reaction of ZrnO2n+x+ with NO gas resulted in the depletion of extremely oxygen-deficient clusters and the formation of oxygen-rich clusters, ZrnO2n+x+ (0 ⩽ x ⩽ 3). Reaction with CO substantially lead to an increase in the amount of ZrnO2n-2+ and ZrnO2n-1+ clusters and depletion in the amount of ZrnO2n+. The catalytic cycle, achieved by regenerating ZrnO2n+ by the oxidation of ZrnO2n-2+ by NO, were discussed in comparison with the reactivity of cerium oxide clusters.

  10. Computational Approach for Ranking Mutant Enzymes According to Catalytic Reaction Rates

    PubMed Central

    Kumarasiri, Malika; Baker, Gregory A.; Soudackov, Alexander V.

    2009-01-01

    A computationally efficient approach for ranking mutant enzymes according to the catalytic reaction rates is presented. This procedure requires the generation and equilibration of the mutant structures, followed by the calculation of partial free energy curves using an empirical valence bond potential in conjunction with biased molecular dynamics simulations and umbrella integration. The individual steps are automated and optimized for computational efficiency. This approach is used to rank a series of 15 dihydrofolate reductase mutants according to the hydride transfer reaction rate. The agreement between the calculated and experimental changes in the free energy barrier upon mutation is encouraging. The computational approach predicts the correct direction of the change in free energy barrier for all mutants, and the correlation coefficient between the calculated and experimental data is 0.82. This general approach for ranking protein designs has implications for protein engineering and drug design. PMID:19235997

  11. Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions.

    PubMed

    Li, Gao; Abroshan, Hadi; Chen, Yuxiang; Jin, Rongchao; Kim, Hyung J

    2015-11-18

    The catalytic activity of Au25(SR)18 nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in the presence of a base, e.g., ammonia or pyridine, and transition-metal ions M(z+), such as Cu(+), Cu(2+), Ni(2+) and Co(2+), as a Lewis acid is studied. The addition of a Lewis acid is found to significantly promote the catalytic activity of Au25(SR)18/CeO2 in the hydrogenation of benzaldehyde and a number of its derivatives. Matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry in conjunction with UV-vis spectroscopy confirm the generation of new species, Au25-n(SR)18-n (n = 1-4), in the presence of a Lewis acid. The pathways for the speciation of Au24(SR)17 from its parent Au25(SR)18 nanocluster as well as its structure are investigated via the density functional theory (DFT) method. The adsorption of M(z+) onto a thiolate ligand "-SR-" of Au25(SR)18, followed by a stepwise detachment of "-SR-" and a gold atom bonded to "-SR-" (thus an "Au-SR" unit) is found to be the most likely mechanism for the Au24(SR)17 generation. This in turn exposes the Au13-core of Au24(SR)17 to reactants, providing an active site for the catalytic hydrogenation. DFT calculations indicate that M(z+) is also capable of adsorbing onto the Au13-core surface, producing a possible active metal site of a different kind to catalyze the aldehyde hydrogenation reaction. This study suggests, for the first time, that species with an open metal site like adducts [nanoparticle-M]((z-1)+) or fragments Au25-n(SR)18-n function as the catalysts rather than the intact Au25(SR)18.

  12. Entropy production of a steady-growth cell with catalytic reactions.

    PubMed

    Himeoka, Yusuke; Kaneko, Kunihiko

    2014-10-01

    Cells generally convert external nutrient resources to support metabolism and growth. Understanding the thermodynamic efficiency of this conversion is essential to determine the general characteristics of cellular growth. Using a simple protocell model with catalytic reaction dynamics to synthesize the necessary enzyme and membrane components from nutrients, the entropy production per unit-cell-volume growth is calculated analytically and numerically based on the rate equation for chemical kinetics and linear nonequilibrium thermodynamics. The minimal entropy production per unit-cell growth is found to be achieved at a nonzero nutrient uptake rate rather than at a quasistatic limit as in the standard Carnot engine. This difference appears because the equilibration mediated by the enzyme exists only within cells that grow through enzyme and membrane synthesis. Optimal nutrient uptake is also confirmed by protocell models with many chemical components synthesized through a catalytic reaction network. The possible relevance of the identified optimal uptake to optimal yield for cellular growth is also discussed. PMID:25375530

  13. Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

    PubMed

    Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

    2016-11-01

    The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. PMID:27573477

  14. Direct observation of enhanced plasmon-driven catalytic reaction activity of Au nanoparticles supported on reduced graphene oxides by SERS.

    PubMed

    Liang, Xiu; You, Tingting; Liu, Dapeng; Lang, Xiufeng; Tan, Enzhong; Shi, Jihua; Yin, Penggang; Guo, Lin

    2015-04-21

    Graphene-based nanocomposites have recently attracted tremendous research interest in the field of catalysis due to their unique optical and electronic properties. However, direct observation of enhanced plasmon-driven catalytic activity of Au nanoparticles (NPs) supported on reduced graphene oxides (Au/rGO) has rarely been reported. Herein, based on the reduction from 4-nitrobenzenethiol (4-NBT) to p,p'-dimercaptoazobenzene (DMAB), the catalytic property of Au/rGO nanocomposites was investigated and compared with corresponding Au NP samples with similar size distribution. Our results show that Au/rGO nanocomposites could serve as a good catalytic and analytic platform for plasmon-driven chemical reactions. In addition, systematic comparisons were conducted during power- and time-dependent surface-enhanced Raman scattering (SERS) experiments, which exhibited a lower power threshold and higher catalytic efficiency for Au/rGO as compared to Au NPs toward the reaction. PMID:25793752

  15. The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions.

    PubMed

    Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang

    2016-04-21

    Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs. PMID:27043428

  16. Asymmetric catalytic cascade reactions for constructing diverse scaffolds and complex molecules.

    PubMed

    Wang, Yao; Lu, Hong; Xu, Peng-Fei

    2015-07-21

    With the increasing concerns about chemical pollution and sustainability of resources, among the significant challenges facing synthetic chemists are the development and application of elegant and efficient methods that enable the concise synthesis of natural products, drugs, and related compounds in a step-, atom- and redox-economic manner. One of the most effective ways to reach this goal is to implement reaction cascades that allow multiple bond-forming events to occur in a single vessel. This Account documents our progress on the rational design and strategic application of asymmetric catalytic cascade reactions in constructing diverse scaffolds and synthesizing complex chiral molecules. Our research is aimed at developing robust cascade reactions for the systematic synthesis of a range of interesting molecules that contain structural motifs prevalent in natural products, pharmaceuticals, and biological probes. The strategies employed to achieve this goal can be classified into three categories: bifunctional base/Brønsted acid catalysis, covalent aminocatalysis/N-heterocyclic carbene catalysis, and asymmetric organocatalytic relay cascades. By the use of rationally designed substrates with properly reactive sites, chiral oxindole, chroman, tetrahydroquinoline, tetrahydrothiophene, and cyclohexane scaffolds were successfully assembled under bifunctional base/Brønsted acid catalysis from simple and readily available substances such as imines and nitroolefins. We found that some of these reactions are highly efficient since catalyst loadings as low as 1 mol % can promote the multistep sequences affording complex architectures with high stereoselectivities and yields. Furthermore, one of the bifunctional base/Brønsted acid-catalyzed cascade reactions for the synthesis of chiral cyclohexanes has been used as a key step in the construction of the tetracyclic core of lycorine-type alkaloids and the formal synthesis of α-lycorane. Guided by the principles of

  17. Insights into the effects of surface properties of oxides on the catalytic activity of Pd for C-C coupling reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Sai; Li, Jing; Gao, Wei; Qu, Yongquan

    2015-02-01

    Understanding the interaction between Pd nanocatalysts and metal oxide supports for heterogeneous C-C coupling reactions is still ambiguous since many factors influence the catalytic behavior of Pd nanocatalysts. Herein, three porous nanorods of CeO2 with controllable surface properties were employed as supports for Pd nanocatalysts with similar dispersion, which avoided the impact of other factors including surface area, morphology and accessible active sites. It provides an ideal approach to probe synergetic catalytic behavior of metal nanoparticles on supports. The results obtained by studying three C-C coupling reactions (Ullman, Suzuki and Heck) indicate a strong correlation between the surface properties of supports and the catalytic activity of Pd nanocatalysts: supports with a strong basicity and a high concentration of oxygen vacancies result in a rich electron density of Pd and accelerate the first step of oxidative addition reaction for C-C coupling. The infrared spectroscopic study on ν[CO] of CO-treated catalysts and XPS analysis of the Pd(3d) core level provide strong evidence supporting the interaction of Pd/supports for C-C coupling reactions.Understanding the interaction between Pd nanocatalysts and metal oxide supports for heterogeneous C-C coupling reactions is still ambiguous since many factors influence the catalytic behavior of Pd nanocatalysts. Herein, three porous nanorods of CeO2 with controllable surface properties were employed as supports for Pd nanocatalysts with similar dispersion, which avoided the impact of other factors including surface area, morphology and accessible active sites. It provides an ideal approach to probe synergetic catalytic behavior of metal nanoparticles on supports. The results obtained by studying three C-C coupling reactions (Ullman, Suzuki and Heck) indicate a strong correlation between the surface properties of supports and the catalytic activity of Pd nanocatalysts: supports with a strong basicity and a

  18. EXAFS studies on gold nanoparticles over novel catalytic materials

    NASA Astrophysics Data System (ADS)

    Akolekar, Deepak B.; Bhargava, Suresh K.; Foran, Garry

    2006-11-01

    Novel nanogold catalytic systems made up of gold nanoparticles (˜2-6 nm) supported on niobium, ytterbium, lanthanum and cerium oxide materials were synthesized. XAS is uniquely suited for studying catalytic systems with low metal and high metal dispersion. Au L 3 edge X-ray absorption spectroscopic measurements were carried out over a series of supported gold nanoparticles. The interesting results obtained from EXAFS and XANES confirms the typical characteristics and structure of gold nanoparticles in these materials.

  19. Studies on reactions of ozone with alkenes.

    PubMed

    Protczak, Agnieszka; Trzeszczynski, Jerzy

    2002-01-01

    In the last years, a continuous increase of the O3 concentration has been recorded in the lower atmospheric layers. Photochemical reactions with NO(x), CO and organic compounds are the main sources of O3 in the troposphere. In this work, an attempt was made to determine the impact of alkenes on the O3 concentration in the troposphere. A study on the gas-phase reactions of 03 with 1-hexene, 1-heptene and 1-nonene was made. The reactions were carried out at room temperature under atmospheric pressure. Ozone was formed by the ultraviolet radiation emitted by a mercury lamp, in order to simulate the atmospheric conditions. The changes with time in the concentration of O3, 1-alkenes and formed aldehydes were investigated. Qualitative and quantitative analyses were done by means of the gas chromatography and colorimetry. The following products were identified: pentanal from 1-hexene; hexanal from 1-heptene; oktanal from 1-nonene. For each of the reactions, HCHO was also determined as a product. The reaction rate constants were calculated and obtained in units of 10(-17) cm(-3) molecule(-1) s(-1): 1.94-0.99 for 1-hexene, 5.54-4.51 for 1-heptene and 1.54-0.76 for 1-nonene. Based on the results obtained, an explanation of O3 concentration variations in the planetary boundary layer can be given. Last year a considerable increase of O3 concentration on the roads of Western Europe was recorded. This increase could have resulted from the decrease of alkene concentration in the air due to common use of the catalytic converters in cars. The unsaturated hydrocarbons rapidly oxidize on the catalyst. In Eastern Europe, where the amount of cars equipped with catalytic converters is smaller than in Western Europe, the alkene content in the exhaust fumes results in a decrease of the O3 concentration in the troposphere.

  20. A General Approach to Catalytic Alkene Anti-Markovnikov Hydrofunctionalization Reactions via Acridinium Photoredox Catalysis.

    PubMed

    Margrey, Kaila A; Nicewicz, David A

    2016-09-20

    the anti-Markovnikov addition of mineral acids to olefins using lutidinium halide salts as convenient reagents to deliver the mineral acids. Acids including HCl, HF, H3PO4, and MeSO3H all participate in the hydrofunctionalization reactions, even with alkenes that are highly prone to polymerization. A combination of transient and steady-state absorption spectroscopy tools were employed to observe alkene cation radicals and the resultant acridine radical, lending support for an electron transfer mechanism. The origin of the anti-Markovnikov selectivity in these reactions is likely the result of a reversible addition of the nucleophile to the alkene cation radical resulting in a greater population of the more stable radical. Loss of a proton followed by reaction of the radical intermediate with the hydrogen atom donor completes the transformations. Again, by means of transient absorption spectroscopy, oxidative turnover of the acridine radical was observed to complete the dual catalytic cycle mechanistic picture. PMID:27588818

  1. A General Approach to Catalytic Alkene Anti-Markovnikov Hydrofunctionalization Reactions via Acridinium Photoredox Catalysis.

    PubMed

    Margrey, Kaila A; Nicewicz, David A

    2016-09-20

    the anti-Markovnikov addition of mineral acids to olefins using lutidinium halide salts as convenient reagents to deliver the mineral acids. Acids including HCl, HF, H3PO4, and MeSO3H all participate in the hydrofunctionalization reactions, even with alkenes that are highly prone to polymerization. A combination of transient and steady-state absorption spectroscopy tools were employed to observe alkene cation radicals and the resultant acridine radical, lending support for an electron transfer mechanism. The origin of the anti-Markovnikov selectivity in these reactions is likely the result of a reversible addition of the nucleophile to the alkene cation radical resulting in a greater population of the more stable radical. Loss of a proton followed by reaction of the radical intermediate with the hydrogen atom donor completes the transformations. Again, by means of transient absorption spectroscopy, oxidative turnover of the acridine radical was observed to complete the dual catalytic cycle mechanistic picture.

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

    PubMed

    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

  3. A combinatorial study on catalytic synergism in supported metal catalysts for fuel cell technology

    NASA Astrophysics Data System (ADS)

    Kobayashi, Tetsuhiko; Ueda, Atsushi; Yamada, Yusuke; Shioyama, Hiroshi

    2004-02-01

    In order to accelerate the catalyst development for the increasing demand on the fuel cell technology, it has been attempted to adopt a combinatorial approach. The catalytic synergism, often observed on the supported metal catalysts for the fuel cell utilization, has been subjected to study. It is proposed herein that not only a comparison of catalysts in one reaction, but also the comparison of interrelated reactions by use of a common catalyst library brings about important information to elucidate the catalytic synergism. Preliminary results of the comparison between the water-gas shift reaction and the steam reforming of MeOH on a given set of catalyst library are presented. An important indicator to predict the serendipitous synergism is expected to be obtained from such information by use of artificial intelligence.

  4. Theoretical modeling study for the phosphonylation mechanisms of the catalytic triad of acetylcholinesterase by sarin.

    PubMed

    Wang, Jing; Gu, Jiande; Leszczynski, Jerzy

    2008-03-20

    Potential energy surfaces for the process of phosphonylation of the catalytic triad of acetylcholinesterase by sarin have been explored at the B3LYP/6-311G(d,p) level of theory through a computational study. It is concluded that the phosphonylation process involves a critical addition-elimination mechanism. The first nucleophilic addition process is the rate-determining step. The following elimination process of the fluoride ion comprises a composite reaction that includes several steps, and it occurs rapidly by comparison with the rate-determining step. The mobility characteristics of histidine play an important role in the reaction. A double proton-transfer mechanism is proposed for the catalytic triad during the phosphonylation process of sarin on AChE. The effect of aqueous solvation has been considered via the polarizable continuum model (PCM). One concludes that the energy barriers are generally lowered in solvent, compared to the gas-phase reactions.

  5. In situ generation of electron acceptor for photoelectrochemical biosensing via hemin-mediated catalytic reaction.

    PubMed

    Zang, Yang; Lei, Jianping; Zhang, Lei; Ju, Huangxian

    2014-12-16

    A novel photoelectrochemical sensing strategy is designed for DNA detection on the basis of in situ generation of an electron acceptor via the catalytic reaction of hemin toward H2O2. The photoelectrochemical platform was established by sequential assembly of near-infrared CdTe quantum dots, capture DNA, and a hemin-labeled DNA probe to form a triple-helix molecular beacon (THMB) structure on an indium tin oxide electrode. According to the highly catalytic capacity of hemin toward H2O2, a photoelectrochemical mechanism was then proposed, in which the electron acceptor of O2 was in situ-generated on the electrode surface, leading to the enhancement of the photocurrent response. The utilization of CdTe QDs can extend the absorption edge to the near-infrared band, resulting in an increase in the light-to-electricity efficiency. After introducing target DNA, the THMB structure is disassembled and releases hemin and, thus, quenches the photocurrent. Under optimized conditions, this biosensor shows high sensitivity with a linear range from 1 to 1000 pM and detection limit of 0.8 pM. Moreover, it exhibits good performance of excellent selectivity, high stability, and acceptable fabrication reproducibility. This present strategy opens an alternative avenue for photoelectrochemical signal transduction and expands the applications of hemin-based materials in photoelectrochemical biosensing and clinical diagnosis.

  6. Nitrogen-Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction.

    PubMed

    Miura, Akira; Rosero-Navarro, Carolina; Masubuchi, Yuji; Higuchi, Mikio; Kikkawa, Shinichi; Tadanaga, Kiyoharu

    2016-07-01

    The catalytic activity of manganese oxynitrides in the oxygen reduction reaction (ORR) was investigated in alkaline solutions to clarify the effect of the incorporated nitrogen atoms on the ORR activity. These oxynitrides, with rock-salt-like structures with different nitrogen contents, were synthesized by reacting MnO, Mn2 O3 , or MnO2 with molten NaNH2 at 240-280 °C. The anion contents and the Mn valence states were determined by combustion analysis, powder X-ray diffraction, and X-ray absorption near-edge structure analysis. An increase in the nitrogen content of rock-salt-based manganese oxynitrides increases the valence of the manganese ions and reinforces the catalytic activity for the ORR in 1 m KOH solution. Nearly single-electron occupancy of the antibonding eg states and highly covalent Mn-N bonding thus enhance the ORR activity of nitrogen-rich manganese oxynitrides. PMID:27193352

  7. Advances in the development of catalytic tethering directing groups for C-H functionalization reactions.

    PubMed

    Sun, Huan; Guimond, Nicolas; Huang, Yong

    2016-09-28

    Transition metal-catalyzed C-H bond insertion is one of the most straightforward strategies to introduce functionalities within a hydrocarbon microenvironment. For the past two decades, selective activation and functionalization of certain inert C-H bonds have been made possible with the help of directing groups (DGs). Despite the enormous advances in the field, an overwhelming majority of systems require two extra steps from their simple precursors: installation and removal of the DGs. Recently, traceless and multitasking groups were invented as a partial solution to DG release. However, installation remains largely unsolved. Ideally, a transient, catalytic DG would circumvent this problem and increase the step- and atom-economy of C-H functionalization processes. In this review, we summarize the recent development of the transient tethering strategy for C-H activation reactions. PMID:27506568

  8. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

    NASA Astrophysics Data System (ADS)

    Parlett, Christopher M. A.; Isaacs, Mark A.; Beaumont, Simon K.; Bingham, Laura M.; Hondow, Nicole S.; Wilson, Karen; Lee, Adam F.

    2016-02-01

    The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

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

    SciTech Connect

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

    2010-04-13

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

  10. Solar photo-thermal catalytic reactions to produce high value chemicals

    SciTech Connect

    Prengle, H.W. Jr.; Wentworth, W.E. )

    1992-04-01

    This report presents a summary of the research work accomplished to date on the utilization of solar photo-thermal energy to convert low cost chemical feedstocks into high $-value chemical products. The rationale is that the solar IR-VIS-UV spectrum is unique, supplying endothermic reaction energy as well as VIS-UV for photochemical activation. Chemical market analysis and product price distribution focused attention on speciality chemicals with prices >$1.00/lb, and a synthesis sequence of n-paraffins to aromatics to partial oxidized products. The experimental work has demonstrated that enhanced reaction effects result from VIS-UV irradiation of catalytically active V2O5/SiO2. Experiments of the past year have been on dehydrogenation and dehydrocyclization of n-paraffins to olefins and aromatics with preference for the latter. Recent results using n-hexane produced 95% conversion with 56% benzene; it is speculated that aromatic yield should reach {approximately}70% by further optimization. Pilot- and commercial-scale reactor configurations have been examined; the odds-on-favorite being a shallow fluid-bed of catalyst with incident radiation from the top. Sequencing for maximum cost effectiveness would be day-time endothermic followed by night-time exothermic reactions to produce the products.

  11. Systematic analysis of palladium-graphene nanocomposites and their catalytic applications in Sonogashira reaction.

    PubMed

    Lee, Kyoung Hoon; Han, Sang-Wook; Kwon, Ki-Young; Park, Joon B

    2013-08-01

    Graphene has been modified with palladium nanoparticles (Pd NPs) to develop high performance catalysts for the Sonogashira cross coupling reaction. In this research, graphite oxide (GO) sheets exfoliated from graphite were impregnated with Pd(OAc)2 to prepare Pd(2+)/GO. Thermal treatments of the Pd(2+)/GO in H2 flow at 100°C produced Pd/graphene (Pd/G) nanocomposites. TEM images show that Pd NPs were distributed quite uniformly on the graphene sheet without obvious aggregation, and the mean size of Pd NPs was determined to be less than 2 nm in diameter. Morphological and chemical structures of the GO, Pd(2+)/GO, and Pd/G were investigated using FT-IR, XRD, XPS, and XAFS. The resulting Pd/G showed excellent catalytic efficiency in the Sonogashira reaction and offers significant advantages over inorganic supported catalysts such as simple recovery and recycling. Finally, deactivation process of the Pd/G in recycling was investigated. We believe that the remarkable reactivity of the Pd/G catalyst toward the Sonogashira reaction is attributed to the high degree of the Pd NP dispersion and thus the increased low coordination numbers of smaller Pd NPs. PMID:23673006

  12. Neutron diffraction studies for realtime leaching of catalytic Ni.

    PubMed

    Iles, Gail N; Devred, François; Henry, Paul F; Reinhart, Guillaume; Hansen, Thomas C

    2014-07-21

    The leaching of Al from intermetallic samples of Nickel Aluminium alloys to form Raney-type nickel catalysts is widely used in the hydrogenation industry, however, little is known of the leaching process itself. In this study, the leaching of Al was measured in realtime, in situ, using the high-flux powder neutron diffractometer, D20, at the Institut Laue-Langevin. Despite the liberation of hydrogen and effervescent nature of the reaction the transformation of the dry powder phases into Raney-type Ni was determined. Samples produced by gas-atomisation were found to leach faster than those produced using the cast and crushed technique. Regardless of processing route of the precursor powder, the formation of spongy-Ni occurs almost immediately, while Ni2Al3 and NiAl3 continue to transform over longer periods of time. Small-angle scattering and broadening of the diffraction peaks is an evidence for the formation of the smaller Ni particles. Understanding the kinetics of the leaching process will allow industry to refine production of catalysts for optimum manufacturing time while knowledge of leaching dynamics of powders produced by different manufacturing techniques will allow further tailoring of catalytic materials. PMID:25053313

  13. Neutron diffraction studies for realtime leaching of catalytic Ni

    SciTech Connect

    Iles, Gail N. Reinhart, Guillaume; Devred, François; Henry, Paul F. Hansen, Thomas C.

    2014-07-21

    The leaching of Al from intermetallic samples of Nickel Aluminium alloys to form Raney-type nickel catalysts is widely used in the hydrogenation industry, however, little is known of the leaching process itself. In this study, the leaching of Al was measured in realtime, in situ, using the high-flux powder neutron diffractometer, D20, at the Institut Laue-Langevin. Despite the liberation of hydrogen and effervescent nature of the reaction the transformation of the dry powder phases into Raney-type Ni was determined. Samples produced by gas-atomisation were found to leach faster than those produced using the cast and crushed technique. Regardless of processing route of the precursor powder, the formation of spongy-Ni occurs almost immediately, while Ni{sub 2}Al{sub 3} and NiAl{sub 3} continue to transform over longer periods of time. Small-angle scattering and broadening of the diffraction peaks is an evidence for the formation of the smaller Ni particles. Understanding the kinetics of the leaching process will allow industry to refine production of catalysts for optimum manufacturing time while knowledge of leaching dynamics of powders produced by different manufacturing techniques will allow further tailoring of catalytic materials.

  14. Neutron diffraction studies for realtime leaching of catalytic Ni

    NASA Astrophysics Data System (ADS)

    Iles, Gail N.; Devred, François; Henry, Paul F.; Reinhart, Guillaume; Hansen, Thomas C.

    2014-07-01

    The leaching of Al from intermetallic samples of Nickel Aluminium alloys to form Raney-type nickel catalysts is widely used in the hydrogenation industry, however, little is known of the leaching process itself. In this study, the leaching of Al was measured in realtime, in situ, using the high-flux powder neutron diffractometer, D20, at the Institut Laue-Langevin. Despite the liberation of hydrogen and effervescent nature of the reaction the transformation of the dry powder phases into Raney-type Ni was determined. Samples produced by gas-atomisation were found to leach faster than those produced using the cast and crushed technique. Regardless of processing route of the precursor powder, the formation of spongy-Ni occurs almost immediately, while Ni2Al3 and NiAl3 continue to transform over longer periods of time. Small-angle scattering and broadening of the diffraction peaks is an evidence for the formation of the smaller Ni particles. Understanding the kinetics of the leaching process will allow industry to refine production of catalysts for optimum manufacturing time while knowledge of leaching dynamics of powders produced by different manufacturing techniques will allow further tailoring of catalytic materials.

  15. Exploring the aldol reaction using catalytic antibodies and "on water" organocatalysts from QM/MM calculations.

    PubMed

    Armacost, Kira; Acevedo, Orlando

    2014-01-01

    The aldol reaction between benzaldehyde and acetone has been investigated using QM/MM Monte Carlo calculations and free-energy perturbation theory to determine the origin of the enhanced rates and enantioselectivities (% ee) derived from an enamine-based catalytic antibody 33F12 and a chiral organocatalyst. Electrostatic stabilization of the general acid/base TyrL36 by TrpH103, SerH100, and AsnL34 enabled the 33F12 active site to exclusively adopt an si-face benzaldehyde orientation for C-C bond formation with the LysH93-enamine. Whereas preorganization was responsible for the exclusive (S)-aldol product in the antibody, the organocatalyst featuring a chiral diphenyl amino alcohol moiety instead derived its preferred (R)-aldol product from an interplay between sterics and electronic stabilization. The si-face benzaldehyde conformation had unfavorable interactions with the organocatalyst in contrast to the re-face. Gas-phase calculations predicted a 73% ee; however, solution boosted the % ee values despite similar reaction geometries. An "on water" environment, defined as a reaction that proceeds in an aqueous organic emulsion, yielded a computed 94% ee (exptl 93% ee) compared to a calculated 87% ee in "neat" acetone (exptl 85% ee). Specific hydrogen bonding between the interfacial waters and an amide oxygen on the catalyst was found to control the % ee. A more compact si-face transition structure reduced solvent accessibility to the amide oxygen with a "closed state" steric barrier compared to an "open state" for the re-face. New insight into the synthetically important aldol reaction and state-of-the-art methodology is presented herein.

  16. Effects of novel supports on the physical and catalytic properties of tungstophosphoric acid for alcohol dehydration reactions

    SciTech Connect

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

    2008-08-17

    The catalytic behavior of tungstophosphoric acid supported on modified mesoporous silica materials for the dehydration of 2-butanol and methanol was studied. Specifically, the supports evaluated here consisted of unmodified MCM-41 and SBA-15 mesoporous silicas, and these materials coated with sub-monolayer quantities of alumina, titania, and zirconia. UV-Vis DRS and 31P-NMR spectroscopy showed that the tungstophosphoric acid species retained their chemical identity in the synthesized supported form, although the spectra were influenced by the specific support material used. In addition, their acidic properties were evaluated using temperature programmed oxidation of isopropyl amine. The differences in reaction rates between the samples reflect both the diversity in the amount of Brønsted acidic sites available for catalysis and dissimilarities in coking resistance. These two characteristics depend, in turn, on the type of support modifier used to prepare the catalyst.

  17. Use of the confined spaces of apo-ferritin and virus capsids as nanoreactors for catalytic reactions.

    PubMed

    Maity, Basudev; Fujita, Kenta; Ueno, Takafumi

    2015-04-01

    Self-assembled protein cages providing nanosized internal spaces which are capable of encapsulating metal ions/complexes, enzymes/proteins have great potential for use as catalytic nanoreactors in efforts to mimic confined cellular environments for synthetic applications. Despite many uses in biomineralization, drug delivery, bio-imaging and so on, applications in catalysis are relatively rare. Because of their restricted size, protein cages are excellent candidates for use as vessels to exert control over reaction kinetics and product selectivity. Virus capsids with larger internal spaces can encapsulate multiple enzymes and can mimic natural enzymatic reactions. The apo-ferritin cage is known to accommodate various metal ions/complexes and suitable for organic transformation reactions in an aqueous medium. This review highlights the importance, prospects and recent significant research on catalytic reactions using the apo-ferritin cage and virus capsids.

  18. Pyranone Natural Products as Inspirations for Catalytic Reaction Discovery and Development

    PubMed Central

    McDonald, Benjamin R.; Scheidt, Karl A.

    2015-01-01

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

  19. Catalytically active polymers obtained by molecular imprinting and their application in chemical reaction engineering.

    PubMed

    Brüggemann, O

    2001-08-01

    Molecular imprinting is a way of creating polymers bearing artificial receptors. It allows the fabrication of highly selective plastics by polymerizing monomers in the presence of a template. This technique primarily had been developed for the generation of biomimetic materials to be used in chromatographic separation, in extraction approaches and in sensors and assays. Beyond these applications, in the past few years molecular imprinting has become a tool for producing new kinds of catalysts. For catalytic applications, the template must be chosen, so that it is structurally comparable with the transition state (a transition state analogue, TSA) of a reaction, or with the product or substrate. The advantage of using these polymeric catalysts is obvious: the backbone withstands more aggressive conditions than a bio material could ever survive. Results are presented showing the applicability of a molecularly imprinted catalyst in different kinds of chemical reactors. It is demonstrated that the catalysts can be utilized not only in batch but also in continuously driven reactors and that their performance can be improved by means of chemical reaction engineering. PMID:11429307

  20. Parameter sensitivity analysis of stochastic models: application to catalytic reaction networks.

    PubMed

    Damiani, Chiara; Filisetti, Alessandro; Graudenzi, Alex; Lecca, Paola

    2013-02-01

    A general numerical methodology for parametric sensitivity analysis is proposed, which allows to determine the parameters exerting the greatest influence on the output of a stochastic computational model, especially when the knowledge about the actual value of a parameter is insufficient. An application of the procedure is performed on a model of protocell, in order to detect the kinetic rates mainly affecting the capability of a catalytic reaction network enclosed in a semi-permeable membrane to retain material from its environment and to generate a variety of molecular species within its boundaries. It is shown that the former capability is scarcely sensitive to variations in the model parameters, whereas a kinetic rate responsible for profound modifications of the latter can be identified and it depends on the specific reaction network. A faster uptaking of limited resources from the environment may have represented a significant advantage from an evolutionary point of view and this result is a first indication in order to decipher which kind of structures are more suitable to achieve a viable evolution. PMID:23246776

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

    PubMed

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

    2016-01-01

    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. PMID:27517898

  2. Conjugate-base-stabilized Brønsted acids: catalytic enantioselective Pictet-Spengler reactions with unmodified tryptamine.

    PubMed

    Mittal, Nisha; Sun, Diana X; Seidel, Daniel

    2014-02-01

    A conjugate-base-stabilized Brønsted acid facilitates catalytic enantioselective Pictet-Spengler reactions with unmodified tryptamine. The chiral carboxylic acid catalyst is readily assembled in just two steps and enables the formation of β-carbolines with up to 92% ee. Achiral acid additives or in situ Boc-protection facilitate catalyst turnover.

  3. N,O-Chelating Four-Membered Metallacyclic Titanium(IV) Complexes for Atom-Economic Catalytic Reactions.

    PubMed

    Ryken, Scott A; Schafer, Laurel L

    2015-09-15

    Titanium, as the second most abundant transition metal in the earth's crust, lends itself as a sustainable and inexpensive resource in catalysis. Its nontoxicity and biocompatibility are also attractive features for handling and disposal. Titanium has excelled as a catalyst for a broad range of transformations, including ethylene and α-olefin polymerizations. However, many reactions relevant to fine chemical synthesis have preferrentially employed late transition metals, and reactive, inexpensive early transition metals have been largely overlooked. In addition to promising reactivity, titanium complexes feature more robust character compared with some other highly Lewis-acidic metals such as those found in the lanthanide series. Since the advent of modulating ligand scaffolds, titanium has found use in a growing variety of reactions as a versatile homogeneous catalyst. These catalytic transformations include hydrofunctionalization reactions (adding an element-hydrogen (E-H) bond across a C-C multiple bond), as well as the ring-opening polymerization of cyclic esters, all of which are atom-economic transformations. Our investigations have focused on tight bite angle monoanionic N,O-chelating ligands, forming four-membered metallacycles. These ligand sets, including amidates, ureates, pyridonates, and sulfonamidates, have flexible binding modes offering a range of stable and reactive intermediates necessary for catalytic activity. Additionally, the simple form of these ligands leads to easily prepared proligands, along with facile tuning of steric and electronic factors. A sterically bulky titanium amidate complex has proven to be a leading catalyst for the selective formation of anti-Markovnikov addition products via intermolecular hydroamination of terminal alkynes, while sterically less demanding titanium pyridonates have opened the path to the selective formation of amine substituted cycloalkanes via the intramolecular hydroaminoalkylation of aminoalkenes over

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

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. PMID:27106147

  5. A Mesoporous Indium Metal-Organic Framework: Remarkable Advances in Catalytic Activity for Strecker Reaction of Ketones.

    PubMed

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

    2016-07-27

    With the aim of developing new highly porous, heterogeneous Lewis acid catalysts for multicomponent reactions, a new mesoporous metal-organic framework, InPF-110 ([In3O(btb)2(HCOO)(L)], (H3btb = 1,3,5-tris(4-carboxyphenyl)benzene acid, L = methanol, water, or ethanol), has been prepared with indium as the metal center. It exhibits a Langmuir surface area of 1470 m(2) g(-1), and its structure consists of hexagonal pores with a 2.8 nm aperture, which allows the diffusion of multiple substrates. This material presents a large density of active metal sites resulting in outstanding catalytic activity in the formation of substituted α-aminonitriles through the one-pot Strecker reaction of ketones. In this respect, InPF-110 stands out compared to other catalysts for this reaction due to the small catalyst loadings required, and without the need for heat or solvents. Furthermore, X-ray single crystal diffraction studies clearly show the framework-substrate interaction through coordination to the accessible indium sites. PMID:27420904

  6. A Mesoporous Indium Metal-Organic Framework: Remarkable Advances in Catalytic Activity for Strecker Reaction of Ketones.

    PubMed

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

    2016-07-27

    With the aim of developing new highly porous, heterogeneous Lewis acid catalysts for multicomponent reactions, a new mesoporous metal-organic framework, InPF-110 ([In3O(btb)2(HCOO)(L)], (H3btb = 1,3,5-tris(4-carboxyphenyl)benzene acid, L = methanol, water, or ethanol), has been prepared with indium as the metal center. It exhibits a Langmuir surface area of 1470 m(2) g(-1), and its structure consists of hexagonal pores with a 2.8 nm aperture, which allows the diffusion of multiple substrates. This material presents a large density of active metal sites resulting in outstanding catalytic activity in the formation of substituted α-aminonitriles through the one-pot Strecker reaction of ketones. In this respect, InPF-110 stands out compared to other catalysts for this reaction due to the small catalyst loadings required, and without the need for heat or solvents. Furthermore, X-ray single crystal diffraction studies clearly show the framework-substrate interaction through coordination to the accessible indium sites.

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

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

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

  8. The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions

    NASA Astrophysics Data System (ADS)

    Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang

    2016-04-01

    Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs.Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the

  9. Catalytic Mechanism Investigation of Lysine-Specific Demethylase 1 (LSD1): A Computational Study

    PubMed Central

    Liang, Zhongjie; Lu, Junyan; Chen, Liang; Shen, Bairong; Li, Donghai; Zheng, Mingyue; Li, Keqin Kathy; Luo, Cheng; Jiang, Hualiang

    2011-01-01

    Lysine-specific demethylase 1 (LSD1), the first identified histone demethylase, is a flavin-dependent amine oxidase which specifically demethylates mono- or dimethylated H3K4 and H3K9 via a redox process. It participates in a broad spectrum of biological processes and is of high importance in cell proliferation, adipogenesis, spermatogenesis, chromosome segregation and embryonic development. To date, as a potential drug target for discovering anti-tumor drugs, the medical significance of LSD1 has been greatly appreciated. However, the catalytic mechanism for the rate-limiting reductive half-reaction in demethylation remains controversial. By employing a combined computational approach including molecular modeling, molecular dynamics (MD) simulations and quantum mechanics/molecular mechanics (QM/MM) calculations, the catalytic mechanism of dimethylated H3K4 demethylation by LSD1 was characterized in details. The three-dimensional (3D) model of the complex was composed of LSD1, CoREST, and histone substrate. A 30-ns MD simulation of the model highlights the pivotal role of the conserved Tyr761 and lysine-water-flavin motif in properly orienting flavin adenine dinucleotide (FAD) with respect to substrate. The synergy of the two factors effectively stabilizes the catalytic environment and facilitated the demethylation reaction. On the basis of the reasonable consistence between simulation results and available mutagenesis data, QM/MM strategy was further employed to probe the catalytic mechanism of the reductive half-reaction in demethylation. The characteristics of the demethylation pathway determined by the potential energy surface and charge distribution analysis indicates that this reaction belongs to the direct hydride transfer mechanism. Our study provides insights into the LSD1 mechanism of reductive half-reaction in demethylation and has important implications for the discovery of regulators against LSD1 enzymes. PMID:21984927

  10. Initial Reaction Mechanism of Platinum Nanoparticle in Methanol-Water System and the Anomalous Catalytic Effect of Water.

    PubMed

    Chen, Shuangming; Yang, Qingying; Wang, Huanhuan; Zhang, Shuo; Li, Jiong; Wang, Yu; Chu, Wangsheng; Ye, Qing; Song, Li

    2015-09-01

    Understanding the detailed reaction mechanism in the early stage of noble metal nanoparticles is very critical for controlling the final crystal's size, morphology, and properties. Here, we report a systematic study on the initial reaction mechanism of Pt nanoparticles in methanol-water system and demonstrate an anomalous catalytic effect of H2O on the reduction of H2PtCl6 to Pt nanoparticles using a combination of UV-vis, X-ray absorption spectroscopy (XAS), liquid chromatography mass spectrometry (LCMS), and first-principles calculation methods. The observations reveal the transformation route [PtCl6](2-) → [PtCl5(CH3O)](2-) → [PtCl4](2-) → [PtCl3(CH3O)](2-) → [PtCl2](2-) and finally to form Pt nanoparticles in a pure CH3OH solution. With 10 vol % water adding in the CH3OH solution, a new and distinct chemical reduction pathway is found in which the precursors change from [PtCl6](2-) to [PtCl5(CH3O)(H2O)](2-) to [PtCl4](2-) to [PtCl3(CH3O)(H2O)](2-) to [PtCl2](2-) and to Pt nanoparticles. Notably, the supernumerary water molecular can significantly accelerate the rate of chemical reduction and greatly shorten the reaction time. This work not only elucidates the initial reaction mechanism of Pt nanoparticles but also highlights the pronounced influence of H2O on the reaction pathway, which will provide useful insights for understanding the formation mechanism of noble metal nanoparticles and open up a high efficient way to synthesize new functional nanomaterial.

  11. Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions.

    PubMed

    Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei

    2015-10-12

    The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction.

  12. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions.

    PubMed

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-01-01

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

  13. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions.

    PubMed

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-09-07

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling.

  14. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions

    PubMed Central

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-01-01

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

  15. Catalytic performance of carbon nanotubes in H2O2 decomposition: experimental and quantum chemical study.

    PubMed

    Voitko, Katerina; Tóth, Ajna; Demianenko, Evgenij; Dobos, Gábor; Berke, Barbara; Bakalinska, Olga; Grebenyuk, Anatolij; Tombácz, Etelka; Kuts, Volodymyr; Tarasenko, Yurij; Kartel, Mykola; László, Krisztina

    2015-01-01

    The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability.

  16. The Catalytic Nanodiode: Detecting Continous Electron Flow atOxide-Metal Interfaces Generated by a Gas-Phase Exothermic Reaction

    SciTech Connect

    Park, Jeong Young; Somorjai, Gabor A.

    2006-10-31

    Continuous flow of ballistic charge carriers is generated by an exothermic chemical reaction and detected using the catalytic metal-semiconductor Schottky diode. We obtained a hot electron current for several hours using two types of catalytic nanodiodes, Pt/TiO2 or Pt/GaN, during carbon monoxide oxidation at pressures of 100 Torr of O2 and 40 Torr of CO at 413-573 K. This result reveals that the chemical energy of an exothermic catalytic reaction is directly converted into hot electrons flux in the catalytic nanodiode. By heating the nanodiodes in He, we could measure the thermoelectric current which is in the opposite direction to the flow of the hot electron current. The chemicurrent is well correlated with the turnover rate of CO oxidation, which is separately measured with gas chromatography. The influence of the flow of hot charge carriers on the chemistry at the oxide-metal interface, and the turnover rate in the chemical reaction are discussed.

  17. IN SITU INFRARED STUDY OF CATALYTIC DECOMPOSITION OF NO

    SciTech Connect

    KHALID ALMUSAITEER; RAM KRISHNAMURTHY; STEVEN S.C. CHUANG

    1998-08-18

    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. Research is proposed to study the reactivity of adsorbates for the direct NO decomposition and to investigate the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. An innovative infrared reactor system will be used to observe and determine the dynamic behavior and the reactivity of adsorbates during NO decomposition, oxygen spillover, and silanation. A series of experiments including X-ray diffraction, temperature programmed desorption, temperature programmed reaction, X-ray photoelectron spectroscopy will be used to characterized the catalysts. The information obtained from this study will provide a scientific basis for developing an effective catalyst for the NO decomposition under practical flue gas conditions.

  18. In Situ Infrared Study of Catalytic Decomposition of NO

    SciTech Connect

    Cher-Dip Tan; Steven S.C. Chuang

    1997-07-17

    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emmissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccesful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. Research is proposed to study the reactivity of adsorbates for the direct NO decomposition and to investigate the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. An innovative infrared reactor system will be used to observe and determine the dynamic behavior and the reactivity of adsorbates during NO decomposition, oxygen spillover, and silanation. A series of experiments including X-ray diffraction, temperature programmed desorption, temperature programmed reaction, X-ray photoelectron spectroscopy will be used to characterized the catalysts. The information obtained from this study will provide a scientific basis for developing an effective catalyst for the NO decomposition under practical flue gas conditions.

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

    PubMed

    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

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

    PubMed

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

    2012-08-01

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

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

    NASA Astrophysics Data System (ADS)

    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

  2. Reactions of diborane with ammonia and ammonia borane: catalytic effects for multiple pathways for hydrogen release.

    PubMed

    Nguyen, Vinh Son; Matus, Myrna H; Nguyen, Minh Tho; Dixon, David A

    2008-10-01

    High-level electronic structure calculations have been used to construct portions of the potential energy surfaces related to the reaction of diborane with ammonia and ammonia borane (B2H6 + NH3 and B2H6 + BH3NH3)to probe the molecular mechanism of H2 release. Geometries of stationary points were optimized at the MP2/aug-cc-pVTZ level. Total energies were computed at the coupled-cluster CCSD(T) theory level with the correlation-consistent basis sets. The results show a wide range of reaction pathways for H2 elimination. The initial interaction of B2H6 + NH3 leads to a weak preassociation complex, from which a B-H-B bridge bond is broken giving rise to a more stable H3BHBH2NH3 adduct. This intermediate, which is also formed from BH3NH3 + BH3, is connected with at least six transition states for H2 release with energies 18-93 kal/mol above the separated reactants. The lowest-lying transition state is a six-member cycle, in which BH3exerts a bifunctional catalytic effect accelerating H2 generation within a B-H-H-N framework. Diborane also induces a catalytic effect for H2 elimination from BH3NH3 via a three-step pathway with cyclic transition states. Following conformational changes, the rate-determining transition state for H2 release is approximately 27 kcal/mol above the B2H6 + BH3NH3 reactants, as compared with an energy barrier of approximately 37 kcal/mol for H2 release from BH3NH3. The behavior of two separated BH3 molecules is more complex and involves multiple reaction pathways. Channels from diborane or borane initially converge to a complex comprising the H3BHBH2NH3adduct plus BH3. The interaction of free BH3 with the BH3 moiety of BH3NH3 via a six-member transition state with diborane type of bonding leads to a lower-energy transition state. The corresponding energy barrier is approximately 8 kcal/mol, relative to the reference point H3BHBH2NH3 adduct + BH3. These transition states are 27-36 kcal/mol above BH3NH3 + B2H6, but 1-9 kcal/mol below the

  3. Pt monolayer coating on complex network substrate with high catalytic activity for the hydrogen evolution reaction

    PubMed Central

    Li, Man; Ma, Qiang; Zi, Wei; Liu, Xiaojing; Zhu, Xuejie; Liu, Shengzhong (Frank)

    2015-01-01

    A deposition process has been developed to fabricate a complete-monolayer Pt coating on a large-surface-area three-dimensional (3D) Ni foam substrate using a buffer layer (Ag or Au) strategy. The quartz crystal microbalance, current density analysis, cyclic voltammetry integration, and X-ray photoelectron spectroscopy results show that the monolayer deposition process accomplishes full coverage on the substrate and the deposition can be controlled to a single atomic layer thickness. To our knowledge, this is the first report on a complete-monolayer Pt coating on a 3D bulk substrate with complex fine structures; all prior literature reported on submonolayer or incomplete-monolayer coating. A thin underlayer of Ag or Au is found to be necessary to cover a very reactive Ni substrate to ensure complete-monolayer Pt coverage; otherwise, only an incomplete monolayer is formed. Moreover, the Pt monolayer is found to work as well as a thick Pt film for catalytic reactions. This development may pave a way to fabricating a high-activity Pt catalyst with minimal Pt usage. PMID:26601247

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

    PubMed

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

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts. PMID:25334050

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

    PubMed

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

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts.

  6. Yolk-shell Fe(0)@SiO2 nanoparticles as nanoreactors for fenton-like catalytic reaction.

    PubMed

    Liu, Chao; Li, Jiansheng; Qi, Junwen; Wang, Jing; Luo, Rui; Shen, Jinyou; Sun, Xiuyun; Han, Weiqing; Wang, Lianjun

    2014-08-13

    Yolk-shell nanoparticles (YSNs) with active metal cores have shown promising applications in nanoreactors with excellent catalytic performance. In this work, Fe(0)@SiO2 YSNs were synthesized by a sequential "two-solvents" impregnation-reduction approach. Specifically, FeSO4 aqueous solution was introduced into the preformed hollow mesoporous silica spheres (HMSS), dispersed in n-hexane, via a "two-solvent" impregnation way. Subsequently, aqueous solution of sodium borohydride (NaBH4) was introduced into the cavity of HMSS by the same way, leading to the formation of Fe core inside the HMSS through the reaction between Fe(2+) and NaBH4. The resulting Fe(0)@SiO2 YSNs possess distinctive structures, including active cores, accessible mesoporous channels, protective shells, and hollow cavities. To present the catalytic performance of YSNs nanoreactors, Fenton-like catalytic oxidation of phenol was chosen as the model catalysis reaction. In addition to the Fe(0)@SiO2 YSNs, two other materials were also applied to the catalytic system for comparison, including Fe@SiO2 composites with iron nanoparticles sticking on the outer shells of HMSS (Fe@SiO2-DI) and bare iron nanoparticles without HMSS (bare Fe(0)), respectively. The catalytic results show that Fe(0)@SiO2 YSNs exhibit higher catalytic rate toward phenol removal at 2-fold and 4-fold as compared to that of Fe@SiO2-DI and bare Fe(0), indicating the outstanding catalytic property of YSNs nanoreactors. To further clarify the relationship between catalytic properties and structural characteristics, the adsorption experiments of the three samples were also performed in the absence of H2O2. Other than catalytic results, Fe(0)@SiO2 YSNs show slightly higher adsorption efficiency than the other two samples, indicating the accessibility of nanoreactors. This result demonstrates that the removal of phenol in the oxidation system of Fe(0)@SiO2 YSNs may have contributed to the structure-enhanced effect of YSNs as nanoreactors.

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

    PubMed

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

    2004-05-21

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

  8. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    PubMed Central

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

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  9. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction.

    PubMed

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

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd(2+) ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  10. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction.

  11. Study of char gasification reactions

    SciTech Connect

    Ballal, G.D.

    1986-01-01

    A Texas lignite, an anthracite and two bituminous coals, Pittsburgh number8 and Illinois number6, were pyrolyzed in a nitrogen atmosphere to prepare chars. Optical microscopy, mercury porosimetry and gas adsorption techniques using nitrogen, CO/sub 2/ and CO, were employed for pore structure characterization. The lignite char exhibited the fastest rates of gaseous diffusion, followed in order of decreasing diffusivities by the Illinois number6, Pittsburgh number8 and anthracite chars. The changes in reactivities and pore structures of chars were measured experimentally during their reaction with oxygen (400-550C) and CO/sub 2/ (800-1000C). For a particular char-gas system, the normalized rate-conversion pattern was invariant with respect to temperature and gaseous concentration. In the case of lignite and Pittsburgh number8 chars, the rate-conversion pattern was similar during reaction with oxygen and CO/sub 2/. Adsorption experiments on partially reacted chars indicated that the micropores in the lignite char were accessible to both reactants. The micropores in the Illinois number6 char were, however, not accessible during its reaction with oxygen. The evolution of pore structure during reaction was modeled by using a probabilistic approach which accounts for overlapping pores with different shapes and sizes. The kinetics of gasification of the lignite and the Pittsburgh number8 chars was studied using a Langmuir-Hinshelwood type kinetic expression to correlate the experimental data. CO was found to inhibit the reaction substantially. The effect of a potassium carbonate catalyst on the reaction of these two chars was also investigated. Substantial increases in reaction rates were observed, and the enhancement was approximately proportional to the catalyst loading.

  12. In situ measurement of molecular diffusion during catalytic reaction by pulsed-field gradient NMR spectroscopy

    SciTech Connect

    Hong, Y.; Kaerger, J.; Hunger, B. ); Feoktistova, N.N.; Zhdanov, S.P. )

    1992-09-01

    Pulsed-field gradient (PFG) NMR spectroscopy is applied to study the intracrystalline diffusivity of the reactant and product molecules during the conversion of cyclopropane to propene in Zeolite X. The diffusivities are found to be large enough that any influence of intracrystalline diffusion on the overall reaction in flow reactors may be excluded.

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

    PubMed

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

    2016-09-01

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

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

    PubMed

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

    2016-09-01

    Surface properties of nanoscale CeO2 catalysts in terms of the surface Ce(3+) fraction and concentration of oxygen vacancy can affect their catalytic performance significantly. Continual adjustment on surface properties of CeO2 with the morphological preservation has not been realized by synthetic methods. The revisited studies show that surface properties of CeO2 nanorods can be effectively regulated by synthetic pressures while the rodlike morphology is well-preserved. Such phenomena are ascribed to the contact possibility between Ce(3+) species and dissolved O2, which is balanced by the rapidly increased and gradually saturated dissolution/recrystallization rate of Ce(OH)3 and linearly increased concentration of dissolved O2 with the increase of total air pressure or partial pressure of O2. Surface-property-dependent catalytic activity of CeO2 nanorods synthesized under various pressures was also demonstrated in two benchmark reactions-catalytic oxidation of CO and hydrolysis of nitrile. Such a finding of the pressure regulation on the reducible metal oxides provides an effective approach to rationally design novel catalysts for specific reactions, where ceria are supports, promoters, or actives. PMID:27534804

  15. Solid State, Surface and Catalytic Studies of Oxides

    SciTech Connect

    Kung, H. H.

    2004-11-23

    This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO{sub x}. Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO{sub x}, it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO{sub 2}/Al{sub 2}O{sub 3}. Ag/Al{sub 2}O{sub 3}, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.

  16. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.

    1991-12-01

    The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal`s structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.

  17. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.

    1991-12-01

    The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal's structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.

  18. Reaction pathway investigation on the selective catalytic reduction of NO with NH3 over Cu/SSZ-13 at low temperatures.

    PubMed

    Su, Wenkang; Chang, Huazhen; Peng, Yue; Zhang, Chaozhi; Li, Junhua

    2015-01-01

    The mechanism of the selective catalytic reduction of NO with NH3 was studied using Cu/SSZ-13. The adspecies of NO and NH3 as well as the active intermediates were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed surface reaction. The results revealed that three reactions were possible between adsorbed NH3 and NOx. NO2(-) could be generated by direct formation or NO3(-) reduction via NO. In a standard selective catalytic reduction (SCR) reaction, NO3(-) was hard to form, because NO2(-) was consumed by ammonia before it could be further oxidized to nitrates. Additionally, adsorbed NH3 on the Lewis acid site was more active than NH4(+). Thus, SCR mainly followed the reaction between Lewis acid site-adsorbed NH3 and directly formed NO2(-). Higher Cu loading could favor the formation of active Cu-NH3, Cu-NO2(-), and Cu-NO3(-), improving the SCR activity at low temperature. PMID:25485842

  19. Reaction pathway investigation on the selective catalytic reduction of NO with NH3 over Cu/SSZ-13 at low temperatures.

    PubMed

    Su, Wenkang; Chang, Huazhen; Peng, Yue; Zhang, Chaozhi; Li, Junhua

    2015-01-01

    The mechanism of the selective catalytic reduction of NO with NH3 was studied using Cu/SSZ-13. The adspecies of NO and NH3 as well as the active intermediates were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed surface reaction. The results revealed that three reactions were possible between adsorbed NH3 and NOx. NO2(-) could be generated by direct formation or NO3(-) reduction via NO. In a standard selective catalytic reduction (SCR) reaction, NO3(-) was hard to form, because NO2(-) was consumed by ammonia before it could be further oxidized to nitrates. Additionally, adsorbed NH3 on the Lewis acid site was more active than NH4(+). Thus, SCR mainly followed the reaction between Lewis acid site-adsorbed NH3 and directly formed NO2(-). Higher Cu loading could favor the formation of active Cu-NH3, Cu-NO2(-), and Cu-NO3(-), improving the SCR activity at low temperature.

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

    PubMed

    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.

  1. Surface state and catalytic activity and selectivity of nickel catalysts in hydrogenation reactions. III. Electronic and catalytic properties of nickel catalysts

    SciTech Connect

    Okamoto, Y.; Nitta, Y.; Imanaka, T.; Teranishi, S.

    1980-08-01

    Various nickel catalysts (nickle-boride, nickel-phosphide, Raney-nickel, Urushibara-nickel, and decomposed-nickel) were investigated to examine the relationships between catalytic and electronic properties of nickel catalysts modified by component elements (boron, phosphorus, aluminum, and zinc) in the catalysts. Based on the x-ray photoelectron spectroscopic results, a parameter ..delta..q was tentatively proposed to characterize the electronic properties of the catalysts. The specific activity (activity per surface area of nickel metal) for hydrogenation reaction, the adsorption equilibrium constant of acetophenone, the resistivity against poisoning, and the characteristic selectivities in hydrogenation of 1,2-butylene oxide were found to be summarized in terms of the parameter ..delta..q. It is suggested that a useful parameter to reflect the electronic properties of the nickel catalysts.

  2. Catalytic partial oxidation of iso-octane over rhodium catalysts: An experimental, modeling, and simulation study

    SciTech Connect

    Hartmann, M.; Minh, H.D.; Maier, L.; Deutschmann, O.

    2010-09-15

    Catalytic partial oxidation of iso-octane over a rhodium/alumina coated honeycomb monolith is experimentally and numerically studied at short-contact times for varying fuel-to-oxygen ratios. A new experimental set-up with well-defined inlet and boundary conditions is presented. The conversion on the catalyst and in the gas-phase is modeled by detailed reaction mechanisms including 857 gas-phase and 17 adsorbed species. Elementary-step based heterogeneous and homogeneous reaction mechanisms are implemented into two-dimensional flow field description of a single monolith channel. Experiment and simulation provide new insights into the complex reaction network leading to varying product distribution as function of fuel-to-oxygen ratio. At fuel rich conditions, the formation of by-products that can serve as coke precursors is observed and interpreted. (author)

  3. The role of acidic sites and the catalytic reaction pathways on the Rh/ZrO2 catalysts for ethanol steam reforming.

    PubMed

    Zhong, Ziyi; Ang, Hanwee; Choong, Catherine; Chen, Luwei; Huang, Lin; Lin, Jianyi

    2009-02-01

    Rh catalysts supported on ZrO(2)-based oxides were studied for ethanol steam reforming (SR) reaction. Pure ZrO(2) as the support resulted in higher H(2) production yield compared to the ZrO(2) oxide decorated with CeO(2), Al(2)O(3), La(2)O(3) or Li(2)O at the reaction temperature of 300 degrees C. Above 450 degrees C, all the catalysts exhibited similar catalytic activity. However, at low reaction temperatures (below 400 degrees C), a significant enhancement in the catalytic activity, selectivity and stability was achieved by replacing the ZrO(2) support prepared by a precipitation method (ZrO(2)-CP) with that prepared by a hydrothermal method (ZrO(2)-HT). A deactivation was observed during the EtOH SR reaction at 300 degrees C on the two catalysts of Rh/ZrO(2)-CP and Rh/ZrO(2)-HT. NH(3)-TPD experiments confirmed that the ZrO(2)-HT support had two types of acidic sites while the ZrO(2)-CP support had only one type of weak acidic sites. DRIFTS studies showed that the absorption of EtOH molecules was strong on the Rh/ZrO(2)-HT catalyst and a number of C(2) oxygenates were accumulated on the catalyst surface. Meanwhile, the EtOH absorption on the Rh/ZrO(2)-CP catalyst was weak and the accumulation of CO, carbonate and CH(x) was observed. It is concluded that the relatively strong Lewis acidic sites in the Rh/ZrO(2)-HT catalyst is responsible for the strong absorption of EtOH molecules, and the subsequent C-H breakage step (formation of acetaldehyde or called as dehydrogenation reaction) is a fast reaction on it; on the Rh/ZrO(2)-CP catalyst, the EtOH adsorption was weak and the C-C breakage was the dominating reaction which led to the accumulation of surface CO, CH(x) and CO(2) species. Therefore, it is believed that, in order to promote the absorption of EtOH molecules and to reduce the formation of metastable carbonaceous species (C(2) oxygenates) during the reaction, the catalyst should be enhanced both with Lewis acidity and with C-C bond breakage function. Also

  4. Catalytic effect of gallium chloride in the diels-alder reaction between maleic anhydride and its derivatives and unsubstituted and substituted anthracenes

    SciTech Connect

    Kiselev, V.D.; Konovalov, A.I.; Shakirov, I.M.

    1985-11-10

    The stability of n, v complexes between gallium chloride and unsubstituted and substituted maleic anhydrides was determined in benzene by a thermochemical method; it was shown that the stability of the complexes decreases in the transition from maleic anhydrides with electron-donating substituents to maleic anhydrides with electron-withdrawing substituents. The reactivity of these dienophiles in the uncatalyzed Diels-Alder reactions with unsubstituted and substituted anthracenes in benzene and in the reactions catalyzed by gallium chloride was studied. The reactivity of the dienophiles varies similarly in the reactions with the investigated dienes, and this rules out treatment of steric hindrances as the reason for the reduced reactivity of the substituted dienophiles. A decrease in the catalytic effect was observed for the unreactive diene-dienophile pairs.

  5. Catalytic behavior and reaction routes of MEK oxidation over Pd/ZSM-5 and Pd-Ce/ZSM-5 catalysts.

    PubMed

    Yue, Lin; He, Chi; Zhang, Xinyan; Li, Peng; Wang, Zhuo; Wang, Hailin; Hao, Zhengping

    2013-01-15

    Catalytic oxidation is a widely used pollution control technology for removing volatile organic compounds. Pd-Ce/ZSM-5 catalysts with different Ce contents were prepared by a co-impregnation method, and their catalytic performance was investigated for the oxidation of methyl ethyl ketone (MEK). The by-products of the reaction were monitored using gas chromatography and collected in thermal desorption tubes, which were further analyzed by gas chromatography/mass spectrometry. The PdCe(9.6)/ZSM-5 catalyst displayed the highest catalytic efficiency, as a consequence of a higher amount of strong acid sites and a superior PdO-Pd redox cycle in the presence of a CeO(2) additive. The introduction of CeO(2) enriched the by-product species. The formation mechanisms and oxidation routes of typical by-products, such as methyl acetate, 1-penten-3-one and 3-buten-2-one, 3-methyl, during MEK oxidation over Pd-Ce/ZSM-5 catalysts was also analyzed. CH(3)* species that formed on the catalyst were identified as reaction intermediaries. Trace amounts of acetic acid and methyl vinyl ketone were also detected and were further oxidized to methyl acetate, 1-penten-3-one and 3-buten-2-one, 3-methyl.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  7. Interfacial Reaction Studies Using ONIOM

    NASA Technical Reports Server (NTRS)

    Cardelino, Beatriz H.

    2003-01-01

    In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.

  8. Visible to near-infrared plasmon-enhanced catalytic activity of Pd hexagonal nanoplates for the Suzuki coupling reaction

    NASA Astrophysics Data System (ADS)

    Trinh, T. Thuy; Sato, Ryota; Sakamoto, Masanori; Fujiyoshi, Yoshifumi; Haruta, Mitsutaka; Kurata, Hiroki; Teranishi, Toshiharu

    2015-07-01

    Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111} and six {100} planes. The Pd hexagonal nanoplates with well-defined and tunable longitudinal localized surface plasmon resonance (LSPR) have enabled the direct harvesting of visible to near-infrared light for catalytic cross coupling reactions. Upon plasmon excitation, the catalytic Suzuki coupling reactions of iodobenzene and phenylboronic acid accelerate by a plasmonic photocatalytic effect of plasmon induced hot electrons. The turnover frequency (TOF) of the Pd hexagonal nanoplates in a reaction illuminated with a λ = 300-1000 nm Xenon lamp at 176 mW cm-2 was 2.5 and 2.7 times higher than that of non-plasmonic {111}-enclosed Pd nanooctahedra and {100}-enclosed Pd nanocubes, respectively, and 1.7 times higher than the TOF obtained when the reaction was thermally heated to the same temperature.Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111

  9. Superior Catalytic Activity of Electrochemically Reduced Graphene Oxide Supported Iron Phthalocyanines toward Oxygen Reduction Reaction.

    PubMed

    Liu, Dong; Long, Yi-Tao

    2015-11-01

    Structure and surface properties of supporting materials are of great importance for the catalytic performance of the catalysts. Herein, we prepared the iron phthalocyanine (FePc) functionalized electrochemically reduced graphene oxide (ERGO) by the electrochemical reduction of FePc/GO. The resultant FePc/ERGO exhibits higher catalytic activity toward ORR than that of FePc/graphene. More importantly, the onset potential for ORR at FePc/ERGO positively shifts by 45 mV compared with commercial Pt/C in alkaline media. Besides, FePc/ERGO displays enhanced durability and selectivity toward ORR. The superior catalytic performance of FePc/ERGO for ORR are ascribed to the self-supported structure of ERGO, uniformly morphology and size of FePc nanoparticles.

  10. Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors.

    PubMed

    Lebedeva, Maria A; Chamberlain, Thomas W; Thomas, Alice; Thomas, Bradley E; Stoppiello, Craig T; Volkova, Evgeniya; Suyetin, Mikhail; Khlobystov, Andrei N

    2016-06-01

    A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor.

  11. Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors

    NASA Astrophysics Data System (ADS)

    Lebedeva, Maria A.; Chamberlain, Thomas W.; Thomas, Alice; Thomas, Bradley E.; Stoppiello, Craig T.; Volkova, Evgeniya; Suyetin, Mikhail; Khlobystov, Andrei N.

    2016-06-01

    A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor.A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction

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

    PubMed

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

    2015-11-01

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

  13. Catalytic asymmetric direct Mannich reaction: a powerful tool for the synthesis of alpha,beta-diamino acids.

    PubMed

    Arrayás, Ramón Gómez; Carretero, Juan C

    2009-07-01

    Optically active alpha,beta-diamino acids are very attractive targets in organic synthesis because of their wide-ranging biological significance and high versatility as synthetic building blocks. Efficient synthesis of such non-proteinogenic amino acid derivatives must face the challenge of generating two contiguous stereocenters with complete diastereo- and enantiocontrol in flexible, acyclic molecules. The catalytic asymmetric direct Mannich reaction has provided elegant and efficient solutions for the stereocontrolled assembly of both syn- and anti-alpha,beta-diamino acid derivatives, including those with a alpha-tetrasubstituted carbon stereocenter, with the aid of either organometallic or purely organic chiral catalysts (or the combination of both). This tutorial review highlights progress in this area, which has recently been boosted through two complementary strategies: the direct Mannich reaction of glycine ester Schiff bases with imines and the direct aza-Henry reaction between nitro compounds and imines. PMID:19551174

  14. Oxidation and reduction of copper ions in catalytic reactions of Rhus laccase.

    PubMed

    Nakamura, T

    1976-01-01

    1) It was demonstrated by colorimetric as well as EPR measurements that the native (aerobic, resting state) Rhus vernicifera laccase contains both Cu2+ and Cu+ (total Cu content was 4.0 gram atoms/mole). The ratio of Cu2+ to total Cu in laccase varied (42-90%) in samples of latex collected from various districts. The absorption maximum at 615 nm was proportional to the content of total Cu in the enzyme sample. Laccase activity was found to almost parallel the content of the Cu2+ form. The oxidized minus reduced difference absorbance of the enzyme at 330 nm shoulder was proportional to the amount of Cu2+. 2) Steady state level of oxidation of laccase copper during the laccase copper catalytic action, the rates of reduction by substrates and the oxidation by O2 were determined by following absorbance changes at 615 and 330 nm by the stopped flow method. 3) All the results from titrimetric and kinetic experiments were consistent with the laccase model previously proposed by Makino and Ogura in which a laccase molecule contains 1 Cu(615) and 3 Cu(330). Our expanded model states that a laccase sample originally contains active as well as inactive enzymes. In the active enzyme, Cu ions are reactive to O2 but in the inactive enzyme, Cu can be oxidized only by oxidizing agents such as H2O2 or ferricyanide, or by a slow intermolecular electron transfer from Cu(615) to the active enzyme. In both species of enzyme rapid reduction of Cu2+ ions by substrate takes place. In comparative studies of the reactivities of Cu ions in various copper proteins, we would like to suggest that oxidatic activity of a copper protein is due to the Cu+ form of the enzyme ions with O2. PMID:134627

  15. Catalytic Asymmetric Synthesis of 3-Hydroxy-3-trifluoromethyl Benzofuranones via Tandem Friedel-Crafts/Lactonization Reaction.

    PubMed

    Ren, Hai; Wang, Pan; Wang, Lijia; Tang, Yong

    2015-10-01

    A highly enantioselective and regioselective chiral Lewis acid catalyzed tandem Friedel-Crafts/lactonization reaction is reported, providing direct access to plenty of 3-hydroxy-3-trifluoromethyl benzofuran-2-ones in up to 94% yields with up to >99% ee. Mechanistic study reveals that the interactions between the phenolic hydroxyl group and trifluoropyruvate are the most likely contributing factor to the high enantio- and regioselectivity. Optically pure (-)-BHFF can be obtained in gram-scale with 0.05 mol % catalyst, demonstrating the potentially utility of this method in medicinal chemistry. PMID:26400069

  16. Development of catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium complexes.

    PubMed

    Tsubogo, Tetsu; Saito, Susumu; Seki, Kazutaka; Yamashita, Yasuhiro; Kobayashi, Shu

    2008-10-01

    Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from calcium isopropoxide and chiral bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford 1,4-addition products, glutamic acid derivatives, in high yields with high enantioselectivities. During the investigation of the 1,4-addition reactions, we unexpectedly found that a [3 + 2] cycloaddition occurred in the reactions with crotonate derivatives, affording substituted pyrrolidine derivatives in high yields with high enantioselectivities. On the basis of this finding, we investigated asymmetric [3 + 2] cycloadditions, and it was revealed that several kinds of optically active substituted pyrrolidine derivatives containing contiguous stereogenic tertiary and quaternary carbon centers were obtained with high diastereo- and enantioselectivities. In addition, optically active pyrrolidine cores of hepatitis C virus RNA-dependent polymerase inhibitors and potential effective antiviral agents have been synthesized using this [3 + 2] cycloaddition reaction. NMR spectroscopic analysis and observation of nonamplification of enantioselectivity in nonlinear effect experiments suggested that a monomeric calcium species with an anionic ligand was formed as an active catalyst. A stepwise mechanism of the [3 + 2] cycloaddition, consisting of 1,4-addition and successive intramolecular Mannich-type reaction was suggested. Furthermore, modification of the Schiff base structure resulted in a modification of the reaction course from a [3 + 2] cycloaddition to a 1,4-addition, affording 3-substituted glutamic acid derivatives with high diasterero- and enantioselectivities.

  17. Development of catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium complexes.

    PubMed

    Tsubogo, Tetsu; Saito, Susumu; Seki, Kazutaka; Yamashita, Yasuhiro; Kobayashi, Shu

    2008-10-01

    Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from calcium isopropoxide and chiral bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford 1,4-addition products, glutamic acid derivatives, in high yields with high enantioselectivities. During the investigation of the 1,4-addition reactions, we unexpectedly found that a [3 + 2] cycloaddition occurred in the reactions with crotonate derivatives, affording substituted pyrrolidine derivatives in high yields with high enantioselectivities. On the basis of this finding, we investigated asymmetric [3 + 2] cycloadditions, and it was revealed that several kinds of optically active substituted pyrrolidine derivatives containing contiguous stereogenic tertiary and quaternary carbon centers were obtained with high diastereo- and enantioselectivities. In addition, optically active pyrrolidine cores of hepatitis C virus RNA-dependent polymerase inhibitors and potential effective antiviral agents have been synthesized using this [3 + 2] cycloaddition reaction. NMR spectroscopic analysis and observation of nonamplification of enantioselectivity in nonlinear effect experiments suggested that a monomeric calcium species with an anionic ligand was formed as an active catalyst. A stepwise mechanism of the [3 + 2] cycloaddition, consisting of 1,4-addition and successive intramolecular Mannich-type reaction was suggested. Furthermore, modification of the Schiff base structure resulted in a modification of the reaction course from a [3 + 2] cycloaddition to a 1,4-addition, affording 3-substituted glutamic acid derivatives with high diasterero- and enantioselectivities. PMID:18783222

  18. Controllable Assembly of Hierarchical Macroporous-Mesoporous LnFeO₃ and Their Catalytic Performance in the CO + NO Reaction.

    PubMed

    Li, Zhen-Xing; Shi, Fu-Bo; Yan, Chun-Hua

    2015-08-11

    A new synthesis strategy to prepare hierarchical macroporous-mesoporous materials employing poly(ethylene oxide)-poly(phenylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) as a single template and an acid adjusting agent was reported. There is a hierarchical structure including macropores with a size of 50-100 nm and mesopores in the macroporous walls with a size of 3-5 nm. The macroporous walls are composed of rare earth orthoferrite nanoparticles with a size of 5-10 nm. These hierarchically porous materials show high catalytic activities for the CO + NO reaction, and NO can be fully converted to N2 at temperatures as low as 350 °C, indicating their potential in the catalytic conversion of automotive exhaust gas and other catalysis-related fields. This synthesis strategy is a facile method for the preparation of hierarchical porous materials and may give us a guideline for the synthesis of functional materials with further catalytic applications.

  19. Controllable Assembly of Hierarchical Macroporous-Mesoporous LnFeO₃ and Their Catalytic Performance in the CO + NO Reaction.

    PubMed

    Li, Zhen-Xing; Shi, Fu-Bo; Yan, Chun-Hua

    2015-08-11

    A new synthesis strategy to prepare hierarchical macroporous-mesoporous materials employing poly(ethylene oxide)-poly(phenylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) as a single template and an acid adjusting agent was reported. There is a hierarchical structure including macropores with a size of 50-100 nm and mesopores in the macroporous walls with a size of 3-5 nm. The macroporous walls are composed of rare earth orthoferrite nanoparticles with a size of 5-10 nm. These hierarchically porous materials show high catalytic activities for the CO + NO reaction, and NO can be fully converted to N2 at temperatures as low as 350 °C, indicating their potential in the catalytic conversion of automotive exhaust gas and other catalysis-related fields. This synthesis strategy is a facile method for the preparation of hierarchical porous materials and may give us a guideline for the synthesis of functional materials with further catalytic applications. PMID:26196258

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

    SciTech Connect

    Ekerdt, J.G.

    1992-02-03

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

  1. Selective nitrogen doping in graphene: Enhanced catalytic activity for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Huang, Sheng-Feng; Terakura, Kiyoyuki; Boero, Mauro; Oshima, Masaharu; Kakimoto, Masa-Aki; Miyata, Seizo

    2011-12-01

    The structural and electronic properties of N-doped zigzag graphene ribbons with various ratios of dihydrogenated to monohydrogenated edge carbons are investigated within the density functional theory framework. We find that the stability of graphitic N next to the edge, which is claimed to play important roles in the catalytic activity in our previous work, will be enhanced with increasing the concentration of dihydrogenated carbons. Furthermore, the dihydrogenated edge carbons turn out to be easily converted into monohydrogenated ones in the presence of oxygen molecules at room temperature. Based on our results, we propose a possible way to enhance the oxygen reduction catalytic activity of N-doped graphene by controlling the degrees of hydrogenation of edge carbons. The characteristic features in the x-ray absorption and emission spectra for each specific N site considered here will also be given.

  2. High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1975-01-01

    An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

  3. Catalytic membranes beckon

    SciTech Connect

    Caruana, C.M.

    1994-11-01

    Chemical engineers here and abroad are finding that the marriage of catalysts and membranes holds promise for faster and more specific reactions, although commercialization of this technology is several years away. Catalytic membrane reactors (CMRs) combine a heterogeneous catalyst and a permselective membrane. Reactions performed by CMRs provide higher yields--sometimes as much as 50% higher--because of better reaction selectivity--as opposed to separation selectivity. CMRs also can work at very high temperatures, using ceramic materials that would not be possible with organic membranes. Although the use of CMRs is not widespread presently, the development of new membranes--particularly porous ceramic and zeolite membranes--will increase the potential to improve yields of many catalytic processes. The paper discusses ongoing studies, metal and advanced materials for membranes, the need for continued research, hydrogen recovery from coal-derived gases, catalytic oxidation of sulfides, CMRs for water purification, and oxidative coupling of methane.

  4. Plasma-catalytic hybrid system using spouted bed with a gliding arc discharge: CH4 reforming as a model reaction

    NASA Astrophysics Data System (ADS)

    Lee, H.; Sekiguchi, H.

    2011-07-01

    A combination of a gliding arc discharge and a spouted catalytic bed was used to investigate a plasma-catalytic hybrid system using CH4 reforming as a model reaction. Alumina-supported catalysts that contained 0.5 wt% of Pt, Pd, Rh, and Ru (denoted as Pt/Al2O3, Pd/Al2O3, Rh/Al2O3 and Ru/Al2O3, respectively) were used. For comparison, active Al2O3 particles were also examined. The conversion of CH4 and the selectivity of the product were investigated by changing the feed flow rate and reaction time. The production of C2H2, H2 and soot was observed in the gliding arc discharge without a catalyst. Using Pt/Al2O3 and Pd/Al2O3with the gliding arc discharge, C2H4, C2H6 and C2H2 were produced. It is considered that C2H4 and C2H6 were formed by the hydrogenation of C2H2 on the active site of Pt/Al2O3 and Pd/Al2O3. A stronger resistance to deactivation was shown in the presence of Pd/Al2O3 than in the presence of Pt/Al2O3, whereas the selectivity of hydrocarbon using Rh/Al2O3 and Ru/Al2O3 showed a tendency similar to that in active Al2O3 and non-catalytic experiments. The proposed reactor has a potential to improve the selectivity of the plasma process.

  5. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions.

    PubMed

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Cejka, Jiří

    2013-01-01

    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate.

  6. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions

    PubMed Central

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Čejka, Jiří

    2013-01-01

    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate. PMID:24790940

  7. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions

    NASA Astrophysics Data System (ADS)

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Čejka, Jiří

    2013-08-01

    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite BEA and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)BEA < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)BEA and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate.

  8. Catalytic activity of bimetallic nickel alloys for solid-oxide fuel cell anode reactions from density-functional theory

    NASA Astrophysics Data System (ADS)

    An, Wei; Gatewood, Daniel; Dunlap, Brett; Turner, C. Heath

    2011-05-01

    We present density-functional theory calculations of the chemisorption of atomic species O, S, C, H and reaction intermediates OH, SH, and CHn (n = 1, 2, and 3) on M/Ni alloy model catalysts (M = Bi, Mo, Fe, Co, and Cu). The activity of the Ni alloy catalysts for solid-oxide fuel cell (SOFC) anode oxidation reactions is predicted, based on a simple descriptor, i.e., the binding energy of oxygen. First, we find that the binding of undesirable intermediates, such as C and S, can be inhibited and the catalytic activity of planar Ni-based anodes can be tuned towards oxidation by selectively forming a bimetallic surface alloy. In particular, Cu/Ni, Fe/Ni, and Co/Ni anode catalysts are found to be most active towards anode oxidation. On the other hand, the Mo/Ni alloy surface is predicted to be the most effective catalyst in terms of inhibiting the deposition of C and S (while still preserving relatively high catalytic activity). The formation of a surface alloy, which has the alloy element enriched on the topmost surface, was found to be critical to the activity of the Ni alloy catalysts.

  9. Reproduction of a Protocell by Replication of a Minority Molecule in a Catalytic Reaction Network

    NASA Astrophysics Data System (ADS)

    Kamimura, Atsushi; Kaneko, Kunihiko

    2010-12-01

    For understanding the origin of life, it is essential to explain the development of a compartmentalized structure, which undergoes growth and division, from a set of chemical reactions. In this study, a hypercycle with two chemicals that mutually catalyze each other is considered in order to show that the reproduction of a protocell with a growth-division process naturally occurs when the replication speed of one chemical is considerably slower than that of the other chemical, and molecules are crowded as a result of replication. It is observed that the protocell divides after a minority molecule is replicated at a slow synthesis rate, and thus, a synchrony between the reproduction of a cell and molecule replication is achieved. The robustness of such protocells against the invasion of parasitic molecules is also demonstrated.

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

    PubMed

    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. PMID:23246939

  11. Experimental and theoretical studies on the effects of magnetic fields on the arrangement of surface spins and the catalytic activity of Pd nanoparticles.

    PubMed

    Li, Ran; Yang, Yang; Li, Ren; Chen, Qianwang

    2015-03-25

    Nanocatalysts have very high catalytic activities due to surface atoms with their unpaired spins. It is the purpose of this paper to investigate the effect of magnetic fields (MFs) on the arrangement of surface spins and their catalytic activities. Pd nanoparticles supported on MIL-100(Cr) were selected as catalysts for the reduction of 4-nitrophenol under MFs. The result demonstrates that MFs can reduce the reaction time from 2.6 to 1.4 min under 0.5 T. This study first shows that the configuration of surface spins has an effect on the catalytic activity, which can be regulated by a foreign MF.

  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

    NASA Astrophysics Data System (ADS)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-01

    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 Sn2+ 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.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 Sn2+ 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

  13. Catalytic, Enantioselective Sulfenofunctionalisation of Alkenes: Mechanistic, Crystallographic, and Computational Studies

    PubMed Central

    Denmark, Scott E.; Hartmann, Eduard; Kornfilt, David J. P.; Wang, Hao

    2015-01-01

    The stereocontrolled introduction of vicinal heteroatomic substituents into organic molecules is one of the most powerful ways of adding value and function. Whereas many methods exist for the introduction of oxygen- and nitrogen-containing substituents, the number stereocontrolled methods for the introduction of sulfur-containing substituents pales by comparison. Previous reports from these laboratories have described the sulfenofunctionalization of alkenes that construct vicinal carbon-sulfur and carbon-oxygen, carbon-nitrogen as well as carbon-carbon bonds with high levels of diastereospecificity and enantioselectivity. This process is enabled by the concept of Lewis base activation of Lewis acids that provides activation of Group 16 electrophiles. To provide a foundation for expansion of substrate scope and improved selectivities, we have undertaken a comprehensive study of the catalytically active species. Insights gleaned from kinetic, crystallographic and computational methods have led to the introduction of a new family of sulfenylating agents that provide significantly enhanced selectivities. PMID:25411883

  14. Asn-150 of Murine Erythroid 5-Aminolevulinate Synthase Modulates the Catalytic Balance between the Rates of the Reversible Reaction.

    PubMed

    Stojanovski, Bosko M; Ferreira, Gloria C

    2015-12-25

    5-Aminolevulinate synthase (ALAS) catalyzes the first step in mammalian heme biosynthesis, the pyridoxal 5'-phosphate (PLP)-dependent and reversible reaction between glycine and succinyl-CoA to generate CoA, CO2, and 5-aminolevulinate (ALA). Apart from coordinating the positioning of succinyl-CoA, Rhodobacter capsulatus ALAS Asn-85 has a proposed role in regulating the opening of an active site channel. Here, we constructed a library of murine erythroid ALAS variants with substitutions at the position occupied by the analogous bacterial asparagine, screened for ALAS function, and characterized the catalytic properties of the N150H and N150F variants. Quinonoid intermediate formation occurred with a significantly reduced rate for either the N150H- or N150F-catalyzed condensation of glycine with succinyl-CoA during a single turnover. The introduced mutations caused modifications in the ALAS active site such that the resulting variants tipped the balance between the forward- and reverse-catalyzed reactions. Although wild-type ALAS catalyzes the conversion of ALA into the quinonoid intermediate at a rate 6.3-fold slower than the formation of the same quinonoid intermediate from glycine and succinyl-CoA, the N150F variant catalyzes the forward reaction at a mere 1.2-fold faster rate than that of the reverse reaction, and the N150H variant reverses the rate values with a 1.7-fold faster rate for the reverse reaction than that for the forward reaction. We conclude that the evolutionary selection of Asn-150 was significant for optimizing the forward enzymatic reaction at the expense of the reverse, thus ensuring that ALA is predominantly available for heme biosynthesis.

  15. Spatial self organization of surface structure during an oscillating catalytic reaction

    NASA Astrophysics Data System (ADS)

    Cox, M. P.; Ertl, G.; Imbihl, R.

    1985-04-01

    Under appropriate conditions, the rate of catalytic CO oxidation on a Pt(100) surface exhibits sustained temporal oscillations which are associated with a periodic surface-structural transformation from, the reconstructed (hex) to the nonreconstructed (1×1) phase and back again. By use of a newly developed scanning low-energy electron diffraction technique it is demonstrated that spatial self-organization in the oscillations involves a wavelike propagation of alternating bands of the two surface-structural modifications across the entire scanned area. These features can be modeled by numerical solution of a set of coupled differential equations.

  16. Chemicals from Lignin by Catalytic Fast Pyrolysis, from Product Control to Reaction Mechanism.

    PubMed

    Ma, Zhiqiang; Custodis, Victoria; Hemberger, Patrick; Bährle, Christian; Vogel, Frédéric; Jeschk, Gunnar; van Bokhoven, Jeroen A

    2015-01-01

    Conversion of lignin into renewable and value-added chemicals by thermal processes, especially pyrolysis, receives great attention. The products may serve as feedstock for chemicals and fuels and contribute to the development of a sustainable society. However, the application of lignin conversion is limited by the low selectivity from lignin to the desired products. The opportunities for catalysis to selectively convert lignin into useful chemicals by catalytic fast pyrolysis and our efforts to elucidate the mechanism of lignin pyrolysis are discussed. Possible research directions will be identified. PMID:26598403

  17. High-throughput methods for the development of new catalytic asymmetric reactions.

    PubMed

    Traverse, John F; Snapper, Marc L

    2002-10-01

    Chiral, single enantiomer pharmaceuticals have become increasingly more important. Therefore, research aimed at providing new methods for their selective preparation has taken on an even greater importance. One of the most efficient strategies for the synthesis of non-racemic, chiral molecules is asymmetric catalysis. There are many variables involved in the discovery of a new catalytic asymmetric transformation; hence, methods for the rapid screening of large numbers of catalysts have been developed. Herein, these techniques and strategies for the rapid discovery of novel asymmetric catalysts are reviewed.

  18. Reaction of catalytic oxidation by liquid water and its application to waste water purification

    SciTech Connect

    Ioffe, I.I.; Rubinskaya, E.V.

    1997-06-01

    In this paper the results of experiments and some considerations of theoretical and practical problems devoted to a new type of chemical reaction--oxidation of organic substances by liquid water with the aid of noble metal catalyst--are given. Some problems of application such as reaction to self-purification of industrial waste waters are also considered.

  19. Nuclear Structure and Reaction Mechanism Studies with Multinucleon Reactions

    SciTech Connect

    Regan, P. H.; Jones, G. A.; Podolyak, Zs.; Abdullah, M.; Gelletly, W.; Langdown, S. D.; Wollel, G.; De Angelis, G.; Gadea, A.; Kroell, Th.; Marginean, N.; Martinez, T.; Napoli, D. R.; Rusu, C.; Tonev, D.; Zhang, Y. H.; Ur, C. A.; Axiotis, M.; Bazzacco, D.; Farnea, E.

    2006-08-14

    This contribution reports on the results of an experiment to study the near-yrast states in selenium- and osmium-like nuclei, following their population in thick-target, multinucleon transfer reactions between an 82Se beam and a 192Os target. The experimental results for the level scheme for 84Se are presented together with investigations into the use of multi-dimensional gamma-ray energy gating to investigate angular momentum population in such heavy-ion binary reactions.

  20. Economic feasibility of ethanol production from biomass and waste resources via catalytic reaction.

    PubMed

    Yeon, Sun-Hwa; Shin, Dae-Hyun; Nho, Nam-Sun; Shin, Kyoung-Hee; Jin, Chang-Soo

    2013-04-01

    An economic evaluation of ethanol (EtOH) production from a thermo-chemical process derived from biomass/waste feedstocks was conducted. The influence of feed amounts, catalytic conversions, and EtOH selling prices was examined as these are the major variables for the economic evaluation of biomass/wastes conversion to EtOH. Among the three feedstock systems of biomass, high-moisture municipal solid waste (MSW), and plastic waste, the plastic waste has far better economic feasibility, with a payback period of 2-5 years at maximum CO conversion (40%) from syngas to ethanol, due to its higher heating value in comparison with biomass and high-moisture MSW. The heating value of the feedstock is a key factor in determining the overall economic efficiency in a thermo-chemical EtOH production system. Furthermore, enhancement of the CO conversion (related to catalytic activity) from syngas to EtOH using a low cost catalyst is necessary to retain economic efficiency because the CO conversion and cost consideration of catalyst are crucial factors to reduce the payback period. PMID:23179512

  1. High-temperature catalytic oxidative conversion of propane to propylene and ethylene involving coupling of exothermic and endothermic reactions

    SciTech Connect

    Choudhary, V.R.; Rane, V.H.; Rajput, A.M.

    2000-04-01

    Coupling of the exothermic catalytic oxidative conversion and endothermic thermal cracking (noncatalytic) reactions of propane to propylene and ethylene over the SrO/La{sub 2}O{sub 3}/SA5205 catalyst in the presence of steam and limited oxygen was investigated at different process conditions (temperature, 700--850 C; C{sub 3}H{sub 8}/O{sub 2} ratio in feed, 2.0--8.0; H{sub 2}O/C{sub 3}H{sub 8} ratio, 0.5--2.5; space velocity, 2,000--15,000 cm{sup 3}/g h). In the presence of steam and limited O{sub 2}, the endothermic thermal cracking and exothermic oxidative conversion reactions occur simultaneously and there is no coke formation on the catalyst. Because of the direct coupling of exothermic and endothermic reactions, this process occurs in a most energy efficient and safe manner. The propane conversion, selectivity for propylene, and net heat of reaction ({Delta}H{sub r}) in the process are strongly influenced by the temperature and concentration of O{sub 2} relative to the propane in the feed. The C{sub 3}H{sub 6}/C{sub 2}H{sub 4} product ratio is also strongly influenced by the temperature, C{sub 3}H{sub 8}/O{sub 2} feed ratio, and space velocity. The net heat of reaction can be controlled by manipulating the reaction temperature and C{sub 3}H{sub 8}/O{sub 2} ratio in the feed; the process exothermicity is reduced drastically with increasing the temperature and/or C{sub 3}H{sub 8}/O{sub 2} feed ratio.

  2. Catalytic effect of nanogold on Cu(II)-N2H4 reaction and its application to resonance scattering immunoassay.

    PubMed

    Jiang, Zhiliang; Liao, Xianjiu; Deng, Anping; Liang, Aihui; Li, Jishun; Pan, Hongcheng; Li, Jianfu; Wang, Sumei; Huang, Yujuan

    2008-11-15

    In the medium of EDTA-NaOH, nanogold strongly catalyzed the slow reaction between hydrazine (N2H4) and Cu(II) to form Cu particles, which exhibited a strong resonance scattering (RS) peak at 602 nm. The increased RS intensity at 602 nm (DeltaI(RS)) was linear to the nanogold concentration in the range of 0.008-2.64 nM, with a detection limit of 1.0 pM Au. The rate equation obtained by the initial rate procedure was V(Cu) = K(Cu)[C(Cu(II))](2)C(OH)(1)C(Au)(1)C(N2)H4(1), with an apparent activation energy of 38 kJ x mol(-1), and the catalytic reaction mechanism was also discussed. An immunonanogold-catalytic resonance scattering spectral (RSS) assay was established for detection of microalbumin (Malb), using 10 nm nanogold to label goat antihuman Malb to obtain an immunonanogold probe (AuMalb) for Malb. In pH 5.0 citric acid-Na2HPO4 buffer solution, the AuMalb aggregated nonspecifically. Upon addition of Malb, it reacted with the probe to form dispersive AuMalb-Malb immunocomplex in the solution. After centrifugation, the supernatant containing AuMalb-Malb was obtained, and exhibited a catalytic effect on the reaction of N2H4-Cu(II) to produce large Cu particles that resulted in the I(602 nm) increasing. The increased RS intensity at 602 nm (DeltaI(602 nm)) was linear to Malb concentration (C(Malb)) in the range of 0.4 to 460 pg x mL(-1), with the regression equation of DeltaI(602 nm) = 0.3713 C(Malb) + 7.2, correlation coefficient of 0.9981 and detection limit of 0.1 pg x mL(-1) Malb. The proposed method was applied to detect Malb in healthy human urine samples, with satisfactory results.

  3. A Diode Laser Study of the Catalytic Oxidation Dynamics of Acetaldehyde on Polycrystalline Platinum

    NASA Astrophysics Data System (ADS)

    Edington, Sean Coleman

    The catalytic oxidation of acetaldehyde on platinum was studied using a flow reactor equipped with a tunable diode laser absorption spectrometer and a quadrupole mass spectrometer. Reaction mixtures containing this molecule in varying proportion with oxygen and with argon as a carrier gas were flowed over a polycrystalline platinum mesh, which was resistively heated to different temperatures between 700 and 1000 K. The products of these reactions were monitored using mass spectrometry and the state-resolved spectra of CO 2 produced were collected using high-resolution tunable diode laser absorption spectroscopy. These data were analyzed to yield information about the dynamics of the reaction. Results indicate that production of CO and CO2 by this reaction proceeds via two distinct pathways. Acetaldehyde adsorbed on the surface decomposes to acetyl, which in turn decomposes CO and CHx. The adsorbed CO so prepared desorbs to yield the bulk of CO generated across all reaction conditions and also yields CO2 with a relatively deactivated asymmetric stretching mode under conditions of high temperature and low oxygen coverage. The acetyl-derived CHx dehydrogenates to yield surface carbon and H adatoms. Total oxidation of this surface carbon is the primary source of CO2 produced under all reaction conditions except those mentioned previously and is found to yield products with a preferentially excited asymmetric stretch. Combination of the CHx-derived H adatoms with surface oxygen drives the production of water by this reaction. During the course of the work described here, two notable improvements were made to our experimental apparatus. The first of these was the modification of the data acquisition process to significantly improve the signal-to-noise ratio achievable by our laser spectrometer with no increase in data collection time. The second was the development of data analysis software which significantly improved the efficiency and thoroughness of the process by

  4. Computational study of a model system of enzyme-mediated [4+2] cycloaddition reaction.

    PubMed

    Gordeev, Evgeniy G; Ananikov, Valentine P

    2015-01-01

    A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.

  5. Ugi four-component reaction of alcohols: stoichiometric and catalytic oxidation/MCR sequences.

    PubMed

    Drouet, Fleur; Masson, Géraldine; Zhu, Jieping

    2013-06-01

    A new, simple, and efficient procedure for the one-pot Ugi four-component reaction of alcohols instead of aldehydes is described. Using a stoichiometric amount of IBX or only 1-2% of sodium 2-iodobenzenesulfonate in the presence of Oxone, a wide range of primary alcohols were oxidized to the aldehyde that were directly engaged in the Ugi four-component reaction to afford α-acetamidoamides in good to excellent yields.

  6. Experimental Study of Serpentinization Reactions

    NASA Technical Reports Server (NTRS)

    Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.

    2004-01-01

    Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.

  7. Room-temperature self-cleaning molecular sensing by catalytic reactions

    NASA Astrophysics Data System (ADS)

    Warnick, Keith H.; Wang, Bin; Cliffel, David E.; Wright, David W.; Haglund, Richard F.; Pantelides, Sokrates T.

    2013-03-01

    New sensing techniques using self-cleaning nanosensors for molecular detection are in demand. Here we describe a room-temperature process in which a nanostructured substrate catalyzes the reaction of a target molecule with atmospheric oxygen and the reaction energy is absorbed by the substrate, where it can in principle be detected. Specifically, we report first-principles calculations describing a reaction catalyzed by Fe-porphyrin at room temperature that breaks O2, incorporates an oxygen into the methyl group of 2,4-dinitrotoluene (DNT) and releases 1.9 eV per reaction. The atomic oxygen left on the Fe site can be removed by reacting with another DNT molecule, making the whole process self-cleaning. The reaction energy absorbed by the substrate can in principle be detected optically, as for example, by detecting the metal-insulator phase transition in VO2. We further explore issues of sensitivity and selectivity in exploiting this reaction for solid-state molecular sensing. This work was supported in part by DTRA grant HDTRA1-10-0047 and by the McMinn Endowment at Vanderbilt University. Calculations were performed on AFRL computing resources.

  8. Simple relationships for estimating intraparticle transport effects for catalytically promoted endothermic reactions

    SciTech Connect

    Brown, L.F.

    1998-06-16

    Relationships for estimating effectiveness factors for porous-solid-catalyzed fluid reactions can result from assuming approximations to temperature and concentration profiles. Approximations designed to simplify the outcome result in simple, explicit, analytic relationships for both isothermal and nonisothermal nth-order reaction systems. For isothermal systems, formulas developed predict effectiveness within 25% of the true isothermal effectiveness factors ({eta}`s) over the range 0.1 > {eta} > 0.99. For isothermal or endothermic reaction systems with {eta} > 0.65, errors are less than 10%. Even in the maximum-error region, estimates for endothermic systems are within a factor of two of those obtained by solution of the rigorous heat and mass transfer equations. For isothermal or endothermic systems with {eta} > 0.95, errors are less than 1%. Thus the formulas can also serve diagnostic uses that confirm presence or absence of significant internal heat or mass transport effects in porous reacting systems. Extension of the approach to non-nth-order reactions is possible; formulas are derived for simple isothermal and nonisothermal Langmuir-Hinshelwood reaction systems. Application of the work to exothermic reactions was not tested, but steeper gradients in such systems would tend to degrade accuracy of the relationships. The equations derived in this work are simpler and easier of application than any others proposed thus far.

  9. Urea-treated carbon nanofibers as efficient catalytic materials for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Dong; Zhang, Xueping; You, Tianyan

    2015-01-01

    Nitrogen-doped carbon nanofibers (NCNFs) are prepared by the thermal treatment of carbon nanofibers (CNFs) using urea as nitrogen source. Scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy have been employed to characterize the morphology and composition of CNFs and NCNFs. Compared with CNFs, NCNFs display thinner diameter, rougher surface and higher content of pyrrolic-N. As a metal-free catalyst for ORR, NCNFs exhibit comparable catalytic activity, significantly enhanced long-time stability and selectivity in comparison with commercial available Pt/C catalyst. Importantly, the self-supported NCNFs films could be conveniently utilized for electrode modification which is attractive in fuel cells. This work offers a promising metal-free catalyst as an alternative for Pt/C catalyst.

  10. Catalytic solid substrate room temperature phosphorimetry for the determination of trace rhamnose based on its condensation reaction with calcein

    NASA Astrophysics Data System (ADS)

    Liu, Jia-Ming; Lin, Li-Ping; Wang, Hong-Xin; Lin, Shao-Qin; Zhang, Li-Hong; Cai, Wen-Lian; Lin, Xuan; Pan, You-Zhu; Wang, Xin-Xing; Li, Zhi-Ming; Jiao, Li; Cui, Ma-Lin

    2011-12-01

    Calcein (R) could not only emit strong and stable room temperature phosphorescence (RTP) on filter paper using I - as perturber, but also could be oxidized by H 2O 2 to form a non-phosphorescence compound (R'), resulting in the quenching of RTP signal of R. Moreover, the ortho-hydrogen of phenolic hydroxyl in R took condensation reaction with rhamnose (Rha) to produce non-phosphorescence compound (R-Rha) causing the RTP signal of R to further quench, and R-Rha was oxidized by H 2O 2 to form R' and Rha, bringing about the sharp RTP signal quenching of R. Thus, a new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace Rha based on its strong catalytic effect on H 2O 2 oxidizing R has been established, with the detection limit (LD) of 7.8 zg spot -1 (corresponding concentration: 2.0 × 10 -17 g ml -1, sample volume: 0.40 μl spot -1). This method has been applied to determine trace Rha in cigarettes and jujubes, with the results coinciding well with those determined by a high performance liquid chromatography (HPLC). The component of R-Rha also was analyzed by means of HPLC, mass spectrometer and nuclear magnetic resonance (NMR) measurements. The mechanism of catalytic SSRTP for the determination of trace Rha was discussed.

  11. Catalytic Effects of Oxide Surfaces on Diels-Alder Cycloaddition between Furan and Methyl Acrylate: A DFT Study

    NASA Astrophysics Data System (ADS)

    Salavati-Fard, Taha; Jenness, Glen; Caratzoulas, Stavros; Doren, Douglas

    Using density functional theory with periodic boundary conditions, we study the catalytic effects of oxide surfaces such as ZrO_2 and HfO_2 on Diels-Alder reaction between furan and methyl acrylate. The cycloadduct can be dehydrated later to produce methyl benzoic which is an important step toward benzoic acid production. The gas-phase and on-surface reaction mechanisms are studied in detail. The surface hydration effects on the reaction mechanism and energy profile are studied as well. Our calculations show that the oxide surfaces catalyze the reaction significantly through the interaction of metal sites with methyl acrylate. The calculations are interpreted by making use of electronic density of states and band structure of the catalyst.

  12. Identification of a catalytic base for sugar oxidation in the pyranose 2-oxidase reaction.

    PubMed

    Wongnate, Thanyaporn; Sucharitakul, Jeerus; Chaiyen, Pimchai

    2011-11-25

    Pyranose 2-oxidase (P2O) catalyzes the oxidation of aldopyranoses to form 2-keto sugars and H(2)O(2) . In this study, the mechanistic role of the conserved residues His548 and Asn593 in P2O was investigated by using site-directed mutagenesis, transient kinetics, and pH-dependence studies. As single mutants of H548 resulted in mixed populations of noncovalently bound and covalently linked FAD, double mutants containing H167A were constructed, in which the covalent histidyl-FAD linkage was removed in addition to having the H548 mutation. Single mutants H548A, H548N, H548S, H548D and double mutants (with H167A) could not be reduced by D-glucose. For the H167A/H548R mutant, the flavin could be reduced by D-glucose with the reduction rate constant about 220 times lower than that of the H167A mutant. The pH-dependence studies of H167A/H548R indicated that the rate constant of flavin reduction increased about 360-fold upon a pH rise corresponding to pK(a) >10.1, whereas the reactions of the wild-type and H167A mutant enzymes were pH independent. Therefore, the data suggest that a pK(a) value of >10.1 in the mutant enzyme is associated with the Arg548 residue, and that this residue must be unprotonated to efficiently catalyze flavin reduction. The data imply that for the wild-type P2O, the conserved His548 should be unprotonated in the pH range studied. The unprotonated His548 can act as a general base to abstract the 2-hydroxyl proton of D-glucose and initiate hydride transfer from the substrate to the flavin. Studies of the single mutant N593H showed that the flavin reduction rate constant was 114 times lower than that of the wild-type enzyme and was pH independent, while the K(d) for D-glucose binding was 19 times greater.

  13. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions.

    PubMed

    Parlett, Christopher M A; Isaacs, Mark A; Beaumont, Simon K; Bingham, Laura M; Hondow, Nicole S; Wilson, Karen; Lee, Adam F

    2016-02-01

    The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

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

    PubMed

    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.

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

    SciTech Connect

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

    2016-01-01

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

  16. Investigation of catalytic activity towards oxygen reduction reaction of Pt dispersed on boron doped graphene in acid medium.

    PubMed

    Pullamsetty, Ashok; Sundara, Ramaprabhu

    2016-10-01

    Boron doped graphene was prepared by a facile method and platinum (Pt) decoration over boron doped graphene was done in various chemical reduction methods such as sodium borohydride (NaBH4), polyol and modified polyol. X-ray diffraction analysis indicates that the synthesized catalyst particles are present in a nanocrystalline structure and transmission and scanning electron microscopy were employed to investigate the morphology and particle distribution. The electrochemical properties were investigated with the help of the rotating disk electrode (RDE) technique and cyclic voltammetry. The results show that the oxygen reduction reaction (ORR) takes place by a four-electron process. The kinetics of the ORR was evaluated using K-L and Tafel plots. The electrocatalyst obtained in modified polyol reduction method has shown the better catalytic activity compared to other two electrocatalysts. PMID:27393888

  17. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.

    PubMed

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya

    2016-06-21

    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

  18. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.

    PubMed

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya

    2016-06-21

    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

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

    PubMed

    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.

  20. Intramolecular hydroarylation of aryl propargyl ethers catalyzed by indium: the mechanism of the reaction and identifying the catalytic species.

    PubMed

    Menkir, Mengistu Gemech; Lee, Shyi-Long

    2016-07-01

    The mechanism and regioselectivity of the intramolecular hydroarylation of phenyl propargyl ether catalyzed by indium in gas and solvent phases were investigated by means of the density functional theory method. The computed results revealed that the reaction proceeds through initial π-coordination of the propargyl moiety to the catalyst, which triggers the nucleophilic attack of the phenyl ring via an exo- or endo-dig pathway in a Friedel-Crafts type mechanism. Calculation results obtained employing InI2(+) as the possible catalyst show similar activation energies for the 5-exo-dig and 6-endo-dig pathways. In contrast, the neural catalyst InI3 shows a kinetic preference for 6-endo-dig versus 5-exo-dig cyclizations leading to the experimentally observed product, 2H-chromene. The calculation results suggest that InI3 could be the real catalytic species for this reaction as it shows regioselectivity in agreement with the experimental observation. Furthermore, the 6-endo-dig cyclization through deprotonation/protonation steps is kinetically more favored than the stepwise two consecutive [1,2]-H shift steps. The rate determining step of the whole catalytic cycle is the deprotonation step with an energy barrier of 18.9 kcal mol(-1) in toluene solvent. The effects of substituents on both the phenyl ring and the propargyl moiety on the selectivity and elementary steps of the hydroarylation process were investigated. A methoxy group, particularly at the meta-position, on the phenyl ring largely decreases the energy barrier of the first step for the 6-endo path, though it shows little effect on the activation energies of the second and third steps. Our calculation results are in good agreement with the experimental results. PMID:27298068

  1. Construction of highly functionalized diazoacetoacetates via catalytic Mukaiyama-Michael reactions.

    PubMed

    Liu, Yu; Zhang, Yu; Jee, Noel; Doyle, Michael P

    2008-04-17

    Functionalized diazo acetoacetates are prepared by an efficient Mukaiyama-Michael reaction between methyl 3-(trialkylsilanoxy)-2-diazo-3-butenoate and alpha,beta-unsaturated enones. Vinyl ether and ketone derivatives are both accessible in good to excellent yield through this methodology. The mild Lewis acid zinc(II) triflate is the optimal catalyst, and its loading can be as low as 0.1 mol %. In addition, zinc triflate was also found to be a superior catalyst for the related Mukaiyama-aldol reaction.

  2. Kinetic studies of elementary chemical reactions

    SciTech Connect

    Durant, J.L. Jr.

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

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

    SciTech Connect

    Battaglia, Francine; Agblevor, Foster; Klein, Michael; Sheikhi, Reza

    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.

  4. Catalytic enantio- and diastereoselective Mannich reaction of α-substituted isocyanoacetates and ketimines.

    PubMed

    de la Campa, Raquel; Gammack Yamagata, Adam D; Ortín, Irene; Franchino, Allegra; Thompson, Amber L; Odell, Barbara; Dixon, Darren J

    2016-08-23

    The highly diastereo- and enantioselective Mannich addition/cyclisation reaction of α-substituted isocyanoacetate ester pronucleophiles and (hetero)aryl and alkyl methyl ketone-derived ketimines using a silver acetate and a cinchona-derived amino phosphine binary catalyst system is reported. PMID:27500289

  5. Oxidation reaction by xanthine oxidase: theoretical study of reaction mechanism.

    PubMed

    Amano, Tatsuo; Ochi, Noriaki; Sato, Hirofumi; Sakaki, Shigeyoshi

    2007-07-01

    The oxidation process by molybdenum-containing enzyme, xanthine oxidase, is theoretically studied with a model complex representing the reaction center and a typical benchmark substrate, formamide. Comparisons were systematically made among reaction mechanisms proposed previously. In the concerted and stepwise mechanisms that were theoretically discussed previously, the oxidation reaction takes place with a moderate activation barrier. However, the product is less stable than the reactant complex, which indicates that these mechanisms are unlikely. Moreover, the product of the concerted mechanism is not consistent with the isotope experimental result. In addition to those mechanisms, another mechanism initiated by the deprotonation of the active site was newly investigated here. In the transition state of this reaction, the carbon atom of formamide interacts with the oxo ligand of the Mo center and the hydrogen atom is moving from the carbon atom to the thioxo ligand. This reaction takes place with a moderate activation barrier and considerably large exothermicity. Furthermore, the product by this mechanism is consistent with the isotope experimental result. Also, our computations clearly show that the deprotonation of the active site occurs with considerable exothermicity in the presence of glutamic acid and substrate. The intermediate of the stepwise mechanism could not be optimized in the case of the deprotonated active site. From all these results, it should be concluded that the one-step mechanism with the deprotonated active site is the most plausible.

  6. Fe-complex of a tetraamido macrocyclic ligand: Spectroscopic characterization and catalytic oxidation studies

    NASA Astrophysics Data System (ADS)

    Sullivan, Shane Z.; Ghosh, Anindya; Biris, Alexandru S.; Pulla, Sharon; Brezden, Anna M.; Collom, Samulel L.; Woods, Ross M.; Munshi, Pradip; Schnackenberg, Laura; Pierce, Brad S.; Kannarpady, Ganesh K.

    2010-10-01

    This work presents the spectroscopic characterization and reaction studies of a Fe III-complex (2) of a tetraamido macrocyclic ligand (1, 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[a,g]cyclotridecene-6,7,14,16-tetraone). 2 was characterized primarily by means of EPR. In agreement with the magnetic moment ( μeff = 3.87 BM), EPR spectroscopy of 2 shows signals consistent with S = 3/2 intermediate-spin ferric-iron. Besides EPR, mass spectrometry, UV/vis spectroscopy and cyclic voltammetry were used to further characterize 2. 2 is soluble in water and activates hydrogen peroxide under ambient conditions. 2 catalytically bleaches dyes, pulp and paper effluents and oxidizes several amines to their corresponding N-oxides with high turnover number and good yields.

  7. Catalytic reduction of NO by CO over rhodium catalysts. 2. Effect of oxygen on the nature, population, and reactivity of surface species formed under reaction conditions

    SciTech Connect

    Kondarides, D.I.; Chafik, T.; Verykios, X.E.

    2000-04-01

    The effect of oxygen on the nature, population, and reactivity of surface species formed during reduction of NO by CO over Rh/TiO{sub 2} catalysts has been examined employing FTIR and transient MS techniques. It has been found that the activity of Rh is hindered by accumulation of surface oxygen originating from NO decomposition and gas-phase oxygen in the feed. Adsorbed CO and reduced TiO{sub 2{minus}x} species in the vicinity of Rh particles act as oxygen atom scavengers and, under fuel-rich conditions, remove atomic oxygen from the surface and restore the catalytic properties. Results of the present study provide additional evidence that production of N{sub 2} is related to dissociation of adsorbed Rh-NO{sup {minus}} while production of N{sub 2}O is related to the presence of Rh(NO){sub 2}. The presence of reduced RH{sup 0} sites is necessary for the formation of both reduction products. In the absence of oxygen in the feed, surface isocyanate species are also observed under reaction conditions. Their formation requires the presence of adjacent Rh{sup 0}-CO and reduced Rh{sup 0} sites. Although these species are favored under conditions in which NO conversion to reduction products is observed, there is no evidence that they are catalytically active species.

  8. Diastereoselective Synthesis of Cyclopenta[c]furans by a Catalytic Multicomponent Reaction.

    PubMed

    Pathipati, Stalin R; van der Werf, Angela; Eriksson, Lars; Selander, Nicklas

    2016-09-19

    A diastereoselective three-component reaction between alkynyl enones, aldehydes and secondary amines is reported. With the aid of a benign indium catalyst, a range of highly substituted cyclopenta[c]furan derivatives can be obtained in a single-step procedure. The formation of the stereodefined heterocyclic motifs takes place via in situ generation of enamines followed by two sequential cyclization steps. PMID:27538999

  9. Identifying reaction intermediates and catalytic active sites through in situ characterization techniques

    SciTech Connect

    Foster, Andrew J.; Lobo, Raul F

    2010-01-01

    This tutorial review centers on recent advances and applications of experimental techniques that help characterize surface species and catalyst structures under in situ conditions. We start by reviewing recent applications of IR spectroscopy of working catalysis, emphasizing newer approaches such as Sum Frequency Generation and Polarization Modulation-infrared reflection absorption spectroscopy. This is followed by a section on solid-state NMR spectroscopy for the detection of surface species and reaction intermediates. These two techniques provide information mainly about the concentration and identity of the prevalent surface species. The following sections center on methods that provide structural and chemical information about the catalyst surface. The increasingly important role of high-pressure X-ray photoelectron spectroscopy in catalyst characterization is evident from the new and interesting information obtained on supported catalysts as presented in recent reports. X-Ray absorption spectroscopy (XANES and EXAFS) is used increasingly under reaction conditions to great advantage, although is inherently limited to systems where the bulk of the species in the sample are surface species. However, the ability of X-rays to penetrate the sample has been used cleverly by a number of groups to understand how changing reaction conditions change the structure and composition of surface atoms on supported catalyst.

  10. Visual detection of thrombin using a strip biosensor through aptamer-cleavage reaction with enzyme catalytic amplification.

    PubMed

    Qin, Chunyan; Wen, Wei; Zhang, Xiuhua; Gu, Haoshuang; Wang, Shengfu

    2015-11-21

    A new class of strip biosensors has been established based on well-distributed thrombin aptamer-linked gold nanoparticle aggregates, which will undergo a cracking reaction when the target recognizes its homologous aptamer. Combining the aptamer-cleavage reaction with the enzyme catalytic amplification system, our proposed lateral flow strip biosensor (LFB) is capable of visually detecting 6.4 pM of thrombin without instrumentation within 12 minutes. Under the optimal conditions, the quantitative detection of thrombin by a portable strip reader exhibited a linear relationship between the peak area and the concentration of thrombin in the range of 6.4 pM-500 nM with a detection limit of 4.9 pM, which is three orders of magnitude lower than that of the aptamer-functionalized gold nanoparticle-based LFB (2.5 nM, Xu et al., Anal. Chem., 2009, 81, 669-675). As the aptamers have no special requirements and the gold nanoparticles can also be replaced by other metallic nanoparticles, this method for strip sensing is expected to be generally applicable in point of care testing, home testing, medical diagnostics, clinical diagnosis, and environmental monitoring. PMID:26451394

  11. Mechanistic Studies of Gold and Palladium Cooperative Dual-Catalytic Cross-Coupling Systems

    PubMed Central

    Al-Amin, Mohammad; Roth, Katrina E.; Blum, Suzanne A.

    2014-01-01

    Double-label crossover, modified-substrate, and catalyst comparison experiments in the gold and palladium dual-catalytic rearrangement/cross-coupling of allenoates were performed in order to probe the mechanism of this reaction. The results are consistent with a cooperative catalysis mechanism whereby 1) gold activates the substrate prior to oxidative addition by palladium, 2) gold acts as a carbophilic rather than oxophilic Lewis acid, 3) competing olefin isomerization is avoided, 4) gold participates beyond the first turnover and therefore does not serve simply to generate the active palladium catalyst, and 5) single-electron transfer is not involved. These experiments further demonstrate that the cooperativity of both gold and palladium in the reaction is essential because significantly lower to zero conversion is achieved with either metal alone in comparison studies that examined multiple potential gold, palladium, and silver catalysts and precatalysts. Notably, employment of the optimized cocatalysts, PPh3AuOTf and Pd2dba3, separately (i.e., only Au or only Pd) results in zero conversion to product at all monitored time points compared to quantitative conversion to product when both are present in cocatalytic reactions. PMID:24757581

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

    PubMed

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

    2014-10-01

    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. PMID:25130565

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

    PubMed

    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.

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

    PubMed

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

    2016-01-01

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H₂ to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H₂, CO and CO₂. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H₂O, CO₂ and H₂. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H₂ and induce higher methane and CO conversions while yielding ultrapure H₂ and compressed CO₂ ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H₂ permeance and purity, high CH₄ conversion levels and reduced CO yields. PMID:27657143

  15. Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries.

    PubMed

    Lu, Yi-Chun; Gasteiger, Hubert A; Shao-Horn, Yang

    2011-11-30

    We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO(4) 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li(+)-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a "volcano-type" trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O(2) cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li(+)-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications.

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

    SciTech Connect

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

    2009-06-03

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

  17. PdCu Nanoalloy Electrocatalysts in Oxygen Reduction Reaction: Role of Composition and Phase State in Catalytic Synergy.

    PubMed

    Wu, Jinfang; Shan, Shiyao; Luo, Jin; Joseph, Pharrah; Petkov, Valeri; Zhong, Chuan-Jian

    2015-11-25

    The catalytic synergy of nanoalloy catalysts depends on the nanoscale size, composition, phase state, and surface properties. This report describes findings of an investigation of their roles in the enhancement of electrocatalytic activity of PdCu alloy nanoparticle catalysts for oxygen reduction reaction (ORR). Pd(n)Cu(100-n) nanoalloys with controlled composition and subtle differences in size and phase state were synthesized by two different wet chemical methods. Detailed electrochemical characterization was performed to determine the surface properties and the catalytic activities. The atomic-scale structures of these catalysts were also characterized by high-energy synchrotron X-ray diffraction coupled with atomic pair distribution function analysis. The electrocatalytic activity and stability were shown to depend on the size, composition, and phase structure. With Pd(n)Cu(100-n) catalysts from both methods, a maximum ORR activity was revealed at Pd/Cu ratio close to 50:50. Structurally, Pd50Cu50 nanoalloys feature a mixed phase consisting of chemically ordered (body-centered cubic type) and disordered (face-centered cubic type) domains. The phase-segregated structure is shown to change to a single phase upon electrochemical potential cycling in ORR condition. While the surface Cu dissolution occurred in PdCu catalysts from the two different synthesis methods, the PdCu with a single-phase character is found to exhibit a tendency of a much greater dissolution than that with the phase segregation. Analysis of the results, along theoretical modeling based on density functional theory calculation, has provided new insights for the correlation between the electrocatalytic activity and the catalyst structures. PMID:26569372

  18. Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research

    SciTech Connect

    Horn, R.; Ihmann, K.; Ihmann, J.; Jentoft, F.C.; Geske, M.; Taha, A.; Pelzer, K.; Schloegl, R.

    2006-05-15

    A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000 deg. C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100 {mu}m sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecular beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10 ms. A detection time resolution of up to 20 ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N{sub 2} and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N{sub 2} to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250 deg. C on a Pt catalyst are presented. The detection of CH{sub 3}{center_dot} radicals is successfully demonstrated.

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

    NASA Technical Reports Server (NTRS)

    Rollbuhler, Jim

    1991-01-01

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

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

    PubMed

    Denmark, Scott E; Heemstra, John R

    2007-07-20

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

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

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-08-01

    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.

  2. Experimental study of humic acid degradation and theoretical modelling of catalytic ozonation.

    PubMed

    Turkay, Ozge; Inan, Hatice; Dimoglo, Anatoli

    2015-01-01

    The efficiency of TiO2 as a catalyst in the ozonation of humic acid (HA) was evaluated in a comprehensive manner. Ozonation, catalytic ozonation and adsorption experiments were conducted using both synthetic HA solution and natural water. HA degradation was evaluated in terms of DOC, VIS400 and UV254. It was shown that the addition of catalyst positively affects the mechanism of ozonation. An increase in HA degradation was observed for all these parameters. The impact of catalyst dose and initial pH value of HA on the efficacy of catalytic ozonation was investigated. The highest removal efficiencies were achieved with the dose of 1 g l(-1) of TiO2 (Degussa P-25) and in the acidic pH region. The catalytic ozonation process was efficient also on natural water component although not at the same level as it was on synthetic water. The adsorptive feature of P-25 was considered to have a clear evidence of the catalytic ozonation mechanism. The mechanism of catalysis on the surface of metal oxides was elucidated with the help of quantum-chemical calculations. In the framework of Density Function Theory (DFT), the O3 decomposition was calculated in the catalytic and non-catalytic processes. Donor-acceptor properties of the frontier (highest occupied and lowest unoccupied molecular orbitals, HOMO/LUMO) orbitals are discussed. Electron density distribution and reaction mechanism of superoxide particles formation, which participate in the process of HA ozonation are analyzed. PMID:25056748

  3. Determination of trace amounts of mercury(II) in water samples using a novel kinetic catalytic ligand substitution reaction of hexacyanoruthenate(II)

    NASA Astrophysics Data System (ADS)

    Naik, Radhey M.; Agarwal, Abhinav; Prasad, Surendra

    2009-11-01

    A simple, sensitive, selective and rapid kinetic catalytic method has been developed for the determination of Hg(II) ions at micro-level. This method is based on the catalytic effect of Hg(II) ion on the rate of substitution of cyanide in hexacyanoruthenate(II) with nitroso-R-salt (NRS) in aqueous medium and provides good accuracy and precision. The concentration of Hg(II) catalyst varied from 4.0 to 10.0 × 10 -6 M and the progress of reaction was followed spectrophotometrically at 525 nm ( λmax of purple-red complex [Ru(CN) 5NRS] 3-, ɛ = 3.1 × 10 3 M -1 s -1) under the optimized reaction conditions; 8.75 × 10 -5 M [Ru(CN) 64-], 3.50 × 10 -4 M [nitroso-R-salt], pH 7.00 ± 0.02, ionic strength, I = 0.1 M (KCl), temp 45.0 ± 0.1 °C. The linear calibration curves, i.e. calibration equations between the absorbance at fixed times ( t = 15, 20 and 25 min) versus concentration of Hg(II) ions were established under the optimized experimental conditions. The detection limit was found to be 1.0 × 10 -7 M of Hg(II). The effect of various foreign ions on the proposed method has also been studied and discussed. The method has been applied to the determination of mercury(II) in aqueous solutions.

  4. Facet-dependent catalytic activity of Cu2O nanocrystals in the one-pot synthesis of 1,2,3-triazoles by multicomponent click reactions.

    PubMed

    Chanda, Kaushik; Rej, Sourav; Huang, Michael H

    2013-11-18

    We report the highly facet-dependent catalytic activity of Cu2O nanocubes, octahedra, and rhombic dodecahedra for the multicomponent direct synthesis of 1,2,3-triazoles from the reaction of alkynes, organic halides, and NaN3. The catalytic activities of clean surfactant-removed Cu2O nanocrystals with the same total surface area were compared. Rhombic dodecahedral Cu2O nanocrystals bounded by {110} facets were much more catalytically active than Cu2O octahedra exposing {111} facets, whereas Cu2O nanocubes displayed the slowest catalytic activity. The superior catalytic activity of Cu2O rhombic dodecahedra is attributed to the fully exposed surface Cu atoms on the {110} facet. A large series of 1,4-disubstituted 1,2,3-triazoles have been synthesized in excellent yields with high regioselectivity under green conditions by using these rhombic dodecahedral Cu2O catalysts, including the synthesis of rufinamide, an antiepileptic drug, demonstrating the potential of these nanocrystals as promising heterogeneous catalysts for other important coupling reactions. PMID:24127396

  5. Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

    SciTech Connect

    Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

    2012-01-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  6. Trends in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium.

    PubMed

    Dathar, Gopi Krishna Phani; Shelton, William A; Xu, Ye

    2012-04-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O2 on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  7. Compartmentalization and Cell Division through Molecular Discreteness and Crowding in a Catalytic Reaction Network

    PubMed Central

    Kamimura, Atsushi; Kaneko, Kunihiko

    2014-01-01

    Explanation of the emergence of primitive cellular structures from a set of chemical reactions is necessary to unveil the origin of life and to experimentally synthesize protocells. By simulating a cellular automaton model with a two-species hypercycle, we demonstrate the reproduction of a localized cluster; that is, a protocell with a growth-division process emerges when the replication and degradation speeds of one species are respectively slower than those of the other species, because of overcrowding of molecules as a natural outcome of the replication. The protocell exhibits synchrony between its division process and replication of the minority molecule. We discuss the effects of the crowding molecule on the formation of primitive structures. The generality of this result is demonstrated through the extension of our model to a hypercycle with three molecular species, where a localized layered structure of molecules continues to divide, triggered by the replication of a minority molecule at the center. PMID:25370530

  8. Compartmentalization and Cell Division through Molecular Discreteness and Crowding in a Catalytic Reaction Network.

    PubMed

    Kamimura, Atsushi; Kaneko, Kunihiko

    2014-01-01

    Explanation of the emergence of primitive cellular structures from a set of chemical reactions is necessary to unveil the origin of life and to experimentally synthesize protocells. By simulating a cellular automaton model with a two-species hypercycle, we demonstrate the reproduction of a localized cluster; that is, a protocell with a growth-division process emerges when the replication and degradation speeds of one species are respectively slower than those of the other species, because of overcrowding of molecules as a natural outcome of the replication. The protocell exhibits synchrony between its division process and replication of the minority molecule. We discuss the effects of the crowding molecule on the formation of primitive structures. The generality of this result is demonstrated through the extension of our model to a hypercycle with three molecular species, where a localized layered structure of molecules continues to divide, triggered by the replication of a minority molecule at the center. PMID:25370530

  9. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  10. Effective catalytic media using graphitic nitrogen-doped site in graphene for a non-aqueous Li-O2 battery: A density functional theory study

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The cell performance of lithium-oxygen batteries using nitrogen doped graphene as a catalytic cathode has been validated in recent research, but the cathode reaction mechanism of lithium and oxygen still remains unclear. Since the oxygen reduction reaction (ORR) mechanism by ionic lithium and catalytic surface is predicted to be distinct for different defective sites such as graphitic, pyridinic, and pyrrolic, it is necessary to observe the behavior of ionic lithium and oxygen gas at each defective site in nitrogen doped graphene. In this study, density functional theory (DFT) calculations are adopted to analyze at an atomic scale how effectively each defective site acts as a catalytic cathode. Interestingly, unlike pyridinic or pyrrolic N is known to be the most effective catalytic site for ORR in fuel cells. Among the other defective sites, it is found that the graphitic N site is the most effective catalytic media activating ORR by ionic lithium in lithium-oxygen batteries due to the electron accepting the reaction of Li-O formation by the graphitic N site.

  11. Study of flame quenching and near-wall combustion of lean burn fuel-air mixture in a catalytically activated spark-ignited lean burn engine

    SciTech Connect

    Nedunchezhian, N.; Dhandapani, S.

    2006-01-01

    A study of the catalytic activation of charge near the combustion chamber wall and of the flame quenching phenomenon was carried out to identify whether flame quenches due to catalytic activation or due to thermal quenching. It was found that (1) the diffusion rate of fuel into the boundary sublayer limits the catalytic surface reaction rate during combustion; (2) the results of the present flame quench model indicate that the flame quenches due to the heat loss to walls, and the depletion of fuel due to the catalyst coated on the combustion chamber walls does not affect flame quenching; (3) the catalysts coated on the combustion chamber surface do not contribute increased hydrocarbon emissions, but actually reduce them; (4) each catalyst has a specific surface temperature, at which the Damkoehler number for surface reaction is unity.

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

    PubMed

    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. PMID:25172465

  13. Reaction mechanism of the epsilon subunit of E. coli DNA polymerase III: insights into active site metal coordination and catalytically significant residues.

    PubMed

    Cisneros, G Andrés; Perera, Lalith; Schaaper, Roel M; Pedersen, Lars C; London, Robert E; Pedersen, Lee G; Darden, Thomas A

    2009-02-01

    The 28 kDa epsilon subunit of Escherichia coli DNA polymerase III is the exonucleotidic proofreader responsible for editing polymerase insertion errors. Here, we study the mechanism by which epsilon carries out the exonuclease activity. We performed quantum mechanics/molecular mechanics calculations on the N-terminal domain containing the exonuclease activity. Both the free-epsilon and a complex epsilon bound to a theta homologue (HOT) were studied. For the epsilon-HOT complex Mg(2+) or Mn(2+) were investigated as the essential divalent metal cofactors, while only Mg(2+) was used for free-epsilon. In all calculations a water molecule bound to the catalytic metal acts as the nucleophile for hydrolysis of the phosphate bond. Initially, a direct proton transfer to H162 is observed. Subsequently, the nucleophilic attack takes place followed by a second proton transfer to E14. Our results show that the reaction catalyzed with Mn(2+) is faster than that with Mg(2+), in agreement with experiment. In addition, the epsilon-HOT complex shows a slightly lower energy barrier compared to free-epsilon. In all cases the catalytic metal is observed to be pentacoordinated. Charge and frontier orbital analyses suggest that charge transfer may stabilize the pentacoordination. Energy decomposition analysis to study the contribution of each residue to catalysis suggests that there are several important residues. Among these, H98, D103, D129, and D146 have been implicated in catalysis by mutagenesis studies. Some of these residues were found to be structurally conserved on human TREX1, the exonuclease domains from E. coli DNA-Pol I, and the DNA polymerase of bacteriophage RB69.

  14. Structural study of the X-ray-induced enzymatic reaction of octahaem cytochrome C nitrite reductase.

    PubMed

    Trofimov, A A; Polyakov, K M; Lazarenko, V A; Popov, A N; Tikhonova, T V; Tikhonov, A V; Popov, V O

    2015-05-01

    Octahaem cytochrome c nitrite reductase from the bacterium Thioalkalivibrio nitratireducens catalyzes the reduction of nitrite to ammonium and of sulfite to sulfide. The reducing properties of X-ray radiation and the high quality of the enzyme crystals allow study of the catalytic reaction of cytochrome c nitrite reductase directly in a crystal of the enzyme, with the reaction being induced by X-rays. Series of diffraction data sets with increasing absorbed dose were collected from crystals of the free form of the enzyme and its complexes with nitrite and sulfite. The corresponding structures revealed gradual changes associated with the reduction of the catalytic haems by X-rays. In the case of the nitrite complex the conversion of the nitrite ions bound in the active sites to NO species was observed, which is the beginning of the catalytic reaction. For the free form, an increase in the distance between the oxygen ligand bound to the catalytic haem and the iron ion of the haem took place. In the case of the sulfite complex no enzymatic reaction was detected, but there were changes in the arrangement of the active-site water molecules that were presumably associated with a change in the protonation state of the sulfite ions.

  15. Studying Reaction Intermediates Formed at Graphenic Surfaces

    NASA Astrophysics Data System (ADS)

    Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

    2014-03-01

    We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

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

    NASA Astrophysics Data System (ADS)

    Gomes, Ruth; Dutta, Saikat; Bhaumik, Asim

    2014-11-01

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

    NASA Astrophysics Data System (ADS)

    Tahmasebi, Vida; Grivani, Gholamhossein; Bruno, Giuseppe

    2016-11-01

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

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

    SciTech Connect

    Gomes, Ruth; Bhaumik, Asim; Dutta, Saikat

    2014-11-01

    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 {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} 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.

  19. Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

    2015-01-01

    Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications.

  20. Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

    2015-01-01

    Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications. PMID:25394186

  1. Manganese Triazacyclononane Oxidation Catalysts Grafted under Reaction Conditions on Solid Co-Catalytic Supports

    SciTech Connect

    Schoenfeldt, Nicholas J.; Ni, Zhenjuan; Korinda, Andrew W.; Meyer, Randall J.; Notestein, Justin M.

    2012-01-23

    Manganese complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) are highly active and selective alkene oxidation catalysts with aqueous H{sub 2}O{sub 2}. Here, carboxylic acid-functionalized SiO{sub 2} simultaneously immobilizes and activates these complexes under oxidation reaction conditions. H{sub 2}O{sub 2} and the functionalized support are both necessary to transform the inactive [(tmtacn)Mn{sup IV}({mu}-O)3Mn{sup IV}(tmtacn)]{sup 2+} into the active, dicarboxylate-bridged [(tmtacn)Mn{sup III}({mu}-O)({mu}-RCOO){sub 2}Mn{sup III}(tmtacn)]{sup 2+}. This transformation is assigned on the basis of comparison of diffuse reflectance UV-visible spectra to known soluble models, assignment of oxidation state by Mn K-edge X-ray absorption near-edge spectroscopy, the dependence of rates on the acid/Mn ratios, and comparison of the surface structures derived from density functional theory with extended X-ray absorption fine structure. Productivity in cis-cyclooctene oxidation to epoxide and cis-diol with 2-10 equiv of solid cocatalytic supports is superior to that obtained with analogous soluble valeric acid cocatalysts, which require 1000-fold excess to reach similar levels at comparable times. Cyclooctene oxidation rates are near first order in H{sub 2}O{sub 2} and near zero order in all other species, including H{sub 2}O. These observations are consistent with a mechanism of substrate oxidation following rate-limiting H{sub 2}O{sub 2} activation on the hydrated, supported complex. This general mechanism and the observed alkene oxidation activation energy of 38 {+-} 6 kJ/mol are comparable to H{sub 2}O{sub 2} activation by related soluble catalysts. Undesired decomposition of H{sub 2}O{sub 2} is not a limiting factor for these solid catalysts, and as such, productivity remains high up to 25 C and initial H{sub 2}O{sub 2} concentration of 0.5 M, increasing reactor throughput. These results show that immobilized carboxylic acids can be utilized and understood

  2. Structural and Kinetic Evidence That Catalytic Reaction of Human UDP-glucose 6-Dehydrogenase Involves Covalent Thiohemiacetal and Thioester Enzyme Intermediates*

    PubMed Central

    Egger, Sigrid; Chaikuad, Apirat; Klimacek, Mario; Kavanagh, Kathryn L.; Oppermann, Udo; Nidetzky, Bernd

    2012-01-01

    Biosynthesis of UDP-glucuronic acid by UDP-glucose 6-dehydrogenase (UGDH) occurs through the four-electron oxidation of the UDP-glucose C6 primary alcohol in two NAD+-dependent steps. The catalytic reaction of UGDH is thought to involve a Cys nucleophile that promotes formation of a thiohemiacetal enzyme intermediate in the course of the first oxidation step. The thiohemiacetal undergoes further oxidation into a thioester, and hydrolysis of the thioester completes the catalytic cycle. Herein we present crystallographic and kinetic evidence for the human form of UGDH that clarifies participation of covalent catalysis in the enzymatic mechanism. Substitution of the putative catalytic base for water attack on the thioester (Glu161) by an incompetent analog (Gln161) gave a UGDH variant (E161Q) in which the hydrolysis step had become completely rate-limiting so that a thioester enzyme intermediate accumulated at steady state. By crystallizing E161Q in the presence of 5 mm UDP-glucose and 2 mm NAD+, we succeeded in trapping a thiohemiacetal enzyme intermediate and determined its structure at 2.3 Å resolution. Cys276 was covalently modified in the structure, establishing its role as catalytic nucleophile of the reaction. The thiohemiacetal reactive C6 was in a position suitable to become further oxidized by hydride transfer to NAD+. The proposed catalytic mechanism of human UGDH involves Lys220 as general base for UDP-glucose alcohol oxidation and for oxyanion stabilization during formation and breakdown of the thiohemiacetal and thioester enzyme intermediates. Water coordinated to Asp280 deprotonates Cys276 to function as an aldehyde trap and also provides oxyanion stabilization. Glu161 is the Brønsted base catalytically promoting the thioester hydrolysis. PMID:22123821

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

    SciTech Connect

    Li, Qingyuan; Jiang, Sai; Ji, Shengfu 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.

  4. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.

    1991-01-01

    When an arene is coordinated to Cr(CO){sub 3}, profound changes in its reactivity occur. Ring and benzylic hydrogen atoms exhibit enhanced acidity, and typical arene reactions such as electrophilic aromatic substitutions are quenched. In contrast, the ring carbon atoms are activated toward attack by nucleophiles. These changes in reactivity are manifestations of the forceful electron withdrawing nature of the Cr(CO){sub 3} component, and of the ability of this group to stabilize charged intermediates. In addition, arenechromium tricarbonyl complexes have been proven to be good catalysts in the hydrogenation of dienes. While most simple complexes such as toluenechromium tricarbonyl require the use of high temperatures and dihydrogen pressures, arenechromium tricarbonyl complexes with napthalene, anthracene, and phenanthrene show remarkable activity under extremely mild conditions. An investigation has been under way in which the chemistry of coal arene-Cr(CO){sub 3} complexes have been studied. 4 figs.

  5. Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds

    NASA Astrophysics Data System (ADS)

    Koledina, K. F.; Gubaidullin, I. M.

    2016-05-01

    The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.

  6. Cobalt Molybdenum Oxynitrides: Synthesis, Structural, Characterization, and Catalytic Activity for the Oxygen Reduction Reaction

    SciTech Connect

    Cao, Bingfei; Veith, Gabriel M; Diaz, Rosa; Liu, Jue; Stach, Eric; Adzic, Radoslav R.; Khalifah, P.

    2013-01-01

    Here, we report the synthesis and characterization of CoxMo1 xOyNz compounds supported on carbon black as potential cathode catalysts for ORR. They were prepared by a conventional impregnation method. Their ORR activities in both acid and alkaline electrolytes were evaluated via half-cell measurements. The synthesis temperature and sample composition both strongly impacted their physical and chemical properties. Factors influencing their crystal structures, morphologies and ORR activities will be discussed based on the results of structural and spectroscopic studies.

  7. Catalytic reactor

    SciTech Connect

    Aaron, Timothy Mark; Shah, Minish Mahendra; Jibb, Richard John

    2009-03-10

    A catalytic reactor is provided with one or more reaction zones each formed of set(s) of reaction tubes containing a catalyst to promote chemical reaction within a feed stream. The reaction tubes are of helical configuration and are arranged in a substantially coaxial relationship to form a coil-like structure. Heat exchangers and steam generators can be formed by similar tube arrangements. In such manner, the reaction zone(s) and hence, the reactor is compact and the pressure drop through components is minimized. The resultant compact form has improved heat transfer characteristics and is far easier to thermally insulate than prior art compact reactor designs. Various chemical reactions are contemplated within such coil-like structures such that as steam methane reforming followed by water-gas shift. The coil-like structures can be housed within annular chambers of a cylindrical housing that also provide flow paths for various heat exchange fluids to heat and cool components.

  8. Catalytic Roles of βLys87 in Tryptophan Synthase: 15N Solid State NMR Studies

    PubMed Central

    Caulkins, Bethany G.; Yang, Chen; Hilario, Eduardo; Fan, Li; Dunn, Michael F.; Mueller, Leonard J.

    2015-01-01

    The proposed mechanism for tryptophan synthase shows βLys87 playing multiple catalytic roles: it bonds to the PLP cofactor, activates C4′ for nucleophilic attack via a protonated Schiff base nitrogen, and abstracts and returns protons to PLP-bound substrates (i.e. acid-base catalysis). ε-15N-lysine TS was prepared to access the protonation state of βLys87 using 15N solid-state nuclear magnetic resonance (SSNMR) spectroscopy for three quasi-stable intermediates along the reaction pathway. These experiments establish that the protonation state of the ε-amino group switches between protonated and neutral states as the β-site undergoes conversion from one intermediate to the next during catalysis, corresponding to mechanistic steps where this lysine residue has been anticipated to play alternating acid and base catalytic roles that help steer reaction specificity in tryptophan synthase catalysis. PMID:25688830

  9. Influence of Montmorillonite on Nucleotide Oligomerization Reactions: A Molecular Dynamics Study

    NASA Astrophysics Data System (ADS)

    Mathew, Damien C.; Luthey-Schulten, Zaida

    2010-03-01

    We investigate a proposed origins of life scenario involving the clay montmorillonite and its catalytic role in forming oligonucleotides from activated mononucleotides. Clay and mineral surfaces are important for concentrating the reactants and for promoting nucleotide polymerization reactions. Using classical molecular dynamics methods we provide atomic details of reactant conformations prior to polynucleotide formation, lending insight into previously reported experimental observations of this phenomenon. The simulations clarify the catalytic role of metal ions, demonstrate that reactions leading to correct linkages take place primarily in the interlayer, and explain the observed sequence selectivity in the elongation of the chain. The study comparing reaction probabilities involving L- and D-chiral forms of the reactants has found enhancement of homochiral over heterochiral products when catalyzed by montmorillonite.

  10. Surface-specific deposition of catalytic metal nanocrystals on hollow carbon nanospheres via galvanic replacement reactions of carbon-encapsulated MnO nanoparticles.

    PubMed

    Lee, Dong-Gyu; Kim, Soo Min; Jeong, Hwakyeung; Kim, Jongwon; Lee, In Su

    2014-05-27

    This paper reports the findings of our efforts toward gaining a more complete understanding and utilization of galvanic replacement reactions involving manganese oxide with noble metals. It was revealed that the site of metal deposition is significantly affected by the variable oxidation state of manganese oxide. The use of carbon-encapsulated MnO nanoparticles as a reaction template led to metal growth specifically on the outermost surfaces of the carbon shells rather than on the MnO cores, which allowed for the selective decoration of the external surfaces of hollow carbon nanospheres with catalytic nanocrystals of various noble metals, including Pt, Pd, Rh, and Ir. By rearranging the sequence between carbon-shell coating and galvanic replacement processes, the deposited metal nanocrystals could be placed on the interior surfaces of hollow carbon nanospheres and, moreover, separately on the internal and the external surfaces, which may enable the respective control of the catalytic functionalities of each specific surface.

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

    PubMed Central

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

    2016-01-01

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields. PMID:27657143

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

    PubMed Central

    Itoh, Susumu; Sonoike, Shotaro; Kitamura, Masanori; Aoki, Shin

    2014-01-01

    Extending carbon frameworks via a series of C–C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C–C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C–C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented. PMID:24481060

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

    PubMed

    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

  14. Catalytic distillation structure

    DOEpatents

    Smith, Jr., Lawrence A.

    1984-01-01

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

  15. Quantum chemical study of the catalytic oxidative coupling of methane

    SciTech Connect

    Onal, I.; Senkan, S.

    1997-10-01

    Oxidative coupling of methane reaction pathways on MgO and lithium-modified MgO were theoretically studied using the semiempirical MNDO-PM3 molecular orbital method. The surface of the MgO catalyst was modeled by a Mg{sub 9}O{sub 9} molecular cluster containing structural defects such as edges and corners. Lithium-promoted magnesia was simulated by isomorphic substitution of Mg{sup 2+} by Li{sup +}; the excess negative charge of the cluster was compensated by a proton connected to a neighboring O{sup 2{minus}} site. Heterolytic adsorption of methane was found to be directly related to the coordination number of both the lattice oxygen and the metal sites. Energetically the most favorable site pair was Mg{sub 3c}-O{sub 3c} with a neighboring Li{sub 4c} site present. Various sequential oxygen and methane adsorption pathways were explored resulting in CH{sub 3}OH formation with lower energy barriers for the Li-modified MgO cluster as compared to unmodified MgO.

  16. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

    PubMed

    Nguyen, Luan; Tao, Franklin Feng

    2016-06-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  17. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

    PubMed

    Nguyen, Luan; Tao, Franklin Feng

    2016-06-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily. PMID:27370473

  18. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    NASA Astrophysics Data System (ADS)

    Nguyen, Luan; Tao, Franklin Feng

    2016-06-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  19. Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures.

    PubMed

    Sarina, Sarina; Zhu, Huaiyong; Jaatinen, Esa; Xiao, Qi; Liu, Hongwei; Jia, Jianfeng; Chen, Chao; Zhao, Jian

    2013-04-17

    The intrinsic catalytic activity of palladium (Pd) is significantly enhanced in gold (Au)-Pd alloy nanoparticles (NPs) under visible light irradiation at ambient temperatures. The alloy NPs strongly absorb light and efficiently enhance the conversion of several reactions, including Suzuki-Miyaura cross coupling, oxidative addition of benzylamine, selective oxidation of aromatic alcohols to corresponding aldehydes and ketones, and phenol oxidation. The Au/Pd molar ratio of the alloy NPs has an important impact on performance of the catalysts since it determines both the electronic heterogeneity and the distribution of Pd sites at the NP surface, with these two factors playing key roles in the catalytic activity. Irradiating with light produces an even more profound enhancement in the catalytic performance of the NPs. For example, the best conversion rate achieved thermally at 30 °C for Suzuki-Miyaura cross coupling was 37% at a Au/Pd ratio of 1:1.86, while under light illumination the yield increased to 96% under the same conditions. The catalytic activity of the alloy NPs depends on the intensity and wavelength of incident light. Light absorption due to the Localized Surface Plasmon Resonance of gold nanocrystals plays an important role in enhancing catalyst performance. We believe that the conduction electrons of the NPs gain the light absorbed energy producing energetic electrons at the surface Pd sites, which enhances the sites' intrinsic catalytic ability. These findings provide useful guidelines for designing efficient catalysts composed of alloys of a plasmonic metal and a catalytically active transition metal for various organic syntheses driven by sunlight.

  20. Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures.

    PubMed

    Sarina, Sarina; Zhu, Huaiyong; Jaatinen, Esa; Xiao, Qi; Liu, Hongwei; Jia, Jianfeng; Chen, Chao; Zhao, Jian

    2013-04-17

    The intrinsic catalytic activity of palladium (Pd) is significantly enhanced in gold (Au)-Pd alloy nanoparticles (NPs) under visible light irradiation at ambient temperatures. The alloy NPs strongly absorb light and efficiently enhance the conversion of several reactions, including Suzuki-Miyaura cross coupling, oxidative addition of benzylamine, selective oxidation of aromatic alcohols to corresponding aldehydes and ketones, and phenol oxidation. The Au/Pd molar ratio of the alloy NPs has an important impact on performance of the catalysts since it determines both the electronic heterogeneity and the distribution of Pd sites at the NP surface, with these two factors playing key roles in the catalytic activity. Irradiating with light produces an even more profound enhancement in the catalytic performance of the NPs. For example, the best conversion rate achieved thermally at 30 °C for Suzuki-Miyaura cross coupling was 37% at a Au/Pd ratio of 1:1.86, while under light illumination the yield increased to 96% under the same conditions. The catalytic activity of the alloy NPs depends on the intensity and wavelength of incident light. Light absorption due to the Localized Surface Plasmon Resonance of gold nanocrystals plays an important role in enhancing catalyst performance. We believe that the conduction electrons of the NPs gain the light absorbed energy producing energetic electrons at the surface Pd sites, which enhances the sites' intrinsic catalytic ability. These findings provide useful guidelines for designing efficient catalysts composed of alloys of a plasmonic metal and a catalytically active transition metal for various organic syntheses driven by sunlight. PMID:23566035

  1. Studies of coupled chemical and catalytic coal conversion methods

    SciTech Connect

    Stock, L.M.

    1990-01-01

    This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

  2. Mechanistic analysis of the immunomodulatory effects of a catalytic antioxidant on antigen-presenting cells: implication for their use in targeting oxidation-reduction reactions in innate immunity.

    PubMed

    Tse, Hubert M; Milton, Martha J; Piganelli, Jon D

    2004-01-15

    Reactive oxygen species (ROS) have an indispensable role in controlling the growth of pathogens. Recent evidence also suggests that they can function as second messengers and modulators of the immune system. The identification of many redox-sensitive signal transduction pathways that are necessary for initiating the innate proinflammatory immune response suggests that modulation of these oxidation-reduction reactions may provide a means of therapeutic benefit for controlling inflammatory-mediated diseases. In order to test this hypothesis we employed two catalytic antioxidants (AEOL 10113 and 10150) for the determination of the role of oxidation-reduction reactions in innate immune system activation. Catalytic antioxidants prevented the initiation of the innate immune response in LPS-stimulated macrophages as evidenced by the suppression of proinflammatory cytokines (TNF-alpha, IL-1beta) and ROS (NO2- and O2-). The suppression of proinflammatory cytokine and ROS production correlated with the inhibition of NF-kappaB DNA binding, without any effects on the mitogen-activated protein kinase signaling pathway. Catalytic antioxidants prevented NF-kappaB from binding DNA by an oxidation mechanism that was reversible with the addition of DTT. Although the primary use of these agents was to reduce and scavenge ROS, surprisingly, we also observed the ability of these compounds to exhibit oxidoreductase activity and oxidize redox-sensitive transcription factors such as NF-kappaB. Catalytic antioxidants exhibit antioxidant and pro-oxidant activities and our data further demonstrate the importance of redox balance for the initiation of proinflammation. The coupling of the innate with the adaptive immune response is dependent on TNF-alpha, IL-1beta, NO2-, and O2- generation; therefore, agents like catalytic antioxidants that decrease proinflammatory cytokines and ROS may provide protective effects in diseases in which chronic inflammation plays a pathogenic role.

  3. Probing the correlations between the defects in metal-organic frameworks and their catalytic activity by an epoxide ring-opening reaction.

    PubMed

    Liu, Yangyang; Klet, Rachel C; Hupp, Joseph T; Farha, Omar

    2016-06-14

    Seven Zr/Hf-based MOFs with different degrees of defects were obtained by modulating the synthetic conditions. The number of missing linkers in these MOFs was calculated based on potentiometric acid-base titration. The number of defects was found to correlate quantitatively with the catalytic activity of UiO-type MOFs for an acid-catalyzed epoxide ring-opening reaction. More importantly, we were able to identify a MOF with inherent defective Zr6 nodes, which showed great activity and regio-selectivity for the epoxide ring-opening reaction. PMID:27229848

  4. Regioselectively N-methylated azacalix[8]arene octamethyl ether prepared by catalytic aryl amination reaction using a temporal N-silylation protocol.

    PubMed

    Ishibashi, Koichi; Tsue, Hirohito; Tokita, Satoshi; Matsui, Kazuhiro; Takahashi, Hiroki; Tamura, Rui

    2006-12-21

    [Structure: see text] A temporal N-silylation protocol in the catalytic aryl amination reaction has been devised to prepare nitrogen-bridged calixarene analogues. The protocol involves a smooth in situ N-silylation before aryl amination reaction, followed by spontaneous cleavage of the N-Si bond in the usual workup process, to furnish secondary aromatic amines as the cross-coupled product with no silyl group on the nitrogen atom. A successful application to the preparation of regioselectively N-methylated azacalix[8]arene is described, together with the crystallographic analysis.

  5. Alpha resonant scattering for astrophysical reaction studies

    NASA Astrophysics Data System (ADS)

    Yamaguchi, H.; Kahl, D.; Nakao, T.; Wakabayashi, Y.; Kubano, S.; Hashimoto, T.; Hayakawa, S.; Kawabata, T.; Iwasa, N.; Teranishi, T.; Kwon, Y. K.; Binh, D. N.; Khiem, L. H.; Duy, N. G.

    2014-05-01

    Several alpha-induced astrophysical reactions have been studied at CRIB (CNS Radioactive Ion Beam separator), which is a low-energy RI beam separator at Center for Nuclear Study (CNS) of the University of Tokyo. One of the methods to study them is the α resonant scattering using the thick-target method in inverse kinematics. Among the recent studies at CRIB, the measurement of 7Be+α resonant scattering is discussed. Based on the result of the experiment, we evaluated the contributions of high-lying resonances for the 7Be(α,γ) reaction, and proposed a new cluster band in 11C.

  6. Alpha resonant scattering for astrophysical reaction studies

    SciTech Connect

    Yamaguchi, H.; Kahl, D.; Nakao, T.; Wakabayashi, Y.; Kubano, S.; Hashimoto, T.; Hayakawa, S.; Kawabata, T.; Iwasa, N.; Teranishi, T.; Kwon, Y. K.; Binh, D. N.; Khiem, L. H.; Duy, N. G.

    2014-05-02

    Several alpha-induced astrophysical reactions have been studied at CRIB (CNS Radioactive Ion Beam separator), which is a low-energy RI beam separator at Center for Nuclear Study (CNS) of the University of Tokyo. One of the methods to study them is the α resonant scattering using the thick-target method in inverse kinematics. Among the recent studies at CRIB, the measurement of {sup 7}Be+α resonant scattering is discussed. Based on the result of the experiment, we evaluated the contributions of high-lying resonances for the {sup 7}Be(α,γ) reaction, and proposed a new cluster band in {sup 11}C.

  7. Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes.

    PubMed

    Coombs, John R; Morken, James P

    2016-02-18

    Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis. PMID:26764019

  8. Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes.

    PubMed

    Coombs, John R; Morken, James P

    2016-02-18

    Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis.

  9. A QM/MM study of the catalytic mechanism of nicotinamidase.

    PubMed

    Sheng, Xiang; Liu, Yongjun

    2014-02-28

    Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications. PMID:24413890

  10. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism.

    PubMed

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-09-13

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg(2+)-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C-O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

  11. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    PubMed Central

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-01-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface. PMID:27619990

  12. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    NASA Astrophysics Data System (ADS)

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-09-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

  13. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism.

    PubMed

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-01-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg(2+)-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C-O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface. PMID:27619990

  14. Theoretical studies of chemical reaction dynamics

    SciTech Connect

    Schatz, G.C.

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  15. Heterogeneous reactions in a stratospheric box model: A sensitivity study

    NASA Astrophysics Data System (ADS)

    Danilin, Michael Y.; McConnell, John C.

    1994-12-01

    Recent laboratory data concerning the reactions of HCl and HOx on/in sulfuric acid aerosol (Hanson et al., 1994), N2O5 and ClONO2 hydrolysis on the frozen aerosol (Hanson and Ravishankara, 1993a) and the temperature dependence of the HNO3 absorption cross section (Burkholder et al., 1993) indicate that a reevaluation of the role of heterogeneous reactions in the chemical balance of the stratosphere is required. A chemical module prepared for a three-dimensional (3-D) global chemistry transport model (CTM) and a general circulation model (GCM) has been used to carry out a sensitivity study of the effects of heterogeneous reactions on/in the sulfate aerosol and on the polar stratospheric cloud (PSC) particles. We present here results for the latitudes 60°S, 70°S and 75°S at the 50-mbar level. Our findings indicate that (1) the new values of the HNO3 cross sections result in lower mixing ratios for NOx and make ozone more vulnerable to catalytic destruction by ClOx; (2) the effect of the heterogeneous reactions OH + HNO3(a) → H2O + NO3 and HO2 +HO2(a) → H2O2 + O2 are small in comparison with the same gas phase reactions and play a negligible role for the ozone balance; (3) the HCl reactions in the sulfuric acid aerosol at 60°S and 70°S increase the chlorine activation up to 0.53 parts per billion by volume (ppbv) and 0.72 ppbv, respectively, for liquid aerosol and up to 0.87 ppbv for frozen aerosol at 70°S for volcanic conditions and this results in considerable ozone depletion at these latitudes; (4) studying the ozone "hole" phenomenon, we have considered the different initial ratios of ClONO2/HCl, of N2O5, galactic cosmic rays (GCRs), and longer lifetimes for the PSC. We have speculated an existence of the reaction N2O5 + HCl(a) → ClNO2 + HNO3.

  16. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    DOE PAGESBeta

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; et al

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs).more » Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.« less

  17. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    SciTech Connect

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; Adzic, Radoslav R.

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs). Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.

  18. Catalytic anisotropy of MoO/sub 3/ in oxidation reactions in the light of bond-strength model of active sites

    SciTech Connect

    Ziolkowski, J.

    1983-04-01

    Catalytic anisotropy of molybdic oxide in oxidation of propylene has been observed. High selectivity to acrolein in the indicated reaction was ascribed to the (100) plane while the (010) plane was found to yield CO/sub 2/. The critical discussion of Volta's experimental data, performed in this paper, has shown that they may be interpreted in three alternative ways, differing in the ascription of the reaction products to the crystallographic planes. Different crystallographic planes exposed by the grains of MoO/sub 3/ have been analyzed in terms of the bond-strength model of active sites developed under the following main assumptions: (i) the reaction path depends on the number and configuration of the active oxygen atoms in the vicinity of the adsorption site, and (ii) the individual catalytic activity of a given surface oxygen atom is proportional to the reciprocal sum of the strength of the bonds to it from the adjacent cations. The analysis provided the arguments to indicate the most probable reaction pattern. According to it the main products expected to be formed in oxidation of propylene on different planes of MoO/sub 3/ are (100), CO, CO/sub 2/; (001), acrolein (acrylic acid, C/sub 2/-O, CO, CO/sub 2/--mainly at longer contact time); (101) and (101), acrolein; (010), inactive (possible minor yield of hexadiene and benzene).

  19. Response of a catalytic reaction to periodic variation of the CO pressure: increased CO2 production and dynamic phase transition.

    PubMed

    Machado, Erik; Buendía, Gloria M; Rikvold, Per Arne; Ziff, Robert M

    2005-01-01

    We present a kinetic Monte Carlo study of the dynamical response of a Ziff-Gulari-Barshad model for CO oxidation with CO desorption to periodic variation of the CO pressure. We use a square-wave periodic pressure variation with parameters that can be tuned to enhance the catalytic activity. We produce evidence that, below a critical value of the desorption rate, the driven system undergoes a dynamic phase transition between a CO2 productive phase and a nonproductive one at a critical value of the period and waveform of the pressure oscillation. At the dynamic phase transition the period-averaged CO2 production rate is significantly increased and can be used as a dynamic order parameter. We perform a finite-size scaling analysis that indicates the existence of power-law singularities for the order parameter and its fluctuations, yielding estimated critical exponent ratios beta/nu approximately 0.12 and gamma/nu approximately 1.77. These exponent ratios, together with theoretical symmetry arguments and numerical data for the fourth-order cumulant associated with the transition, give reasonable support for the hypothesis that the observed nonequilibrium dynamic phase transition is in the same universality class as the two-dimensional equilibrium Ising model.

  20. EPR Spectroscopy of catalytic systems based on nickel complexes of 1,4-diaza-1,3-butadiene (α-diimine) ligands in hydrogenation and polymerization reactions

    NASA Astrophysics Data System (ADS)

    Titova, Yu. Yu.; Belykh, L. B.; Schmidt, F. K.

    2015-01-01

    EPR spectroscopy is used to study catalytic hydration and polymerization reaction systems based on α-diimine complexes of Ni(0) and Ni(II) with the general formula NiBr2(DAD-R) (R = -C3H7 or -CH3) or Ni(DAD-CH3)2 (DAD(-C3H7) = 1,4-bis(2,6-diiso-propylphenyl)-2,3-(dimethyl-1,4-diazabuta-1,3-diene, DAD(-CH3) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene)), in combination with Lewis acids (AlEt3, AlEt2Cl, AlEtCl2, B(F5C6)3, BF3.OEt2). Ni(I) complexes of the form (DAD-R)NiX2AlX'y(C2H5)3-y composition (an aluminum atom can be replaced by a boron atom) were identified, where R = -CH3 or -C3H7, X = Br, and X' = Cl or -C2H5 and α-diimine anion radicals are included in derivatives of aluminum or boron. Oxidation reactions of the Ni(DAD-CH3)2 complex with aluminum alkyl halides and boron derivatives with formation of paramagnetic nickel complexes are observed. It is found that there is no direct relationship between the polymerization activity of ethylene or hydration of the alkenes and the concentration of paramagnetic particles.

  1. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    DOE PAGESBeta

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; et al

    2016-05-18

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has amore » sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.« less

  2. Catalytic deactivation on methane steam reforming catalysts. 2. Kinetic study

    SciTech Connect

    Agnelli, M.E.; Ponzi, E.N.; Yeramian, A.A.

    1987-08-01

    The kinetics of methane steam reforming reaction over an alumina-supported nickel catalyst was investigated at a temperature range of 640-740/sup 0/C in a flow reactor at atmospheric pressure. The experiments were performed varying the inlet concentration of methane, hydrogen, and water. A kinetic scheme of the Houghen-Watson type was satisfactorily proposed assuming the dissociative adsorption of CH/sub 4/ as the rate-limiting step, but this kinetic scheme can be easily replaced by a first-order kinetics (r/sub CH/4/sub / = kapparho/sub CH/4/sub /) for engineering purposes. Catalyst activation with H/sub 2/ and N/sub 2/ mixtures or with the reactant mixture results in the same extent of reaction.

  3. Theoretical study of stabilities, electronic, and catalytic performance of supported platinum on modified graphene

    NASA Astrophysics Data System (ADS)

    Hongwei, Tian; Wei, Feng; Rui, Wang; Huiling, Liu; Xuri, Huang

    2015-11-01

    The geometry, electronic structure, and catalytic properties for CO oxidation of Pt atom supported on pri-graphene (PG), Haeckelite (H), and Stone-Wales-defect-graphene are investigated by density functional theory (DFT) calculations. In contrast to a Pt atom on PG, defective graphene, especially the Haeckelite, strongly stabilises the Pt atom and makes it more positive and thus the CO poisoning. At the same time the catalytic activities are as high as the pristine one. Langmuir-Hinshelwood mechanisms are favoured as the starting state and are followed by the Eley-Rideal reaction. The results indicate the benefit of Haeckelite as a substrate for the Pt atom and validate the reactivity of catalysts on the atomic scale with low cost and high activity.

  4. Environmentally-benign catalysts for the selective catalytic reduction of NO(x) from diesel engines: structure-activity relationship and reaction mechanism aspects.

    PubMed

    Liu, Fudong; Yu, Yunbo; He, Hong

    2014-08-11

    Selective catalytic reduction of NOx using NH3 or hydrocarbons (NH3-SCR or HC-SCR) in oxygen-rich exhaust from diesel engines remains a major challenge in environmental catalysis. The development of highly efficient, stable and environmentally-benign catalysts for SCR processes is very important for practical use. In this feature article, the structure-activity relationship of vanadium-free catalysts in the NH3-SCR reaction is discussed in detail, including Fe-, Ce-based oxide catalysts and Fe-, Cu-based zeolite catalysts, which is beneficial for catalyst redesign and activity improvement. Based on our research, a comprehensive mechanism contributing to the performance of Ag/Al2O3 in HC-SCR is provided, giving a clue to the design of a catalytic system with high efficiency.

  5. A highly selective nanogold-aptamer catalytic resonance scattering spectral assay for trace Hg(2+) using HAuCl(4)-ascorbic acid as indicator reaction.

    PubMed

    Jiang, Zhiliang; Wen, Guiqing; Fan, Yanyan; Jiang, Caina; Liu, Qingye; Huang, Zhi; Liang, Aihui

    2010-01-15

    Single strand DNA (ssDNA) was used to modify nanogold to obtain a nanogold-aptamer resonance scattering (RS) probe (NGssDNA) for Hg(2+), based on the formation of stable thymine-Hg(2+)-thymine (T-Hg(2+)-T) mismatches and aggregation of the released nanogold particles. After removing the aggregated particles by filtrate membrane, the excess NGssDNA in the filtration solution exhibit catalytic effect on the gold particle reaction between HAuCl(4) and ascorbic acid (AA) that appear as RS peak at 596nm. When Hg(2+) concentration increased, the RS intensity at 596nm decreased. The decreased intensity is linear to Hg(2+) concentration in the range of 0.00008-0.888ng/mL Hg(2+), with detection limit of 0.000034ng/mL. The nanogold-aptamer catalytic RS assay was applied to determination of Hg(2+) in water with satisfactory results.

  6. Cyclopentadienyl nickel(ii) N,C-chelating benzothiazolyl NHC complexes: synthesis, characterization and application in catalytic C-C bond formation reactions.

    PubMed

    Teo, Wei Jie; Wang, Zhe; Xue, Fei; Andy Hor, T S; Zhao, Jin

    2016-04-25

    Cyclopentadienyl (Cp) Ni(ii) complexes [CpNiL][PF6] containing hybrid N,C chelating benzothiazolyl NHC ligands (L1 = 1-(2-benzothiazolyl)-3-methylimidazol-2-ylidene, ; L2 = 1-(2-benzothiazolyl)-3-allylimidazol-2-ylidene, ; L3 = 1-(2-benzothiazolyl)-3-benzylimidazol-2-ylidene, ) have been synthesized and fully characterized. The catalytic activity of in some C-C bond formation reactions has been examined. They are efficient catalysts for the homo-coupling of benzyl bromide in the presence of MeMgCl at r.t. with good functional group tolerance. Complex is active in the catalytic oxidative homo-coupling of Grignard reagents with 1,2-dichloroethane as an oxidant at r.t. PMID:27011227

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

    PubMed

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

    2001-09-15

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

  8. Catalytic distillation process

    DOEpatents

    Smith, Jr., Lawrence A.

    1982-01-01

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

  9. Catalytic distillation process

    DOEpatents

    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.

  10. Theoretical study of catalytic mechanism for single-site water oxidation process

    PubMed Central

    Lin, Xiangsong; Hu, Xiangqian; Concepcion, Javier J.; Chen, Zuofeng; Liu, Shubin; Meyer, Thomas J.; Yang, Weitao

    2012-01-01

    Water oxidation is a linchpin in solar fuels formation, and catalysis by single-site ruthenium complexes has generated significant interest in this area. Combining several theoretical tools, we have studied the entire catalytic cycle of water oxidation for a single-site catalyst starting with [RuII(tpy)(bpm)(OH2)]2+ (i.e., [RuII-OH2]2+; tpy is 2,2′∶6′,2′′-terpyridine and bpm is 2,2′-bypyrimidine) as a representative example of a new class of single-site catalysts. The redox potentials and pKa calculations for the first two proton-coupled electron transfers (PCETs) from [RuII-OH2]2+ to [RuIV = O]2+ and the following electron-transfer process to [RuV = O]3+ suggest that these processes can proceed readily in acidic or weakly basic conditions. The subsequent water splitting process involves two water molecules, [RuV = O]3+ to generate [RuIII-OOH]2+, and H3O+ with a low activation barrier (∼10 kcal/mol). After the key O---O bond forming step in the single-site Ru catalysis, another PECT process oxidizes [RuIII-OOH]2+ to [RuIV-OO]2+ when the pH is lower than 3.7. Two possible forms of [RuIV-OO]2+, open and closed, can exist and interconvert with a low activation barrier (< 7 kcal/mol) due to strong spin-orbital coupling effects. In Pathway 1 at pH = 1.0, oxygen release is rate-limiting with an activation barrier ∼12 kcal/mol while the electron-transfer step from [RuIV-OO]2+ to [RuV - OO]3+ becomes rate-determining at pH = 0 (Pathway 2) with Ce(IV) as oxidant. The results of these theoretical studies with atomistic details have revealed subtle details of reaction mechanisms at several stages during the catalytic cycle. This understanding is helpful in the design of new catalysts for water oxidation. PMID:22615356

  11. Asymmetric Catalytic Enantio- and Diastereoselective Boron Conjugate Addition Reactions of α-Functionalized α,β-Unsaturated Carbonyl Substrates.

    PubMed

    Xie, Jian-Bo; Lin, Siqi; Qiao, Shuo; Li, Guigen

    2016-08-01

    An efficient catalytic system has been established for the asymmetric boron conjugate addition of B2pin2 onto α-functionalized (involving C, N, O, and Cl) α,β-unsaturated carbonyls under mild, neutral conditions involving Cu[(S)-(R)-ppfa]Cl, AgNTf2, and alcohols. The dual additives of AgNTf2 and alcohols were found to play crucial roles for achieving high catalytic activity and enantio- and diastereoselectivity (up to 98% ee and 70:1 dr).

  12. Direct Catalytic Asymmetric Mannich Reaction with Dithiomalonates as Excellent Mannich Donors: Organocatalytic Synthesis of (R)-Sitagliptin.

    PubMed

    Bae, Han Yong; Kim, Mun Jong; Sim, Jae Hun; Song, Choong Eui

    2016-08-26

    In this study, dithiomalonates (DTMs) were demonstrated to be exceptionally efficient Mannich donors in terms of reactivity and stereoselectivity in cinchona-based-squaramide-catalyzed enantioselective Mannich reactions of diverse imines or α-amidosulfones as imine surrogates. Owing to the superior reactivity of DTMs as compared to conventional malonates, the catalyst loading could be reduced to 0.1 mol % without the erosion of enantioselectivity (up to 99 % ee). Furthermore, by the use of a DTM, even some highly challenging primary alkyl α-amidosulfones were smoothly converted into the desired adducts with excellent enantioselectivity (up to 97 % ee), whereas the use of a malonate or monothiomalonate resulted in no reaction under identical conditions. The synthetic utility of the chiral Mannich adducts obtained from primary alkyl substrates was highlighted by the organocatalytic, coupling-reagent-free synthesis of the antidiabetic drug (-)-(R)-sitagliptin. PMID:27486059

  13. Comparison of the catalytic activity for the Suzuki-Miyaura reaction of (η(5)-Cp)Pd(IPr)Cl with (η(3)-cinnamyl)Pd(IPr)(Cl) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl).

    PubMed

    Melvin, Patrick R; Hazari, Nilay; Lant, Hannah M C; Peczak, Ian L; Shah, Hemali P

    2015-01-01

    Complexes of the type (η(3)-allyl)Pd(L)(Cl) and (η(3)-indenyl)Pd(L)(Cl) are highly active precatalysts for the Suzuki-Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η(5)-Cp)Pd(L)(Cl) for Suzuki-Miyaura reactions. Here, we compare the catalytic activity of (η(5)-Cp)Pd(IPr)(Cl) (IPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene, Cp) with two commercially available catalysts (η(3)-cinnamyl)Pd(IPr)(Cl) (Cin) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl) ( (tBu) Ind). We show that Cp gives slightly better catalytic activity than Cin, but significantly inferior activity than (tBu) Ind. This order of activity is rationalized by comparing the rates at which the precatalysts are activated to the monoligated Pd(0) active species along with the tendency of the starting precatalysts to comproportionate with monoligated Pd(0) to form inactive Pd(I) dimers. As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (Cp (Dim) ) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently Cp (Dim) is a poor catalyst for the Suzuki-Miyaura reaction.

  14. Steam reformer with catalytic combustor

    DOEpatents

    Voecks, Gerald E.

    1990-03-20

    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.

  15. Steam reformer with catalytic combustor

    NASA Technical Reports Server (NTRS)

    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.

  16. Auto-combustion synthesis, Mössbauer study and catalytic properties of copper-manganese ferrites

    NASA Astrophysics Data System (ADS)

    Velinov, N.; Petrova, T.; Tsoncheva, T.; Genova, I.; Koleva, K.; Kovacheva, D.; Mitov, I.

    2016-12-01

    Spinel ferrites with nominal composition Cu 0.5Mn 0.5Fe 2 O 4 and different distribution of the ions are obtained by auto-combustion method. Mössbauer spectroscopy, X-ray Diffraction, Thermogravimetry-Differential Scanning Calorimetry, Scanning Electron Microscopy and catalytic test in the reaction of methanol decomposition is used for characterization of synthesized materials. The spectral results evidence that the phase composition, microstructure of the synthesized materials and the cation distribution depend on the preparation conditions. Varying the pH of the initial solution microstructure, ferrite crystallite size, cation oxidation state and distribution of ions in the in the spinel structure could be controlled. The catalytic behaviour of ferrites in the reaction of methanol decomposition also depends on the pH of the initial solution. Reduction transformations of mixed ferrites accompanied with the formation of Hägg carbide χ-Fe 5 C 2 were observed by the influence of the reaction medium.

  17. Study on the thermal deactivation of motorcycle catalytic converters by laboratory aging tests.

    PubMed

    Chen, Yi-Chi; Chen, Lu-Yen; Yu, Yi-Hsien; Jeng, Fu-Tien

    2010-03-01

    Catalytic converters are used to curb exhaust pollution from motorcycles in Taiwan. A number of factors, including the length of time the converter is used for and driving conditions, affect the catalysts' properties during periods of use. The goal of this study is to resolve the thermal deactivation mechanism of motorcycle catalytic converters. Fresh catalysts were treated under different aging conditions by laboratory-scale aging tests to simulate the operation conditions of motorcycle catalytic converters. The aged catalysts were characterized by analytical techniques in order to provide information for investigating deactivation phenomena. The time-dependent data of specific surface areas were subsequently used to construct kinetics of sintering at the specific temperature. According to the analytical results of the catalysts' properties, the increase in aging temperature causes an increase in pore size of the catalysts and a decrease in the specific surface area. The aged catalysts all exhibited lower performances than the fresh ones. The reduction in catalytic activity is consistent with the reduction in the loss of specific surface area. The finding of catalytic properties' dependence on temperature is consistent with the thermally activated theory. In contrast, the effect of the aging time on the specific surface area was only significant during the initial few hours. The high correlation between specific surface areas measured by the Brunauer-Emmett-Teller (BET) method and predicted by the constructed model verifies that the prediction models can predict the sintering rate reasonably under the aging conditions discussed in this study. As compared to automobile catalytic converters, the differences of structures and aging conditions are made less obvious by the deactivation phenomena of motorcycles.

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

    SciTech Connect

    Xu, Ling; Wang, Chunhua; Guan, Jingqi

    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.

  19. Study on catalysis effect of TEPB on the curing reaction of HTPB binder system

    NASA Astrophysics Data System (ADS)

    Chang, S. J.; Tang, J.; Liu, X.; Yan, W.

    2016-07-01

    The catalysis effect of tri (exhoxyphenyl) bismuthine (TEPB) on the curing reaction of HTPB binder system was studied by using DSC method. The curing peak temperatures of the catalyst systems were measured to calculate kinetic parameters by using Kissinger and Crane methods, respectively. Two curing reaction kinetic equations were established. The results show that TEPB has high catalytic activity and can decrease the curing temperature of HTPB binder system, down to 35 °C, in which the optimum volume of TEPB is 0.5% of HTPB binder system.

  20. Numerical study of influence of surface reaction and heat-loss on flame intensity of methane-air flames

    NASA Astrophysics Data System (ADS)

    Hayashi, N.; Yamashita, H.

    2014-11-01

    This paper reports a numerical study of influence of radical quenching and heat loss on bulk flame characteristics in narrow parallel channels. Flame-wall interaction is an important phenomenon on combustors. Especially, the wall effects on the flame characteristics in a small scale combustor become larger than those on normal scale one. The wall effects are caused by heat loss and surface reaction. The surface reaction on many common non-catalytic materials may weaken or quench the flames, although those for a catalytic wall can strengthen the flames. Authors have investigated the influence of the surface reaction and the heat loss on a noncatalytic wall using numerical simulation. In this study, a two-dimensional slit burner between two parallel plates with or without surface reaction is modelled. The wall temperature is 500 and 1200 K. The flame behavior and heat release rate distributions are examined when the distance between two plates is changed.

  1. Catalytic oxidation of propylene--6. Mechanistic studies utilizing isotopic tracers

    SciTech Connect

    Krenzke, L.D.; Keulks, G.W.

    1980-02-01

    The oxidation of deuterated propylene with oxygen and of propylene with oxygen-18 on well-characterized Bi/sub 2/Mo/sub 3/O/sub 12/, Bi/sub 2/MoO/sub 6/, and Bi/sub 3/FeMo/sub 2/O/sub 12/ catalysts at 350/sup 0/-450/sup 0/C revealed that acrolein formed only by the redox mechanism and not by the peroxide mechanism on the catalysts tested. Carbon dioxide formed only by consecutive oxidation of acrolein on the two bismuth molybdate catalysts and its formation involved only lattice oxygen, but on the bismuth iron molybdate, carbon dioxide formed by parallel and consecutive reactions involving adsorbed and lattice oxygen. The rate-determining step of acrolein production on all three catalysts was the formation of an allylic species by abstraction of a methyl hydrogen from propylene.

  2. Molecular beam studies of reaction dynamics

    SciTech Connect

    Lee, Y.T.

    1993-12-01

    The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.

  3. A theoretical study on the reaction of ozone with aqueous iodide.

    PubMed

    Gálvez, Óscar; Baeza-Romero, M Teresa; Sanz, Mikel; Pacios, Luis F

    2016-03-21

    Atmospheric iodine chemistry plays a key role in tropospheric ozone catalytic destruction, new particle formation, and as one of the possible sinks of gaseous polar elemental mercury. Moreover, it has been recently proposed that reaction of ozone with iodide on the sea surface could be the major contributor to the chemical loss of atmospheric ozone. However, the mechanism of the reaction between aqueous iodide and ozone is not well known. The aim of this paper is to improve the understanding of such a mechanism. In this paper, an ab initio study of the reaction of aqueous iodide and ozone is presented, evaluating thermodynamic data of the different reactions proposed in previous experimental studies. In addition, the structures, energetics and possible evolution of the key IOOO(-) intermediate are discussed for the first time.

  4. A theoretical study on the reaction of ozone with aqueous iodide.

    PubMed

    Gálvez, Óscar; Baeza-Romero, M Teresa; Sanz, Mikel; Pacios, Luis F

    2016-03-21

    Atmospheric iodine chemistry plays a key role in tropospheric ozone catalytic destruction, new particle formation, and as one of the possible sinks of gaseous polar elemental mercury. Moreover, it has been recently proposed that reaction of ozone with iodide on the sea surface could be the major contributor to the chemical loss of atmospheric ozone. However, the mechanism of the reaction between aqueous iodide and ozone is not well known. The aim of this paper is to improve the understanding of such a mechanism. In this paper, an ab initio study of the reaction of aqueous iodide and ozone is presented, evaluating thermodynamic data of the different reactions proposed in previous experimental studies. In addition, the structures, energetics and possible evolution of the key IOOO(-) intermediate are discussed for the first time. PMID:26906609

  5. Influence of sp(3)-sp(2) Carbon Nanodomains on Metal/Support Interaction, Catalyst Durability, and Catalytic Activity for the Oxygen Reduction Reaction.

    PubMed

    Campos-Roldán, Carlos A; Ramos-Sánchez, Guadalupe; Gonzalez-Huerta, Rosa G; Vargas García, Jorge R; Balbuena, Perla B; Alonso-Vante, Nicolas

    2016-09-01

    In this work, platinum nanoparticles were impregnated by two different techniques, namely the carbonyl chemical route and photodeposition, onto systematically surface-modified multiwalled carbon nanotubes. The different interactions between platinum nanoparticles with sp(2)-sp(3) carbon nanodomains were investigated. The oxidation of an adsorbed monolayer of carbon monoxide, used to probe electronic catalytic modification, suggests a selective nucleation of platinum nanoparticles onto sp(2) carbon nanodomains when photodeposition synthesis is carried out. XPS attests the catalytic center electronic modification obtained by photodeposition. DFT calculations were used to determine the interaction energy of a Pt cluster with sp(2) and sp(3) carbon surfaces as well as with oxidized ones. The interaction energy and electronic structure of the platinum cluster presents dramatic changes as a function of the support surface chemistry, which also modifies its catalytic properties evaluated by the interaction with CO. The interaction energy was calculated to be 8-fold higher on sp(3) and oxidized surfaces in comparison to sp(2) domains. Accelerated Stability Test (AST) was applied only on the electronic-modified materials to evaluate the active phase degradation and their activity toward oxygen reduction reaction (ORR). The stability of photodeposited materials is correlated with the surface chemical nature of supports indicating that platinum nanoparticles supported onto multiwalled carbon nanotubes with the highest sp(2) character show the higher stability and activity toward ORR. PMID:27494283

  6. Influence of sp(3)-sp(2) Carbon Nanodomains on Metal/Support Interaction, Catalyst Durability, and Catalytic Activity for the Oxygen Reduction Reaction.

    PubMed

    Campos-Roldán, Carlos A; Ramos-Sánchez, Guadalupe; Gonzalez-Huerta, Rosa G; Vargas García, Jorge R; Balbuena, Perla B; Alonso-Vante, Nicolas

    2016-09-01

    In this work, platinum nanoparticles were impregnated by two different techniques, namely the carbonyl chemical route and photodeposition, onto systematically surface-modified multiwalled carbon nanotubes. The different interactions between platinum nanoparticles with sp(2)-sp(3) carbon nanodomains were investigated. The oxidation of an adsorbed monolayer of carbon monoxide, used to probe electronic catalytic modification, suggests a selective nucleation of platinum nanoparticles onto sp(2) carbon nanodomains when photodeposition synthesis is carried out. XPS attests the catalytic center electronic modification obtained by photodeposition. DFT calculations were used to determine the interaction energy of a Pt cluster with sp(2) and sp(3) carbon surfaces as well as with oxidized ones. The interaction energy and electronic structure of the platinum cluster presents dramatic changes as a function of the support surface chemistry, which also modifies its catalytic properties evaluated by the interaction with CO. The interaction energy was calculated to be 8-fold higher on sp(3) and oxidized surfaces in comparison to sp(2) domains. Accelerated Stability Test (AST) was applied only on the electronic-modified materials to evaluate the active phase degradation and their activity toward oxygen reduction reaction (ORR). The stability of photodeposited materials is correlated with the surface chemical nature of supports indicating that platinum nanoparticles supported onto multiwalled carbon nanotubes with the highest sp(2) character show the higher stability and activity toward ORR.

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

    SciTech Connect

    Contreras, Anthony Marshall

    2006-05-20

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

  8. Silver nanocluster catalytic microreactors for water purification

    NASA Astrophysics Data System (ADS)

    Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.

    2016-07-01

    A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.

  9. Catalysis and Multi-Component Reactions

    NASA Astrophysics Data System (ADS)

    Shibasaki, Masakatsu; Yus, Miguel; Bremner, Stacy; Comer, Eamon; Shore, Gjergji; Morin, Sylvie; Organ, Michael G.; van der Eycken, Erik; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Ryabukhin, Sergey V.; Ostapchuk, Eugeniy N.; Plaskon, Andrey S.; Volochnyuk, Dmitriy M.; Shivanyuk, Alexander N.; Tolmachev, Andrey A.; Sheibani, Hassan; Babaie, Maryam; Behzadi, Soheila; Dabiri, Minoo; Bahramnejad, Mahboobeh; Bashiribod, Sahareh; Hekmatshoar, Rahim; Sadjadi, Sodeh; Khorasani, Mohammad; Polyakov, Anatoliy I.; Eryomina, Vera A.; Medvedeva, Lidiya A.; Tihonova, Nadezhda I.; Listratova, Anna V.; Voskressensky, Leonid G.; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Sheibani, Hassan; Esfandiarpoor, Zeinab; Behzadi, Soheila; Titova, Julia A.; Fedorova, Olga V.; Ovchinnikova, Irina G.; Valova, Marina S.; Koryakova, Olga V.; Rusinov, Gennady L.; Charushin, Valery N.; Hekmatshoar, Rahim; Sadjadi, Sodeh

    We have been studying the development of new asymmetric two-center catalysis using rare earth alkoxides and bifunctional sugar and related ligands. In The Fourth International Conference on Multi-Component Reactions and Related Chemistry (MCR 2009), new catalytic asymmetric reactions using catalysts 1 and 2 and catalytic asymmetric syntheses of ranirestat 3 and tamiflu 4 will be presented.

  10. Theoretical Study of OH Reaction with Toluene

    NASA Astrophysics Data System (ADS)

    Suh, I.; Zhang, D.; Zhang, R.; Molina, L. T.; Molina, M. J.

    2001-12-01

    Aromatic hydrocarbons constitute a major faction of total volatile organic compounds (VOCs) in the urban and regional atmosphere, and are emitted primarily from anthropogenic sources, i.e. emission from automobiles, fuel-based vehicles, and industry. In addition to their important role in gas-phase chemistry of urban air pollution, oxidation of aromatic hydrocarbons leads to formation of various non-volatile and semi-volatile organic compounds, which are responsible for the formation of secondary organic aerosols. Toluene is the most abundant aromatic hydrocarbon. Reactions of toluene in the atmosphere are mainly initiated by attack from hydroxyl radical OH. In this study, we report a theoretical study of the reaction of toluene with OH. Density functional theory (DFT) and ab initio calculations have been employed to investigate the OH-toluene adduct isomers. The geometries and energetics of the four isomers of the OH-toluene adduct radicals as well as their corresponding transition states are presented. The DFT and ab initio theories applicable to the OH-toluene reaction system are evaluated. We also present calculations of the rate constants and isomeric branching ratios of the formation of the OH-toluene adduct isomers.

  11. A General Catalytic Enantioselective Transfer Hydrogenation Reaction of β,β-Disubstituted Nitroalkenes Promoted by a Simple Organocatalyst.

    PubMed

    Bernardi, Luca; Fochi, Mariafrancesca

    2016-01-01

    Given its synthetic relevance, the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes has received a great deal of attention. Several bio-, metal-, and organo-catalytic methods have been developed, which however are usually applicable to single classes of nitroalkene substrates. In this paper, we present an account of our previous work on this transformation, which implemented with new disclosures and mechanistic insights results in a very general protocol for nitroalkene reductions. The proposed methodology is characterized by (i) a remarkably broad scope encompassing various nitroalkene classes; (ii) Hantzsch esters as convenient (on a preparative scale) hydrogen surrogates; (iii) a simple and commercially available thiourea as catalyst; (iv) user-friendly procedures. Overall, the proposed protocol gives a practical dimension to the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes, offering a useful and general platform for the preparation of nitroalkanes bearing a stereogenic center at the β-position in a highly enantioenriched form. A transition state model derived from control kinetic experiments combined with literature data is proposed and discussed. This model accounts and justifies the observed experimental results. PMID:27483233

  12. Exploring reaction pathways for O-GlcNAc transferase catalysis. A string method study.

    PubMed

    Kumari, Manju; Kozmon, Stanislav; Kulhánek, Petr; Štepán, Jakub; Tvaroška, Igor; Koča, Jaroslav

    2015-03-26

    The inverting O-GlcNAc glycosyltransferase (OGT) is an important post-translation enzyme, which catalyzes the transfer of N-acetylglucosamine from UDP-N-acetylglucosamine (UDP-GlcNAc) to the hydroxyl group of the Ser/Thr of cytoplasmic, nuclear, and mitochondrial proteins. In the past, three different catalytic bases were proposed for the reaction: His498, α-phosphate, and Asp554. In this study, we used hybrid quantum mechanics/molecular mechanics (QM/MM) Car-Parrinello molecular dynamics to investigate reaction paths using α-phosphate and Asp554 as the catalytic bases. The string method was used to calculate the free-energy reaction profiles of the tested mechanisms. During the investigations, an additional mechanism was observed. In this mechanism, a proton is transferred to α-phosphate via a water molecule. Our calculations show that the mechanism with α-phosphate acting as the base is favorable. This reaction has a rate-limiting free-energy barrier of 23.5 kcal/mol, whereas reactions utilizing Asp554 and water-assisted α-phosphate have barriers of 41.7 and 40.9 kcal/mol, respectively. Our simulations provide a new insight into the catalysis of OGT and may thus guide rational drug design of transition-state analogue inhibitors with potential therapeutic use. PMID:25731954

  13. Exploring reaction pathways for O-GlcNAc transferase catalysis. A string method study.

    PubMed

    Kumari, Manju; Kozmon, Stanislav; Kulhánek, Petr; Štepán, Jakub; Tvaroška, Igor; Koča, Jaroslav

    2015-03-26

    The inverting O-GlcNAc glycosyltransferase (OGT) is an important post-translation enzyme, which catalyzes the transfer of N-acetylglucosamine from UDP-N-acetylglucosamine (UDP-GlcNAc) to the hydroxyl group of the Ser/Thr of cytoplasmic, nuclear, and mitochondrial proteins. In the past, three different catalytic bases were proposed for the reaction: His498, α-phosphate, and Asp554. In this study, we used hybrid quantum mechanics/molecular mechanics (QM/MM) Car-Parrinello molecular dynamics to investigate reaction paths using α-phosphate and Asp554 as the catalytic bases. The string method was used to calculate the free-energy reaction profiles of the tested mechanisms. During the investigations, an additional mechanism was observed. In this mechanism, a proton is transferred to α-phosphate via a water molecule. Our calculations show that the mechanism with α-phosphate acting as the base is favorable. This reaction has a rate-limiting free-energy barrier of 23.5 kcal/mol, whereas reactions utilizing Asp554 and water-assisted α-phosphate have barriers of 41.7 and 40.9 kcal/mol, respectively. Our simulations provide a new insight into the catalysis of OGT and may thus guide rational drug design of transition-state analogue inhibitors with potential therapeutic use.

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

    NASA Astrophysics Data System (ADS)

    Ding, Tao; Wang, Wenliang; Zhou, Xiaoli; Zhang, Li; Wang, Chunde; Jiang, Jun; Yang, Weilai; Yang, Qing

    2016-01-01

    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.

  15. Kinetic-spectrophotometric determination of trace amounts of vanadium(V) based on its catalytic effect on the reaction of DBM-arsenazo and potassium bromate

    NASA Astrophysics Data System (ADS)

    Zhai, Qing-zhou; Zhang, Xiao-xia; Huang, Chong

    2008-03-01

    A simple and sensitive kinetic-spectrophotometric method is developed for the determination of trace vanadium(V), based on the catalytic effect of vanadium(V) on the oxidation of DBM-arsenazo by potassium bromate in 0.0138 mol l -1 phosphoric acid medium and at 100 °C in the presence of citric acid as activator. The absorbance is measured at 528 nm with the fixed-time method. The optimization of the operating conditions regarding concentrations of the reagents, temperature and interferences are also investigated. The working curve is linear over the concentration range 0-20 ng ml -1 of vanadium(V) with good precision and accuracy and the detection limit was down to 3.44 ng l -1. The relative standard deviation for a standard solution of 14 ng ml -1 is 0.28% ( n = 11). The apparent activity energies of the catalytic reaction and the non-catalytic reaction are 73.48, 113.5 kJ/mol, respectively. The proposed method proved highly sensitive, selective and relatively rapid for the assay of vanadium at low-level range of 0-20 ng ml -1 without any pre-concentration step. Thw method was applied to the determination of vanadium(V) in steels, rice, flour, cabbage, potato, fish, shrimp and tea samples with satisfactory results. The obtained results for the steel samples were excellent agreement with the standard reference values. The analytical results of the rice, flour, cabbage, potato, fish, shrimp and tea samples were excellent agreement with those of atomic absorption spectrometry. The recovery experiments have been made for the rice, flour, cabbage, potato, fish, shrimp and tea samples except the steels; excellent results were obtained. The relative standard deviations were over the range of 0.18-2.60% and the recoveries were over the range of 98.00-102.4%, respectively. The analytical results obtained were satisfactory.

  16. Catalytic roles of βLys87 in tryptophan synthase: (15)N solid state NMR studies.

    PubMed

    Caulkins, Bethany G; Yang, Chen; Hilario, Eduardo; Fan, Li; Dunn, Michael F; Mueller, Leonard J

    2015-09-01

    The proposed mechanism for tryptophan synthase shows βLys87 playing multiple catalytic roles: it bonds to the PLP cofactor, activates C4' for nucleophilic attack via a protonated Schiff base nitrogen, and abstracts and returns protons to PLP-bound substrates (i.e. acid-base catalysis). ε-¹⁵N-lysine TS was prepared to access the protonation state of βLys87 using ¹⁵N solid-state nuclear magnetic resonance (SSNMR) spectroscopy for three quasi-stable intermediates along the reaction pathway. These experiments establish that the protonation state of the ε-amino group switches between protonated and neutral states as the β-site undergoes conversion from one intermediate to the next during catalysis, corresponding to mechanistic steps where this lysine residue has been anticipated to play alternating acid and base catalytic roles that help steer reaction specificity in tryptophan synthase catalysis. This article is part of a Special Issue entitled: Cofactor-dependent proteins: evolution, chemical diversity and bio-applications. Guest Editors: Andrea Mozzarelli and Loredano Pollegioni.

  17. Theoretical study of the catalytic CO oxidation by Pt catalyst supported on Ge-doped grapheme.

    PubMed

    Tang, Yanan; Yang, Zongxian; Dai, Xianqi; Lu, Zhansheng; Zhang, Yanxing; Fu, Zhaoming

    2014-09-01

    The geometry, electronic structure and catalytic properties of the anchored Pt atom on the Ge-doped graphene (Pt/Ge-graphene) substrates are investigated using the first-principles computations. It is found that Ge atoms can form strong covalent bonds with the carbon atoms at the vacancy site on the defective graphene. The Ge-graphene as substrate can effectively anchored Pt atoms and form supported Pt catalyst, which exhibits good catalytic activity for CO oxidation with a two-step route, starting with the Langmuir-Hinshelwood (LH) reaction followed by the Eley-Rideal (ER) reaction. The Ge dopant in graphene plays a vital role in enhancing the substrate-adsorbate interaction through facilitating the charge redistribution at their interfaces. The Ge-graphene can be used as the reactive support to control the stability and activity of the Pt catalysts. This work provides valuable guidance on fabricating carbon-based catalysts for CO oxidation, and validates the reactivity of single-atom catalyst for designing atomic-scale catalysts.

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

    PubMed

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

    2016-06-29

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

  19. Synthesis, structures and properties of the catalytic bromination reaction of a series of novel scorperate oxidovanadium complexes with the potential detection of hydrogen peroxide in water

    NASA Astrophysics Data System (ADS)

    Zhang, Rui; Liu, Jing; Chen, Chen; Xing, Yong-Heng; Guan, Qing-Lin; Hou, Ya-Nan; Wang, Xuan; Zhang, Xiao-Xi; Bai, Feng-Ying

    2013-11-01

    A series of scorpionate oxovanadium (IV) complexes: [VO(Tp4I)(pz)(SCN)]·1/2CH2Cl2 (1), [VO(Tp)(pzTp)]·2H2O (2), [VO(Bp)(Tp4I)] (3) and [VO(C5H7O2)(Tp4I)]·CH3OH (4) (Bp: [H2B(pz)2-], Tp: [HB(pz)3-], Tp4I: [HB(4I-pz)3-], pzTp: [B(pz)4-]) have been synthesized and characterized by elemental analysis, IR spectra, UV-Vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and thermal gravimetric analysis (TG). Structural analysis shows that the coordination environment of vanadium atom is N5O, to form a distorted octahedron geometry. In addition, the catalytic activities of the bromination reactions for complexes 1 and 2 in phosphate buffer with phenol red as a trap were evaluated primary by UV/Vis spectroscopy, and a practical application of H2O2 detection was firstly observed in the catalytic reaction system.

  20. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi

    2013-11-01

    Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol-1), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.

  1. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation.

    PubMed

    Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi

    2013-01-01

    Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol(-1)), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.

  2. A novel green one-step synthesis of silver nanoparticles using chitosan: catalytic activity and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Venkatesham, Maragoni; Ayodhya, Dasari; Madhusudhan, Alle; Veera Babu, Nagati; Veerabhadram, Guttena

    2014-01-01

    Stable silver nanoparticles were synthesized using chitosan acting as both reducing and stabilizing agent without using any toxic chemicals. This reaction was carried out in an autoclave at a pressure of 15 psi and 120 °C temperature by varying the time. The influence of different parameters such as time, change of concentration of silver nitrate and concentration of chitosan on the formation of silver nanoparticles were studied. The synthesized silver nanoparticles were characterized by UV-visible spectroscopy, Fourier transform infrared, X-ray diffraction and transmission electron microscopy. The results of catalytic reduction of 4-nitrophenol by sodium borohydride in the presence of green synthesized silver nanoparticles were presented. The antimicrobial activity of silver nanoparticles was tested against Escherichia coli and Micrococcus luteus and was found to be possessing inhibiting property.

  3. Catalytic effect of water, formic acid, or sulfuric acid on the reaction of formaldehyde with OH radicals.

    PubMed

    Zhang, Weichao; Du, Benni; Qin, Zhenglong

    2014-07-01

    In this paper, for the hydrogen abstraction reaction of HCHO by OH radicals assisted by water, formic acid, or sulfur acid, the possible reaction mechanisms and kinetics have been investigated theoretically using quantum chemistry methods and transition-state theory. The potential energy surfaces calculated at the CCSD(T)/6-311++G(df,pd)//MP2(full)/6-311++G(df,pd) levels of theory reveal that, due to the formation of strong hydrogen bond(s), the relative energies of the transition states involving catalyst are significantly reduced compared to that reaction without catalyst. However, the kinetics calculations show that the rate constants are smaller by about 3, 9, or 10 orders of magnitude for water, formic acid, or sulfur acid assisted reactions than that uncatalyzed reaction, respectively. Consequently, none of the water, formic acid, or sulfur acid can accelerate the title reaction in the atmosphere.

  4. Study of enzyme adsorption and reaction kinetics for cellulose hydrolysis

    SciTech Connect

    Gilbert, I.G.

    1982-01-01

    Enzymatic hydrolysis of cellulose occurs due to the combined catalytic action of two types of cellulase components commonly referred to as C/sub 1/ and C/sub x/. However, before the hydrolysis reaction can begin, it is necessary for these enzymes to first adsorb onto the accessible surfaces of the insoluble cellulose substrate. The objective of the study was to gain a better understanding of the relationships between the adsorption of these enzyme components, the hydrolysis kinetics, the cellulosic surface area accessible to the enzymes, and the cellulose crystallinity. These relationships were investigated by passing a Trichoderma viride cellulase solution through columns of cellulose powder having different accessibility and crystallinity, and then analyzing the quantities of the different enzyme components and the hydrolysis product in the effluent. The amounts of the different cellulase components were analyzed using high-performance anion-exchange chromatography. Additional adsorption and hydrolysis experiments were done using columns of cellulose beads specially developed to provide amodel substrate for this analysis. A mathematical model has been formulated to describe the kinetics of enzyme adsorption and the resultant, initial hydrolysis rate in cellulose column. The analytical solutions obtained have been linearized into a convenient form so that the kinetic parameters of the model can be readily determined from experimental breakthrough curves.

  5. Catalytic distillation structure

    DOEpatents

    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.

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

    SciTech Connect

    Grunes, Jeffrey Benjamin

    2004-05-15

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

  7. Pulsed-field gradient nuclear magnetic resonance study of transport properties of fluid catalytic cracking catalysts.

    PubMed

    Kortunov, P; Vasenkov, S; Kärger, J; Fé Elía, M; Perez, M; Stöcker, M; Papadopoulos, G K; Theodorou, D; Drescher, B; McElhiney, G; Bernauer, B; Krystl, V; Kocirik, M; Zikanova, A; Jirglova, H; Berger, C; Gläser, R; Weitkamp, J; Hansen, E W

    2005-02-01

    Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts.

  8. Plasmonic swings during the Fenton reaction: catalytic sensing of organics in water via fullerene-decorated gold nanoparticles.

    PubMed

    Wei, Zheng-Nan; Mo, Zhi-Hong; Pu, Xiao-Li; Xu, Yi-Chong

    2015-08-01

    Fullerene-decorated gold nanoparticles were used to catalyse the Fenton reaction and the electron transfer cycle of the catalyst shifts the gold surface plasmon resonance back and forth. The plasmonic swing frequency is in accord with the redox reaction rate and could be applied for detection of organics in water.

  9. Experimental studies of gas-aerosol reactions

    NASA Astrophysics Data System (ADS)

    Gupta, Anand

    1991-05-01

    The aqueous phase oxidation of SO2 by H2O2 is believed to the principle mechanism for atmospheric sulfate formation in cloud droplets. However, no studies in noncloud aerosol systems have been reported. The objective is to quantify the importance of the noncloud liquid phase reactions of SO2 by H2O2 in the atmosphere. Growth rates of submicron droplets exposed to SO2 and H2O2 were measured using the tandem differential mobility analyzer (TDMA) technique (Rader and McMurry, 1986). The technique uses differential mobility analyzers (DMA's) to generate monodisperse particles and to measure particle size after the reaction. To facilitate submicron monodisperse droplet production with the DMA, a low-ion-concentration charter capable of generating singly charged particles up to 1.0 microns was developed and experimentally evaluated. The experiments were performed using dry and deliquesced (NH4)2SO4 particles with SO2 and H2O2 concentrations from 0-860 ppb and 0-150 ppb, respectively. No growth was observed for dry particles. For droplets greater than or equal to 0.3 microns, the fractional diameter growth was independent of particle size and for droplets less than or equal to 0.2 microns, it decreased as particle size decreased. The observed decrease is due to NH3 evaporation. As ammonia evaporates, droplet pH decreases causing the oxidation rate to decrease, leading to a lower growth rate. To predict the size-dependent growth rates, a theoretical model was developed using solution thermodynamics, gas/particle equilibrium, and chemical kinetics. The experimental and theoretical results are in reasonable agreement. For dry (NH4)2SO4 particles exposed to SO2, H2O2, NH3, and H2O vapor, surface reaction-controlled growth was observed. Particle growth was very sensitive to particle composition. No growth was observed for Polystyrene latex particles, whereas (NH4)2SO4 particles doped with catalysts (Fe(2+), Fe(3+), Mn(2+) and Cu(2+)) in a molar ratio of 1:500 grew slower than

  10. Monitoring Adverse Drug Reactions: A Preliminary Study

    PubMed Central

    Reynolds, J. L.

    1981-01-01

    The feasibility of family physicians functioning as monitors of adverse drug reactions (ADR) was examined over one month in ten practices. This was done as a preliminary trial, before attempting to use the 200 family physicians of the National Reporting System of the College of Family Physicians of Canada to monitor ADRs on a national basis. Both of these trials were designed to examine the feasibility of family physicians acting as prospective monitors of ADRs in newly marketed drugs and to identify a drug group suitable for monitoring. This study examined the detection of ADRs, prescribing and practice profiles. No firm conclusion could be reached as to the value of family doctors monitoring ADRs. This study supports the evidence that older patients receive more drugs and are at even greater risk of an ADR. Antibiotics, cardiovascular, anti-inflammatory or antidepressant drugs are suggested as those most suitable for prospective monitoring in a family practice setting. PMID:21289786

  11. Study of Single Catalytic Events at Copper-in-Charcoal: Localization of Click Activity Through Subdiffraction Observation of Single Catalytic Events.

    PubMed

    Decan, Matthew R; Scaiano, Juan C

    2015-10-15

    Single molecule fluorescence microscopy reveals that copper-in-charcoal--a high performance click catalyst- has remarkably few catalytic sites, with 90% of the charcoal particles being inactive, and for the catalytic ones the active sites represent a minute fraction (∼0.003%) of the surface. The intermittent nature of the catalytic events enables subdiffraction resolution and mapping of the catalytic sites.

  12. Activation of Aryl Halides by Nickel(I) Pincer Complexes: Reaction Pathways of Stoichiometric and Catalytic Dehalogenations.

    PubMed

    Rettenmeier, Christoph A; Wenz, Jan; Wadepohl, Hubert; Gade, Lutz H

    2016-08-15

    Homolytic C-X bond cleavage of organohalides by the T-shaped nickel(I) complexes [LigNi(I)] 1 bearing the iso-PyrrMeBox ligand had been found previously to be the crucial activation step in the asymmetric hydrodehalogenation of geminal dihalides. Here, this mechanistic investigation is extended to aryl halides, which allowed a systematic study of the activation process by a combination of experimental data and density functional theory modeling. While the activation of both aryl chlorides and geminal dichlorides appears to proceed via an analogous transition state, the generation of a highly stabile nickel(II)aryl species in the reaction of the aryl chlorides for the former represents a major difference in the reactive behavior. This difference was found to have a crucial impact on the activity of these nickel pincer systems as catalysts in the dehalogenation of aryl chlorides compared to geminal dichlorides and highlights the importance of the regulatory pathways controlling the nickel(I) concentration throughout the catalysis. These results along with the identification and characterization of novel nickel(II)aryl species are presented. PMID:27483018

  13. Construction of Vicinal Tetrasubstituted Stereocenters with a C-F Bond through a Catalytic Enantioselective Detrifluoroacetylative Mannich Reaction.

    PubMed

    Liu, Xihong; Zhang, Jinlong; Zhao, Long; Ma, Shixiong; Yang, Dongxu; Yan, Wenjin; Wang, Rui

    2015-12-18

    An efficient asymmetric detrifluoroacetylative Mannich reaction of 2-fluoro-1,3-diketones/hydrates with isatin-derived ketimines catalyzed by a chiral copper(II)-diamine complex has been realized. The reaction afforded a series of 3-substituted 3-amino-2-oxindoles bearing fluorine-containing vicinal tetrasubstituted stereocenters in high yields (up to 99%) with excellent diastereoselectivities (up to >20:1 dr) and enantioselectivities (up to 94% ee). PMID:26574779

  14. Synthesis, characterization and photo catalytic studies of the composites by tantalum oxide and zinc oxide nanorods

    NASA Astrophysics Data System (ADS)

    Chennakesavulu, K.; Reddy, M. Madhusudhana; Reddy, G. Ramanjaneya; Rabel, A. M.; Brijitta, J.; Vinita, V.; Sasipraba, T.; Sreeramulu, J.

    2015-07-01

    In-situ synthesis of ZnO:Ta2O5 composites in basic medium by using tantalum chloride and zinc chloride as precursors. The prepared composites were characterized by Fourier Transform Infrared spectroscopy (FTIR), confocal Raman spectroscopy, diffuse reflectance UV-Vis spectrophotometer (DRS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, N2-sorption isotherms, Thermo Gravimetric Analysis (TGA), High Resolution Transmission Electron Microscope (HRTEM), X-ray Photoelectron Spectroscopy (XPS), and Field Emission Scanning Electron Microscopy (FESEM/EDS). The composite materials were used as photocatalyst in the degradation Rhodamine-B (RhB) dye under visible light irradiation. The catalytic activity and removal percentage of the dye was determined by the spectrophotometric method. This indicates the percentage of degradation was more for the ZnO:Ta2O5 composites. The kinetic parameter obeys pseudo-first order reaction. It may be due to fixed amount the catalysts and concentration of dye solution. The catalytic activity of the recycled ZnO:Ta2O5 catalyst was compared with fresh catalyst.

  15. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    DOE PAGESBeta

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

  16. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    SciTech Connect

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

  17. Catalytic Activity of Cationic and Neutral Silver(I)-XPhos Complexes with Nitrogen Ligands or Tolylsulfonate for Mannich and Aza-Diels-Alder Coupling Reactions.

    PubMed

    Grirrane, Abdessamad; Álvarez, Eleuterio; García, Hermenegildo; Corma, Avelino

    2016-01-01

    Cationic and neutral silver(I)-L complexes (L=Buchwald-type biaryl phosphanes) with nitrogen co-ligands or organosulfonate counter ions have been synthesised and characterised through their structural and spectroscopic properties. At room temperature, both cationic and neutral silver(I)-L complexes are extremely active catalysts in the promotion of the single and double A(3) coupling of terminal (di)alkynes, pyrrolidine and formaldehyde. In addition, the aza-Diels-Alder two- and three-component coupling reactions of Danishefsky's diene with an imine or amine and aldehyde are efficiently catalysed by these cationic or neutral silver(I)-L complexes. The solvent influences the catalytic performance due to limited complex solubility or solvent decomposition and reactivity. The isolation of new silver(I)-L complexes with reagents as ligands lends support to mechanistic proposals for such catalytic processes. The activity, stability and metal-distal arene interaction of these silver(I)-L catalysts have been compared with those of analogous cationic gold(I) and copper(I) complexes. PMID:26598792

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

    PubMed

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

    2001-04-01

    We have determined the sequence requirements for the N-terminal protein hinge of the active-site lid of triosephosphate isomerase. The codons for the hinge (PVW) were replaced with a genetic library of all possible 8000 amino acid combinations. The most active of these 8000 mutants were selected using in vivo complementation of a triosephosphate isomerase-deficient strain of Escherichia coli, DF502. Approximately 0.3 % of the mutants complement DF502 with an activity that is between 10 and 70 % of wild-type activity. They all contain Pro at the first position. Furthermore, the sequences of these hinge mutants reveal that hydrophobic packing is very important for efficient formation of the enediol intermediate. However, the reduced catalytic activities observed are not due to increased rates of loop opening. To explore the relationship between the N-terminal and C-terminal hinges, three semi-active mutants from the N-terminal hinge selection experiment (PLH, PHS and PTF), and six active C-terminal hinge mutants from previous work (NSS, LWA, YSL, KTK, NPN, KVA) were combined to form 18 "double-hinge" mutants. The activities of these mutants suggest that the N-terminal and C-terminal hinge structures affect one another. It appears that specific side-chain interactions are important for forming a catalytically active enzyme, but not for preventing release of the unstable enediol intermediate from the active site of the enzyme. The independence of intermediate release on amino acid sequence is consistent with the absence of a "universal" hinge sequence in structurally related enzymes. PMID:11286559

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

    PubMed

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

    2001-04-01

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

  20. A study of switchgrass pyrolysis: Product variability and reaction kinetics

    NASA Astrophysics Data System (ADS)

    Bovee, Jonathan Matthew

    Samples of the same cultivar of cave-in-rock switchgrass were harvested from plots in Frankenmuth, Roger City, Cass County, and Grand Valley, Michigan. It was determined that variation exists, between locations, among the pyrolytic compounds which can lead to variability in bio-oil and increased processing costs at bio-refineries to make hydrocarbon fuels. Washed and extractives-free switchgrass samples, which contain a lower alkali and alkaline earth metals content than untreated samples, were shown to produce lower amounts of acids, esters, furans, ketones, phenolics, and saccharides and also larger amounts of aldehydes upon pyrolysis. Although the minerals catalyzed pyrolytic reactions, there was no evidence indicating their effect on reducing the production of anhydrosugars, specifically levoglucosan. To further link minerals present in the biomass to a catalytic pathway, mathematic models were employed to determine the kinetic parameters of the switchgrass. While the calculated activation energies of switchgrass, using the FWO and KAS methods, were 227.7 and 217.8 kJ/mol, correspondingly, it was concluded that the activation energies for the switchgrass hemicellulose and cellulose peaks were 115.5 and 158.2 kJ/mol, respectively, using a modified model-fitting method. The minerals that effect the production of small molecules and levoglucosan also have an observable catalytic effect on switchgrass reaction rate, which may be quantifiable through the use of reaction kinetics so as to determine activation energy.

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

    PubMed

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

    2015-06-15

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

  2. Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid.

    PubMed

    Su, Chia-Hung

    2013-02-01

    The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse.

  3. Ruthenium(II) hydrazone Schiff base complexes: Synthesis, spectral study and catalytic applications

    NASA Astrophysics Data System (ADS)

    Manikandan, R.; Viswanathamurthi, P.; Muthukumar, M.

    2011-12-01

    Ruthenium(II) hydrazone Schiff base complexes of the type [RuCl(CO)(B)(L)] (were B = PPh 3, AsPh 3 or Py; L = hydrazone Schiff base ligands) were synthesized from the reactions of hydrazone Schiff base ligand (obtained from isonicotinoylhydrazide and different hydroxy aldehydes) with [RuHCl(CO)(EPh 3) 2(B)] (where E = P or As; B = PPh 3, AsPh 3 or Py) in 1:1 molar ratio. All the new complexes have been characterized by analytical and spectral (FT-IR, electronic, 1H, 13C and 31P NMR) data. They have been tentatively assigned an octahedral structure. The synthesized complexes have exhibited catalytic activity for oxidation of benzyl alcohol to benzaldehyde and cyclohexanol to cyclohexanone in the presence of N-methyl morpholine N-oxide (NMO) as co-oxidant. They were also found to catalyze the transfer hydrogenation of aliphatic and aromatic ketones to alcohols in KOH/Isopropanol.

  4. Carbon bridged triphenolate lanthanide complexes: synthesis, characterization, DFT studies and catalytic activities for isoprene polymerization.

    PubMed

    Zhang, Min; Liang, Zhenhua; Ling, Jun; Ni, Xufeng; Shen, Zhiquan

    2015-06-28

    The dinuclear lanthanide complexes [Ln2(L)2(THF)n] (Ln = Nd (1) n = 4, Gd (2) n = 3, Lu (3) n = 2) supported by carbon bridged triphenolate ligands [LH3 = tris(3,5-di-tert-butyl-2-hydroxyphenyl)methane] were synthesized via a salt metathesis reaction between lanthanide trichlorides and LNa3 in THF. All complexes were characterized by elemental analysis and X-ray crystallography, and complex 3 was characterized by (1)H and (13)C NMR spectroscopy. Agostic interactions were found in these complexes and were further substantiated by DFT calculations of complex 3. These lanthanide complexes in combination with aluminum alkyls and [Ph3C](+)[B(C6F5)4](-) generated efficient homogeneous catalysts for the cis-1,4 polymerization of isoprene, with complex 1 having the best catalytic activity. PMID:26008592

  5. Catalytic behavior of `Pt-atomic chain encapsulated gold nanotube': A density functional study

    NASA Astrophysics Data System (ADS)

    Nigam, Sandeep; Majumder, Chiranjib

    2016-05-01

    With an aim to design novel material and explore its catalytic performance towards CO oxidation, Pt atomic chain was introduced inside gold nanotube (Au-NT). Theoretical calculations at the level of first principles formalism was carried out to investigate the atomic and electronic properties of the composite. Geometrically Pt atoms prefer to align in zig-zag fashion. Significant electronic charge transfer from inside Pt atoms to the outer wall Au atoms is observed. Interaction of O2 with Au-NT wall follows by injection of additional electronic charge in the anti-bonding orbital of oxygen molecule leading to activation of the O-O bond. Further interaction of CO molecule with the activated oxygen molecule leads to spontaneous oxidation reaction and formation of CO2.

  6. Treatment of aniline by catalytic wet air oxidation: comparative study over CuO/CeO2 and NiO/Al2O3.

    PubMed

    Ersöz, Gülin; Atalay, Süheyda

    2012-12-30

    The treatment of aniline by catalytic wet air oxidation (CWAO) was studied in a bubble reactor. The experiments were performed to investigate the effects of catalyst loading, temperature, reaction time, air flow rate, and pressure on aniline removal. The catalytic effects of the prepared nanostructured catalysts, CuO/CeO(2) (10% wt) and NiO/Al(2)O(3) (10% wt), on the CWAO treatment efficiency were also examined and compared. The prepared catalysts seem to be active having an aniline removal of 45.7% with CuO/CeO(2) and 41.9% with NiO/Al(2)O(3). The amount of N(2) formed was approximately the same for both of the catalysts.

  7. Treatment of aniline by catalytic wet air oxidation: comparative study over CuO/CeO2 and NiO/Al2O3.

    PubMed

    Ersöz, Gülin; Atalay, Süheyda

    2012-12-30

    The treatment of aniline by catalytic wet air oxidation (CWAO) was studied in a bubble reactor. The experiments were performed to investigate the effects of catalyst loading, temperature, reaction time, air flow rate, and pressure on aniline removal. The catalytic effects of the prepared nanostructured catalysts, CuO/CeO(2) (10% wt) and NiO/Al(2)O(3) (10% wt), on the CWAO treatment efficiency were also examined and compared. The prepared catalysts seem to be active having an aniline removal of 45.7% with CuO/CeO(2) and 41.9% with NiO/Al(2)O(3). The amount of N(2) formed was approximately the same for both of the catalysts. PMID:23041516

  8. N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd-NHC complexes: synthesis, characterization and catalytic activity in carbon-carbon bond-forming reactions.

    PubMed

    Akkoç, Senem; Gök, Yetkin; İlhan, İlhan Özer; Kayser, Veysel

    2016-01-01

    A series of novel benzimidazolium salts (1-4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5-8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of (1)H and (13)C{(1)H} NMR, UV-vis (for 5-8), ESI-FTICR-MS (for 2, 4, 6-8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki-Miyaura cross-coupling (for 1-8) and arylation (for 5-8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C-C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810

  9. Green synthesis, characterization and catalytic activity of the Pd/TiO2 nanoparticles for the ligand-free Suzuki-Miyaura coupling reaction.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

    2016-03-01

    A green synthesis process was developed for production of the Pd/TiO2 nanoparticles (NPs) without using toxic, hazardous and dangerous materials. Myrtus communis L. leaf extract serves as a mild, renewable and non-toxic reducing agent. The advantages of this biosynthesis method include use of cheap, clean, nontoxic and environmentally benign precursors and simple procedures without time-consuming polymerization and problems with treatment of a highly viscous polymeric resin. More importantly, the synthesized Pd/TiO2 NPs presented excellent catalytic activity for ligand-free Suzuki-Miyaura coupling which could be easily separated from the reaction mixture and reused many times with no loss of activity. Therefore, these properties indicate demonstrative benefits of the catalyst. The Pd/TiO2 NPs was characterized by FESEM, TEM, FT-IR, UV-vis spectroscopy and EDS. PMID:26674227

  10. Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions-Influence of Fe(II)/Fe(III) ratio on catalytic performance.

    PubMed

    Rusevova, Klara; Kopinke, Frank-Dieter; Georgi, Anett

    2012-11-30

    Nano-sized Fe(II, III) oxides with various Fe(II)/Fe(III) ratios were characterized and tested as catalysts for the oxidative degradation of phenol via Fenton-like reactions at neutral pH. Under conditions typically applied for wet peroxide oxidation, Fe(II) in magnetite is oxidized to Fe(III), successively converting the mineral into maghemite. The residual Fe(II) content in the catalyst core is of only minor benefit for the catalytic activity in phenol oxidation, i.e. magnetite is not superior to maghemite. Achievable reaction rates for phenol degradation appeared to be rather low, e.g. phenol half-life of about 12 h when 3 g L(-1) magnetite and 5 g L(-1) H(2)O(2) were applied. Preceding surface-reduction of maghemite by NaBH(4), leading to an over-stoichiometric Fe(II) content compared to magnetite, only enhanced the non-productive decomposition of H(2)O(2) rather than the rate of phenol degradation. Reaction rates were shown to be relatively insensitive to catalyst concentration in the range of 1-10 g L(-1), probably resulting from a scavenging of reactive species by the catalyst surface, whereby particle agglomeration seems to play a key role. Degradation experiments with various structurally distinct compounds were carried out, indicating a similar selectivity of the heterogeneous Fenton-like system to that known for oxidation with ·OH.

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

    PubMed

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

    2013-04-01

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

  12. Catalytic wet air oxidation of phenol using CeO2 as the catalyst. Kinetic study and mechanism development.

    PubMed

    Chang, Dong-Jang; Lin, Shiow-Shyung; Chen, Chun-Liang; Wang, Shu-Pin; Ho, Wei-Lun

    2002-08-01

    Using a CeO2 catalyst prepared from CeCl3.7H2O under high thermal impact, the catalytic wet air oxidation (CWAO) of phenol was effectively implemented. With initial phenol concentrations of between (400 and 2500) mg/L, and at a temperature of 160 degrees C, the rate of phenol conversion increased with increased catalyst loading (0.2g/L-1.0g/L) and oxygen pressure (0.5 MPa-1.5 MPa). Even at an initial concentration of 2500 mg/L, conversion of phenol was as high as 95% after 3 h reaction. The effect of phenol concentration, catalyst loading, and oxygen pressure on the initial rate of phenol conversion was evaluated in a kinetic study. The initial rate equation derived from kinetic study is: Ro=k1 x [Ph]1.3-1.4 x W0.5-0.6 x PO2(0.9-1.1), where k1 is a rate constant, and [Ph], W and PO2 refer to phenol concentration, catalyst loading and oxygen pressure, respectively. A free-radical involved reaction mechanism was proposed and an initial rate expression based on this mechanism was derived: Ro = k2 x [Ph]1.5 x W0.5, where k2 is also a rate constant. Fitting of experimental data with the theoretically derived initial rate equation resulted in good correlation: the coefficient is greater than 0.99.

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

    SciTech Connect

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

    2013-02-07

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

    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.

  15. Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions.

    PubMed

    Ayala Quezada, Alejandro; Ohara, Keisuke; Ratanawimarnwong, Nuanlaor; Nacapricha, Duangjai; Murakami, Hiroya; Teshima, Norio; Sakai, Tadao

    2015-11-01

    An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures.

  16. Size-dependent catalytic kinetics and dynamics of Pd nanocubes: a single-particle study.

    PubMed

    Chen, Tao; Zhang, Yuwei; Xu, Weilin

    2016-08-10

    Due to the well-known significant effect of the size on the catalytic activity of nanocatalysts, here we use single-molecule fluorescence microscopy to study the size-dependent catalytic kinetics and dynamics of individual Pd nanocubes. A series of size-dependent catalytic properties were revealed in both product formation and product desorption processes. It was found that, due to the different adsorption mechanisms of substrate molecules on Pd nanocubes, H2 adsorption is independent of the size of Pd nanocubes, while the large flat resazurin molecules show stronger adsorption on larger sized Pd nanocubes. Apparently, the Pd nanocubes can be divided into three types: when the size of the Pd nanocube is small, substrate binding can prohibit product desorption and product desorption prefers the direct pathway; when the size is in an appropriate range, the product desorption process could be independent of substrate binding and shows no selectivity between two parallel desorption pathways; if the size is large enough, substrate binding can promote product desorption and product desorption prefers the indirect pathway. We also observed the surface-restructuring-induced dynamic heterogeneity of individual Pd nanocubes in both product formation and desorption processes with timescales of about tens to one hundred seconds. The activity fluctuation of individual Pd nanocubes was found to be mainly due to the spontaneous surface-restructuring rather than the catalysis. Furthermore, we estimated the size-dependent activation energies and time scales of spontaneous dynamic surface restructuring, which are fundamental to heterogeneous catalysis. The work presented here reveals new insight into nanocatalysis and exemplifies the advantages of the single-molecule approach in probing the catalytic properties of nanocatalysts. PMID:27465438

  17. Experimental study of an integral catalytic combustor: Heat exchanger for Stirling engines

    NASA Technical Reports Server (NTRS)

    Bulzan, D. L.

    1982-01-01

    The feasibility of using catalytic combustion with heat removal for the Stirling engine to reduce exhaust emissions and also improve heat transfer to the working fluid was studied using spaced parallel plates. An internally air-cooled heat exchanger was placed between two noble metal catalytic plates. A preheated fuel-air mixture passed between the plates and reacted on the surface of the catalyzed plates. Heat was removed from the catalytic surface by radiation and convection to the aircooled heat exchangers to control temperature and minimize thermal nitrogen oxide emissions. Test conditions were inlet combustion air temperatures from 850 to 900 K, inlet velocities of about 10 m/s, equivalence ratios from 0.5 to 0.9, and pressures from 1.3x10 to the 5th power to 2.0x10 to the 5th power Pa. Propane fuel was used for all testing. Combustion efficiencies greater than 99.5 percent were measured. Nitrogen oxide emissions ranged from 1.7 to 3.3 g NO2/kg fuel. The results demonstrate the feasibility of the concept and indicate that further investigation of the concept is warranted.

  18. Catalytic Asymmetric Reactions of 4‐Substituted Indoles with Nitroethene: A Direct Entry to Ergot Alkaloid Structures

    PubMed Central

    Romanini, Simone; Galletti, Emilio; Caruana, Lorenzo; Mazzanti, Andrea; Himo, Fahmi

    2015-01-01

    Abstract A domino Friedel–Crafts/nitro‐Michael reaction between 4‐substituted indoles and nitroethene is presented. The reaction is catalyzed by BINOL‐derived phosphoric acid catalysts, and delivers the corresponding 3,4‐ring‐fused indoles with very good results in terms of yields and diastereo‐ and enantioselectivities. The tricyclic benzo[cd]indole products bear a nitro group at the right position to serve as precursors of ergot alkaloids, as demonstrated by the formal synthesis of 6,7‐secoagroclavine from one of the adducts. DFT calculations suggest that the outcome of the reaction stems from the preferential evolution of a key nitronic acid intermediate through a nucleophilic addition pathway, rather than to the expected “quenching” through protonation. PMID:26486074

  19. Quantum Mechanics and Molecular Mechanics Study of the Catalytic Mechanism of Human AMSH-LP Domain Deubiquitinating Enzymes.

    PubMed

    Zhu, Wenyou; Liu, Yongjun; Ling, Baoping

    2015-08-25

    Deubiquitinating enzymes (DUBs) catalyze the cleavage of the isopeptide bond in polyubiquitin chains to control and regulate the deubiquitination process in all known eukaryotic cells. The human AMSH-LP DUB domain specifically cleaves the isopeptide bonds in the Lys63-linked polyubiquitin chains. In this article, the catalytic mechanism of AMSH-LP has been studied using a combined quantum mechanics and molecular mechanics method. Two possible hydrolysis processes (Path 1 and Path 2) have been considered. Our calculation results reveal that the activation of Zn(2+)-coordinated water molecule is the essential step for the hydrolysis of isopeptide bond. In Path 1, the generated hydroxyl first attacks the carbonyl group of Gly76, and then the amino group of Lys63 is protonated, which is calculated to be the rate limiting step with an energy barrier of 13.1 kcal/mol. The energy barrier of the rate limiting step and the structures of intermediate and product are in agreement with the experimental results. In Path 2, the protonation of amino group of Lys63 is prior to the nucleophilic attack of activated hydroxyl. The two proton transfer processes in Path 2 correspond to comparable overall barriers (33.4 and 36.1 kcal/mol), which are very high for an enzymatic reaction. Thus, Path 2 can be ruled out. During the reaction, Glu292 acts as a proton transfer mediator, and Ser357 mainly plays a role in stabilizing the negative charge of Gly76. Besides acting as a Lewis acid, Zn(2+) also influences the reaction by coordinating to the reaction substrates (W1 and Gly76).

  20. Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process.

    PubMed

    Zhang, Yanwen; Cai, Ningsheng; Yang, Jingbiao; Xu, Bo

    2008-10-01

    The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000 ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000 ppm methane and 0.051 g min(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100 ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000 ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.

  1. New Insight into the Catalytic Mechanism of Bacterial MraY from Enzyme Kinetics and Docking Studies.

    PubMed

    Liu, Yao; Rodrigues, João P G L M; Bonvin, Alexandre M J J; Zaal, Esther A; Berkers, Celia R; Heger, Michal; Gawarecka, Katarzyna; Swiezewska, Ewa; Breukink, Eefjan; Egmond, Maarten R

    2016-07-15

    Phospho-MurNAc-pentapeptide translocase (MraY) catalyzes the synthesis of Lipid I, a bacterial peptidoglycan precursor. As such, MraY is essential for bacterial survival and therefore is an ideal target for developing novel antibiotics. However, the understanding of its catalytic mechanism, despite the recently determined crystal structure, remains limited. In the present study, the kinetic properties of Bacillus subtilis MraY (BsMraY) were investigated by fluorescence enhancement using dansylated UDP-MurNAc-pentapeptide and heptaprenyl phosphate (C35-P, short-chain homolog of undecaprenyl phosphate, the endogenous substrate of MraY) as second substrate. Varying the concentrations of both of these substrates and fitting the kinetics data to two-substrate models showed that the concomitant binding of both UDP-MurNAc-pentapeptide-DNS and C35-P to the enzyme is required before the release of the two products, Lipid I and UMP. We built a model of BsMraY and performed docking studies with the substrate C35-P to further deepen our understanding of how MraY accommodates this lipid substrate. Based on these modeling studies, a novel catalytic role was put forward for a fully conserved histidine residue in MraY (His-289 in BsMraY), which has been experimentally confirmed to be essential for MraY activity. Using the current model of BsMraY, we propose that a small conformational change is necessary to relocate the His-289 residue, such that the translocase reaction can proceed via a nucleophilic attack of the phosphate moiety of C35-P on bound UDP-MurNAc-pentapeptide. PMID:27226570

  2. Eco-friendly green synthesis of silver nanoparticles using salmalia malabarica: synthesis, characterization, antimicrobial, and catalytic activity studies

    NASA Astrophysics Data System (ADS)

    Murali Krishna, I.; Bhagavanth Reddy, G.; Veerabhadram, G.; Madhusudhan, A.

    2016-06-01

    An economically viable and "green" process has been developed for the synthesis of silver nanoparticles (AgNPs) with an average size of 7 nm using non-toxic and renewable salmalia malabarica gum (SMG) as reducing and capping agent without using any chemical reducing agent. The effect of various parameters such as concentration of SMG and silver nitrate and reaction time for the synthesis of AgNPs was studied. The synthesized AgNPs are systematically characterized by UV/Vis spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction and Transmission electron microscopy. The resultant SMG-capped AgNPs are highly stable and had significant antibacterial action on both Escherichia coli ( E. coli) and Staphylococcus aureus ( S. aureus). The catalytic action of the SMG-capped AgNPs to initiate the reduction of 4-nitrophenol (4-NP) in the presence of NaBH4 has also been reported. The kinetics of the reaction was found to be of pseudo-first-order with respect to the 4-NP.

  3. Preparation of zeolite supported TiO2, ZnO and ZrO2 and the study on their catalytic activity in NOx reduction and 1-pentanol dehydration

    NASA Astrophysics Data System (ADS)

    Fatimah, Is

    2016-03-01

    Preparation of zeolite supported TiO2, ZnO and ZrO2 and their catalytic activity was studied. Activated natural zeolite from Indonesia was utilized for the preparation and catalytic activity test on NOx reduction by NH3 and also 1-pentanol dehydration were examined. Physicochemical characterization of materials was studied by x-ray diffraction (XRD) measurement, scanning electron microscope, solid acidity determination and also gas sorption analysis. The results confirmed that the preparation gives some improvements on physicochemical characters suitable for catalysis mechanism in those reactions. Solid acidity and specific surface area contributed significantly to the activity.

  4. Ab initio study of the kinetics of hydrogen abstraction reactions on toluene and tetralin

    SciTech Connect

    Beste, Ariana; Britt, Phillip F; Buchanan III, A C; Harrison, Robert J; Hathorn, Bryan C

    2008-01-01

    Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the reaction barriers and rate constants for the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are calculated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. Thermolysis of PPE occurs by a free radical chain mechanism in which the product selectivity arises from competitive hydrogen abstraction at the benzylic and nonbenzylic methylen sites by chain carrying benzyl and phenoxyl radicals. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE through comparison of the rate constants and the reaction enthalpies with reliable experimental values. In this study, we used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment. Absolute and relative rate constants were calculated using transition state theory. We found that the relative rate constant using the B3LYP functional agrees within a factor of 2.0 with experiment at the experimental temperature of 333 K, indicating that the B3LYP functional will be successful in predicting relative rate constants for hydrogen abstraction reactions participating in the pyrolysis of PPE.

  5. Study of char gasification in a reaction/adsorption apparatus

    SciTech Connect

    Sotirchos, S.V.; Crowley, J.A.

    1987-09-01

    The reaction of an activated carbon (coconut char) with CO/sub 2/ was studied in a reaction/adsorption apparatus which allows successive reactivity and physical adsorption measurements to be made on the same solid sample. Reaction and surface area evolution data were obtained in the temperature range from 800 to 900/sup 0/C. All reaction rate trajectories obtained in this study showed a maximum in the reaction rate, 2-3 times higher than the initial rate, at about 85% conversion. There was no correlation between these results and the evolution of the internal surface area although the reaction appeared to take place initially in the kinetically controlled regime.

  6. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

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

    PubMed

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

    2015-05-26

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

  8. Crossed reaction networks in catalytic hydrodenitrogenation of synthetic liquid fuels. Quarterly report, August 1, 1980-October, 31, 1980

    SciTech Connect

    Satterfield, Charles N.; Hsi, Shan

    1980-01-01

    During the third quarter, the following have been accomplished: (1) The trickle bed reactor system has been tested at pressures and temperatures above operating conditions. (2) A suitable carrier liquid for the reaction has been developed by hydrogenation of commercially-available ..cap alpha..-olefins. Equipment has been constructed and operated to produce this liquid regularly on a scale suitable for our purposes. (3) Procedures for the gas chromatographic analysis have been tested.

  9. Metal-ligand cooperation in catalytic intramolecular hydroamination: a computational study of iridium-pyrazolato cooperative activation of aminoalkenes.

    PubMed

    Tobisch, Sven

    2012-06-01

    The present study comprehensively explores diverse mechanistic pathways for intramolecular hydroamination of prototype 2,2-dimethyl-4-penten-1-amine by Cp*Ir chloropyrazole (1; Cp*=pentamethylcyclopentadienyl) in the presence of KOtBu base with the aid of density functional theory (DFT) calculations. The most accessible mechanistic pathway for catalytic turnover commences from Cp*Ir pyrazolato (Pz) substrate adduct 2⋅S, representing the catalytically competent compound and proceeds via initial electrophilic activation of the olefin C=C bond by the metal centre. It entails 1) facile and reversible anti nucleophilic amine attack on the iridium-olefin linkage; 2) Ir-C bond protonolysis via stepwise transfer of the ammonium N-H proton at the zwitterionic [Cp*IrPz-alkyl] intermediate onto the metal that is linked to turnover-limiting, reductive, cycloamine elimination commencing from a high-energy, metastable [Cp*IrPz-hydrido-alkyl] species; and 3) subsequent facile cycloamine liberation to regenerate the active catalyst species. The amine-iridium bound 2 a⋅S likely corresponds to the catalyst resting state and the catalytic reaction is expected to proceed with a significant primary kinetic isotope. This study unveils the vital role of a supportive hydrogen-bonded network involving suitably aligned β-basic pyrazolato and cycloamido moieties together with an external amine molecule in facilitating metal protonation and reductive elimination. Cooperative hydrogen bonding thus appears pivotal for effective catalysis. The mechanistic scenario is consonant with catalyst performance data and furthermore accounts for the variation in performance for [Cp*IrPz] compounds featuring a β- or γ-basic pyrazolato unit. As far as the route that involves amine N-H bond activation is concerned, a thus far undocumented pathway for concerted amidoalkene → cycloamine conversion through olefin protonation by the pyrazole N-H concurrent with N-C ring closure is disclosed as a

  10. Studies of photoredox reactions on nanosize semiconductors

    SciTech Connect

    Wilcoxon, J.P.; Parsapour, F.; Kelley, D.F.

    1997-08-01

    Light induced electron transfer (ET) from nanosize semiconductors of MoS{sub 2} to organic electron acceptors such as 2,2{prime}-bipyridine (bpy) and methyl substituted 4,4{prime},5,5{prime}-tetramethyl-2,2{prime}-bipyridine (tmb) was studied by static and time resolved photoluminescence spectroscopy. The kinetics of ET were varied by changing the nanocluster size (the band gap), the electron acceptor, and the polarity of the solvent. MoS{sub 2} is an especially interesting semiconductor material as it is an indirect semiconductor in bulk form, and has a layered covalent bonding arrangement which is highly resistant to photocorrosion. Et occurs following photoexcitation of the direct band gap. Quantum confinement results in the smaller nanoclusters having higher conduction band energies, and therefore larger ET driving forces. The ET reaction energies may be varied by changing the electron acceptor, by varying the size of the MoS{sub 2} nanocluster or by varying the polarity of the solvent. In addition, varying the polarity of the solvent affects the reorganization energy and the barrier to electron transfer. TMB is harder to reduce, and thus has a smaller ET driving force than bpy. The solvent polarity is varied by varying the composition of acetonitrile/benzene mixed solvents.

  11. Effects of N{sub 2}O gas addition on the properties of ZnO films grown by catalytic reaction-assisted chemical vapor deposition

    SciTech Connect

    Yasui, Kanji Morioka, Makoto; Kanauchi, Shingo; Ohashi, Yuki; Kato, Takahiro; Tamayama, Yasuhiro

    2015-11-15

    The influence of N{sub 2}O gas addition on the properties of zinc oxide (ZnO) films grown on a-plane (11–20) sapphire (a-Al{sub 2}O{sub 3}) substrates was investigated, using a chemical vapor deposition method based on the reaction between dimethylzinc and high-temperature H{sub 2}O produced by a catalytic H{sub 2}-O{sub 2} reaction on platinum (Pt) nanoparticles. The addition of N{sub 2}O was found to increase the size of the crystalline facets and to improve the crystal orientation along the c-axis. The electron mobility at 290 K was also increased to 234 cm{sup 2}/Vs following the addition of N{sub 2}O gas at a pressure of 3.2 × 10{sup −3 }Pa. In addition, the minimum full width at half maximum of the most intense photoluminescence peak derived from neutral donor bound excitons at 10 K decreased to 0.6 meV by the addition of N{sub 2}O gas at a pressure of 3.1 × 10{sup −2 }Pa.

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

    PubMed Central

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

    2015-01-01

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550

  13. Interaction Induced High Catalytic Activities of CoO Nanoparticles Grown on Nitrogen-Doped Hollow Graphene Microspheres for Oxygen Reduction and Evolution Reactions

    NASA Astrophysics Data System (ADS)

    Jiang, Zhong-Jie; Jiang, Zhongqing

    2016-06-01

    Nitrogen doped graphene hollow microspheres (NGHSs) have been used as the supports for the growth of the CoO nanoparticles. The nitrogen doped structure favors the nucleation and growth of the CoO nanoparticles and the CoO nanoparticles are mostly anchored on the quaternary nitrogen doped sites of the NGHSs with good monodispersity since the higher electron density of the quaternary nitrogen favors the nucleation and growth of the CoO nanoparticles through its coordination and electrostatic interactions with the Co2+ ions. The resulting NGHSs supported CoO nanoparticles (CoO/NGHSs) are highly active for the oxygen reduction reaction (ORR) with activity and stability higher than the Pt/C and for the oxygen evolution reaction (OER) with activity and stability comparable to the most efficient catalysts reported to date. This indicates that the CoO/NGHSs could be used as efficient bi-functional catalysts for ORR and OER. Systematic analysis shows that the superior catalytic activities of the CoO/NGHSs for ORR and OER mainly originate from the nitrogen doped structure of the NGHSs, the small size of the CoO nanoparticles, the higher specific and electroactive surface area of the CoO/NGHSs, the good electric conductivity of the CoO/NGHSs, the strong interaction between the CoO nanoparticles and the NGHSs, etc.

  14. Interaction Induced High Catalytic Activities of CoO Nanoparticles Grown on Nitrogen-Doped Hollow Graphene Microspheres for Oxygen Reduction and Evolution Reactions

    PubMed Central

    Jiang, Zhong-Jie; Jiang, Zhongqing

    2016-01-01

    Nitrogen doped graphene hollow microspheres (NGHSs) have been used as the supports for the growth of the CoO nanoparticles. The nitrogen doped structure favors the nucleation and growth of the CoO nanoparticles and the CoO nanoparticles are mostly anchored on the quaternary nitrogen doped sites of the NGHSs with good monodispersity since the higher electron density of the quaternary nitrogen favors the nucleation and growth of the CoO nanoparticles through its coordination and electrostatic interactions with the Co2+ ions. The resulting NGHSs supported CoO nanoparticles (CoO/NGHSs) are highly active for the oxygen reduction reaction (ORR) with activity and stability higher than the Pt/C and for the oxygen evolution reaction (OER) with activity and stability comparable to the most efficient catalysts reported to date. This indicates that the CoO/NGHSs could be used as efficient bi-functional catalysts for ORR and OER. Systematic analysis shows that the superior catalytic activities of the CoO/NGHSs for ORR and OER mainly originate from the nitrogen doped structure of the NGHSs, the small size of the CoO nanoparticles, the higher specific and electroactive surface area of the CoO/NGHSs, the good electric conductivity of the CoO/NGHSs, the strong interaction between the CoO nanoparticles and the NGHSs, etc. PMID:27255562

  15. Characteristics of vestibulosensory reactions studied by experimental caloric test

    NASA Technical Reports Server (NTRS)

    Kapranov, V. Z.

    1980-01-01

    Vestibulo-sensory reactions were studied in 135 workers who were in contact with nitroethers, by the method of an experimental caloric test. The response vestibulo-sensory reactions were recorded by means of an electroencephalograph. The changes in the sensory reaction depended on the duration of the workers' contact with toxic agents. A study of illusion reactions by the labyrinth calorization widens diagnostic possibilities in the examination of functional condition of the vestibular analyser considerably.

  16. Study of Single Catalytic Events at Copper-in-Charcoal: Localization of Click Activity Through Subdiffraction Observation of Single Catalytic Events.

    PubMed

    Decan, Matthew R; Scaiano, Juan C

    2015-10-15

    Single molecule fluorescence microscopy reveals that copper-in-charcoal--a high performance click catalyst- has remarkably few catalytic sites, with 90% of the charcoal particles being inactive, and for the catalytic ones the active sites represent a minute fraction (∼0.003%) of the surface. The intermittent nature of the catalytic events enables subdiffraction resolution and mapping of the catalytic sites. PMID:26722775

  17. Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.

    1987-01-01

    Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

  18. Density functional study of chemical reaction equilibrium for dimerization reactions in slit and cylindrical nanopores.

    PubMed

    Malijevský, Alexandr; Lísal, Martin

    2009-04-28

    We present a theoretical study of the effects of confinement on chemical reaction equilibrium in slit and cylindrical nanopores. We use a density functional theory (DFT) to investigate the effects of temperature, pore geometry, bulk pressure, transition layering, and capillary condensation on a dimerization reaction that mimics the nitric oxide dimerization reaction, 2NO <==> (NO)(2), in carbonlike slit and cylindrical nanopores in equilibrium with a vapor reservoir. In addition to the DFT calculations, we also utilize the reaction ensemble Monte Carlo method to supplement the DFT results for reaction conversion. This work is an extension of the previous DFT study by Tripathi and Chapman [J. Chem. Phys. 118, 7993 (2003)] on the dimerization reactions confined in the planar slits.

  19. Modelling ignition characteristics of rich H2/O2 mixture in a monolithic catalytic reactor

    NASA Technical Reports Server (NTRS)

    Tien, Ta-Ching; T'Ien, James S.

    1988-01-01

    Ignition of rich hydrogen-oxygen mixture in a monolithic catalytic reactor is studied using a transient combustion model. The model assumes a quasi-steady gas phase and a thermally-thin substrate. The ignition time lag is due to the thermal inertia of the substrate. One-step global chemical reaction is assumed both on the surface and in the gas phase. An effectiveness factor is introduced to account for the transition from a kinetically-limited catalytic surface reaction to a diffusion-limit one during ignition. Results presented include a catalytic ignition boundary, ignition delay time and the transient response in the catalytic bed.

  20. Soot Reaction Properties (Ground-Based Study)

    NASA Technical Reports Server (NTRS)

    Dai, Z.; El-Leathy, A. M.; Lin, K.-C.; Sunderland, P. B.; Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2000-01-01

    Three major soot reaction processes are needed to predict soot properties in flame environments: soot growth, or the formation of soot on soot nuclei and soot particles; soot oxidation, or the reaction of soot with oxidizing species to yield the combustion products of soot oxidation; and soot nucleation, or the formation of soot nuclei from soot precursors having large molecular weights (generally thought to be large and particularly stable PAH molecules in flame environments, called stabilomers). These processes are addressed in the following, considering soot growth, oxidation and nucleation, in turn, by exploiting the soot and flame structure results for premixed and diffusion flames already discussed in Section 2.

  1. Bismuth sulphides prepared by thermal and hydrothermal decomposition of a single source precursor: the effect of reaction parameters on morphology, microstructure and catalytic activity.

    PubMed

    Siqueira, Guilherme Oliveira; de Oliveira Porto, Arilza; Viana, Marcelo Machado; da Silva, Herculano Vieira; de Souza, Yara Gonçalves; da Silva, Hugo Wallison Alves; de Lima, Geraldo Magela; Matencio, Tulio

    2013-10-14

    Bismuth sulphides were prepared by thermal and hydrothermal decomposition of a precursor, bismuth tris-diethyldithiocarbamate, at different temperatures and times. The obtained results showed that the thermal decomposition of the precursor in a tube furnace was not very appropriate to control particle size and morphology. XRD results showed that at 310 °C the precursor was not fully decomposed but at 500 °C besides the orthorhombic bismuth sulphide, the metallic bismuth also started to be formed. At the highest temperature 1D crystals were formed with an apparent mean crystal size of 138 nm. However, hydrothermal decomposition was shown to be a very suitable method to control particle size and morphology just by varying some parameters such as temperature and time. For 6 hours reaction time, as temperature increased, the apparent mean crystal size decreased. The particle morphology was also very affected by this parameter, at 180 °C only 1D particles (nanorods) with lengths varying from 25 to 4700 nm were formed but at 200 °C not only 1D particles but also 2D particles were (nanosheets) obtained. Bismuth sulphide particles obtained at 180 °C and 24 hours reaction time were shown to be formed mostly by 2D particles compared to those obtained at 6 hours. It was clearly seen that the increase in reaction time and temperature led to the formation of bi-dimensional particles. The presence of 1D crystals in the samples obtained by hydrothermal decomposition at 180 °C/6 h and 180 °C/24 h is responsible for their high catalytic efficiency towards methylene blue dye degradation. PMID:23994884

  2. Staff Reactions to Challenging Behaviour: An Observation Study

    ERIC Educational Resources Information Center

    Lambrechts, Greet; Van Den Noortgate, Wim; Eeman, Lieve; Maes, Bea

    2010-01-01

    Staff reactions play an important role in the development and maintaining of clients' challenging behaviour. Because there is a paucity of research on staff reactions in naturalistic settings, this study examined sequential associations between challenging behaviour and staff reactions by means of a descriptive analysis. We analysed video…

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

    ERIC Educational Resources Information Center

    Gozzi, Christel; Bouzidi, Naoual

    2008-01-01

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

  4. B-Methylated Amine-Boranes: Substituent Redistribution, Catalytic Dehydrogenation, and Facile Metal-Free Hydrogen Transfer Reactions.

    PubMed

    Stubbs, Naomi E; Schäfer, André; Robertson, Alasdair P M; Leitao, Erin M; Jurca, Titel; Sparkes, Hazel A; Woodall, Christopher H; Haddow, Mairi F; Manners, Ian

    2015-11-16

    Although the dehydrogenation chemistry of amine-boranes substituted at nitrogen has attracted considerable attention, much less is known about the reactivity of their B-substituted analogues. When the B-methylated amine-borane adducts, RR'NH·BH2Me (1a: R = R' = H; 1b: R = Me, R' = H; 1c: R = R' = Me; 1d: R = R' = iPr), were heated to 70 °C in solution (THF or toluene), redistribution reactions were observed involving the apparent scrambling of the methyl and hydrogen substituents on boron to afford a mixture of the species RR'NH·BH3-xMex (x = 0-3). These reactions were postulated to arise via amine-borane dissociation followed by the reversible formation of diborane intermediates and adduct reformation. Dehydrocoupling of 1a-1d with Rh(I), Ir(III), and Ni(0) precatalysts in THF at 20 °C resulted in an array of products, including aminoborane RR'N═BHMe, cyclic diborazane [RR'N-BHMe]2, and borazine [RN-BMe]3 based on analysis by in situ (11)B NMR spectroscopy, with peak assignments further supported by density functional theory (DFT) calculations. Significantly, very rapid, metal-free hydrogen transfer between 1a and the monomeric aminoborane, iPr2N═BH2, to yield iPr2NH·BH3 (together with dehydrogenation products derived from 1a) was complete within only 10 min at 20 °C in THF, substantially faster than for the N-substituted analogue MeNH2·BH3. DFT calculations revealed that the hydrogen transfer proceeded via a concerted mechanism through a cyclic six-membered transition state analogous to that previously reported for the reaction of the N-dimethyl species Me2NH·BH3 and iPr2N═BH2. However, as a result of the presence of an electron donating methyl substituent on boron rather than on nitrogen, the process was more thermodynamically favorable and the activation energy barrier was reduced. PMID:26535961

  5. Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions.

    PubMed

    Wang, Meihua; Gao, Zhe; Zhang, Bin; Yang, Huimin; Qiao, Yan; Chen, Shuai; Ge, Huibin; Zhang, Jiankang; Qin, Yong

    2016-06-13

    Metal-support interfaces play a prominent role in heterogeneous catalysis. However, tailoring the metal-support interfaces to realize full utilization remains a major challenge. In this work, we propose a graceful strategy to maximize the metal-oxide interfaces by coating confined nanoparticles with an ultrathin oxide layer. This is achieved by sequential deposition of ultrathin Al2 O3 coats, Pt, and a thick Al2 O3 layer on carbon nanocoils templates by atomic layer deposition (ALD), followed by removal of the templates. Compared with the Pt catalysts confined in Al2 O3 nanotubes without the ultrathin coats, the ultrathin coated samples have larger Pt-Al2 O3 interfaces. The maximized interfaces significantly improve the activity and the protecting Al2 O3 nanotubes retain the stability for hydrogenation reactions of 4-nitrophenol. We believe that applying ALD ultrathin coats on confined catalysts is a promising way to achieve enhanced performance for other catalysts.

  6. The strong catalytic effect of Pb(II) on the oxygen reduction reaction on 5 nm gold nanoparticles.

    PubMed

    Wang, Ying; Laborda, Eduardo; Plowman, Blake J; Tschulik, Kristina; Ward, Kristopher R; Palgrave, Robert G; Damm, Christine; Compton, Richard G

    2014-02-21

    Citrate-capped gold nanoparticles (AuNPs) of 5 nm in diameter are synthesized via wet chemistry and deposited on a glassy carbon electrode through electrophoresis. The kinetics of the oxygen reduction reaction (ORR) on the modified electrode is determined quantitatively in oxygen-saturated 0.5 M sulphuric acid solution by modelling the cathode as an array of interactive nanoelectrodes. Quantitative analysis of the cyclic voltammetry shows that no apparent ORR electrocatalysis takes place, the kinetics on AuNPs being effectively the same as on bulk gold. Contrasting with the above, a strong ORR catalysis is found when Pb(2+) is added to the oxygen saturated solution or when the modified electrode is cycled in lead alkaline solution such that lead dioxide is repeatedly electrodeposited and stripped off on the nanoparticles. In both cases, the underpotential deposition of lead on the gold nanoparticles is found to be related to the catalysis.

  7. Catalytic hydrotreating process

    DOEpatents

    Karr, Jr., Clarence; McCaskill, Kenneth B.

    1978-01-01

    Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  8. Effect of Sb Segregation on Conductance and Catalytic Activity at Pt/Sb-Doped SnO2 Interface: A Synergetic Computational and Experimental Study.

    PubMed

    Fu, Qiang; Colmenares Rausseo, Luis César; Martinez, Umberto; Dahl, Paul Inge; García Lastra, Juan Maria; Vullum, Per Erik; Svenum, Ingeborg-Helene; Vegge, Tejs

    2015-12-23

    Antimony-doped tin dioxide (ATO) is considered a promising support material for Pt-based fuel cell cathodes, displaying enhanced stability over carbon-based supports. In this work, the effect of Sb segregation on the conductance and catalytic activity at Pt/ATO interface was investigated through a combined computational and experimental study. It was found that Sb-dopant atoms prefer to segregate toward the ATO/Pt interface. The deposited Pt catalysts, interestingly, not only promote Sb segregation, but also suppress the occurrence of Sb(3+) species, a charge carrier neutralizer at the interface. The conductivity of ATO was found to increase, to a magnitude close to that of activated carbon, with an increment of Sb concentration before reaching a saturation point around 10%, and then decrease, indicating that Sb enrichment at the ATO surface may not always favor an increment of the electric current. In addition, the calculation results show that the presence of Sb dopants in ATO has little effect on the catalytic activity of deposited three-layer Pt toward the oxygen reduction reaction, although subsequent alloying of Pt and Sb could lower the corresponding catalytic activity. These findings help to support future applications of ATO/Pt-based materials as possible cathodes for proton exchange membrane fuel cell applications with enhanced durability under practical applications. PMID:26615834

  9. In situ DRIFTS studies on MnOx nanowires supported by activated semi-coke for low temperature selective catalytic reduction of NOx with NH3

    NASA Astrophysics Data System (ADS)

    Chen, Yan; Zhang, Zuotai; Liu, Lili; Mi, Liang; Wang, Xidong

    2016-03-01

    To mitigate the threat of NOx on the environment, MnOx nanowires were fabricated on activated semi-coke (MnOx NW/ASC) for the first time. The prepared MnOx NW/ASC was used for the low temperature selective catalytic reduction (SCR) of NOx with NH3, which achieved an efficiency of over 90% with a low loading content of 1.64 wt% at 150-210 °C. This high performance could be ascribed to synergistic effect between MnOx and ASC. Specifically, the large specific surface area and reducible property of ASC facilitated the dispersion of MnOx and the formation of Mn3+, respectively. Meanwhile, MnOx nanowires provided more redox sites and lattice oxygen species due to the coexistence of Mn3+ and Mn4+, which accelerated the catalytic cycle. The in situ DRIFTS studies revealed that ASC was conducive to the adsorption of NO and NH3. Most importantly, the existence of Mn3+ favored the formation of amide species and the subsequent reduction reaction. Furthermore, the Langmuir-Hinshelwood (L-H) route between coordinated NH3 and bidentate nitrate was predominating in the SCR process and responsible for the high catalytic activity at low temperature.

  10. Study of the kinetics of catalytic decomposition of hydrazine vapors on palladium

    NASA Technical Reports Server (NTRS)

    Khomenko, A. A.; Apelbaum, L. O.

    1987-01-01

    The decomposition rates of N2H4 on a palladium surface are studied. Experiments were conducted in a circulating unit at atmosphere pressure. The experimental method is described. The laws found for the reaction kinetics are explained by equations.

  11. Surface-catalyzed air oxidation reactions of hydrazines: Tubular reactor studies

    NASA Technical Reports Server (NTRS)

    Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

    1988-01-01

    The surface-catalyzed air oxidation reactions of hydrazine, monomethylhydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine and tetramethylhydrazine were investigated in a metal-powder packed turbular flow reactor at 55 plus or minus 3 C. Hydrazine was completely reacted on all surfaces studied. The major products of monomethylhydrazine (MMH) oxidation were methanol, methane and methyldiazene. The di-, tri- and tetra-methyl hydrazines were essentially unreactive under these conditions. The relative catalytic reactivities toward MMH are: Fe greater than Al2O3 greater than Ti greater than Zn greater than 316 SS greater than Cr greater than Ni greater than Al greater than 304L SS. A kinetic scheme and mechanism involving adsorption, oxidative dehydrogenation and reductive elimination reactions on a metal oxide surface are proposed.

  12. Experimental Study of Stellar Reactions at CNS

    SciTech Connect

    Kubono, S.; Yamaguchi, H.; Wakabayashi, Y.; Amadio, G.; Hayakawa, S.; He, J. J.; Saito, A.; Teranishi, T.; Nishimura, S.; Fukunishi, N.; Iwasa, N.; Inafuku, K.; Kato, S.; Tanaka, M. H.; Fuchi, Y.; Moon, J. Y.; Kwon, K.; Lee, C. S.; Khiem, Le Hong; Chen, A.

    2006-11-02

    After a brief review on low-energy RI beam production technology, nuclear astrophysics programs at CNS are presented including a scope of the field in the Wako campus. The CRIB project involves a total development of the whole facility to maximize the low-energy RI beam intensities, including the ion source, the AVF cyclotron and the low-energy RI beam separator CRIB, Some recent nuclear astrophysics experiments performed with the RI beams were discussed, including the measurement of the 14O({alpha},p)17F reaction, the key stellar reaction for the onset of the high-temperature rp-process. The first experiment performed with a newly installed high-resolution magnetic spectrograph PA of CNS was also presented. Collaboration possibilities for nuclear astrophysics in the RIKEN campus are also touched.

  13. Experimental Study of Stellar Reactions at CNS

    NASA Astrophysics Data System (ADS)

    Kubono, S.; Yamaguchi, H.; Wakabayashi, Y.; Amadio, G.; Hayakawa, S.; He, J. J.; Saito, A.; Teranishi, T.; Nishimura, S.; Fukunishi, N.; Iwasa, N.; Inafuku, K.; Kato, S.; Tanaka, M. H.; Fuchi, Y.; Moon, J. Y.; Kwon, K.; Lee, C. S.; Khiem, Le Hong; Chen, A.; Pearson, J.

    2006-11-01

    After a brief review on low-energy RI beam production technology, nuclear astrophysics programs at CNS are presented including a scope of the field in the Wako campus. The CRIB project involves a total development of the whole facility to maximize the low-energy RI beam intensities, including the ion source, the AVF cyclotron and the low-energy RI beam separator CRIB, Some recent nuclear astrophysics experiments performed with the RI beams were discussed, including the measurement of the 14O(α,p)17F reaction, the key stellar reaction for the onset of the high-temperature rp-process. The first experiment performed with a newly installed high-resolution magnetic spectrograph PA of CNS was also presented. Collaboration possibilities for nuclear astrophysics in the RIKEN campus are also touched.

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

    PubMed

    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.

  15. Theoretical study of chemical reactions in solution

    SciTech Connect

    Yokogawa, D.

    2015-12-31

    Quantum chemical calculations in solution are becoming more and more important in chemistry. Reference interaction site model self-consistent field (RISM-SCF) is one of the powerful approaches to perform quantum chemical calculations in solution. In this work, we developed a new generation of RISM-SCF, where a robust fitting method was newly introduced. We applied the new method to tautomerization reaction of cytosine in aqueous phase. Our calculation reproduced experimentally obtained relative stabilities and relative free energies correctly.

  16. IN SITU INFRARED STUDY OF CATALYTIC DECOMPOSITION OF NITRIC OXIDE (NO)

    SciTech Connect

    Unknown

    1999-12-31

    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. The authors have investigated the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. The silanation approach failed to stabilize Cu-ZSM-5 activity under hydrothermal condition. Silanation blocked the oxygen migration and inhibited oxygen desorption. Oxygen spillover was found to be an effective approach for promoting NO decomposition activity on Pt-based catalysts. Detailed mechanistic study revealed the oxygen inhibition in NO decomposition and reduction as the most critical issue in developing an effective catalytic approach for controlling NO emission.

  17. Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

    SciTech Connect

    Gold, T.; Gordon, B.E.; Streett, W.; Bilson, E.; Patnaik, P.

    1986-11-01

    In order to assess the possible role of methane in petroleum formation, they studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250/sup 0/C in the presence of montmorillonite, a natural clay catalyst. Since they expected very slow reaction rates and thus low yields, we used /sup 14/C labeled methane to trace the reaction products. They report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C/sub 2/ addition occurred, although very small amounts of products corresponding to C/sub 1/ addition were also detected. They propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.

  18. Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

    NASA Astrophysics Data System (ADS)

    Gold, Thomas; Gordon, Benjamin E.; Streett, William; Bilson, Elizabeth; Patnaik, Pradyot

    1986-11-01

    In order to assess the possible role of methane in petroleum formation, we studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250°C in the presence of montmorillonite, a natural clay catalyst. Since we expected very slow reaction rates and thus low yields, we used 14C labeled methane to trace the reaction products. We report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C 2 addition occurred, although very small amounts of products corresponding to C 1 addition were also detected. We propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.

  19. [Performance Study of Bromochloracetonitrile Degradation in Drinking Water by Fe/Cu Catalytic Reduction].

    PubMed

    Ding, Chun-sheng; Ma, Hai-long; Fu, Yang-ping; Zhao, Shi-du; Li, Dong-bing

    2015-06-01

    The paper used the method of iron copper catalyst reduction to degrade low concentrations of bromochloracetonitrile (BCAN) to lighten the damage to human being, which is a kind of disinfection by-products (DBPs) produced during the chlorination process of drinking water. The removal efficiency of BCAN and its influencing factors were investigated. The mechanism of degradation and kinetics were also explored. The results indicated that iron copper had a greater degradation ability towards BCAN, and the degradation rate of iron copper (mass ratio of 10:1) was 1.5 times that of the zero-valent iron. The removal of BCAN increased obviously with the increase of Fe/Cu dosage. When the initial concentration was set at 20 microg x L(-1), after a reaction time of 150 min, removal of BCAN was improved from 51.1% to 89.5% with the increase of iron copper (mass ratio of 10:1) dosage from 5 g x L(-1) to 10 g x L(-1). The temperature also had great impact on BCAN removal and the removal increased with the increase of temperature. However, BCAN removal did not change a lot with the variation of the initial concentration of BCAN when it was at a low level. The BCAN degradation by iron copper catalytic-reduction followed the first-order kinetics model. PMID:26387315

  20. [Performance Study of Bromochloracetonitrile Degradation in Drinking Water by Fe/Cu Catalytic Reduction].

    PubMed

    Ding, Chun-sheng; Ma, Hai-long; Fu, Yang-ping; Zhao, Shi-du; Li, Dong-bing

    2015-06-01

    The paper used the method of iron copper catalyst reduction to degrade low concentrations of bromochloracetonitrile (BCAN) to lighten the damage to human being, which is a kind of disinfection by-products (DBPs) produced during the chlorination process of drinking water. The removal efficiency of BCAN and its influencing factors were investigated. The mechanism of degradation and kinetics were also explored. The results indicated that iron copper had a greater degradation ability towards BCAN, and the degradation rate of iron copper (mass ratio of 10:1) was 1.5 times that of the zero-valent iron. The removal of BCAN increased obviously with the increase of Fe/Cu dosage. When the initial concentration was set at 20 microg x L(-1), after a reaction time of 150 min, removal of BCAN was improved from 51.1% to 89.5% with the increase of iron copper (mass ratio of 10:1) dosage from 5 g x L(-1) to 10 g x L(-1). The temperature also had great impact on BCAN removal and the removal increased with the increase of temperature. However, BCAN removal did not change a lot with the variation of the initial concentration of BCAN when it was at a low level. The BCAN degradation by iron copper catalytic-reduction followed the first-order kinetics model.