Sample records for stable selective catalyst

  1. Highly Efficient, Selective, and Stable CO2 Electroreduction on a Hexagonal Zn Catalyst. (United States)

    Won, Da Hye; Shin, Hyeyoung; Koh, Jaekang; Chung, Jaehoon; Lee, Hee Sang; Kim, Hyungjun; Woo, Seong Ihl


    Electrocatalytic CO2 conversion into fuel is a prospective strategy for the sustainable energy production. However, still many parts of the catalyst such as low catalytic activity, selectivity, and stability are challenging. Herein, a hierarchical hexagonal Zn catalyst showed highly efficient and, more importantly, stable performance as an electrocatalyst for selectively producing CO. Moreover, we found that its high selectivity for CO is attributed to morphology. In electrochemical analysis, Zn (101) facet is favorable to CO formation whereas Zn (002) facet favors the H2 evolution during CO2 electrolysis. Indeed, DFT calculations showed that (101) facet lowers a reduction potential for CO2 to CO by more effectively stabilizing a (.) COOH intermediate than (002) facet. This further suggests that tuning the crystal structure to control (101)/(002) facet ratio of Zn can be considered as a key design principle to achieve a desirable product from Zn catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Catalysts and conditions for the highly efficient, selective and stable heterogeneous oligomerisation of ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Heveling, J.; Nicolaides, C.P.; Scurrell [Catalysis Programme, Division of Energy Technology, CSIR, PO Box 395, Pretoria 0001 (South Africa)


    The oligomerisation of ethylene into products in the C{sub 4}-C{sub 20} range over heterogeneous nickel catalysts in a fixed-bed reactor at low temperature and high pressure (LT-HP) is reported. The catalysts were obtained by Ni(II) exchange or impregnation of two differently prepared amorphous and mesoporous silica-alumina supports. A plot of catalytic activity versus temperature at 35bar and MHSV=2 produces a volcano-type curve with a maximum around 120C. Experiments performed under the LT-HP reaction conditions, viz. 120C, 35bar and MHSV=2, give an ethylene conversion level of 99% and a 97% selectivity to products with an even number of carbon atoms. The product spectrum (C{sub n} distribution) was dependent on the type of catalyst used, with the percentage of the C{sub 10+} coligomers lying in the range 23-41% by mass. Of practical significance, these types of catalyst were found to be extremely stable in use showing no detectable drop in conversion after 108 days on stream under the LT-HP employed

  3. Nickel Particles Selectively Confined in the Mesoporous Channels of SBA-15 Yielding a Very Stable Catalyst for DRM Reaction. (United States)

    Rodriguez-Gomez, Alberto; Pereñiguez, Rosa; Caballero, Alfonso


    A series of four Ni catalysts supported on SBA-15 and on a high SiO 2 surface area have been prepared by modified impregnation (ImU) and deposition-precipitation (DP) methods. The catalysts have been extensively characterized, including in situ XAS (bulk sensitive) and XPS (surface sensitive) techniques, and their catalytic activities evaluated in the dry reforming reaction of methane (DRM). The combined use of XPS and XAS has allowed us to determine the location of nickel particles on each catalyst after reduction at high temperature (750 °C). Both Ni/SiO 2 -DP and Ni/SBA-15-DP catalysts yield well-dispersed and homogeneous metallic phases mainly located in the mesoporosity of both supports. On the contrary, the Ni/SiO 2 -ImU and Ni/SBA-15-ImU catalysts present a bimodal distribution of the reduced nickel phase, with nickel metallic particles located out and into the mesoporous structure of SiO 2 or the SBA-15 channels. The Ni/SBA-15-DP catalyst was found the most stable and performing system, with a very low level of carbon deposition, about an order of magnitude lower than the equivalent ImU catalyst. This outstanding performance comes from the confinement of small and homogeneous nickel particles in the mesoporous channels of SBA-15, which, in strong interaction with the support, are resistant to sintering and coke deposition during the demanding reaction conditions of DRM.

  4. Thermally Stable, Latent Olefin Metathesis Catalysts


    Thomas, Renee M.; Fedorov, Alexey; Keitz, Benjamin K.; Grubbs, Robert H.


    Highly thermally stable N-aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to i...

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

    KAUST Repository

    Zhu, Haibo


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

  6. Ce0.95Cr0.05O2 and Ce0.97Cu0.03O2: active, selective and stable catalysts for selective hydrogen combustion. (United States)

    Beckers, Jurriaan; Rothenberg, Gadi


    Ceria-based materials are promising solid "oxygen reservoirs" for propane oxidative dehydrogenation. The ceria lattice oxygen can selectively combust hydrogen from the dehydrogenation mixture at 550 degrees C. This shifts the dehydrogenation equilibrium to the desired products side, generates heat aiding the endothermic dehydrogenation, and simplifies product separation. The process is also safer, since it avoids mixing O(2) and H(2) at high temperatures. While ceria itself is unselective, its catalytic properties can be tuned by doping. We study the effects of dopant type, concentration and the crystallite size on the catalytic properties. Doping with Cr or Cu increases both the selectivity and activity of the ceria, albeit that propane combustion also increases linearly with the Cu-concentration. The Cu-doped catalysts give selectivities up to 95% and combust up to 8% of the hydrogen feed. The best results are obtained with Cr-doped ceria, with selectivities up to 98%, and combustion of up to 15% of the hydrogen feed. The Cr-doped catalysts are stable in the reductive gas feed, and no extra coke is formed when the catalyst is subjected to an extra 10 min in the dehydrogenation mixture, after the hydrogen combustion reaction has stopped. This robustness is essential for industrial dehydrogenation applications.

  7. Highly Stable and Active Catalyst for Sabatier Reactions (United States)

    Hu, Jianli; Brooks, Kriston P.


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

  8. Deactivation-resistant catalyst for selective catalyst reduction of NOx

    DEFF Research Database (Denmark)


    The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

  9. Design of sintering-stable heterogeneous catalysts

    DEFF Research Database (Denmark)

    Gallas-Hulin, Agata

    the crystalline framework of a zeolite creates a steric hindrance against agglomeration into larger clusters. In the present study, experimental protocols for encapsulation of metal nanoparticles inside zeolites were developed. Two different methodologies were proposed to encapsulate gold, palladium and platinum......One of the major issues in the use of metal nanoparticles in heterogeneous catalysis is sintering. Sintering occurs at elevated temperatures because of increased mobility of nanoparticles, leading to their agglomeration and, as a consequence, to the deactivation of the catalyst. It is an emerging...... problem especially for the noble metals-based catalysis. These metals being expensive and scarce, it is worth developing catalyst systems which preserve their activity over time. Encapsulation of nanoparticles inside zeolites is one of the ways to prevent sintering. Entrapment of nanoparticles inside...

  10. Two Catalysts for Selective Oxidation of Contaminant Gases (United States)

    Wright, John D.


    Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

  11. Design criteria for stable Pt/C fuel cell catalysts

    Directory of Open Access Journals (Sweden)

    Josef C. Meier


    Full Text Available Platinum and Pt alloy nanoparticles supported on carbon are the state of the art electrocatalysts in proton exchange membrane fuel cells. To develop a better understanding on how material design can influence the degradation processes on the nanoscale, three specific Pt/C catalysts with different structural characteristics were investigated in depth: a conventional Pt/Vulcan catalyst with a particle size of 3–4 nm and two Pt@HGS catalysts with different particle size, 1–2 nm and 3–4 nm. Specifically, Pt@HGS corresponds to platinum nanoparticles incorporated and confined within the pore structure of the nanostructured carbon support, i.e., hollow graphitic spheres (HGS. All three materials are characterized by the same platinum loading, so that the differences in their performance can be correlated to the structural characteristics of each material. The comparison of the activity and stability behavior of the three catalysts, as obtained from thin film rotating disk electrode measurements and identical location electron microscopy, is also extended to commercial materials and used as a basis for a discussion of general fuel cell catalyst design principles. Namely, the effects of particle size, inter-particle distance, certain support characteristics and thermal treatment on the catalyst performance and in particular the catalyst stability are evaluated. Based on our results, a set of design criteria for more stable and active Pt/C and Pt-alloy/C materials is suggested.

  12. Modified calcium oxide as stable solid base catalyst for Aldol ...

    Indian Academy of Sciences (India)

    The influence of several reaction parameters, such as temperature, catalyst loading, was investigated. The humidity test over modified CaO reveals that the basic centres of modified CaO are stable for CO2 and moisture. From the results of Fourier transform-infrared (FT-IR) and Thermogravity analysis (TG) characterization, ...

  13. Modified calcium oxide as stable solid base catalyst for Aldol ...

    Indian Academy of Sciences (India)

    A highly efficient and stable solid-base catalyst for Aldol condensation was prepared by modifying commercial CaO with benzyl bromide in a simple way. It was found that modified CaO can effectively catalyse the Aldol condensation of cyclohexanone and benzaldehyde, as well as various benzaldehydes, to produce ...

  14. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

    Energy Technology Data Exchange (ETDEWEB)

    Jones, John; Xiong, Haifeng; DelaRiva, Andrew; Peterson, Eric J.; Pham, Hien; Challa, Sivakumar R.; Qi, Gongshin; Oh, Se H.; Wiebenga, Michelle H.; Pereira Hernandez, Xavier I.; Wang, Yong; Datye, Abhaya K.


    Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoring the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.

  15. Ligand iron catalysts for selective hydrogenation (United States)

    Casey, Charles P.; Guan, Hairong


    Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

  16. Facile Synthesis of Effcient and Selective Ruthenium Olefin Metathesis Catalysts with Sulfonate and Phosphate Ligands


    Teo, Peili; Grubbs, Robert H.


    A series of novel, air-stable ruthenium NHC catalysts with sulfonate and phosphate anions have been prepared easily in one pot at high yields using commercially available precursors. The catalysts were found to be effective for ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis. The catalysts showed higher cis-selectivity in olefin cross-metathesis reactions as compared to earlier known ruthenium-based olefin metathesis catalysts, with allylbenzene and cis-1...

  17. Bismuth-doped ceria, Ce0.90Bi0.10O2: A selective and stable catalyst for clean hydrogen combustion

    NARCIS (Netherlands)

    Beckers, J.; Lee, A.F.; Rothenberg, G.


    Bismuth-doped cerias are successfully applied as solid oxygen reservoirs in the oxidative dehydrogenation of propane. The lattice oxygen of the ceria is used to selectively combust hydrogen from the dehydrogenation mixture at 550 °C. This process has three key advantages: it shifts the

  18. Sexual selection studies: A NESCent catalyst meeting

    NARCIS (Netherlands)

    Roughgarden, J.; Adkins-Regan, E.; Akcay, E.; Hinde, C.A.; Hoquet, T.; O'Connor, C.; Prokop, Z.M.; Prum, R.O.; Shafir, S.; Snow, S.S.; Taylor, D.; Cleve, Van J.; Weisberg, M.


    A catalyst meeting on sexual selection studies was held in July 2013 at the facilities of the National Evolutionary Synthesis Center (NESCent) in Durham, NC. This article by a subcommittee of the participants foregrounds some of the topics discussed at the meeting. Topics mentioned here include the

  19. Catalysis by nonmetals rules for catalyst selection

    CERN Document Server

    Krylov, Oleg V


    Catalysis by Non-metals: Rules of Catalyst Selection presents the development of scientific principles for the collection of catalysts. It discusses the investigation of the mechanism of chemosorption and catalysis. It addresses a series of properties of solid with catalytic activity. Some of the topics covered in the book are the properties of a solid and catalytic activity in oxidation-reduction reactions; the difference of electronegativities and the effective charges of atoms; the role of d-electrons in the catalytic properties of a solid; the color of solids; and proton-acid and proton-ba

  20. Selective Oxidations using Nanostructured Heterogeneous Catalysts

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen

    The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available and b...... stability, catalytic activity and selectivity for the gas-phase oxidation of bioethanol to acetaldehyde, which may become a favourable and green alternative to the ethylene route.......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available......, the chapter focuses on the use of supported metal catalysts for the selective oxidation of alcohols, which are currently dominated by the platinum group metals. Chapter 2 deals with the most important methods to characterise heterogeneous catalysts, including X-ray powder diffraction, physisorption analysis...

  1. Investigation of activity and selectivity of redox catalysts in oxidative ...

    African Journals Online (AJOL)

    In this study, oxidative coupling of methane on Redox catalysts in fluidized bed reactor was investigated. For this purpose, the catalyst Mn-Na2WO4/SiO2 was selected as a Redox catalyst. In order to investigate this catalyst, transient state experiments were designed and performed. Then, the different reaction conditions on ...

  2. Selective catalyst reduction light-off strategy (United States)

    Gonze, Eugene V [Pinckney, MI


    An emissions control system includes a temperature determination module and an emissions control module. The temperature determination module determines a first temperature of a heater element of a diesel particulate filter (DPF) assembly in an exhaust system and determines a second temperature of a catalyst of the DPF assembly. The emissions control module selectively activates the heater element, selectively initiates a predefined combustion process in an engine based upon the first temperature, and selectively starts a reductant injection process based upon the second temperature.

  3. Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion. (United States)

    Casavola, Marianna; Xie, Jingxiu; Meeldijk, Johannes D; Krans, Nynke A; Goryachev, Andrey; Hofmann, Jan P; Dugulan, A Iulian; de Jong, Krijn P


    Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na 2 S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer-Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters.

  4. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama


    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  5. Copper (0) nanoparticles onto silica: A stable and facile catalyst for ...

    Indian Academy of Sciences (India)

    Vol. 128, No. 5, May 2016, pp. 849–854. c Indian Academy of Sciences. DOI 10.1007/s12039-016-1080-6. Copper (0) nanoparticles onto silica: A stable and facile catalyst ... Studies comparing these supported catalysts were done with the synthesis of arylmethylene-bis- ... organic synthesis is gaining much attention but the.

  6. Ce0.95Cr0.05O2 and Ce0.97Cu0.03O2: Active, selective and stable catalysts for selective hydrogen combustion

    NARCIS (Netherlands)

    Beckers, J.; Rothenberg, G.


    Ceria-based materials are promising solid oxygen reservoirs for propane oxidative dehydrogenation. The ceria lattice oxygen can selectively combust hydrogen from the dehydrogenation mixture at 550 °C. This shifts the dehydrogenation equilibrium to the desired products side, generates heat aiding the

  7. Multiphase catalysts for selective reduction of NOx with hydrocarbons

    International Nuclear Information System (INIS)

    Maisuls, S.E.


    Among the existing proposed solutions to reduce emission of NOx there is a promising alternative, the so-called (HC-SCR) selective catalytic reduction of NOx using hydrocarbons as reductant. This thesis is part of a worldwide effort devoted to gain knowledge on the selective catalytic reduction of NOx with hydrocarbons with the final goal to contribute to the development of suitable catalysts for the above mentioned process. Chapter 2 describes the details of the experimental set-up and of the analytical methods employed. Among the catalyst for HC-SCR, Co-based catalyst are known to be active and selective, thus, a study on a series of Co-based catalysts, supported on zeolites, was undertaken and the results are presented in Chapter 3. Correlation between catalytic characteristics and kinetic results are employed to understand the working catalyst and this is used as a basis for catalyst optimization. With the intention to prepare a multi-functional catalyst that will preserve the desired characteristics of the individual components, minimizing their negative aspects, catalysts based on Co-Pt, supported on ZSM-5, were investigated. In Chapter 4 the results of this study are discussed. A bimetallic Co-Pt/ZSM-5 catalysts with low Pt contents (0.1 wt %) showed a synergistic effect by combining high stability and activity of Pt catalysts with the high N2 selectivity of Co catalysts. Furthermore, it was found to be sulfur- and water-tolerant. Its positive qualities brought us to study the mechanism that takes place over this catalyst during HC-SCR. The results of an in-situ i.r mechanistic study over this catalyst is reported in Chapter 5. From the results presented in Chapter 5 a mechanism operating over the Co-Pt/ZSM-5 catalyst is proposed. The modification of Co catalyst with Pt improved the catalysts. However, further improvement was found to be hindered by high selectivity to N2O. Since Rh catalysts are generally less selective to N2O, the modification of Co

  8. Exceptionally Stable and Efficient Solid Supported Hoveyda-Type Catalyst

    Czech Academy of Sciences Publication Activity Database

    Skowerski, K.; Pastva, J.; Czarnocki, S. J.; Janošcová, Jana


    Roč. 19, č. 7 (2015), s. 872-877 ISSN 1083-6160 Institutional support: RVO:61388955 Keywords : OLEFIN - METATHESIS CATALYSTS * RING-CLOSING METATHESIS * N-HETEROCYCLIC CARBENES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.922, year: 2015

  9. Highly efficient and stable catalyst for peroxynitrite decomposition (United States)

    Yurii V. Geletii; Alan J. Bailey; Jennifer J. Cowan; Ira A. Weinstock; Craig L. Hill


    The new cobalt substituted-polyoxometalate K7[CoAlW11O39]•15H2O and the simple CoCl2•6H2O salt are efficient catalysts for peroxynitrite decomposition. These compounds also catalyze the oxidation of ascorbic acid and the nitration of phenol by peroxynitrite.

  10. Chelated ruthenium catalysts for Z-selective olefin metathesis. (United States)

    Endo, Koji; Grubbs, Robert H


    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands that catalyze highly Z-selective olefin metathesis. A very simple and convenient procedure for the synthesis of such catalysts has been developed. Intramolecular C-H bond activation of the NHC ligand, promoted by anion ligand substitution, forms the appropriate chelate for stereocontrolled olefin metathesis.

  11. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    This work presents a study of the deactivation behavior of Fe-Mo oxide catalyst during selective oxidation of methanol to formaldehyde in a period of 5 days. The structural changes in the catalyst have been investigated in situ for the initial 10 h by Raman spectroscopy, and the structure after 5...

  12. Capsule-controlled selectivity of a rhodium hydroformylation catalyst

    NARCIS (Netherlands)

    Bocokić, V.; Kalkan, A.; Lutz, M.; Spek, A.L.; Gryko, D.T.; Reek, J.N.H.


    Chemical processes proceed much faster and more selectively in the presence of appropriate catalysts, and as such the field of catalysis is of key importance for the chemical industry, especially in light of sustainable chemistry. Enzymes, the natural catalysts, are generally orders of magnitude

  13. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    as the Formox process [1]. The average lifetime of the industrial catalyst is only 1–2 years depending on the operating conditions. The catalyst consists of a bulk phase of Fe2(MoO4)3 and a surface layer phase of MoO3. The MoO3 surfaceis selective towards formaldehyde while the iron in the sublayer increases...... the activity of the catalyst [2]. Pure MoO3 in itself has low activity. Literature from the last decades agrees that the major reason for the deactivation is loss of molybdenum from the catalyst. Molybdenum forms volatile species with methanol, which can leave behind Mo poor zones. The catalyst is usually...... prepared with excess MoO3 (Mo/Fe > 1.5) to counter the loss of Mo. This work focuses on understanding the structural changes occurring in the catalyst and its behavior during deactivation via prolonged activity testing and spectroscopic investigations....

  14. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure (United States)

    Sachtler, Wolfgang M. H.; Huang, Yin-Yan


    Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

  15. Catalysts for the selective oxidation of hydrogen sulfide to sulfur (United States)

    Srinivas, Girish; Bai, Chuansheng


    This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

  16. Potential application of palladium nanoparticles as selective recyclable hydrogenation catalysts

    International Nuclear Information System (INIS)

    Mukherjee, DebKumar


    The search for more efficient catalytic systems that might combine the advantages of both homogeneous (catalyst modulation) and heterogeneous (catalyst recycling) catalysis is one of the most exciting challenges of modern chemistry. More recently with the advances of nanochemistry, it has been possible to prepare soluble analogues of heterogeneous catalysts. These nanoparticles are generally stabilized against aggregation into larger particles by electrostatic or steric protection. Herein we demonstrate the use of room temperature ionic liquid for the stabilization of palladium nanoparticles that are recyclable catalysts for the hydrogenation of carbon-carbon double bonds and application of these catalysts to the selective hydrogenation of internal or terminal C=C bonds in unsaturated primary alcohols. The particles suspended in room temperature ionic liquid show no metal aggregation or loss of catalytic activity even on prolonged use

  17. Alkali resistivity of Cu based selective catalytic reduction catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Jensen, Anker Degn; Riisager, Anders


    The deactivation of V2O5–WO3–TiO2, Cu–HZSM5 and Cu–HMOR plate type monolithic catalysts was investigated when exposed to KCl aerosols in a bench-scale reactor. Fresh and exposed catalysts were characterized by selective catalytic reduction (SCR) activity measurements, scanning electron microscope...... and Cu–HMOR catalysts only experienced a slight loss of acidity while the V2O5–WO3–TiO2 catalyst lost most of the acidity. High alkali resistivity seems to be characteristic of the zeolite supported SCR catalysts which thus could be attractive for flue gas cleaning in biomass plants....

  18. Comparison of environmentally friendly, selective polyurethane catalysts

    Czech Academy of Sciences Publication Activity Database

    Strachota, Adam; Strachotová, Beata; Špírková, Milena


    Roč. 23, č. 6 (2008), s. 566-570 ISSN 1042-6914 R&D Projects: GA MPO FT-TA3/034 Institutional research plan: CEZ:AV0Z40500505 Keywords : amine catalyst * foam * gelation * kinetics * polyurethane Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.706, year: 2008

  19. Pt Monolayer Shell on Nitrided Alloy Core—A Path to Highly Stable Oxygen Reduction Catalyst

    Directory of Open Access Journals (Sweden)

    Jue Hu


    Full Text Available The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC. Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared PtMLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability of the PtMLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.

  20. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.

  1. Hydrothermally Stable Fe–W–Ti SCR Catalysts Prepared by Deposition–Precipitation

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Mossin, Susanne


    Fe/TiO2 based catalysts were prepared by incipient wetness impregnation and deposition–precipitation (DP). The catalysts were characterized by activity measurements, N2 physisorption, X-ray powder diffraction, electron paramagnetic resonance spectroscopy, energy dispersive X-ray spectroscopy, H2......-temperature programmed reduction and NH3-temperature programmed desorption. The 3 wt% Fe–10 wt% WO3/TiO2 (3Fe–10WTi-DP) catalyst prepared by DP using ammonium carbamate as a precipitating agent was found to be the most active and hydrothermally stable with 11 vol% H2O in air at 650 °C for 3 h....... The hydrothermal stability of the catalyst can be attributed to the retained crystal structure, and mild change in acidic and redox properties of the catalyst. Furthermore, hydrothermal stability of the 3Fe–10WTi-DP catalyst is competitive with that of 3Fe–ZSM-5 and much better than 3V2O5–10WO3–TiO2 catalysts...

  2. Towards stable catalysts by control over the collective features of supported metal nanoparticles

    NARCIS (Netherlands)

    Prieto, G.; Zecevic, J.|info:eu-repo/dai/nl/341386715; Friedrich, H.|info:eu-repo/dai/nl/304837350; de Jong, K.P.|info:eu-repo/dai/nl/06885580X; de Jongh, P.E.|info:eu-repo/dai/nl/186125372


    Supported metal nanoparticles play a pivotal role in areas such as nanoelectronics, energy storage/conversion1 and as catalysts for the sustainable production of fuels and chemicals2–4. However, the tendency of nanoparticles to grow into larger crystallites is an impediment for stable

  3. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of a mesoporous aluminosilicate catalyst, AlSBA-15. The Al-SBA-15 mesoporous catalyst contains strong Br{umlt o}nsted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt % Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at a temperature of 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into a psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst is being evaluated for the conversion of a heavy petroleum feedstock to naphtha and middle distillates. This phase was significantly delayed during the past six months due to a serious malfunction of the fume hoods in the Clark Atlanta University's Research Center for Science and Technology, where the project is being conducted. The fume hood system was repaired and the catalyst evaluation is now underway.

  5. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis


    Endo, Koji; Grubbs, Robert H.


    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis.

  6. Stable catalyst layers for hydrogen permeable composite membranes (United States)

    Way, J. Douglas; Wolden, Colin A


    The present invention provides a hydrogen separation membrane based on nanoporous, composite metal carbide or metal sulfide coated membranes capable of high flux and permselectivity for hydrogen without platinum group metals. The present invention is capable of being operated over a broad temperature range, including at elevated temperatures, while maintaining hydrogen selectivity.

  7. Modified calcium oxide as stable solid base catalyst for Aldol ...

    Indian Academy of Sciences (India)

    rated and washed with methanol to remove excess modi- fier, and the modified CaO was obtained after a vacuum drying process. In order to increase the reproducibili- ty, the particles were sieved before use. Particles of. 100–160 mesh size were selected for all experiments. 2.2 Humidity test. Amount of commercial CaO ...

  8. Catalytic Membranes Embedding Selective Catalysts: Preparation and Applications (United States)

    Drioli, Enrico; Fontananova, Enrica

    The embedding of a catalyst in membranes is today recognized as a promising strategy to develop highly efficient and eco-friendly heterogeneous catalytic chemical processes. When a catalyst is heterogenized within or on the surface of a membrane, the membrane composition (characteristics of the membrane material: hydrophobic or hydrophilic, presence of chemical groups with specific functionality, etc.) and the membrane structure (dense or porous, symmetric or asymmetric), can positively influence the catalyst performance, not only by the selective sorption and diffusion of reagents and/or products, but also influencing the catalyst activity by electronic and conformational effect. These effects are similar to those occurring in biological membranes. In this chapter, after a preliminary presentation of the basic principles of membrane reactors and polymer membranes, the preparation, characterization and applications of polymeric catalytic membranes, will be discussed.

  9. Improved ruthenium catalysts for Z-selective olefin metathesis. (United States)

    Keitz, Benjamin K; Endo, Koji; Patel, Paresma R; Herbert, Myles B; Grubbs, Robert H


    Several new C-H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products. © 2011 American Chemical Society

  10. Stable gold(III) catalysts by oxidative addition of a carbon-carbon bond. (United States)

    Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch; Toste, F Dean


    Low-valent late transition-metal catalysis has become indispensable to chemical synthesis, but homogeneous high-valent transition-metal catalysis is underdeveloped, mainly owing to the reactivity of high-valent transition-metal complexes and the challenges associated with synthesizing them. Here we report a carbon-carbon bond cleavage at ambient conditions by a Au(i) complex that generates a stable Au(iii) cationic complex. In contrast to the well-established soft and carbophilic Au(i) catalyst, this Au(iii) complex exhibits hard, oxophilic Lewis acidity. For example, we observed catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(iii)-activated cinnamaldehyde intermediate. The concepts revealed suggest a strategy for accessing high-valent transition-metal catalysis from readily available precursors.

  11. Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction. (United States)

    Kibsgaard, Jakob; Jaramillo, Thomas F


    Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non-noble-metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed-metal alloy catalysts are well-known, MoP|S represents a more uncommon mixed-anion catalyst where synergistic effects between sulfur and phosphorus produce a high-surface-area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water-splitting cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Subnanometer and nanometer catalysts, method for preparing size-selected catalysts (United States)

    Vajda, Stefan [Lisle, IL; Pellin, Michael J [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR


    Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

  13. Novel vanadium phosphate phases as catalysts for selective oxidation

    Indian Academy of Sciences (India)


    Abstract. In our effort to induce novel modifications in the structure of some important vanadium phosphate phases used as selective oxidation catalysts, it has been observed that metal ions such as Zn2+, Ni2+, Pd2+ can be incorporated into the vanadyl hydrogen phosphate VOHPO4⋅0⋅5H2O phase in very different ways.


    DEFF Research Database (Denmark)


    A catalyst comprising a mixture of metal A selected from the group of Fe, Co and Ni and metal B selected from the group of Zn and Ga, and a support material, wherein the two metals are present in an intermetallic composition; A method for the manufacture of the catalyst; and the use of above...

  15. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons (United States)

    Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.


    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

  16. Catalytic Metallodrugs: Substrate-Selective Metal Catalysts as Therapeutics. (United States)

    Yu, Zhen; Cowan, James A


    Metal complexes that catalyze inactivation and degradation of biomolecular targets can be developed into novel therapeutics (catalytic metallodrugs) against a variety of diseases. Despite recent advances in the field, a lack of substrate selectivity is a major hindrance to the development of catalytic metallodrugs for application in clinical practice. Improved targeting can minimize nonselective activity and the potential for side effects. Herein, we focus on recent developments toward novel metal catalysts that exhibit substrate selectivity against a variety of therapeutically relevant biomolecules. Design strategies for developing selective catalytic metallodrugs are also highlighted. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pt5Gd as a Highly Active and Stable Catalyst for Oxygen Electroreduction

    DEFF Research Database (Denmark)

    Escribano, Maria Escudero; Verdaguer-Casadevall, Arnau; Verdaguer Casadevall, Arnau


    The activity and stability of Pt5Gd for the oxygen reduction reaction (ORR) have been studied, using a combination of electrochemical measurements, angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and density functional theory calculations. Sputter-cleaned, polycrystalline Pt5Gd shows a ...... can be explained by means of compressive strain effects. Furthermore, these novel bimetallic electrocatalysts are highly stable, which, in combination with their enhanced activity, makes them very promising for the development of new cathode catalysts for fuel cells....

  18. Selective hydrogenation of citral over supported Pt catalysts: insight into support effects

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaofeng [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States); Hu, Weiming; Deng, Baolin [University of Missouri, Department of Civil and Environmental Engineering (United States); Liang, Xinhua, E-mail: [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States)


    Highly dispersed platinum (Pt) nanoparticles (NPs) were deposited on various substrates by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. The substrates included multi-walled carbon nanotubes (MWCNTs), silica gel (SiO{sub 2}), commercial γ-Al{sub 2}O{sub 3}, and ALD-prepared porous Al{sub 2}O{sub 3} particles (ALD-Al{sub 2}O{sub 3}). The results of TEM analysis showed that ~1.3 nm Pt NPs were highly dispersed on all different supports. All catalysts were used for the reaction of selective hydrogenation of citral to unsaturated alcohols (UA), geraniol, and nerol. Both the structure and acidity of supports affected the activity and selectivity of Pt catalysts. Pt/SiO{sub 2} showed the highest activity due to the strong acidity of SiO{sub 2} and the conversion of citral reached 82% after 12 h with a selectivity of 58% of UA. Pt/MWCNTs showed the highest selectivity of UA, which reached 65% with a conversion of 38% due to its unique structure and electronic effect. The cycling experiments indicated that Pt/MWCNTs and Pt/ALD-Al{sub 2}O{sub 3} catalysts were more stable than Pt/SiO{sub 2}, as a result of the different interactions between the Pt NPs and the supports.

  19. Selective propene oxidation on mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    James, David William


    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

  20. Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols (United States)


    The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

  1. Active and Stable Methane Oxidation Nano-Catalyst with Highly-Ionized Palladium Species Prepared by Solution Combustion Synthesis

    Directory of Open Access Journals (Sweden)

    Mahmoud M. Khader


    Full Text Available We report on the synthesis and testing of active and stable nano-catalysts for methane oxidation. The nano-catalyst was palladium/ceria supported on alumina prepared via a one-step solution-combustion synthesis (SCS method. As confirmed by X-ray photoelectron spectroscopy (XPS and high-resolution transmission electron microscopy (HTEM, SCS preparative methodology resulted in segregating both Pd and Ce on the surface of the Al2O3 support. Furthermore, HTEM showed that bigger Pd particles (5 nm and more were surrounded by CeO2, resembling a core shell structure, while smaller Pd particles (1 nm and less were not associated with CeO2. The intimate Pd-CeO2 attachment resulted in insertion of Pd ions into the ceria lattice, and associated with the reduction of Ce4+ into Ce3+ ions; consequently, the formation of oxygen vacancies. XPS showed also that Pd had three oxidation states corresponding to Pd0, Pd2+ due to PdO, and highly ionized Pd ions (Pd(2+x+ which might originate from the insertion of Pd ions into the ceria lattice. The formation of intrinsic Ce3+ ions, highly ionized (Pd2+ species inserted into the lattice of CeO2 Pd ions (Pd(2+x+ and oxygen vacancies is suggested to play a major role in the unique catalytic activity. The results indicated that the Pd-SCS nano-catalysts were exceptionally more active and stable than conventional catalysts. Under similar reaction conditions, the methane combustion rate over the SCS catalyst was ~18 times greater than that of conventional catalysts. Full methane conversions over the SCS catalysts occurred at around 400 °C but were not shown at all with conventional catalysts. In addition, contrary to the conventional catalysts, the SCS catalysts exhibited superior activity with no sign of deactivation in the temperature range between ~400 and 800 °C.

  2. Solid Catalyst with Ionic Liquid Layer (SCILL). A concept to improve the selectivity of selective hydrogenations

    Energy Technology Data Exchange (ETDEWEB)

    Jess, A.; Korth, W. [Bayreuth Univ. (Germany). Chair of Chemical Engineering


    Catalytic hydrogenations are important for refinery processes, petrochemical applications as well as for numerous processes of the fine chemicals industry. In some cases, hydrogenations consist of a sequence of consecutive reactions, and the desired product is the intermediate. An important goal is then a high yield and selectivity to the intermediate, if possible at a high conversion degree. The selectivity to an intermediate primarily depends on the chemical nature of the catalyst, but may also be influenced by diffusion processes. Ionic liquids (ILs) are low melting salts (< 100 C) and represent a promising solvent class. This paper focuses on the concept of a Solid Catalyst with Ionic Liquid Layer (SCILL), where the solid catalyst is coated with a thin IL layer to improve the selectivity. (orig.)

  3. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.


    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  5. Development of active, and stable water-gas-shift reaction catalysts for fuel cell applications

    NARCIS (Netherlands)

    Azzam, K.G.H.; Babich, Igor V.; Seshan, Kulathu Iyer; Lefferts, Leon


    Water-gas-shift (WGS) reaction CO + H2O = CO2 + H2, is a key step in the generation of H2 for fuel cells. Noble metal-based catalysts are promising single stage WGS catalysts because they less sensitive than LTS catalysts (Cu based) and more active than the HTS (Ni) catalysts. High activity in CO

  6. Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

    DEFF Research Database (Denmark)

    Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus


    Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9...

  7. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds (United States)

    Allendorf, Mark D.; Stavila, Vitalie


    The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.

  8. Highly selective hydrogenation of arenes using nanostructured ruthenium catalysts modified with a carbon–nitrogen matrix (United States)

    Cui, Xinjiang; Surkus, Annette-Enrica; Junge, Kathrin; Topf, Christoph; Radnik, Jörg; Kreyenschulte, Carsten; Beller, Matthias


    Selective hydrogenations of (hetero)arenes represent essential processes in the chemical industry, especially for the production of polymer intermediates and a multitude of fine chemicals. Herein, we describe a new type of well-dispersed Ru nanoparticles supported on a nitrogen-doped carbon material obtained from ruthenium chloride and dicyanamide in a facile and scalable method. These novel catalysts are stable and display both excellent activity and selectivity in the hydrogenation of aromatic ethers, phenols as well as other functionalized substrates to the corresponding alicyclic reaction products. Furthermore, reduction of the aromatic core is preferred over hydrogenolysis of the C–O bond in the case of ether substrates. The selective hydrogenation of biomass-derived arenes, such as lignin building blocks, plays a pivotal role in the exploitation of novel sustainable feedstocks for chemical production and represents a notoriously difficult transformation up to now. PMID:27113087

  9. Immobilized Bis-Indenyl Ligands for Stable and Cost-Effective Metallocene Catalysts of Hydrogenation and Polymerization Reactions (United States)

    Simerly, Thomas Max

    Reactions of catalytic hydrogenations and polymerizations are widely used in industry for manufacture of fine chemicals, pharmaceuticals, and plastics. Homogeneous catalysts for the processes that have low stability and their separation is difficult. Therefore, the development of new highly active and stable catalysts for hydrogenations and polymerizations is a necessity. The objective of this research was the development of a strategy for immobilization of heterogeneous metallocene catalysts. First, a methodology of immobilization of bis-indenyl ligands on the surface of mesoporous silica gel was designed. Four bis-indenyl ligands containing functionalized tethers of various lengths with terminal alkene groups were synthesized. All bis-indenyl ligands were immobilized on the surface of mesoporous functionalized silica gel by two methods: hydrosilylation and thiol-ene coupling of the double bond. After comparing the results, the second strategy was chosen as more efficient. The materials can be used further as intermediates for synthesis of supported metallocene catalysts.

  10. Towards Highly Performing and Stable PtNi Catalysts in Polymer Electrolyte Fuel Cells for Automotive Application

    Directory of Open Access Journals (Sweden)

    Sabrina C. Zignani


    Full Text Available In order to help the introduction on the automotive market of polymer electrolyte fuel cells (PEFCs, it is mandatory to develop highly performing and stable catalysts. The main objective of this work is to investigate PtNi/C catalysts in a PEFC under low relative humidity and pressure conditions, more representative of automotive applications. Carbon supported PtNi nanoparticles were prepared by reduction of metal precursors with formic acid and successive thermal and leaching treatments. The effect of the chemical composition, structure and surface characteristics of the synthesized samples on their electrochemical behavior was investigated. The catalyst characterized by a larger Pt content (Pt3Ni2/C presented the highest catalytic activity (lower potential losses in the activation region among the synthesized bimetallic PtNi catalysts and the commercial Pt/C, used as the reference material, after testing at high temperature (95 °C and low humidification (50% conditions for automotive applications, showing a cell potential (ohmic drop-free of 0.82 V at 500 mA·cm−2. In order to assess the electro-catalysts stability, accelerated degradation tests were carried out by cycling the cell potential between 0.6 V and 1.2 V. By comparing the electrochemical and physico-chemical parameters at the beginning of life (BoL and end of life (EoL, it was demonstrated that the Pt1Ni1/C catalyst was the most stable among the catalyst series, with only a 2% loss of voltage at 200 mA·cm−2 and 12.5% at 950 mA·cm−2. However, further improvements are needed to produce durable catalysts.

  11. Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti-Stabilized MnO2

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Paoli, Elisa Antares; Chorkendorff, Ib


    Catalysts are required for the oxygen evolution reaction, which are abundant, active, and stable in acid. MnO2 is a promising candidate material for this purpose. However, it dissolves at high overpotentials. Using first-principles calculations, a strategy to mitigate this problem by decorating...

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

    Energy Technology Data Exchange (ETDEWEB)



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

  13. Efficient Pd@MIL-101(Cr) hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity

    KAUST Repository

    Yin, Dongdong


    Pd@MIL-101(Cr) hetero-catalysts have been successfully prepared using the metal-organic chemical vapour deposition (MOCVD) approach, by choosing [Pd(η-CH)(η-CH)] as a volatile precursor, and the hydrothermally stable metal-organic framework, MIL-101(Cr) as a support. The prepared Pd@MIL-101(Cr) hetero-catalysts characterized with various analytical techniques, exhibited highly monodispersed immobilized Pd nanoparticles in the MIL-101(Cr) cavities, while retaining the pristine crystallinity and porosity. The intact hybrid Pd@MIL-101(Cr) has been demonstrated to be an efficient catalyst for 2-butyne-1,4-diol hydrogenation with excellent activity, stability and selectivity (2-butene-1,4-diol (>94%)).

  14. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. (United States)

    Choi, Minkee; Na, Kyungsu; Kim, Jeongnam; Sakamoto, Yasuhiro; Terasaki, Osamu; Ryoo, Ryong


    Zeolites-microporous crystalline aluminosilicates-are widely used in petrochemistry and fine-chemical synthesis because strong acid sites within their uniform micropores enable size- and shape-selective catalysis. But the very presence of the micropores, with aperture diameters below 1 nm, often goes hand-in-hand with diffusion limitations that adversely affect catalytic activity. The problem can be overcome by reducing the thickness of the zeolite crystals, which reduces diffusion path lengths and thus improves molecular diffusion. This has been realized by synthesizing zeolite nanocrystals, by exfoliating layered zeolites, and by introducing mesopores in the microporous material through templating strategies or demetallation processes. But except for the exfoliation, none of these strategies has produced 'ultrathin' zeolites with thicknesses below 5 nm. Here we show that appropriately designed bifunctional surfactants can direct the formation of zeolite structures on the mesoporous and microporous length scales simultaneously and thus yield MFI (ZSM-5, one of the most important catalysts in the petrochemical industry) zeolite nanosheets that are only 2 nm thick, which corresponds to the b-axis dimension of a single MFI unit cell. The large number of acid sites on the external surface of these zeolites renders them highly active for the catalytic conversion of large organic molecules, and the reduced crystal thickness facilitates diffusion and thereby dramatically suppresses catalyst deactivation through coke deposition during methanol-to-gasoline conversion. We expect that our synthesis approach could be applied to other zeolites to improve their performance in a range of important catalytic applications.

  15. Simple and highly Z-selective ruthenium-based olefin metathesis catalyst. (United States)

    Occhipinti, Giovanni; Hansen, Fredrik R; Törnroos, Karl W; Jensen, Vidar R


    A one-step substitution of a single chloride anion of the Grubbs-Hoveyda second-generation catalyst with a 2,4,6-triphenylbenzenethiolate ligand resulted in an active olefin metathesis catalyst with remarkable Z selectivity, reaching 96% in metathesis homocoupling of terminal olefins. High turnover numbers (up to 2000 for homocoupling of 1-octene) were obtained along with sustained appreciable Z selectivity (>85%). Apart from the Z selectivity, many properties of the new catalyst, such as robustness toward oxygen and water as well as a tendency to isomerize substrates and react with internal olefin products, resemble those of the parent catalyst.

  16. Selection of medical treatment in stable angina pectoris

    DEFF Research Database (Denmark)

    Ardissino, D; Savonitto, S; Egstrup, K


    pectoris. BACKGROUND: The characteristics of anginal symptoms and the results of exercise testing are considered of great importance for selecting medical treatment in patients with chronic stable angina pectoris. However, little information is available on how this first evaluation may be used to select......, the patients were randomly allocated to double-blind treatment for 6 weeks with either metoprolol (Controlled Release, 200 mg once daily) or nifedipine (Retard, 20 mg twice daily) according to a parallel group design. At the end of this period, exercise tests were repeated 1 to 4 h after drug intake. RESULTS....... CONCLUSIONS: The results of a baseline exercise test, but not the characteristics of anginal symptoms, may offer useful information for selecting medical treatment in stable angina pectoris....

  17. Superior Stability of Au/SiO2Compared to Au/TiO2Catalysts for the Selective Hydrogenation of Butadiene. (United States)

    Masoud, Nazila; Delannoy, Laurent; Schaink, Herrick; van der Eerden, Ad; de Rijk, Jan Willem; Silva, Tiago A G; Banerjee, Dipanjan; Meeldijk, Johannes D; de Jong, Krijn P; Louis, Catherine; de Jongh, Petra E


    Supported gold nanoparticles are highly selective catalysts for a range of both liquid-phase and gas-phase hydrogenation reactions. However, little is known about their stability during gas-phase catalysis and the influence of the support thereon. We report on the activity, selectivity, and stability of 2-4 nm Au nanoparticulate catalysts, supported on either TiO 2 or SiO 2 , for the hydrogenation of 0.3% butadiene in the presence of 30% propene. Direct comparison of the stability of the Au catalysts was possible as they were prepared via the same method but on different supports. At full conversion of butadiene, only 0.1% of the propene was converted for both supported catalysts, demonstrating their high selectivity. The TiO 2 -supported catalysts showed a steady loss of activity, which was recovered by heating in air. We demonstrated that the deactivation was not caused by significant metal particle growth or strong metal-support interaction, but rather, it is related to the deposition of carbonaceous species under reaction conditions. In contrast, all the SiO 2 -supported catalysts were highly stable, with very limited formation of carbonaceous deposits. It shows that SiO 2 -supported catalysts, despite their 2-3 times lower initial activities, clearly outperform TiO 2 -supported catalysts within a day of run time.

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

    KAUST Repository

    Shaikh Ali, Anaam


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

  19. Volume 1, 1st Edition, Multiscale Tailoring of Highly Active and Stable Nanocomposite Catalysts, Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Veser, Goetz


    Nanomaterials have gained much attention as catalysts since the discovery of exceptional CO oxidation activity of nanoscale gold by Haruta. However, many studies avoid testing nanomaterials at the high-temperatures relevant to reactions of interest for the production of clean energy (T > 700°C). The generally poor thermal stability of catalytically active noble metals has thus far prevented significant progress in this area. We have recently overcome the poor thermal stability of nanoparticles by synthesizing a platinum barium-hexaaluminate (Pt-BHA) nanocomposite which combines the high activity of noble metal nanoparticles with the thermal stability of hexaaluminates. This Pt-BHA nanocomposite demonstrates excellent activity, selectivity, and long-term stability in CPOM. Pt-BHA is anchored onto a variety of support structures in order to improve the accessibility, safety, and reactivity of the nanocatalyst. Silica felts prove to be particularly amenable to this supporting procedure, with the resulting supported nanocatalyst proving to be as active and stable for CPOM as its unsupported counterpart. Various pre-treatment conditions are evaluated to determine their effectiveness in removing residual surfactant from the active nanoscale platinum particles. The size of these particles is measured across a wide temperature range, and the resulting “plateau” of stability from 600-900°C can be linked to a particle caging effect due to the structure of the supporting ceramic framework. The nanocomposites are used to catalyze the combustion of a dilute methane stream, and the results indicate enhanced activity for both Pt-BHA as well as ceria-doped BHA, as well as an absence of internal mass transfer limitations at the conditions tested. In water-gas shift reaction, nanocomposite Pt-BHA shows stability during prolonged WGS reaction and no signs of deactivation during start-up/shut-down of the reactor. The chemical and thermal stability, low molecular weight, and

  20. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.


    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic...... ammonia synthesis activity, to a first approximation, is a function only of the binding energy of nitrogen to the catalyst. Therefore, it is possible to evaluate which nitrogen binding energy is optimal under given reaction conditions. This leads to the concept of optimal catalyst curves, which illustrate...... the nitrogen binding energies of the optimal catalysts at different temperatures, pressures, and synthesis gas compositions. Using this concept together with the ability to prepare catalysts with desired binding energies it is possible to optimize the ammonia process. In this way a link between first...

  1. Highly stable and active Ni-doped ordered mesoporous carbon catalyst on the steam reforming of ethanol application

    Directory of Open Access Journals (Sweden)

    Josh Y.Z. Chiou


    Full Text Available A novel one-step direct synthesis of nickel embedded in an ordered mesoporous carbon catalyst (NiOMC is done in a basic medium of nonaqueous solution by a solvent evaporation-induced self-assembly process. The NiOMC sample is characterized by a variety of analytical and spectroscopy techniques, e.g., N2 adsorption/desorption isotherm measurement, X-ray diffraction (XRD, transmission electron microscopy (TEM and temperature-programed reduction (TPR. In this study, the NiOMC catalyst is found to exhibit superior catalytic activity for the steam reforming of ethanol (SRE, showing high hydrogen selectivity and durability. Ethanol can be completely converted at 350 °C over the NiOMC catalyst. Also, the durability of the NiOMC catalyst on the SRE reaction exceeds 100 h at 450 °C, with SH2 approaching 65% and SCO of less than 1%.

  2. Selective methane oxidation over promoted oxide catalysts. Topical report, September 8, 1992--September 7, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.


    The objective of this research was to selectively oxidize methane to C{sub 2} hydrocarbons and to oxygenates, in particular formaldehyde and methanol, in high space time yields using air at the oxidant under milder reaction conditions that heretofore employed over industrially practical oxide catalysts. The research carried out under this US DOE-METC contract was divided into the following three tasks: Task 1, maximizing selective methane oxidation to C{sub 2}{sup +} products over promoted SrO/La{sub 2}O{sub 3} catalysts; Task 2, selective methane oxidation to oxygenates; and Task 3, catalyst characterization and optimization. Principal accomplishments include the following: the 1 wt% SO{sub 4}{sup 2{minus}}/SrO/La{sub 2}O{sub 3} promoted catalyst developed here produced over 2 kg of C{sub 2} hydrocarbons/kg catalyst/hr at 550 C; V{sub 2}O{sub 5}/SiO{sub 2} catalysts have been prepared that produce up to 1.5 kg formaldehyde/kg catalyst/hr at 630 C with low CO{sub 2} selectivities; and a novel dual bed catalyst system has been designed and utilized to produce over 100 g methanol/kg catalyst/hr at 600 C with the presence of steam in the reactant mixture.

  3. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts (United States)

    Murillo, Luis E.

    also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.


    1,10-Phenanthroline-stabilized palladium nanoparticles dispersed in a polyethylene glycol (PEG) matrix is synthesized which is found to be a stable and active catalyst for the selective hydrogenation of olefins using molecular hydrogen under mild reaction conditions. A variety of...

  5. Highly stable ceria-zirconia-yttria supported Ni catalysts for syngas production by CO2 reforming of methane (United States)

    Muñoz, M. A.; Calvino, J. J.; Rodríguez-Izquierdo, J. M.; Blanco, G.; Arias, D. C.; Pérez-Omil, J. A.; Hernández-Garrido, J. C.; González-Leal, J. M.; Cauqui, M. A.; Yeste, M. P.


    Ni/CeO2/YSZ and Ni/Ce0.15Zr0.85O2 have been investigated as catalysts for the dry reforming of methane at 750 °C. Ni was incorporated by the impregnation method. The supports were previously activated by using a thermo-chemical protocol consisting on a severe reduction (H2/Ar) at 950 °C followed by a mild oxidation (O2/He) at 500 °C. According to TPR results, this protocol leads to the development of unique redox properties in the case of the CeO2/YSZ oxide. Two types of CO2 + CH4 (1:1) mixtures (helium-diluted and undiluted) were used to feed the reactor. When using the Ni/Ce0.15Zr0.85O2 catalyst with undiluted feed, the reactor became plugged by coke. By contrast, Ni/CeO2/YSZ behaved as an active and stable catalyst even under the most severe operation conditions. The characterization of the spent Ni/CeO2/YSZ using TGA, TEM, Raman and XPS spectroscopy revealed that only a limited amount of graphitic carbon, in form of nanotubes, was formed. No evidences of deactivating carbonaceous forms were obtained. The singular redox properties of the activated CeO2/YSZ oxides are proposed as a key for designing Ni catalysts highly stable in reforming processes.

  6. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    NARCIS (Netherlands)

    Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.


    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts(1-4). Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon


    Directory of Open Access Journals (Sweden)

    A.B. da Silva


    Full Text Available Low-temperature reduced TiO2-supported Pt and Pt-Fe catalysts are much more active and selective for the liquid–phase hydrogenation of cinnamaldehyde to unsaturated cinnamyl alcohol than the corresponding carbon-supported catalysts. High-temperature reduced catalysts, where the SMSI effect should be present, are almost inactive for this reaction. There is at present no definitive explanation for this effect but an electronic metal-support interaction is most probably involved.

  8. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.


    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic...... ammonia synthesis activity, to a first approximation, is a function only of the binding energy of nitrogen to the catalyst. Therefore, it is possible to evaluate which nitrogen binding energy is optimal under given reaction conditions. This leads to the concept of optimal catalyst curves, which illustrate...

  9. Design of a stable steam reforming catalyst - A promising route to sustainable hydrogen form biomass oxygenates

    NARCIS (Netherlands)

    Matas Güell, B.; Babych, Igor V.; Nichols, K.P.F.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer


    The influence of the support and the presence of oxygen were investigated in the steam reforming of acetic acid, a bio-oil model compound, over Pt/ZrO2 and Pt/CeO2 catalysts. In the absence of oxygen, all catalysts suffered from deactivation. Acetone, formed via condensation/dehydration of acetic

  10. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene

    DEFF Research Database (Denmark)

    Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas


    The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts ( often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional...... dispersed on an oxide support were selective for acetylene hydrogenation at low pressures....

  11. A Highly Active and Selective Manganese Oxide Promoted Cobalt-on-Silica Fischer-Tropsch Catalyst

    NARCIS (Netherlands)

    den Breejen, Johan P.|info:eu-repo/dai/nl/304837318; Frey, Anne M.|info:eu-repo/dai/nl/341358851; Yang, Jia; Holmen, Anders; van Schooneveld, Matti M.|info:eu-repo/dai/nl/315032863; de Groot, Frank M. F.|info:eu-repo/dai/nl/08747610X; Stephan, Odile; Bitter, Johannes H.|info:eu-repo/dai/nl/160581435; de Jong, Krijn P.|info:eu-repo/dai/nl/06885580X

    A highly active and selective manganese oxide-promoted silica-supported cobalt catalyst for the Fischer-Tropsch reaction is reported. Co/MnO/SiO2 catalysts were prepared via impregnation of a cobalt nitrate and manganese nitrate precursor, followed by drying and calcination in an NO/He flow. The

  12. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William


    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were charac...


    Oxidation of various alcohols is studied in liquid phase under nitrogen atmosphere over vanadium phosphorus oxide catalyst in an environmentally friendly protocol using hydrogen peroxide. The catalyst and the method are found to be suitable for the selective oxidation of a variet...

  14. Bio-oil hydrodeoxygenation catalysts produced using strong electrostatic adsorption (United States)

    We synthesized hydrothermally stable metal catalysts with controlled particle size and distribution, with the goal of determining which catalyst(s) can selectively catalyze the production of aromatics from bio-oil (from pyrolysis of biomass). Both precious and base transition metal catalysts (Ru, Pt...

  15. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts (United States)

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin


    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant pholyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system. PMID:23863916

  16. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts. (United States)

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin


    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant polyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system.

  17. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation. (United States)

    Zhao, Yanyan; Yang, Ke R; Wang, Zechao; Yan, Xingxu; Cao, Sufeng; Ye, Yifan; Dong, Qi; Zhang, Xizi; Thorne, James E; Jin, Lei; Materna, Kelly L; Trimpalis, Antonios; Bai, Hongye; Fakra, Sirine C; Zhong, Xiaoyan; Wang, Peng; Pan, Xiaoqing; Guo, Jinghua; Flytzani-Stephanopoulos, Maria; Brudvig, Gary W; Batista, Victor S; Wang, Dunwei


    Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-Fe 2 O 3 is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-Fe 2 O 3 anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward H 2 O photooxidation.

  18. A stable rhodium single-site catalyst encapsulated within dendritic mesoporous nanochannels. (United States)

    Tian, Jun; Yang, Dali; Wen, Jianguo; Filatov, Alexander S; Liu, Yuzi; Lei, Aiwen; Lin, Xiao-Min


    Catalysis plays an essential role in the modern chemical industry. However, it still remains a great challenge to improve the efficiency of many heterogeneous catalysts based on a per metal atom basis. Single-site catalysts (SsCs) with isolated metal atoms/ions anchored to the supports are thus highly desirable, providing an innovative solution towards highly efficient usage of precious metal atoms in heterogeneous catalysts. Creating SsCs with high metal loading proves to be challenging because, without robust anchoring, atoms tend to diffuse to form large aggregates during catalytic reactions. We report a facile ligand exchange method to anchor a single-site Rh catalyst inside the individual channels of three-dimensional dendritic mesoporous silica nanospheres (MSNSs). The short porous channels inside MSNSs provide an easy access of reactants and the strong binding of the ligand prevents the aggregation of catalyst sites. The as-synthesized Rh 1 @MSNS-NH 2 catalyst shows excellent activity, stability and reusability in the reduction of 4-nitrophenol. The same catalyst shows high regioselectivity in the hydrosilylation of terminal alkynes to yield α-vinylsilanes through the Markovnikov addition.

  19. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    The title of my PhD thesis is “Design of Heterogeneous Catalysts”. Three reactions have been investigated: the methanation reaction, the Fischer-Tropsch reaction, and the NH3-based selective catalytic reduction (SCR) of NO. The experimental work performed in connection with the methanation reaction...... hydrogenation. For both systems a maximum in catalytic activity was found for some of the bimetallic catalysts being superior to the monometallic catalysts. This resulted in volcano curves for all investigated systems. In the Fischer-Tropsch reaction promotion of cobalt catalysts with manganese was studied...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

  20. Highly Active and Stable Fe-N-C Catalyst for Oxygen Depolarized Cathode Applications. (United States)

    Li, Jingkun; Jia, Qingying; Ghoshal, Shraboni; Liang, Wentao; Mukerjee, Sanjeev


    Anion immunity toward the oxygen reduction reaction (ORR) has tremendous implications in electrocatalysis with applications for fuel cells, metal-air batteries, and oxygen depolarized cathodes (ODCs) in the anodic evolution of chlorine. The necessity of exploring ORR catalysts with immunity to anion adsorption is particularly significant considering that platinum group metal (PGM) catalysts are costly and highly vulnerable to impurities such as halides. Herein, we report a metal organic framework (MOF)-derived Fe-N-C catalyst that exhibits a dramatically improved half-wave potential of 240 mV compared to the state-of-the-art Rh x S y /C catalyst in a rotating disk electrode in the presence of Cl - . The Fe-N 4 active sites in Fe-N-C are intrinsically immune to Cl - poisoning, in contrast to Pt/C, which is severely susceptible to Cl - poisoning. As a result, the activity of Fe-N-C decreases only marginally in the presence of Cl - , far exceeding that of Pt/C. The viability of this catalyst as ODCs is further demonstrated in real-life hydrochloric acid electrolyzers using highly concentrated HCl solution saturated with Cl 2 gas as the electrolyte. The introduction of Fe-N-C materials as ODC catalysts here overcomes the limitations of (i) the low intrinsic ORR activity of Rh x S y /C as the state-of-the-art ODC catalyst; (ii) the vulnerability to Cl - poisoning of Pt/C as the state-of-the-art ORR catalyst; and (iii) the high cost of precious metals in these two materials, resulting in a cost-effective ODC catalyst with the overall performance exceeding that of all previously reported materials.

  1. Polystyrene-supported pyridinium chloroaluminate ionic liquid as a new heterogeneous Lewis acid catalyst for selective synthesis of benzimidazoles

    Directory of Open Access Journals (Sweden)

    Parvanak Boroujeni Kaveh


    Full Text Available Polystyrene-supported pyridinium chloroaluminate ionic liquid was prepared from the reaction of Merrifield resin with pyridine followed by reaction with aluminium chloride. This catalyst was used as a new chemoselective Lewis acid catalyst for the exclusive synthesis of 2-substituted benzimidazoles from the reaction of aldehydes with o-phenylenediamines. The catalyst is stable (as a bench top catalyst and can be easily recovered and reused without appreciable change in its efficiency.

  2. Correction: Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions. (United States)

    Parapat, Riny Y; Wijaya, Muliany; Schwarze, Michael; Selve, Sören; Willinger, Marc; Schomäcker, Reinhard


    Correction for 'Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions' by Riny Y. Parapat et al., Nanoscale, 2013, 5, 796-805.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Copper (0) nanoparticles onto silica: A stable and facile catalyst for ...

    Indian Academy of Sciences (India)

    crystallization from EtOAc: petroleum ether (0.2 mL. EtOAc in 10 mL petroleum ether). The catalyst ... tent with the expected elemental composition of the catalyst (figure S3 in SI). .... (5 mL) was stirred at refluxing temperature; cIsolated yields refer to the yields obtained by the crystallization from ethyl acetate:petroleum ether ...

  5. Potent Heterogeneous Catalyst for Low Temperature Selective Oxidation of Cyclohexanol by Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Haroon ur Rashid


    Full Text Available Platinum supported on zirconium dioxide catalyst was prepared by standard method and characterized by SEM, EDX, XRD, BET surface area and pore size analyzer, and FT-IR. The catalyst was screened for its catalytic activity in a model reaction, selective oxidation of cyclohexanol. The only one major product, cyclohexanone 31%, with 99.8% selectivity was obtained. Experimental data was analyzed through different kinetic models and we deduced that the reaction follows Langmuir-Hinshelwood mechanism. The apparent activation energy for the model reaction was calculated as 45 kJ/mole. The catalyst was regenerated several times with same efficiency.

  6. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol


    Khalid Khazzal Hummadi; Karim H. Hassan; Phillip C.H. Mitchell


    The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK), 10 atm (1013 kPa), with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III) molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a c...

  7. E- and Z-Selective Transfer Semihydrogenation of Alkynes Catalyzed by Standard Ruthenium Olefin Metathesis Catalysts. (United States)

    Kusy, Rafał; Grela, Karol


    Selective transfer semihydrogenation of alkynes to yield alkenes was achieved with commercial first and second generation Hoveyda-Grubbs catalysts and formic acid as a hydrogen donor. This catalytic system is distinguished by its selectivity and compatibility with many functional groups (halogens, cyano, nitro, sulfide, alkenes). The metathetic activity of the ruthenium catalysts may be utilized in tandem sequences of olefin metathesis plus alkyne reduction.

  8. An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water Electro-oxidation at Neutral pH

    KAUST Repository

    Chen, Ba-Tian


    The synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine is described. Hydrophobicity was identified as the key variable in mediating the catalytic competence of the complexes. The change in this parameter correlates with both the conformational mobility of the ligand core and the structural changes in the local solvent environment around the metal site. The optimal Co complex identified is hydrophobic, because of three semifluorinated side chains. It catalyzes water electro-oxidation efficiently at neutral pH, with an overpotential of 390 mV and a turnover frequency (TOF) of 1.83 s-1 in the absence of soluble Co salts. The catalyst can be immobilized through physisorption, and it remains stable in prolonged electrolysis experiments. © 2016 American Chemical Society.

  9. Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis. (United States)

    Afewerki, Samson; Córdova, Armando


    The cooperation and interplay between organic and metal catalyst systems is of utmost importance in nature and chemical synthesis. Here innovative and selective cooperative catalyst systems can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy can permit chemical transformations unmanageable by either of the catalysts alone. This review summarizes innovations and developments in selective organic synthesis that have used cooperative dual catalysis by combining simple aminocatalysts with metal catalysts. Considerable efforts have been devoted to this fruitful field. This emerging area employs the different activation modes of amine and metal catalysts as a platform to address challenging reactions. Here, aminocatalysis (e.g., enamine activation catalysis, iminium activation catalysis, single occupied molecular orbital (SOMO) activation catalysis, and photoredox activation catalysis) is employed to activate unreactive carbonyl substrates. The transition metal catalyst complements by activating a variety of substrates through a range of interactions (e.g., electrophilic π-allyl complex formation, Lewis acid activation, allenylidene complex formation, photoredox activation, C-H activation, etc.), and thereby novel concepts within catalysis are created. The inclusion of heterogeneous catalysis strategies allows for "green" chemistry development, catalyst recyclability, and the more eco-friendly synthesis of valuable compounds.

  10. Selective production of aromatics from alkylfurans over solid acid catalysts

    DEFF Research Database (Denmark)

    Wang, Dong; Dumesic, James A.; Osmundsen, Christian Mårup


    Solid acid catalysts were studied at temperatures near 523K for the production of benzene, toluene, and p-xylene by the reaction of ethylene with furan, 2-methylfuran, and 2,5-dimethylfuran, respectively, through the combination of cycloaddition and dehydrative aromatization reactions. Catalysts...... for this reaction, because amorphous solid acids and homogeneous Brønsted acids demonstrate significant activity for p-xylene production. The production of p-xylene from 2,5-dimethylfuran proceeded at higher rates compared with the production of toluene and benzene from 2-methylfuran and furan, respectively. Both...... to deactivation by carbon deposition than do microporous materials. Results from Raman spectroscopy and the trend of turnover frequency with varying tungsten surface densities for a series of WOx-ZrO2 catalysts are consistent with previous investigations of other acid-catalyzed reactions; this suggests...


    Directory of Open Access Journals (Sweden)

    María Juliana Maccarrone


    Full Text Available Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+ species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z -3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a the electronic effects, related to the high charge of W (+6, causing an intensive dipole moment in the hydrogen molecule (van der Waals forces and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K. The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z -3-hexene (94% at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst

  12. Selective side-chain oxidation of alkyl aromatic compounds catalyzed by cerium modified silver catalysts

    DEFF Research Database (Denmark)

    Beier, Matthias Josef; Schimmoeller, Bjoern; Hansen, Thomas Willum


    . In addition, flame-made catalysts were more stable against silver leaching compared to the impregnated catalysts. The structure of the silver catalysts was studied in detail both by X-ray absorption spectroscopy and transmission electron microscopy suggesting metallic silver to be required for catalytic......Silver supported on silica effectively catalyzes the aerobic side-chain oxidation of alkyl aromatic compounds under solvent-free conditions. Toluene, p-xylene, ethylbenzene and cumene were investigated as model substrates. Typically, the reaction was performed at ambient pressure; only for toluene...... an elevated pressure was required. Carboxylic acids, such as benzoic acid or p-toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation...

  13. Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation (United States)

    Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman


    Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

  14. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    The objective of this project is to synthesize nanocrystals of highly acidic zeolite Y nanoclusters, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates, and evaluate the 'zeolite Y/Nanoporous host' composites as catalysts for the upgrading of heavy petroleum feedstocks. In comparison to conventionally-used zeolite Y catalysts of micron size particles, the nanocrystals (< 100 nm particle size) which contain shorter path lengths, are expected to allow faster diffusion of large hydrocarbon substrates and the catalysis products within and out of the zeolite's channels and cages (<1 nm size). This is expected to significantly reduce deactivation of the catalyst and to prolong their period of reactivity. Encapsulating zeolite Y nanocrystals within the nanoporous materials is expected to protect its external surfaces and pore entrances from being blocked by large hydrocarbon substrates, since these substrates will initially be converted to small molecules by the nanoporous host (a catalyst in its own right). The project consisted of four major tasks as follows: (1) synthesis of the nanoparticles of zeolite Y (of various chemical compositions) using various techniques such as the addition of organic additives to conventional zeolite Y synthesis mixtures to suppress zeolite Y crystal growth; (2) synthesis of nanoporous silicate host materials of up to 30 nm pore diameter, using poly (alkylene oxide) copolymers which when removed will yield a mesoporous material; (3) synthesis of zeolite Y/Nanoporous Host composite materials as potential catalysts; and (4) evaluation of the catalyst for the upgrading of heavy petroleum feedstocks.

  15. The influence of phase transfer catalyst structure on reaction selectivity

    International Nuclear Information System (INIS)

    Demlov, Eh.V.


    A concise review is given of systematic studies which are concerned with the tuning of regio, frequentio-, chemo-, and diastereoselectivity by the structure or type of phase transfer catalyst. Use of MEI as an alkylating agent is described. Refs. 36, figs. 11

  16. zeolite catalysts for the selective synthesis of mono- and diethylamines

    NARCIS (Netherlands)

    Veefkind, V.A.; Lercher, J.A.


    The kinetics and mechanism of ethylamine synthesis from ammonia and ethanol over several large pore acid catalysts are described. Mordenite produced higher monoethylamine yields than the zeolites beta, Y, mazzite, and amorphous silica–alumina. The reaction proceeds via the initial formation of

  17. Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation

    KAUST Repository

    Zhang, Zailei


    Single-atom metal catalysts offer a promising way to utilize precious noble metal elements more effectively, provided that they are catalytically active and sufficiently stable. Herein, we report a synthetic strategy for Pt single-atom catalysts with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural integrity and excellent performance for the selective hydrogenation of 1,3-butadiene after exposure to a reductive atmosphere at 200 °C for 24 h. Compared to commercial Pt nanoparticle catalyst on Al2O3 and control samples, this system exhibits significantly enhanced stability and performance for n-hexane hydro-reforming at 550 °C for 48 h, although agglomeration of Pt single-atoms into clusters is observed after reaction. In CO oxidation, the Pt single-atom identity was fully maintained after 60 cycles between 100 and 400 °C over a one-month period.

  18. Stable amorphous georgeite as a precursor to a high-activity catalyst

    DEFF Research Database (Denmark)

    Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.


    Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable-and hence little known and largely ignored-georgeite. The first three of these minerals are widely used as catalyst precursors for th...

  19. Stable Fe/ZSM-5 Nanosheet Zeolite Catalysts for the Oxidation of Benzene to Phenol. (United States)

    Meng, Lingqian; Zhu, Xiaochun; Hensen, Emiel J M


    Fe/ZSM-5 nanosheet zeolites of varying thickness were synthesized with di- and tetraquaternary ammonium structure directing agents and extensively characterized for their textural, structural, and catalytic properties. Introduction of Fe 3+ ions in the framework of nanosheet zeolites was slightly less effective than in bulk ZSM-5 zeolite. Steaming was necessary to activate all catalysts for N 2 O decomposition and benzene oxidation. The higher the Fe content, the higher the degree of Fe aggregation was after catalyst activation. The degree of Fe aggregation was lower when the crystal domain size of the zeolite or the Fe content was decreased. These two parameters had a substantial influence on the catalytic performance. Decreasing the number of Fe sites along the b -direction strongly suppressed secondary reactions of phenol and, accordingly, catalyst deactivation. This together with the absence of diffusional limitations in nanosheet zeolites explains the much higher phenol productivity obtainable with nanostructured Fe/ZSM-5. Steamed Fe/ZSM-5 zeolite nanosheet synthesized using C 22-6-3 ·Br 2 (domain size in b -direction ∼3 nm) and containing 0.24 wt % Fe exhibited the highest catalytic performance. During the first 24 h on stream, this catalyst produced 185 mmol phenol g -1 . Calcination to remove the coke deposits completely restored the initial activity.

  20. Copper (0) nanoparticles onto silica: A stable and facile catalyst for ...

    Indian Academy of Sciences (India)

    Abstract. Solid supported copper (0) nanoparticles were prepared by physical adsorption of copper (0)nanoparticles (synthesized through bottom-up approach) on the solid supports such as silica, HAP, cellulose andbasic alumina. Studies comparing these supported catalysts were done with the synthesis of ...

  1. Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

    KAUST Repository

    Shuai, Danmeng


    Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

  2. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis. (United States)

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe


    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Catalyst-Controlled Site-Selectivity Switching in Pd-Catalyzed Cross-Coupling of Dihaloarenes

    Directory of Open Access Journals (Sweden)

    Kei Manabe


    Full Text Available Pd-catalyzed, site-selective mono-cross-coupling of substrates with two identical halo groups is a useful method for synthesizing substituted monohalogenated arenes. Such arenes constitute an important class of compounds, which are commonly identified as drug components and synthetic intermediates. Traditionally, these site-selective reactions have been realized in a “substrate-controlled” manner, which is based on the steric and electronic differences between the two carbon-halogen bonds of the substrate. Recently, an alternative strategy, “catalyst-controlled” site-selective cross-coupling, has emerged. In this strategy, the preferred reaction site of a dihaloarene can be switched, merely by changing the catalyst used. This type of selective reaction further expands the utility of Pd-catalyzed cross-coupling. In this review, we summarize the reported examples of catalyst-controlled site-selectivity switching in Pd-catalyzed cross-coupling of dihaloarenes.

  4. Selective Hydrogenation of Concentrated Vinyl Acetylene Mixed C4 by Modified Pd Catalysts: Effect of Cu

    Directory of Open Access Journals (Sweden)

    Paisan Insorn


    Full Text Available The Pd and Pd-Cu on alumina catalysts were tested for hydrogenation of vinyl acetylene in mixed C4 in a circulating tubular reactor. The results showed that adding proper amounts of Cu improved the reaction activity, but inhibited 1,3-butadiene selectivity. Moreover, the presence of Cu retarded the carbon deposition on catalysts during the reaction. Temperature programmed oxidation (TPO, Temperature programmed reduction (TPR, H2 chemisorption, and X-ray photoelectron spectroscopy (XPS were utilized to characterize the catalysts. The characterization suggested both geometric and electronic modifications.

  5. Selective growth of two-dimensional phosphorene on catalyst surface. (United States)

    Qiu, L; Dong, J C; Ding, F


    Although the study of black phosphorene (BP) and its isomers has attracted enormous attention, the method of synthesizing high-quality samples in a large area is still pending. Here we explore the potential of using the chemical vapor deposition method to synthesize large-area two-dimensional (2D) phosphorene films on metal surfaces. Our ab initio calculations show that BP can be synthesized by using tin (Sn) as a catalyst, while one of its isomers, blue phosphorene (BLP), is very possible to be synthesized by using most other metals, such as Ag and Au. Besides, our study also suggests that the large binding energy between the 2D phosphorene and the active metal substrate may prohibit the exfoliation of the 2D phosphorene for real applications and, therefore, tin, silver and gold are predicted to be the most suitable catalysts for the synthesis of BP and BLP.

  6. Effect of chemically reduced palladium supported catalyst on sunflower oil hydrogenation conversion and selectivity

    Directory of Open Access Journals (Sweden)

    Abdulmajid Alshaibani


    Full Text Available Catalytic hydrogenation of sunflower oil was studied in order to improve the conversion and to reduce the trans-isomerization selectivity. The hydrogenation was performed using Pd–B/γ-Al2O3 prepared catalyst and Pd/Al2O3 commercial catalyst under similar conditions. The Pd–B/γ-Al2O3 catalyst was prepared by wet impregnation and chemical reduction processes. It was characterized by Brunauer–Emmett–Teller surface area analysis (BET, X-ray powder diffraction (XRD, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. The result of sunflower oil hydrogenation on Pd–B/γ-Al2O3 catalyst showed a 17% higher conversion and a 23% lower trans-isomerization selectivity compared to the commercial Pd/Al2O3 catalyst. The chemical reduction of palladium supported catalyst using potassium borohydride (KBH4 has affected the Pd–B/γ-Al2O3 catalyst’s structure and particle size. These most likely influenced its catalytic performance toward higher conversion and lower trans-isomerization selectivity.

  7. Particle size effects for carbon nanofiber supported platinum and ruthenium catalysts for the selective hydrogenation of cinnamaldehyde

    NARCIS (Netherlands)

    Plomp, A.J.; Vuori, H.; Krause, A.O.I.; de Jong, K.P.; Bitter, J.H.


    The selective hydrogenation of cinnamaldehyde was studied over carbon nanofibers (CNF) supported platinum and ruthenium catalysts. The catalysts differed independently in their metal particle sizes and amount of acidic oxygen groups on the CNF surface. For the catalysts with oxygen on the CNF

  8. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Khalid Khazzal Hummadi


    Full Text Available The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK, 10 atm (1013 kPa, with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum selectivity (82.3% was obtained at 573oK when the conversion was 59.7%. Catalysts prepared by reacting iron (III and molybdate by kneading or precipitation followed by evaporation, omitting a filtration stage, were less active and less selective. The selectivity-activity relationships of these catalysts as a function of temperature were discussed in relation to the method of preparation, surface areas and composition. By combing this catalytic data with data from the patent literature we demonstrate a synergy between iron and molybdenum in regard to methanol oxidation to formaldehyde; the optimum composition corresponded to an iron mole fraction 0.2-0.3. The selectivity to formaldehyde was practically constant up to an iron mole fraction 0.3 and then decreased at higher iron concentrations. The iron component can be regarded as the activity promoter. The iron molybdate catalysts can thus be related to other two-component MoO3-based selective oxidation catalysts, e.g. bismuth and cobalt molybdates. The iron oxide functions as a relatively basic oxide abstracting, in the rate-controlling step, a proton from the methyl of a bound methoxy group of chemisorbed methanol. It was proposed that a crucial feature of the sought after iron(III molybdate catalyst is the presence of -O-Mo-O-Fe-O-Mo-O- groups as found in the compound Fe2(MoO43 and for Fe3+ well dispersed in MoO3 generally. At the higher iron(III concentrations the loss of

  9. Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst (United States)

    Keitz, Benjamin K.; Endo, Koji; Herbert, Myles B.


    The cross-metathesis of terminal olefins using a novel ruthenium catalyst results in excellent selectivity for the Z-olefin homodimer. The reaction was found to tolerate a large number of functional groups, solvents, and temperatures while maintaining excellent Z-selectivity, even at high reaction conversions. PMID:21649443

  10. The behaviour of a single catalyst pellet for the selective hydrogenation of ethyne in ethene

    NARCIS (Netherlands)

    Bos, A.N.R.; Bos, A.N.R.; Hof, E.; Kuper, W.; Westerterp, K.R.


    The steady-state and dynamic behaviour of a single Pd---Al2O3 catalyst particle is studied for the selective hydrogenation of ethyne in the presence of ethene, without addition of carbon monoxide. The particle-to-gas heat transfer in the reactor is characterized. During selective hydrogenation, not

  11. Pt-based Thin Films as Efficient and Stable Catalysts for Oxygen Electroreduction

    DEFF Research Database (Denmark)

    Zamburlini, Eleonora

    Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). The investigated films included pure Pt sputtered thin films, as well as PtxGd and PtxY thin film alloys of different compositions and thicknesses, with the aim of a model study...... be due to the different kind of surfaces generated by sputtering. Both the Pt5Gd and Pt3Y films maintain over 80 % of the initial ORR activity when cycled 10000 times between 0.6 and 1.0 V vs. RHE in 0.1 M HClO4, and that is an indicator of the good stability of these catalysts. Investigation......, and the proposed solutions. The characterization of the catalysts focused mainly on the electrochemical testing using a Rotating Ring Disk Electrode (RRDE) setup, and includes X-ray Diffraction (XRD), X-ray Photoemission Spectroscopy (XPS), Angle-Resolved X-ray Photoelectron Spectroscopy (AR-XPS), Scanning...

  12. Highly Active Ruthenium Metathesis Catalysts Exhibiting Unprecedented Activity and Z-Selectivity (United States)

    Rosebrugh, Lauren E.; Herbert, Myles B.; Marx, Vanessa M.; Keitz, Benjamin K.; Grubbs, Robert H.


    A novel chelated ruthenium-based metathesis catalyst bearing an N-2,6-diisopropylphenyl group is reported and displays near-perfect selectivity for the Z-olefin (>95%), as well as unparalleled TONs of up to 7400, in a variety of homodimerization and industrially relevant metathesis reactions. This derivative and other new catalytically-active species were synthesized using an improved method employing sodium carboxylates to induce the salt metathesis and C-H activation of these chelated complexes. All of these new ruthenium-based catalysts are highly Z-selective in the homodimerization of terminal olefins. PMID:23317178

  13. Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

    KAUST Repository

    Date, Nandan S


    Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

  14. Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures (United States)

    Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar


    The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

  15. Towards long-term stable solid state electrolyzers with infiltrated catalysts

    DEFF Research Database (Denmark)

    Ovtar, Simona; Chen, Ming; Brodersen, Karen

    Renewable energy sources like wind and solar are widely considered as the key technologies to cover our growing demands. However, the fluctuating nature of these sources requires a flexible energy system and storage technologies to ensure that energy supply can be covered in a stable and affordable...

  16. Characterization and Design of Zeolite Catalysts Solid Acidity, Shape Selectivity and Loading Properties

    CERN Document Server

    Niwa, Miki; Okumura, Kazu


    Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents. Zeolite-based catalysts are used by industrial chemical companies in the interconversion of hydrocarbons and the alkylation of aromatic compounds. The current book deals with the characterization of specific properties of Zeolites and calculations for the design of catalysts. Measurements and utilization of solid acidity, shape selectivity, and loading properties, that are three prominent properties of a Zeolite catalyst, are treated in detail. These features concern chemical vapor deposition of silica, shape selectivity, loading properties, solid activity, Brønsted or Lewis character, ammonia temperature programmed desorption, control of the pore-opening size by chemical vapor deposition of silica and XAFS analysis of metals being highly dispersed inside and outside a framework.

  17. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.


    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  18. Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions. (United States)

    Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo


    As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Catalysts Supported on Carbon Materials for the Selective Hydrogenation of Citral

    Directory of Open Access Journals (Sweden)

    Agustín F. Pérez-Cadenas


    Full Text Available The heterogeneously catalyzed selective-hydrogenation of citral is one of the more feasible ways for obtaining its appreciated unsaturated-alcohols, nerol and geraniol, which are present in over 250 essential oils. Thus, citral has very recently come to be produced petro-chemically in very large quantities, and so partial hydrogenation of citral has become a very economical route for the production of these compounds. However, the selective hydrogenation of citral is not easy, because citral is an α,β-unsaturated aldehyde which possesses three double bonds that can be hydrogenated: an isolated C=C bond and the conjugated C=O and C=C bonds. For this reason, in catalyst selection there are several important issues which affect the product selectivity, for example, the active metal and metal particle size which are factors related to the catalyst preparation method, catalyst precursor, or support surface area, as well as other factors such as porosity, the addition of a second catalytic metal, and, of course, the type of catalyst support. About this last one, carbon materials are very interesting supports for this type of hydrogenation reaction due to their unique chemical and textural properties. This review collects and analyzes the results obtained in the selective hydrogenation of citral catalyzed by carbon material supported metals.

  20. Highly Selective Continuous Gas-Phase Methoxycarbonylation of Ethylene with Supported Ionic Liquid Phase (SILP) Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; Garcia Suárez, Eduardo José; Fehrmann, Rasmus


    Supported ionic liquid phase (SILP) technology was applied for the first time to the Pd-catalyzed continuous, gas-phase methoxycarbonylation of ethylene to selectively produce methyl propanoate (MP) in high yields. The influence of catalyst and reaction parameters such as, for example, ionic liquid...

  1. Catalysts for selective oxidation of ammonia in a gas containing hydrogen

    DEFF Research Database (Denmark)


    The invention contributes to a cost effective way to solve the problem of trace ammonia removal from hydrogen containing gas. The set of catalysts of the invention selectively oxidised ammonia in ppm concentration even in gas mixture containing hydrogen gas in concentration of three orders...

  2. Catalysts for selective oxidation of ammonia in a gas containing hydrogen

    DEFF Research Database (Denmark)


    The invention contributes to a cost effective way to solve the problem of trace ammonia removal from a hydrogen and nitrogen containing gas. The set of catalysts of the invention selectively oxidised ammonia in ppm concentration even in gas mixtures containing hydrogen gas in concentrations...

  3. Catalyst-Free and Highly Selective N,N-Diallylation of Anilines in Aqueous Phase

    Directory of Open Access Journals (Sweden)

    Zhengyin Du


    Full Text Available A highly selective diallylation reaction of anilines with allyl bromide was achieved in aqueous alcohol solution in the presence of potassium carbonate and without the use of any catalyst. The reaction tolerates a wide range of functionalities, and various tertiary amines were obtained in the yield of up to 99% with complete conversion of anilines.

  4. On the Role of Surface Modifications of Palladium Catalysts in the Selective Hydrogenation of Acetylene

    DEFF Research Database (Denmark)

    Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas


    Summing Me up: DFT calculations have shown that alloying, subsurface carbon, and hydride formation, all increase the selectivity of Pd catalysts for acetylene hydrogenation by weakening the surface–adsorbate bond. A simple descriptor—the adsorption energy of a methyl group—has been used to quantify...

  5. Activity and selectivity control in reductive amination of butyraldehyde over noble metal catalysts.

    NARCIS (Netherlands)

    Bodis, E.; Lefferts, Leonardus; Muller, T.E.; Pestman, R.; Lercher, J.A.


    Approaches to control selectivity and activity in the catalytic reductive amination of butyraldehyde with ammonia over carbon supported noble metal catalysts (Ru, Rh, Pd, and Pt) were explored. Detailed analysis of the reaction network shows that the Schiff base N-[butylidene]butan-1-amine is the

  6. Chance and necessity in the selection of nucleic acid catalysts (United States)

    Lorsch, J. R.; Szostak, J. W.


    In Tom Stoppard's famous play [Rosencrantz and Guildenstern are Dead], the ill-fated heroes toss a coin 101 times. The first 100 times they do so the coin lands heads up. The chance of this happening is approximately 1 in 10(30), a sequence of events so rare that one might argue that it could only happen in such a delightful fiction. Similarly rare events, however, may underlie the origins of biological catalysis. What is the probability that an RNA, DNA, or protein molecule of a given random sequence will display a particular catalytic activity? The answer to this question determines whether a collection of such sequences, such as might result from prebiotic chemistry on the early earth, is extremely likely or unlikely to contain catalytically active molecules, and hence whether the origin of life itself is a virtually inevitable consequence of chemical laws or merely a bizarre fluke. The fact that a priori estimates of this probability, given by otherwise informed chemists and biologists, ranged from 10(-5) to 10(-50), inspired us to begin to address the question experimentally. As it turns out, the chance that a given random sequence RNA molecule will be able to catalyze an RNA polymerase-like phosphoryl transfer reaction is close to 1 in 10(13), rare enough, to be sure, but nevertheless in a range that is comfortably accessible by experiment. It is the purpose of this Account to describe the recent advances in combinatorial biochemistry that have made it possible for us to explore the abundance and diversity of catalysts existing in nucleic acid sequence space.

  7. use of safety first rule in selecting stable barley cultivars

    African Journals Online (AJOL)


    Jun 13, 1993 ... or bankruptcy are associated with low yields, which likelyisthecaseforsubsistence farmers. RESULTS. The indices as well as the mean yield indicated the high yielding potential forB3072 as well as its stability, the low yielding and less stable lines were also indicated (Tables 2 and 3). The EV, FWand SH ...

  8. Selective aerobic oxidation of hydrocarbons over supported gold catalysts

    NARCIS (Netherlands)

    Hereijgers, B.P.C.|info:eu-repo/dai/nl/314131116


    The selective oxidation of hydrocarbons is of vital importance for the production of valuable chemicals from crude oil and natural gas resources. Unfortunately, when using molecular oxygen as an environmentally benign oxidant, these processes face tremendous difficulties, most importantly in

  9. Selective catalytic dehydration of furfuryl alcohol to 2, 2'-difurfuryl ether using a polyoxometalate catalyst. (United States)

    Yang, Shaoxiang; Hao, Yanfeng; Wang, Jialin; Wang, Hao; Zheng, Yimeng; Tian, Hongyu; Liu, Yongguo; Sun, Baoguo


    The spice flavour compound 2, 2'-difurfuryl ether (DFE) is widely utilised in the food industry as it has a coffee-like, nutty, earthy, mushroom-like odour. However, despite intensive research efforts, to date, an environmentally friendly and practical synthetic preparation technique for 2, 2'-difurfuryl ether is still unavailable. Here, we investigate a new approach using polyoxometalate catalysts to selectively catalytically dehydrate furfuryl alcohol to 2, 2'-difurfuryl ether. We have successfully applied this methodology using the polyoxometalate (POMs) catalyst {[(CH 3 CH 2 CH 2 CH 2 ) 4 N] 2 [SMo 12 O 40 ]} to produce 2,2'-difurfuryl ether in a 30.86% isolated yield.

  10. Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers. (United States)

    Schieweck, Benjamin G; Klankermayer, Jürgen


    Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH 2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Single-atom catalysts for CO2electroreduction with significant activity and selectivity improvements. (United States)

    Back, Seoin; Lim, Juhyung; Kim, Na-Young; Kim, Yong-Hyun; Jung, Yousung


    A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO 2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO 2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO 2 reduction reaction over a competitive H 2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential U L = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH 3 OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH 4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH 3 OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.


    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    Composite materials of SBA-15/zeolite Y were synthesized from zeolite Y precursor and a synthesis mixture of mesoporous silicate SBA-15 via a hydrothermal process in the presence of a slightly acidic media of pH 4-6 with 2M H{sub 2}SO{sub 4}. The SBA-15/ZY composites showed Type IV adsorption isotherms, narrow BJH average pore size distribution of 4.9 nm, surface areas up to 800 m{sup 2}2/g and pore volumes 1.03 cm{sup 3}, all comparable to pure SBA-15 synthesized under similar conditions. Chemical analysis revealed Si/Al ratio down to 8.5 in the most aluminated sample, and {sup 27}AlSS MAS NMR confirmed aluminum was in tetrahedral coordination. This method of introduction of Al in pure T{sub d} coordination is effective in comparison to other direct and post synthesis alumination methods. Bronsted acid sites were evident from a pyridinium peak at 1544 cm-1 in the FTIR spectrum after pyridine adsorption, and from NH{sub 3} -TPD experiments. SBA-15/ZY composites showed significant catalytic activities for the dealkylation of isopropylbenzene to benzene and propene, similar to those of commercial zeolite Y. It was observed that higher conversion for catalysts synthesized with high amount of ZY precursor mixture added to the SBA-15. Over all the composites has shown good catalytic activity. Further studies will be focused on gaining a better understand the nature of the precursor, and to characterize and to locate the acid sites in the composite material. The composite will also be evaluated for heavy oil conversion to naphtha and middle distillates.

  13. Phosphorylated mesoporous carbon as effective catalyst for the selective fructose dehydration to HMF

    Energy Technology Data Exchange (ETDEWEB)

    Villa, Alberto [Universita di Milano, Italy; Schiavoni, Marco [University of Milan and INFN, Milano, Italy; Fulvio, Pasquale F [ORNL; Mahurin, Shannon Mark [ORNL; Dai, Sheng [ORNL; Mayes, Richard T [ORNL; Veith, Gabriel M [ORNL; Prati, Laura [Universita di Milano, Italy


    Phosphorylated mesoporous carbons (PMCs) have been synthesized using an already reported one pot methodology. These materials have been applied as acidic catalysts in the dehydration of fructose to hydroxymethylfurfural (HMF). PMCs showed better selectivity to HMF compared to sulfonated carbon catalyst (SC) despite lower activity. The concentration of P-O groups correlates to the activity/selectivity of the catalysts; the higher the P-O concentration the higher the activity. However, the higher the P-O content the lower the selectivity to HMF. Indeed a lower concentration of the P-O groups (and even the acidic groups) minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines, water insoluble by-products derived from the dehydration of fructose, blocking the active site of the catalyst. Increasing the amount of P-O groups, higher amount of humines are formed; therefore carbons containing lower amount of phosphorylated groups, such as P/N-0.25, are less prone to deactivation. Keywords: Phosphorylated mesoporous carbons; fructose dehydration; HMF

  14. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal (United States)

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka


    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

  15. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

    Directory of Open Access Journals (Sweden)

    Eero eSalminen


    Full Text Available The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat benzalkonium [ADBA] (alkyldimethylbenzylammonium was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs. Typically, a SILCA contains metal nanoparticles, enzymes or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC. The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70 % molar yield towards citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide.

  16. Synthesis, structure and topological analysis of glycine templated highly stable cadmium sulfate framework: A New Lewis Acid catalyst (United States)

    Paul, Avijit Kumar


    One new open-framework two-dimensional layer, [Cd(NH3CH2COO)(SO4)], I, has been synthesized using amino acid as templating agent. Single crystal structural analysis shows that the compound crystallizes in monoclinic cell with non-centrosymmetric space group P21, a = 4.9513(1) Å, b = 7.9763(2) Å, c = 8.0967(2) Å, β = 105.917(1)° and V = 307.504(12) Å3. The compound has connectivity between the Cd-centers and the sulfate units forming a two-dimensional layer structure. Sulfate unit is coordinated to metal center with η3, μ4 mode possessing a coordination free oxygen atom. The zwitterionic form of glycine molecule is present in the structure bridging with two metal centers through μ2-mode by carboxylate oxygens. The topological analysis reveals that the two-dimensional network is formed with a novel 4- and 6-connected binodal net of (32,42,52)(34,44,54,63) topology. Although one end of the glycine molecule is free from coordination, the structure is highly stable up to 350 °C. Strong N-H⋯ O hydrogen bonding interactions play an important role in the stabilization and formation of three-dimensional supramolecular structure. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicates good catalytic behavior. The present study illustrates the usefulness of the amino acid for the structure building in less studied sulfate based framework materials as well as designing of new heterogeneous catalysts for the broad application. The compound has also been characterized through elemental analysis, PXRD, IR, SEM and TG-DT studies.

  17. Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

    International Nuclear Information System (INIS)

    Wu, Hua-Yi; Wang, Hai-Bo; Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua; Huang, Chuan-Jing; Weng, Wei-Zheng; Wan, Hui-Lin


    Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N 2 -adsorption, XRD, SEM, Raman, XPS, EPR and H 2 -TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO) 2 P 2 O 7 . All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO 4 phases and the influence of Sm were also described and discussed

  18. Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Polo-Garzon, Felipe [Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Yang, Shi-Ze [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Fung, Victor [Department of Chemistry, University of California, Riverside CA 92521 USA; Foo, Guo Shiou [Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Bickel, Elizabeth E. [Department of Chemical Engineering, Tennessee Technological University, Cookeville TN 38505 USA; Chisholm, Matthew F. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Jiang, De-en [Department of Chemistry, University of California, Riverside CA 92521 USA; Wu, Zili [Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA


    Although well known in the material science field, surface reconstruction of perovskites has not been implemented in heterogeneous catalysis. In this work, we employ multiple surface sensitive techniques to characterize the surface reconstruction of SrTiO3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface reconstruction of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO2. Density functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on differently reconstructed surfaces of STO. Similar catalytic tunability is also observed on BaZrO3, highlighting the generality of the finding from this work.

  19. Novel Reforming Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, Lisa D; Haller, Gary L


    Aqueous phase reforming is useful for processing oxygenated hydrocarbons to hydrogen and other more useful products. Current processing is hampered by the fact that oxide based catalysts are not stable under high temperature hydrothermal conditions. Silica in the form of structured MCM-41 is thermally a more stable support for Co and Ni than conventional high surface area amorphous silica but hydrothermal stability is not demonstrated. Carbon nanotube supports, in contrast, are highly stable under hydrothermal reaction conditions. In this project we show that carbon nanotubes are stable high activity/selectivity supports for the conversion of ethylene glycol to hydrogen.

  20. Investigation and Demonstration of Catalyst/Initiator-Driven Selectivity in Thiol-Michael Reactions. (United States)

    Frayne, Stephen H; Murthy, Raghavendra R; Northrop, Brian H


    Thiol-Michael "click" reactions are essential synthetic tools in the preparation of various materials including polymers, dendrimers, and other macromolecules. Despite increasing efforts to apply thiol-Michael chemistry in a controlled fashion, the selectivity of base- or nucleophile-promoted thiol-Michael reactions in complex mixtures of multiple thiols and/or acceptors remains largely unknown. Herein, we report a thorough fundamental study of the selectivity of thiol-Michael reactions through a series of 270 ternary reactions using 1 H NMR spectroscopy to quantify product selectivity. The varying influences of different catalysts/initiators are explored using ternary reactions between two Michael acceptors and a single thiol or between a single Michael acceptor and two thiols using three different catalysts/initiators (triethylamine, DBU, and dimethylphenylphosphine) in chloroform. The results from the ternary reactions provide a platform from which sequential quaternary, one-pot quaternary, and sequential senary thiol-Michael reactions were designed and their selectivities quantified. These results provide insights into the design of selective thiol-Michael reactions that can be used for the synthesis and functionalization of multicomponent polymers and further informs how catalyst/initiator choice influences the reactivity between a given thiol and Michael acceptor.

  1. Microwave-activated Ni/carbon catalysts for highly selective hydrogenation of nitrobenzene to cyclohexylamine. (United States)

    Lu, Xinhuan; He, Jie; Jing, Run; Tao, Peipei; Nie, Renfeng; Zhou, Dan; Xia, Qinghua


    Biocarbon supported Ni catalysts have been prepared by facile impregnation of Ni species by microwave-heating and used for selective hydrogenation of nitrobenzene to cyclohexylamine. These catalysts were characterized by X-ray diffraction, Raman spectra, N2 sorption measurement, X-ray photoelectron spectroscopy, temperature programmed reduction of H2 and H2 temperature-programmed desorption. The morphology and particle size of catalysts were imaged by scanning electron microscope and transmission electron microscope. For the hydrogenation of nitrobenzene to cyclohexylamine, 10%Ni/CSC-II(b) exhibits the best catalytic activity to achieve 100 mol% conversion of nitrobenzene and 96.7% selectivity of cyclohexylamine under reaction conditions of 2.0 MPa H2 and 200 °C, ascribed to high dispersion of Ni species and formation of nanosized Ni particles on the support aided by microwave-heating. Thus-prepared Ni/CSC catalyst is greatly activated, in which the addition of precious metal like Rh is totally avoided.

  2. Biomass-Derived Catalysts for Selective Hydrogenation of Nitroarenes. (United States)

    Sahoo, Basudev; Formenti, Dario; Topf, Christoph; Bachmann, Stephan; Scalone, Michelangelo; Junge, Kathrin; Beller, Matthias


    Development of catalytically active materials from biowaste represents an important aspect of sustainable chemical research. Three heterogeneous materials were synthesized from inexpensive biomass-based chitosan and abundant Co(OAc) 2 using complexation followed by pyrolysis at various temperatures. These materials were applied in the catalytic hydrogenation of nitroarenes using molecular hydrogen. A variety of diversely functionalized nitroarenes including some pharmaceutically active compounds were converted into aromatic amines in high yields, with high selectivity, and with excellent functional group tolerance. This green protocol has also been implemented for the synthesis of a biologically important TRPC3 inhibitor. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. (Invited) Towards the Development of Active, Stable and Abundant Catalysts for Oxygen Evolution in Acid

    DEFF Research Database (Denmark)

    Stephens, Ifan; Paoli, Elisa Antares; Frydendal, Rasmus


    to the TW level. State-of the art PEM electrolysers employ IrOx, which is both expensive and scarce, to catalyse oxygen evolution.(1) Around a decade’s worth of Ir production would be required to scale up PEM electrolysis to the TW scale: this is clearly untenable.(2) It turns out that RuOx has a higher...... and also most prone to dissolution, could be stabilised by TiOx. We test this notion by performing oxygen evolution on Mn-TiOx thin films. We probe the composition using X-ray photoelectron spectroscopy measurements and dissolution with inductively coupled plasma mass spectroscopy. We confirm that Ti......Ox does indeed engender MnOx with modest stability. Further development of this strategy opens up the possibility of developing active, stable and abundant non-precious metal oxides for oxygen evolution in acid. References 1. M. K. Debe, S. M. Hendricks, G. D. Vernstrom, M. Meyers, M. Brostrom, M...

  5. Catalyst and method for production of methylamines (United States)

    Klier, Kamil; Herman, Richard G.; Vedage, Gamini A.


    This invention relates to an improved catalyst and method for the selective production of methylamines. More particularly, it is concerned with the preparation of stable highly active catalysts for producing methylamines by a catalytic reaction of ammonia or substituted amines and binary synthesis gas (CO+H.sub.2).

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

    DEFF Research Database (Denmark)

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


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

  7. Selective Production of Aromatics from 2-Octanol on Zinc Ion-Exchanged MFI Zeolite Catalysts


    Iwamoto, Masakazu; Takezawa, Ryota; Morimoto, Masao


    The aromatization of 2-octanol derived from castor oil as a byproduct in the formation of sebacic acid was investigated on various zeolite catalysts. Zn ion-exchanged MFI (ZSM-5) zeolites with small silica/alumina ratios and zinc contents of 0.5 to 2.0 wt. % were determined to exhibit good and stable activity for the reaction at 623 to 823 K. The yield of aromatics was 62% at 773 K and the space velocity 350 to 1400 h−1. The temperature and contact time dependences of the product distribution...

  8. Selective adsorption of manganese onto cobalt for optimized Mn/Co/TiO2 Fischer-Tropsch catalysts

    NARCIS (Netherlands)

    Feltes, T.E.; Espinosa-Alonso, L.; de Smit, E.|info:eu-repo/dai/nl/304824232; D'Souza, L.; Meyer, R.J.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Regalbuto, J.R.


    The Strong Electrostatic Adsorption (SEA) method was applied to the rational design of a promoted Co catalyst for Fischer–Tropsch (FT) synthesis. A series of Mn/Co/TiO2 catalysts were prepared by selective deposition of the [MnO4] anion onto the supported Co3O4 phase. Qualitative ICP-OES and XPS

  9. New insights into the active surface species of silver alumina catalysts in the selective catalytic reduction of NO

    NARCIS (Netherlands)

    Korhonen, S.T.|info:eu-repo/dai/nl/326090606; Beale, A.M.|info:eu-repo/dai/nl/325802068; Newton, M.A.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397


    The performance of silver alumina catalysts and silver aluminate was studied in the selective catalytic reduction (SCR) of NO by propene. The use of boehmite during the impregnation step ensured a strong interaction between the silver species and the alumina surface in the final calcined catalyst.

  10. Molecularly Tailored Nickel Precursor and Support Yield a Stable Methane Dry Reforming Catalyst with Superior Metal Utilization. (United States)

    Margossian, Tigran; Larmier, Kim; Kim, Sung Min; Krumeich, Frank; Fedorov, Alexey; Chen, Peter; Müller, Christoph R; Copéret, Christophe


    Syngas production via the dry reforming of methane (DRM) is a highly endothermic process conducted under harsh conditions; hence, the main difficulty resides in generating stable catalysts. This can, in principle, be achieved by reducing coke formation, sintering, and loss of metal through diffusion in the support. [{Ni(μ 2 -OCHO)(OCHO)(tmeda)} 2 (μ 2 -OH 2 )] (tmeda = tetramethylethylenediamine), readily synthesized and soluble in a broad range of solvents, was developed as a molecular precursor to form 2 nm Ni(0) nanoparticles on alumina, the commonly used support in DRM. While such small nanoparticles prevent coke deposition and increase the initial activity, operando X-ray Absorption Near-Edge Structure (XANES) spectroscopy confirms that deactivation largely occurs through the migration of Ni into the support. However, we show that Ni loss into the support can be mitigated through the Mg-doping of alumina, thereby increasing significantly the stability for DRM. The superior performance of our catalytic system is a direct consequence of the molecular design of the metal precursor and the support, resulting in a maximization of the amount of accessible metallic nickel in the form of small nanoparticles while preventing coke deposition.

  11. A comparative study of metal oxide and sulfate catalysts for selective catalytic reduction of NO with NH3. (United States)

    Zhu, Lin; Zhong, Zhaoping; Yang, Han; Wang, Chunhua


    The properties and characteristics of metal oxide and sulfate catalysts with different active elements for selective catalytic reduction of NO with NH 3 were investigated. Cerium-based oxide catalyst showed the widest temperature window for NO x removal and manganese-based oxide catalyst exhibited the best catalytic performance at low temperature. For all the catalysts, the SCR activities at low temperature were directly related with the redox abilities of catalysts. The existence of sulfate groups inhibited the redox abilities of active species for sulfate catalysts compared with the metal oxide catalysts. The catalytic activities of CeWTi-S and MnWTi-S were seriously decreased in contrast to CeWTi-N and MnWTi-N. The temperature window of CuWTi-S was shifted toward higher temperature comparing with CuWTi-N. The FeWTi-N and FeWTi-S catalysts both showed high NO x conversion in the temperature range between 300°C and 400°C and N 2 O concentrations for iron-based samples were least among the same kind of catalysts. The abundance of acid sites and weak stability of surface sulfate groups for iron- and copper-based sulfate catalysts might be the main reasons accounting for the better NO x conversion in the medium-temperature range.

  12. Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes (United States)

    Anderson, Donde R.; Ung, Thay; Mkrtumyan, Garik; Bertrand, Guy; Grubbs, Robert H.; Schrodi, Yann


    The evaluation of ruthenium olefin metathesis catalysts 4–6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4–6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes. PMID:18584055

  13. High sintering resistance of size-selected platinum cluster catalysts by suppressed ostwald ripening

    DEFF Research Database (Denmark)

    Wettergren, Kristina; Schweinberger, Florian F.; Deiana, Davide


    Employing rationally designed model systems with precise atom-by-atom particle size control, we demonstrate by means of combining noninvasive in situ indirect nanoplasmonic sensing and ex situ scanning transmission electron microscopy that monomodal size-selected platinum cluster catalysts...... on different supports exhibit remarkable intrinsic sintering resistance even under reaction conditions. The observed stability is related to suppression of Ostwald ripening by elimination of its main driving force via size-selection. This study thus constitutes a general blueprint for the rational design...... of sintering resistant catalyst systems and for efficient experimental strategies to determine sintering mechanisms. Moreover, this is the first systematic experimental investigation of sintering processes in nanoparticle systems with an initially perfectly monomodal size distribution under ambient conditions....

  14. Prolinate Salt as a Catalyst in the syn-Selective, Asymmetric Mannich Reaction of Alkynyl Imine. (United States)

    Hayashi, Yujiro; Yamazaki, Tatsuya; Kawauchi, Genki; Sato, Itaru


    Prolinate salt is an efficient catalyst in the Mannich reaction of alkynyl imine and aldehyde, to afford synthetically useful chiral propargyl amine derivatives with excellent syn-selectivity and nearly perfect control of the absolute configuration. The counterion of the prolinate salt does not affect the enantioselectivity. This is a rare example, in which proline alkali metals, alkaline-earth metals, or ammonium salt show higher reactivity and better stereoselectivity than the parent proline.

  15. Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts (United States)

    Chia, Mei

    The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value-added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally-observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Bronsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to gamma-valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range


    Directory of Open Access Journals (Sweden)

    Fatimah Zahara Abdullah

    Full Text Available Esterification of oleic acid with polyethylene glycol 600 (PEG-600 to produce polyethylene glycol monooleate (PEG-monooleate and polyethylene glycol dioleate (PEG-dioleate as by-product has been studied in the presence of heterogeneous acid catalysts, i.e. cesium heteropoly acid (Cs HPA. The results are compared with those obtained from a classical homogeneous acid catalyst; p-toluene sulphonic acid (p-TSA. The reaction was conducted under nitrogen flow with vigorous stirring at 130 ºC and 150 ºC. The catalyst loading kept at 4% and the reaction was monitored at 1, 3, 7 and 24 hours. Reaction samples were analyzed using high performance liquid chromatography (HPLC equipped with evaporative light scattering detector (ELSD. The results obtained showed that Cs HPAs exhibit 100% selectivity of PEG-monooleate from the first hour until 24 hours. However, this does not happen with homogeneous p-TSA, where formation of by-product; PEG-dioleate is observed in the initial stage. It is also showed that the mole ratio is the most important parameter not only to produce high yield of monoester but also to maintain it along the reaction. Chemical and physical properties of catalysts were characterized using Thermal Gravimetric Analysis (TGA, Differential Scanning Calorimetry (DSC, Fourier Tranmittance Infra-Red (FTIR, ammonia temperature programmed desorption (NH3-TPD and X-ray Diffraction (XRD.

  17. Dehydration of alcohols over oxide catalysts: γ-eliminations -- stereospecificity and selectivity

    International Nuclear Information System (INIS)

    Siddhan, S.; Narayanan, K.


    The effect of alkali impregnation on alumina catalysts has been investigated by a physicochemical study of pure and modified alumina catalyst samples. The stereospecificity and selectivity of dehyration reactions, as well as the incidence of γ-elimination, have been studied by passing suitable substrates over catalyst samples. There was a change in the acidity-basicity balance in the sodium-impregnated alumina samples vis a vis pure alumina, while the surface area virtually remained constant. A higher propensity for γ-elimination was noticed with increases in basicity of the catalyst. 1-Olefin formation was found to be larger in more basic alumina- and thoria-catalyzed dehydration reactions. Thoria was strikingly unique in its capacity to dehydrate only alcohols, which have at least one β-hydrogen atom. Neopentyl alcohol could not be dehydrated even under drastic conditions. The modes of elimination in the case of alumina and thoria have been shown to be anti and syn, respectively, from the results of the dehydration studies with threo-3-methyl-2-pentanol. Studies of alcohols with proper β-substituents revealed that the cis preference is not universal in all catalytic eliminations but, in fact, depends on the mode of elimination. While cis-preference was noticed in alumina-catalyzed anti eliminations, trans-olefin was formed to a major amount in thoria-catalyzed syn-elimination processes. 9 figures, 13 tables

  18. Selective methane chlorination to methyl chloride by zeolite Y-based catalysts (United States)

    Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu


    The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2

  19. Impact of catalyst reduction mode on selective hydrogenation of cinnamaldehyde over Ru-Sn sol-gel catalysts

    Czech Academy of Sciences Publication Activity Database

    Hájek, J.; Kumar, N.; Salmi, T.; Murzin, DY.; Karhu, H.; Väyrynen, J.; Červený, L.; Paseka, Ivo


    Roč. 42, č. 2 (2003), s. 295-305 ISSN 0888-5885 R&D Projects: GA ČR GA104/00/1009 Institutional research plan: CEZ:AV0Z4032918 Keywords : Supported ruthenium catalysts * Ru-Sn-Al2O3 catalysts * benzene Subject RIV: CA - Inorganic Chemistry Impact factor: 1.317, year: 2003

  20. Selective phenol methylation to 2,6-dimethylphenol in a fluidized bed of iron-chromium mixed oxide catalyst with o-cresol circulation. (United States)

    Zukowski, Witold; Berkowicz, Gabriela; Baron, Jerzy; Kandefer, Stanisław; Jamanek, Dariusz; Szarlik, Stefan; Wielgosz, Zbigniew; Zielecka, Maria


    2,6-dimethylphenol (2,6-DMP) is a product of phenol methylation, especially important for the plastics industry. The process of phenol methylation in the gas phase is strongly exothermic. In order to ensure good temperature equalization in the catalyst bed, the process was carried out using a catalyst in the form of a fluidized bed - in particular, the commercial iron-chromium catalyst TZC-3/1. Synthesis of 2,6-dimethylphenol from phenol and methanol in fluidized bed of iron-chromium catalyst was carried out and the fluidization of the catalyst was examined. Stable state of fluidized bed of iron-chromium catalyst was achieved. The measured velocities allowed to determine the minimum flow of reactants, ensuring introduction of the catalyst bed in the reactor into the state of fluidization. Due to a high content of o-cresol in products of 2,6-dimethylphenol synthesis, circulation in the technological node was proposed. A series of syntheses with variable amount of o-cresol in the feedstock allowed to determine the parameters of stationary states. A stable work of technological node with o-cresol circulation is possible in the temperature range of350-380°C, and o-cresolin/phenolin molar ratio of more than 0.48. Synthesis of 2,6-DMP over the iron-chromium catalyst is characterized by more than 90% degree of phenol conversion. Moreover, the O-alkylation did not occur (which was confirmed by GC-MS analysis). By applying o-cresol circulation in the 2,6-DMP process, selectivity of more than 85% degree of 2,6-DMP was achieved. The participation levels of by-products: 2,4-DMP and 2,4,6-TMP were low. In the optimal conditions based on the highest yield of 2,6-DMP achieved in the technological node applying o-cresol circulation, there are 2%mol. of 2,4-DMP and 6%mol. of 2,4,6-TMP in the final mixture, whereas 2,4,6-TMP can be useful as a chain stopper and polymer's molar mass regulator during the polymerization of 2,6-DMP.

  1. Carbon induced selective regulation of cobalt-based Fischer-Tropsch catalysts by ethylene treatment. (United States)

    Zhai, Peng; Chen, Pei-Pei; Xie, Jinglin; Liu, Jin-Xun; Zhao, Huabo; Lin, Lili; Zhao, Bo; Su, Hai-Yan; Zhu, Qingjun; Li, Wei-Xue; Ma, Ding


    Various carbonaceous species were controllably deposited on Co/Al 2 O 3 catalysts using ethylene as carbon source during the activation process for Fischer-Tropsch synthesis (FTS). Atomic, polymeric and graphitic carbon were distinguished by Raman spectroscopy, thermoanalysis and temperature programmed hydrogenation. Significant changes occurred in both the catalytic activity and selectivity toward hydrocarbon products after ethylene treatment. The activity decreased along with an increase in CH 4 selectivity, at the expense of a remarkable decrease of heavy hydrocarbon production, resulting in enhanced selectivity for the gasoline fraction. In situ XPS experiments show the possible electron transfer from cobalt to carbon and the blockage of metallic cobalt sites, which is responsible for the deactivation of the catalyst. DFT calculations reveal that the activation barrier (E a ) of methane formation decreases by 0.61 eV on the carbon-absorbed Co(111) surface, whereas the E a of the CH + CH coupling reaction changes unnoticeably. Hydrogenation of CH x to methane becomes the preferable route among the elementary reactions on the Co(111) surface, leading to dramatic changes in the product distribution. Detailed coke-induced deactivation mechanisms of Co-based catalysts during FTS are discussed.

  2. Electrochemically Stable Titanium Oxy-Nitride Support for Platinum Electro-Catalyst for PEM Fuel Cell Applications

    International Nuclear Information System (INIS)

    Seifitokaldani, A.; Savadogo, O.


    Titanium Oxy-Nitride is prepared by an in-situ urea-based sol-gel method as a support for the platinum electro-catalyst for the oxygen reduction reaction (ORR). XRD, BET, SEM and EDX are used to analyze the physicochemical properties of the prepared Pt/TiON catalyst; and its electrochemical properties are evaluated by CV and RDE tests. Electrochemical active surface area is determined and compared to that of the commercial Pt/C electro-catalyst. Pt/TiON electro-catalyst showed a better electrochemical stability than those of the commercial Pt/C electro-catalyst. It is also found that the ORR proceeds via four electron transfer mechanism on both Pt/C and Pt/TiON electro-catalysts

  3. Crystal-plane-controlled selectivity of Cu(2)O catalysts in propylene oxidation with molecular oxygen. (United States)

    Hua, Qing; Cao, Tian; Gu, Xiang-Kui; Lu, Jiqing; Jiang, Zhiquan; Pan, Xiaorong; Luo, Liangfeng; Li, Wei-Xue; Huang, Weixin


    The selective oxidation of propylene with O2 to propylene oxide and acrolein is of great interest and importance. We report the crystal-plane-controlled selectivity of uniform capping-ligand-free Cu2 O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O2 : Cu2 O octahedra exposing {111} crystal planes are most selective for acrolein; Cu2 O cubes exposing {100} crystal planes are most selective for CO2 ; Cu2 O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One-coordinated Cu on Cu2 O(111), three-coordinated O on Cu2 O(110), and two-coordinated O on Cu2 O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO2 , respectively. These results reveal that crystal-plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles. (United States)

    Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng


    Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

  5. Gold Supported on Graphene Oxide: An Active and Selective Catalyst for Phenylacetylene Hydrogenations at Low Temperatures

    DEFF Research Database (Denmark)

    Shao, Lidong; Huang, Xing; Teschner, Detre


    A constraint to industrial implementation of gold-catalyzed alkyne hydrogenation is that the catalytic activity was always inferior to those of other noble metals. In this work, gold was supported on graphene oxide (Au/GO) and used in a hydrogenation application. A 99% selectivity toward styrene...... with a 99% conversion in the hydrogenation of phenylacetylene was obtained at 60 °C, which is 100 to 200 °C lower than optimal temperatures in most previous reports on Au catalysts. A series of gold- and palladium-based reference catalysts were tested under the same conditions for phenylacetylene...... hydrogenation, and the performance of Au/GO was substantiated by studying the role of functionalized GO in governing the geometrical structure and thermal stability of supported Au nanoparticles under reaction conditions....

  6. Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review

    Directory of Open Access Journals (Sweden)

    Bin Liu


    Full Text Available Glycerol has been utilized in an extremely diversified manner throughout human civilization—ranging from food, to various consumer products, to pharmaceuticals, and even explosives. Large surplus in glycerol supply thanks to biodiesel production and biomass processing has created a demand to further boost its utility. One growing area is to expand the use of glycerol as an alternative feedstock to supplement fuels and chemicals production. Various catalytic processes have been developed. This review summarizes catalytic materials for glycerol reforming, hydrodeoxygenation, and oxidation. In particular, rationale for catalyst selection and new catalyst design will be discussed aided by the knowledge of reaction mechanisms. The role of theoretical density functional theory (DFT in elucidating complex glycerol conversion chemistries is particularly emphasized.

  7. Selective dissolution of critical metals from diesel and naptha spent hydrodesulphurization catalysts

    International Nuclear Information System (INIS)

    Angelidis, T.N.; Tourasanidis, E.; Marinou, E.; Stalidis, G.A.


    The petroleum refining industry makes extensive use of catalysts, containing critical metals, such as, Mo, Co and Ni, for the desulphurization of various oil fractions. The selective recovery of these metals from two uncrushed and at low temperature calcined industrial hydrodesulphurization (Mo-Co/Al 2 O 3 and Mo-Ni/Al 2 O 3 -SiO 2 ) catalysts was studied, applying a two-step alkali-acid procedure. Fundamental kinetic aspects of the process, such as, reaction time, leaching reagents concentration and reaction temperature, were studied. Recoveries up to 97% for Mo and up to 92% for Co or Ni in separate solutions were achieved, using low cost and easily available reagents, such as sodium hydroxide and sulphuric acid

  8. Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts

    KAUST Repository

    Chen, Jiawei


    This contribution reports the first example of highly selective reduction of CO2 into CH4 via tandem hydrosilylation with mixed main-group organo-Lewis acid (LA) catalysts [Al(C6F5)3 + B(C6F5)3] {[Al] + [B]}. As shown by this comprehensive experimental and computational study, in this unique tandem catalytic process, [Al] effectively mediates the first step of the overall reduction cycle, namely the fixation of CO2 into HCOOSiEt3 (1) via the LA-mediated C=O activation, while [B] is incapable of promoting the same transformation. On the other hand, [B] is shown to be an excellent catalyst for the subsequent reduction steps 2–4, namely the hydrosilylation of the more basic intermediates [1 to H2C(OSiEt3)2 (2) to H3COSiEt3 (3) and finally to CH4] through the frustrated-Lewis-pair (FLP)-type Si–H activation. Hence, with the required combination of [Al] and [B], a highly selective hydrosilylative reduction of CO2 system has been developed, achieving high CH4 production yield up to 94%. The remarkably different catalytic behaviors between [Al] and [B] are attributed to the higher overall Lewis acidity of [Al] derived from two conflicting factors (electronic and steric effects), which renders the higher tendency of [Al] to form stable [Al]–substrate (intermediate) adducts with CO2 as well as subsequent intermediates 1, 2 and 3. Overall, the roles of [Al] and [B] are not only complementary but also synergistic in the total reduction of CO2, which render both [Al]-mediated first reduction step and [B]-mediated subsequent steps catalytic.

  9. Synthesis of Ethanol from Syngas over Rh/MCM-41 Catalyst: Effect of Water on Product Selectivity

    Directory of Open Access Journals (Sweden)

    Luis Lopez


    Full Text Available The thermochemical processing of biomass is an alternative route for the manufacture of fuel-grade ethanol, in which the catalytic conversion of syngas to ethanol is a key step. The search for novel catalyst formulations, active sites and types of support is of current interest. In this work, the catalytic performance of an Rh/MCM-41 catalyst has been evaluated and compared with a typical Rh/SiO2 catalyst. They have been compared at identical reaction conditions (280 °C and 20 bar, at low syngas conversion (2.8% and at same metal dispersion (H/Rh = 22%. Under these conditions, the catalysts showed different product selectivities. The differences have been attributed to the concentration of water vapor in the pores of Rh/MCM-41. The concentration of water vapor could promote the water-gas-shift-reaction generating some extra carbon dioxide and hydrogen, which in turn can induce side reactions and change the product selectivity. The extra hydrogen generated could facilitate the hydrogenation of a C2-oxygenated intermediate to ethanol, thus resulting in a higher ethanol selectivity over the Rh/MCM-41 catalyst as compared to the typical Rh/SiO2 catalyst; 24% and 8%, respectively. The catalysts have been characterized, before and after reaction, by N2-physisorption, X-ray photoelectron spectroscopy, X-ray diffraction, H2-chemisorption, transmission electron microscopy and temperature programmed reduction.

  10. Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction. (United States)

    Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun


    The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

  11. Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst. (United States)

    Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi


    A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

  12. Low-temperature Selective Catalytic Reduction of NO with NH3 over CuOx/CNTs Catalyst (United States)

    Ren, B. N.


    The metal oxide catalyst was prepared by loading CuOx on carbon nanotubes (CNTs) with impregnation method. The catalyst was characterized by BET, TEM and XPS, and the catalytic activity of the catalyst for selective catalytic reduction (SCR) of NO was investigated. The results showed that the species of active components loaded on the catalyst was given priority to with CuO. The NO conversion was improved with temperature increase under the range of 150 to 300°C. The oxygen content had an outstanding influence on the NO conversion of catalysts at lower concentration range. Once the oxygen content was enhanced over 5%, there was no significant increase. Increasing of mole ratio of NH3/NO could increase the NO conversion. When mole ratio of NH3/NO was continued to exceed 1.1, the NO conversion decreased. With the increasing of space velocity, the NO conversion was decreased under the reaction conditions.

  13. Sulfur and Water Resistance of Mn-Based Catalysts for Low-Temperature Selective Catalytic Reduction of NOx: A Review

    Directory of Open Access Journals (Sweden)

    Chen Gao


    Full Text Available Selective catalytic reduction (SCR with NH3 is the most efficient and economic flue gas denitrification technology developed to date. Due to its high low-temperature catalytic activity, Mn-based catalysts present a great prospect for application in SCR de-NOx at low temperatures. However, overcoming the poor resistance of Mn-based catalysts to H2O and SO2 poison is still a challenge. This paper reviews the recent progress on the H2O and SO2 resistance of Mn-based catalysts for the low-temperature SCR of NOx. Firstly, the poison mechanisms of H2O and SO2 are introduced in detail, respectively. Secondly, Mn-based catalysts are divided into three categories—single MnOx catalysts, Mn-based multi-metal oxide catalysts, and Mn-based supported catalysts—to review the research progress of Mn-based catalysts for H2O and SO2 resistance. Thirdly, several strategies to reduce the poisonous effects of H2O and SO2, such as metal modification, proper support, the combination of metal modification and support, the rational design of structure and morphology, are summarized. Finally, perspectives and future directions of Mn-based catalysts for the low-temperature SCR of NOx are proposed.

  14. Diastereo- and enantioselective anti-selective hydrogenation of α-amino-β-keto ester hydrochlorides and related compounds using transition-metal-chiral-bisphosphine catalysts. (United States)

    Hamada, Yasumasa


    This review describes our recent works on the diastereo- and enantioselective synthesis of anti-β-hydroxy-α-amino acid esters using transition-metal-chiral-bisphosphine catalysts. A variety of transition metals, namely ruthenium (Ru), rhodium (Rh), iridium (Ir), and nickel (Ni), in combination with chiral bisphosphines, worked well as catalysts for the direct anti-selective asymmetric hydrogenation of α-amino-β-keto ester hydrochlorides, yielding anti-β-hydroxy-α-amino acid esters via dynamic kinetic resolution (DKR) in excellent yields and diastereo- and enantioselectivities. The Ru-catalyzed asymmetric hydrogenation of α-amino-β-ketoesters via DKR is the first example of generating anti-β-hydroxy-α-amino acids. Complexes of iridium and axially chiral bisphosphines catalyze an efficient asymmetric hydrogenation of α-amino-β-keto ester hydrochlorides via dynamic kinetic resolution. A homogeneous Ni-chiral-bisphosphine complex also catalyzes an efficient asymmetric hydrogenation of α-amino-β-keto ester hydrochlorides in an anti-selective manner. As a related process, the asymmetric hydrogenation of the configurationally stable substituted α-aminoketones using a Ni catalyst via DKR is also described. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge. (United States)

    Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping


    Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

  16. Selective Production of Aromatics from 2-Octanol on Zinc Ion-Exchanged MFI Zeolite Catalysts

    Directory of Open Access Journals (Sweden)

    Masakazu Iwamoto


    Full Text Available The aromatization of 2-octanol derived from castor oil as a byproduct in the formation of sebacic acid was investigated on various zeolite catalysts. Zn ion-exchanged MFI (ZSM-5 zeolites with small silica/alumina ratios and zinc contents of 0.5 to 2.0 wt. % were determined to exhibit good and stable activity for the reaction at 623 to 823 K. The yield of aromatics was 62% at 773 K and the space velocity 350 to 1400 h−1. The temperature and contact time dependences of the product distributions indicated the reaction pathways of 2-octanol→dehydration to 2-octene→decomposition to C5 and C3 compounds→further decomposition to small alkanes and alkenes→aromatization with dehydrogenation. Alcohols with carbon numbers of 5 to 8 exhibited similar distributions of products compared to 2-octanol, while corresponding carbonyl compounds demonstrated different reactivity.

  17. Highly Selective Liquid-Phase Benzylation of Anisole with Solid-Acid Zeolite Catalysts

    DEFF Research Database (Denmark)

    Poreddy, Raju; Shunmugavel, Saravanamurugan; Riisager, Anders


    Zeolites were evaluated as solid acid catalysts for the liquid-phase benzylation of anisole with benzyl alcohol, benzyl bromide, and benzyl chloride at 80 °C. Among the examined zeolites, H-mordenite-10 (H-MOR-10) demonstrated particular high activity (>99 %) and excellent selectivity (>96...... %) to the monobenzylated products, ortho/para benzyl anisole, using benzyl alcohol as reagent (anisole/alcohol molar ratio = 28). Analogous reactions with benzyl halides resulted in lower yields of the desired monobenzylated products. The conversion of benzyl alcohol was confirmed to be proportional to the amount of added...

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  19. Selective formation of diamond-like carbon coating by surface catalyst patterning

    DEFF Research Database (Denmark)

    Palnichenko, A.V.; Mátéfi-Tempfli, M.; Mátéfi-Tempfli, Stefan


    The selective formation of diamond-like carbon coating by surface catalyst patterning was studied. DLC films was deposited using plasma enhanced chemical vapor deposition, filtered vacuum arc deposition, laser ablation, magnetron sputtering and ion-beam lithography methods. The DLC coatings were...... obtained by means of a single short and intensive carbon plasma deposition pulse. The deposited DLC coating was characterized by micro-Raman spectroscopy measurements. The DLC coating process gave rise to wide potential possibilities in micro-devices manufacturing productions....

  20. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst (United States)

    Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan


    Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because of the extreme inertness of CO2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

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

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz


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

  2. System and method for controlling an engine based on ammonia storage in multiple selective catalytic reduction catalysts (United States)

    Sun, MIn; Perry, Kevin L.


    A system according to the principles of the present disclosure includes a storage estimation module and an air/fuel ratio control module. The storage estimation module estimates a first amount of ammonia stored in a first selective catalytic reduction (SCR) catalyst and estimates a second amount of ammonia stored in a second SCR catalyst. The air/fuel ratio control module controls an air/fuel ratio of an engine based on the first amount, the second amount, and a temperature of a substrate disposed in the second SCR catalyst.

  3. Developing Selective Oxidation Catalysts of Light Alkanes:. from Fundamental Understanding to Rational Design (United States)

    Fu, Gang; Yi, Xiaodong; Huang, Chuanjing; Xu, Xin; Weng, Weizheng; Xia, Wensheng; Wan, Hui-Lin

    Selective oxidation of light alkanes remains to be a great challenge for the wider use of alkanes as feedstocks. To achieve high activity and at the same time high selectivity, some key issues have to be addressed: (1) the stability of the desired products with respect to the reactants; (2) the roles of the active components in the catalysts, the structure and the functionality of the active centers; (3) the reducibility of the metal cations, the Lewis acid sites and their synergic effects with the basic sites of the lattice oxygen anions; (4) spatial isolation of the active centers; and (5) the mechanisms for the formation and transformation of the intermediates and their kinetic controls. In this contribution, we took selective oxidation of propane to acrolein as our target reaction, and reviewed mainly our own work, trying to provide some thinking and answers to these five questions.

  4. Selective Heck Arylation of Cyclohexene with Homogeneous and Heterogeneous Palladium Catalysts

    Directory of Open Access Journals (Sweden)

    Ewa Mieczyńska


    Full Text Available Palladium catalysts containing Pd(II supported on Al2O3 and alumina-based mixed oxides, Al2O3-ZrO2, Al2O3-CeO2, and Al2O3-Fe2O3, are very effective in the Heck coupling of iodobenzene with cyclohexene in DMF solution. The best results, up to 81% of monoarylated products with a selectivity to 4-phenylcyclohexene (3 close to 90% were obtained with KOH as a base. The catalytic activity of palladium supported on alumina-based oxides was compared with that of homogeneous precursors, such as Pd(OAc2 and PdCl2(PhCN2, used in [Bu4N]Br as the reaction medium. Under such conditions homogeneous systems were more selective and produced up to 60% of monoarylated products with a selectivity to 3 close to 60%.

  5. Effect of copper loading on copper-ceria catalysts performance in CO selective oxidation for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Ayastuy, J.L.; Gurbani, A.; Gonzalez-Marcos, M.P.; Gutierrez-Ortiz, M.A. [Departamento de Ingenieria Quimica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, E-48080 Bilbao (Spain); Unidad Asociada ' ' Tecnologias Quimicas para la Sostenibilidad Ambiental' ' , CSIC-UPV/EHU (Spain)


    Copper-ceria catalysts with three different Cu loadings (1, 7 and 15 wt%) were prepared by incipient wet impregnation, dried at 120 C and calcined in air at 500 C. The as-prepared catalysts were characterized by XRD, BET, Diffuse Reflectance Spectroscopy (DRS-UV-visible), Raman spectroscopy, CO and H{sub 2}-TPR, CO-TPR, CO-TPD and Oxygen Storage Capacity (OSC) measurements (with CO and O{sub 2} concentration step-changes). The results indicated a good dispersion of copper for catalysts with 1 and 7 wt% Cu; however, bulk CuO was present for catalyst with 15 wt% Cu loading. Catalyst with 7 wt% Cu was observed to have very high capacity to release lattice oxygen to oxidize CO at low temperature. Activity results for CO oxidation in the absence and in the presence of 60% H{sub 2}, demonstrated a very similar performance for catalysts with 7 and 15 wt% Cu (both with T{sub 100} = 112 C), and much better than that of catalyst loaded with 1 wt% Cu. Catalyst with 7 wt% of copper shows very high activity (100% in a wide temperature window) and selectivity (higher than 85%), which makes an attractive for its use in purification of hydrogen for fuel cell applications. The presence of a mixture of CO{sub 2} and H{sub 2}O inhibited catalyst activity, with CuO/CeO{sub 2} catalyst with 7 wt% Cu exhibiting the best performance in the overall reaction temperature range. This could be attributed to the presence of highly disperse copper, only part of it in deep interaction with ceria. The effect of O{sub 2}/CO ratio ({lambda}) and the potential reversibility of the inhibitory effect of CO{sub 2} and H{sub 2}O were also investigated. (author)

  6. Combined fast selective reduction using Mn-based catalysts and nonthermal plasma for NOx removal. (United States)

    Chen, Jun Xiang; Pan, Kuan Lun; Yu, Sheng Jen; Yen, Shaw Yi; Chang, Moo Been


    In this study, the concept of fast SCR for NO reduction with NH 3 as reducing agent is realized via the combination of nonthermal plasma (NTP) with Mn-based catalyst. Experimental results indicate that 10% wt. Mn-Ce-Ni/TiO 2 possesses better physical and chemical properties of surface, resulting in higher NO removal efficiency if compared with 10% wt. Mn-Ce/TiO 2 and 10% wt. Mn-Ce-Cu/TiO 2 . Mn-Ce-Ni/TiO 2 of 10% wt. achieves 100% NO x conversion at 150 °C, while 10% wt. Mn-Ce/TiO 2 and 10% wt. Mn-Ce-Cu/TiO 2 need to be operated at a temperature above 200 °C for 100% NO x conversion. However, NO conversion achieved with 10% wt. Mn-Ce-Ni/TiO 2 is significantly reduced as H 2 O (g) and SO 2 are introduced into the SCR system simultaneously. Further, two-stage system (SCR with DBD) is compared with the catalyst-alone for NO x conversion and N 2 selectivity. The results indicate that 100% NO x conversion can be achieved with two-stage system at 100 °C, while N 2 selectivity reaches 80%. Importantly, NO x conversion achieved with two-stage system could maintain >95% in the presence of C 2 H 4 , CO, SO 2 , and H 2 O (g) , indicating that two-stage system has better tolerance for complicated gas composition. Overall, this study demonstrates that combining NTP with Mn-based catalyst is effective in reducing NO x emission at a low temperature (≤200 °C) and has good potential for industrial application.

  7. Design Criteria, Operating Conditions, and Nickel-Iron Hydroxide Catalyst Materials for Selective Seawater Electrolysis. (United States)

    Dionigi, Fabio; Reier, Tobias; Pawolek, Zarina; Gliech, Manuel; Strasser, Peter


    Seawater is an abundant water resource on our planet and its direct electrolysis has the advantage that it would not compete with activities demanding fresh water. Oxygen selectivity is challenging when performing seawater electrolysis owing to competing chloride oxidation reactions. In this work we propose a design criterion based on thermodynamic and kinetic considerations that identifies alkaline conditions as preferable to obtain high selectivity for the oxygen evolution reaction. The criterion states that catalysts sustaining the desired operating current with an overpotential seawater-mimicking electrolyte. The catalyst was synthesized by a solvothermal method and the activity, surface redox chemistry, and stability were tested electrochemically in alkaline and near-neutral conditions (borate buffer at pH 9.2) and under both fresh seawater conditions. The Tafel slope at low current densities is not influenced by pH or presence of chloride. On the other hand, the addition of chloride ions has an influence in the temporal evolution of the nickel reduction peak and on both the activity and stability at high current densities at pH 9.2. Faradaic efficiency close to 100 % under the operating conditions predicted by our design criteria was proven using in situ electrochemical mass spectrometry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions (United States)

    Parapat, Riny Y.; Wijaya, Muliany; Schwarze, Michael; Selve, Sören; Willinger, Marc; Schomäcker, Reinhard


    We recently introduced a new method to synthesize an active and stable Pt catalyst, namely thermo-destabilization of microemulsions (see R. Y. Parapat, V. Parwoto, M. Schwarze, B. Zhang, D. S. Su and R. Schomäcker, J. Mater. Chem., 2012, 22 (23), 11605-11614). We are able to produce Pt nanocrystals with a small size (2.5 nm) of an isotropic structure i.e. truncated octahedral and deposit them well on support materials. Although we have obtained good results, the performance of the catalyst still needed to be improved and optimized. We followed the strategy to retain the small size but change the shape to an anisotropic structure of Pt nanocrystals which produces more active sites by means of a weaker reducing agent. We found that our catalysts are more active than those we reported before and even show the potential to be applied in a challenging reaction such as hydrogenation of levulinic acid.We recently introduced a new method to synthesize an active and stable Pt catalyst, namely thermo-destabilization of microemulsions (see R. Y. Parapat, V. Parwoto, M. Schwarze, B. Zhang, D. S. Su and R. Schomäcker, J. Mater. Chem., 2012, 22 (23), 11605-11614). We are able to produce Pt nanocrystals with a small size (2.5 nm) of an isotropic structure i.e. truncated octahedral and deposit them well on support materials. Although we have obtained good results, the performance of the catalyst still needed to be improved and optimized. We followed the strategy to retain the small size but change the shape to an anisotropic structure of Pt nanocrystals which produces more active sites by means of a weaker reducing agent. We found that our catalysts are more active than those we reported before and even show the potential to be applied in a challenging reaction such as hydrogenation of levulinic acid. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32122j

  9. Radio-Frequency-Based NH3-Selective Catalytic Reduction Catalyst Control: Studies on Temperature Dependency and Humidity Influences

    Directory of Open Access Journals (Sweden)

    Markus Dietrich


    Full Text Available The upcoming more stringent automotive emission legislations and current developments have promoted new technologies for more precise and reliable catalyst control. For this purpose, radio-frequency-based (RF catalyst state determination offers the only approach for directly measuring the NH3 loading on selective catalytic reduction (SCR catalysts and the state of other catalysts and filter systems. Recently, the ability of this technique to directly control the urea dosing on a current NH3 storing zeolite catalyst has been demonstrated on an engine dynamometer for the first time and this paper continues that work. Therefore, a well-known serial-type and zeolite-based SCR catalyst (Cu-SSZ-13 was investigated under deliberately chosen high space velocities. At first, the full functionality of the RF system with Cu-SSZ-13 as sample was tested successfully. By direct RF-based NH3 storage control, the influence of the storage degree on the catalyst performance, i.e., on NOx conversion and NH3 slip, was investigated in a temperature range between 250 and 400 °C. For each operation point, an ideal and a critical NH3 storage degree was found and analyzed in the whole temperature range. Based on the data of all experimental runs, temperature dependent calibration functions were developed as a basis for upcoming tests under transient conditions. Additionally, the influence of exhaust humidity was observed with special focus on cold start water and its effects to the RF signals.

  10. Catalysts and conditions for the highly efficient, selective and stable heterogeneous oligomerisation of ethylene

    CSIR Research Space (South Africa)

    Heveling, J


    Full Text Available analysis On- and off-line analyses were carried out using Carlo Erba 4200 gas chromatographs equipped with FID detectors and a 60 m SEG OV1 or BP-1 capillary column. Liquid products were condensed with a water-cooled condenser and the volume of gaseous... that the unhydrogenated gasoline fraction, on the other hand, had a RON of 86.2. Further, from 13C ? NMR it can be determined that aromatics are essentially absent from the fuel samples produced under the LT-HP conditions [14]. An estimation of the amount of linear...

  11. Aldehyde-Selective Wacker-Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co-Catalyst

    KAUST Repository

    Wickens, Zachary K.


    Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O-labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt.

  12. Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle-Size Effects. (United States)

    O'Brien, Casey P; Dostert, Karl-Heinz; Schauermann, Swetlana; Freund, Hans-Joachim


    The selectivity in the hydrogenation of acrolein over Fe 3 O 4 -supported Pd nanoparticles has been investigated as a function of nanoparticle size in the 220-270 K temperature range. While Pd(111) shows nearly 100 % selectivity towards the desired hydrogenation of the C=O bond to produce propenol, Pd nanoparticles were found to be much less selective towards this product. In situ detection of surface species by using IR-reflection absorption spectroscopy shows that the selectivity towards propenol critically depends on the formation of an oxopropyl spectator species. While an overlayer of oxopropyl species is effectively formed on Pd(111) turning the surface highly selective for propenol formation, this process is strongly hindered on Pd nanoparticles by acrolein decomposition resulting in CO formation. We show that the extent of acrolein decomposition can be tuned by varying the particle size and the reaction temperature. As a result, significant production of propenol is observed over 12 nm Pd nanoparticles at 250 K, while smaller (4 and 7 nm) nanoparticles did not produce propenol at any of the temperatures investigated. The possible origin of particle-size dependence of propenol formation is discussed. This work demonstrates that the selectivity in the hydrogenation of acrolein is controlled by the relative rates of acrolein partial hydrogenation to oxopropyl surface species and of acrolein decomposition, which has significant implications for rational catalyst design. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow. (United States)

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael


    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Stamenković Vojislav


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

  15. Nanocasting Design and Spatially Selective Sulfonation of Polystyrene-Based Polymer Networks as Solid Acid Catalysts. (United States)

    Richter, Felix H; Sahraoui, Laila; Schüth, Ferdi


    Nanocasting is a general and widely applied method in the generation of porous materials during which a sacrificial solid template is used as a mold on the nanoscale. Ideally, the resulting structure is the inverse of the template. However, replication is not always as direct as anticipated, so the influences of the degree of pore filling and of potential restructuring processes after removal of the template need to be considered. These apparent limitations give rise to opportunities in the synthesis of poly(styrene-co-divinylbenzene) (PSD) polymer networks of widely varying porosities (BET surface area=63-562 m(2)  g(-1) ; Vtot =0.18-1.05 cm(3)  g(-1) ) by applying a single synthesis methodology. In addition, spatially selective sulfonation on the nanoscale seems possible. Together, nanocasting and sulfonation enable rational catalyst design. The highly porous nanocast and predominantly surface-sulfonated PSD networks approach the activity of the corresponding molecular catalyst, para-toluenesulfonic acid, and exceed those of commercial ion-exchange polymers in the depolymerization of macromolecular inulin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Oxide-supported IrNiO(x) core-shell particles as efficient, cost-effective, and stable catalysts for electrochemical water splitting. (United States)

    Nong, Hong Nhan; Oh, Hyung-Suk; Reier, Tobias; Willinger, Elena; Willinger, Marc-Georg; Petkov, Valeri; Teschner, Detre; Strasser, Peter


    Active and highly stable oxide-supported IrNiO(x) core-shell catalysts for electrochemical water splitting are presented. IrNi(x)@IrO(x) nanoparticles supported on high-surface-area mesoporous antimony-doped tin oxide (IrNiO(x)/Meso-ATO) were synthesized from bimetallic IrNi(x) precursor alloys (PA-IrNi(x) /Meso-ATO) using electrochemical Ni leaching and concomitant Ir oxidation. Special emphasis was placed on Ni/NiO surface segregation under thermal treatment of the PA-IrNi(x)/Meso-ATO as well as on the surface chemical state of the particle/oxide support interface. Combining a wide array of characterization methods, we uncovered the detrimental effect of segregated NiO phases on the water splitting activity of core-shell particles. The core-shell IrNiO(x)/Meso-ATO catalyst displayed high water-splitting activity and unprecedented stability in acidic electrolyte providing substantial progress in the development of PEM electrolyzer anode catalysts with drastically reduced Ir loading and significantly enhanced durability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Raising distillate selectivity and catalyst life time in Fischer-Tropsch synthesis by using a novel dual-bed reactor

    International Nuclear Information System (INIS)

    Tavasoli, A.; Sadaghiani, K.; Khodadadi, A. A.; Mortazavi, Y.


    In a novel dual bed reactor Fischer-Tropsch synthesis was studied by using two diff rent cobalt catalysts. An alkali-promoted cobalt catalyst was used in the first bed of a fixed-bed reactor followed by a Raiment promoted cobalt catalyst in the second bed. The activity, product selectivity and accelerated deactivation of the system were assessed and compared with a conventional single bed reactor system. The methane selectivity in the dual-bed reactor was about 18.9% less compared to that of the single-bed reactor. The C 5+ selectivity for the dual-bed reactor was 10.9% higher than that of the single-bed reactor. Accelerated deactivation of the catalysts in the dual-bed reactor was 42% lower than that of the single-bed reactor. It was revealed that the amount of catalysts activity recovery after regeneration at 400 d eg C in the dual-bed system is higher than that of the single-bed system

  18. Methods of making textured catalysts (United States)

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA


    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  19. Shape-selective catalysts for Fischer-Tropsch chemistry. Final report : January 1, 2001 - December 31, 2008.

    Energy Technology Data Exchange (ETDEWEB)

    Cronauer, D. C. (Chemical Sciences and Engineering Division)


    Argonne National Laboratory carried out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry-specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it was desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It was desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The original goal was to produce shape-selective catalysts that had the potential to limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' This cage would also restrict their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. Such catalysts were prepared with silica-containing fractal cages. The activity and strength was essentially the same as that of catalysts without the cages. Since there was no improvement, the program plan was modified as discussed below. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those

  20. Shape-selective catalysts for Fischer-Tropsch chemistry. Final report: January 1, 2001 - December 31, 2008

    International Nuclear Information System (INIS)

    Cronauer, D.C.


    Argonne National Laboratory carried out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry-specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it was desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It was desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The original goal was to produce shape-selective catalysts that had the potential to limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' This cage would also restrict their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. Such catalysts were prepared with silica-containing fractal cages. The activity and strength was essentially the same as that of catalysts without the cages. Since there was no improvement, the program plan was modified as discussed below. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for

  1. System and method for controlling ammonia levels in a selective catalytic reduction catalyst using a nitrogen oxide sensor (United States)



    A system according to the principles of the present disclosure includes an air/fuel ratio determination module and an emission level determination module. The air/fuel ratio determination module determines an air/fuel ratio based on input from an air/fuel ratio sensor positioned downstream from a three-way catalyst that is positioned upstream from a selective catalytic reduction (SCR) catalyst. The emission level determination module selects one of a predetermined value and an input based on the air/fuel ratio. The input is received from a nitrogen oxide sensor positioned downstream from the three-way catalyst. The emission level determination module determines an ammonia level based on the one of the predetermined value and the input received from the nitrogen oxide sensor.

  2. Detection of CO{sub 2} using CNT-based sensors: Role of Fe catalyst on sensitivity and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Tit, Nacir, E-mail: [Physics Department, UAE University, P.O. Box 15551, Al-Ain (United Arab Emirates); Ezzi, Mohammed M. Al; Abdullah, Hasan M. [Physics Department, King Fahd University of Petroleum and Minerals, P.O. Box 1690, Dhahran, 31261 (Saudi Arabia); Yusupov, Maksudbek [Research Group PLASMANT, Department of Chemistry, University of Antwerp, Universiteitsplein 1, BE-2610, Wilrijk-Antwerp (Belgium); Kouser, Summayya [Theoretical Sciences Unit, Jawaharlal Nehru Center for Advanced Scientific Research, Jakkur, Bangalore (India); Bahlouli, Hocine [Physics Department, King Fahd University of Petroleum and Minerals, P.O. Box 1690, Dhahran, 31261 (Saudi Arabia); Yamani, Zain H. [Physics Department, King Fahd University of Petroleum and Minerals, P.O. Box 1690, Dhahran, 31261 (Saudi Arabia); Center for Research Excellence in Nanotechnology, KFUPM, P.O. Box 5040, Dhahran 31261 (Saudi Arabia)


    The adsorption of CO{sub 2} on surfaces of graphene and carbon nanotubes (CNTs), decorated with Fe atoms, are investigated using the self-consistent-charge density-functional tight-binding (SCC-DFTB) method, neglecting the heat effects. Fe ad-atoms are more stable when they are dispersed on hollow sites. They introduce a large density of states at the Fermi level (N{sub F}); where keeping such density low would help in gas sensing. Furthermore, the Fe ad-atom can weaken the C=O double bonds of the chemisorbed CO{sub 2} molecule, paving the way for oxygen atoms to drain more charges from Fe. Consequently, chemisorption of CO{sub 2} molecules reduces both N{sub F} and the conductance while it enhances the sensitivity with the increasing gas dose. Conducting armchair CNTs (ac-CNTs) have higher sensitivity than graphene and semiconducting zigzag CNTs (zz-CNTs). Comparative study of sensitivity of ac-CNT-Fe composite towards various gases (e.g., O{sub 2}, N{sub 2}, H{sub 2}, H{sub 2}O, CO and CO{sub 2}) has shown high sensitivity and selectivity towards CO, CO{sub 2} and H{sub 2}O gases. - Highlights: • DFTB is used to study Adsorptions of CO{sub 2} molecule on pG and CNT, with Fe catalyst. • Armchair CNT-Fe has higher sensitivity to detect CO{sub 2} than zigzag CNT-Fe and pG-Fe. • Ac-CNT-Fe is highly sensitive and selective towards CO, CO{sub 2} and H{sub 2}O gases. • Keeping Fe ad-atoms dispersed and with low density enhances sensitivity. • Our theoretical results corroborate the experimental findings of Ref. .

  3. Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO (United States)

    Liu, Changxiang; Gong, Lei; Dai, Runying; Lu, Meijuan; Sun, Tingting; Liu, Qian; Huang, Xigen; Huang, Zhong


    Mesoporous Mn-doped Co3O4 catalysts were successfully prepared via a dry soft reactive grinding method based on solid state reaction, and their catalytic performances on CO oxidation were evaluated at a high space velocity of 49,500 mL g-1 h-1. A significant promoted effect was observed once the atomic ratios of Mn/(Co+Mn) were lower than 10%, for instance, the temperature for 50% conversion decreased to about -60 °C, showing superior catalytic performance compared to the single metal oxide. Especially, the Mn-promoted Co3O4 catalyst with a Mn/(Co+Mn) molar ratio of 10% could convert 100% CO after 3000 min of time-on-steam without any deactivation at room temperature. As prepared catalysts were characterized by XRD, N2-adsorption/desorption, TEM, H2-TPR, O2-TPD and CO-titration analysis. The significant enhancement of performance for oxidation of CO over Mn-Co-O mixed oxides was associated with the high active oxygen species concentrations formed during the pretreatment in O2 atmosphere.

  4. Oxidative dehydrogenation of C{sub 3}-C{sub 4} paraffins in the presence of CO{sub 2} over chromium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Botavina, M.A.; Agafonov, A.A.; Trushin, D.V.; Makashov, A.V.; Nekrasov, N.V.; Gaidai, N.A. [N.D. Zelinsky Inst. of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)


    Supported chromium catalysts show good activity and selectivity in the reaction of propane and isobutane oxidative dehydrogenation in the presence of CO{sub 2}. The most active, selective and stable is the catalyst containing 5% (wt.%) of Cr supported on silica and prepared by impregnation method. It was found that the addition up to 5,0% (vol.) of oxygen results in a significant increase of catalyst activity and stability at little decrease of catalyst selectivity. (orig.)

  5. Micro/milliflow processing with selective catalyst microwave heating in the Cu-catalyzed Ullmann etherification reaction: a μ(2)-process. (United States)

    Benaskar, Faysal; Patil, Narendra G; Rebrov, Evgeny V; Ben-Abdelmoumen, Alladin; Meuldijk, Jan; Hulshof, Lumbertus A; Hessel, Volker; Schouten, Jaap C


    A μ(2)-process in the Ullmann-type C-O coupling of potassium phenolate and 4-chloropyridine was successfully performed in a combined microwave (MW) and microflow process. Selective MW absorption in a micro-fixed-bed reactor (μ-FBR) by using a supported Cu nanocatalyst resulted in an increased activity compared to an oil-bath heated process. Yields of up to 80 % were attained by using a multisegmented μ-FBR without significant catalyst deactivation. The μ-FBR was packed with beads coated with Cu/TiO(2) and CuZn/TiO(2) catalysts. Temperature measurements along axial positions of the reactor were performed by using a fiber-optic probe in the catalyst bed. The simultaneous application of MW power and temperature sensors resulted in an isothermal reactor at 20 W. Initially, only solvent was used to adjust the MW field density in the cavity and optimize the power utility. Subsequently, the reaction mixture was added to ensure the maximum MW power transfer by adjusting the waveguide stub tuners to steady-state operations as a result of the changed reaction mixture composition and, therefore, the dielectric properties. Finally, the beneficial influence of the Cu/TiO(2)- and CuZn/TiO(2)-coated glass beads (200 μm) on the MW absorption as a result of the additional absorbing effect of the metallic Cu nanoparticles was optimized in a fine-tuning step. For the catalyst synthesis, various sol-gel, deposition, and impregnation methods provided Cu catalyst loadings of around 1 wt %. The addition of Zn to the Cu nanocatalyst revealed an increased catalyst activity owing to the presence of stable Cu(0). Multilaminar mixing was necessary because of the large difference in fluid viscosities. To the best of our knowledge, this work is the first extended experimental survey of the decisive parameters to combine microprocess and single-mode MW technology following the concepts of "novel process windows" for organic syntheses. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGa

  6. Selective production of oxygenates from CO2 hydrogenation over mesoporous silica supported Cu-Ga nanocomposite catalyst

    KAUST Repository

    Huang, Kuo-Wei


    Carbon dioxide hydrogenation to oxygenates (methanol and dimethyl ether (DME)) was investigated over bifunctional supported copper catalysts promoted with gallium (Ga). Supported Cu-Ga nanocomposite catalysts were characterized by X-ray diffraction, transmission electron microscopy with energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and H2 temperature programmed reduction. In comparison with Cu-SBA-15 based catalysts, Ga promoted catalysts prepared by the urea deposition method (CuGa/SBA-15-UDP) was found active and selective for CO2 hydrogenation to oxygenates. The use of Ga as the promoter showed increased acidic sites as confirmed by the NH3-TPD, Pyridine-IR and 2,6-lutidine-IR studies. The favorable effect of Ga on CO2 conversion and selectivity to oxygenate may come from the strong interaction of Ga with silica, which is responsible for the enhanced metal surface area, formation of nanocomposite and metal dispersion. Notably, incorporation of Ga to Cu/SiO2 showed a several-fold higher rate for methanol formation (13.12 mol/gCu·sec) with a reasonable rate for the DME formation (2.15 mol/gCu·sec) as compared to those of Cu/SiO2 catalysts.

  7. In situ vibrational spectroscopic investigation of C4 hydrocarbon selective oxidation over vanadium-phosphorus-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Zhi -Yang [Iowa State Univ., Ames, IA (United States)


    n-Butane selective oxidation over the VPO catalyst to maleic anhydride is the first and only commercialized process of light alkane selective oxidation. The mechanism of this reaction is still not well known despite over twenty years of extensive studies, which can partially be attributed to the extreme difficulties to characterize catalytic reactions real-time under typical reaction conditions. In situ spectroscopic characterization techniques such as Infrared spectroscopy and laser Raman spectroscopy were used in the current mechanistic investigations of n-butane oxidation over VPO catalysts. To identify the reaction intermediates, oxidation of n-butane, 1,3-butadiene and related oxygenates on the VPO catalyst were monitored using FTIR spectroscopy under transient conditions. n-Butane was found to adsorb on the VPO catalyst to form olefinic species, which were further oxidized to unsaturated, noncyclic carbonyl species. The open chain dicarbonyl species then experienced cycloaddition to form maleic anhydride. VPO catalyst phase transformations were investigated using in situ laser Raman spectroscopy. This report contains Chapter 1: General introduction; Chapter 2: Literature review; and Chapter 5: Conclusion and recommendations.

  8. Efficient and selective chemical transformations under flow conditions: The combination of supported catalysts and supercritical fluids. (United States)

    Burguete, M Isabel; García-Verdugo, Eduardo; Luis, Santiago V


    This paper reviews the current trends in the combined use of supported catalytic systems, either on solid supports or in liquid phases and supercritical fluids (scFs), to develop selective and enantioselective chemical transformations under continuous and semi-continuous flow conditions. The results presented have been selected to highlight how the combined use of those two elements can contribute to: (i) Significant improvements in productivity as a result of the enhanced diffusion of substrates and reagents through the interfaces favored by the scF phase; (ii) the long term stability of the catalytic systems, which also contributes to the improvement of the final productivity, as the use of an appropriate immobilization strategy facilitates catalyst isolation and reuse; (iii) the development of highly efficient selective or, when applicable, enantioselective chemical transformations. Although the examples reported in the literature and considered in this review are currently confined to a limited number of fields, a significant development in this area can be envisaged for the near future due to the clear advantages of these systems over the conventional ones.

  9. In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts. (United States)

    Zieliński, Grzegorz Krzysztof; Samojłowicz, Cezary; Wdowik, Tomasz; Grela, Karol


    A system for transfer hydrogenation of alkenes, composed of a ruthenium metathesis catalyst and HCOOH, is presented. This operationally simple system can be formed directly after a metathesis reaction to effect hydrogenation of the metathesis product in a single-pot. These hydrogenation conditions are applicable to a wide range of alkenes and offer remarkable selectivity.

  10. Selective CO Methanation on Ru/TiO2 Catalysts: Role and Influence of Metal-Support Interactions

    DEFF Research Database (Denmark)

    Abdel-Mageed, Ali M.; Widmann, D.; Olesen, Sine Ellemann


    Aiming at a detailed understanding of the role of metal-support interactions in the selective methanation of CO in CO2-rich reformate gases, we have investigated the catalytic performance of a set of Ru/TiO2 catalysts with comparable Ru loading, Ru particle size, and TiO2 phase composition but very...


    Acetophenone, a very useful industrial chemical for fragrance and flavoring agent and a solvent for plastics and resins, is usually produced as a byproduct of phenol production from cumeme. Aluminia supported vandium oxide catalyst is now explored for the selective oxidation of e...

  12. Hydrogen-Permeable Tubular Membrane Reactor: Promoting Conversion and Product Selectivity for Non-Oxidative Activation of Methane over an Fe©SiO2Catalyst. (United States)

    Sakbodin, Mann; Wu, Yiqing; Oh, Su Cheun; Wachsman, Eric D; Liu, Dongxia


    Non-oxidative methane conversion over Fe©SiO 2 catalyst was studied for the first time in a hydrogen (H 2 ) permeable tubular membrane reactor. The membrane reactor is composed of a mixed ionic-electronic SrCe 0.7 Zr 0.2 Eu 0.1 O 3-δ thin film (≈20 μm) supported on the outer surface of a one-end capped porous SrCe 0.8 Zr 0.2 O 3-δ tube. Significant improvement in CH 4 conversion was achieved upon H 2 removal from the membrane reactor compared to that in a fixed-bed reactor. The Fe©SiO 2 catalyst in the H 2 permeable membrane reactor demonstrated a stable ≈30 % C 2+ single-pass yield, with up to 30 % CH 4 conversion and 99 % selectivity to C 2 (ethylene and acetylene) and aromatic (benzene and naphthalene) products, at the tested conditions. The selectivity towards C 2 or aromatics was manipulated purposely by adding H 2 into or removing H 2 from the membrane reactor feed and permeate gas streams. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Selective and Stable Ethylbenzene Dehydrogenation to Styrene over Nanodiamonds under Oxygen-lean Conditions. (United States)

    Diao, Jiangyong; Feng, Zhenbao; Huang, Rui; Liu, Hongyang; Hamid, Sharifah Bee Abd; Su, Dang Sheng


    For the first time, significant improvement of the catalytic performance of nanodiamonds was achieved for the dehydrogenation of ethylbenzene to styrene under oxygen-lean conditions. We demonstrated that the combination of direct dehydrogenation and oxidative dehydrogenation indeed occurred on the nanodiamond surface throughout the reaction system. It was found that the active sp(2)-sp(3) hybridized nanostructure was well maintained after the long-term test and the active ketonic carbonyl groups could be generated in situ. A high reactivity with 40% ethylbenzene conversion and 92% styrene selectivity was obtained over the nanodiamond catalyst under oxygen-lean conditions even after a 240 h test, demonstrating the potential of this procedure for application as a promising industrial process for the ethylbenzene dehydrogenation to styrene without steam protection. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The synthesis of tritium, carbon-14 and stable isotope labelled selective estrogen receptor degraders. (United States)

    Bragg, Ryan A; Bushby, Nick; Ericsson, Cecilia; Kingston, Lee P; Ji, Hailong; Elmore, Charles S


    As part of a Medicinal Chemistry program aimed at developing an orally bioavailable selective estrogen receptor degrader, a number of tritium, carbon-14, and stable isotope labelled (E)-3-[4-(2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-1-yl)phenyl]prop-2-enoic acids were required. This paper discusses 5 synthetic approaches to this compound class. Copyright © 2016 John Wiley & Sons, Ltd.

  15. Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders


    Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...

  16. Selective nano alumina supported vanadium oxide catalysts for oxidative dehydrogenation of ethylbenzene to styrene using CO2 as soft oxidant

    Directory of Open Access Journals (Sweden)

    A.M. Elfadly


    Full Text Available Nano alumina-supported V2O5 catalysts with different loadings have been tested for the dehydrogenation of ethylbenzene with CO2 as an oxidant. High surface area nano-alumina was prepared and used as support for V2O5 as the catalyst. The catalysts were synthesized by impregnation techniques followed by calcinations and microwave treatment, denoted as V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW, respectively. The V2O5 loading was varied on nano-alumina from 5 to 30 wt%. The support and catalysts were characterized by X-ray diffraction (XRD, Barett–Joyner–Halenda (BJH pore-size distribution, N2-adsorption isotherms, Fourier transform infrared (FT-IR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and temperature programed desorption (TPD-NH3. The characterization results indicated that V2O5 is highly dispersed on alumina up to 30%-V2O5/γ-Al2O3-MW prepared by MW method. The TPD studies indicated that there are significant differences in acid amount and strength for V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW-catalysts. The catalytic activity of the prepared catalysts was evaluated in the temperature range 450–600 °C in relation to the physicochemical properties and surface acidity. The results revealed that optimum catalytic activity and selectivity (∼100% toward styrene production were obtained using 10% V2O5/γ-Al2O3-MW catalyst treated with microwave.

  17. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels. (United States)

    Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P


    A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

  18. Selective adsorption of refractory sulfur species on active carbons and carbon based CoMo catalyst. (United States)

    Farag, Hamdy


    Adsorption technique could be a reliable alternative in removing to a certain remarkable extent the sulfur species from the feedstock of petroleum oil. The performance of various carbons on adsorption of model sulfur compounds in a simulated feed solution and the sulfur containing compounds in the real gas oil was evaluated. The adsorption experiments have been carried out in a batch scale at ambient temperature and under the atmospheric pressure. In general, the most refractory sulfur compounds in the hydrotreatment reactions were selectively removed and adsorbed. It was found that the adsorbents affinities to dibenzothiophene and 4,6-dimethyldibenzothiophene were much more favored and pronounced than the aromatic matrices like fluorene, 1-methylnaphthalene and 9-methylanthracene. Among the sulfur species, 4,6-dimethyldibenzothiophene was the highest to be removed in terms of both selectivity and capacity over all the present adsorbents. The studied adsorbents showed significant capacities for the polyaromatic thiophenes. The electronic characteristics seem to play a certain role in such behavior. Regeneration of the used adsorbent was successfully attained either by washing it with toluene or by the release of the adsorbates through heat treatment. A suggested adsorptive removal process of sulfur compounds from petroleum distillate over carbon supported CoMo catalyst was discussed.

  19. Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst. (United States)

    Audemar, Maïté; Ciotonea, Carmen; De Oliveira Vigier, Karine; Royer, Sébastien; Ungureanu, Adrian; Dragoi, Brindusa; Dumitriu, Emil; Jérôme, François


    The hydrogenation of furfural to furfuryl alcohol was performed in the presence of a Co/SBA-15 catalyst. High selectivity (96 %) at a conversion higher than 95 % is reported over this catalytic system. As the conversion of furfural to furfuryl alcohol occurs over metallic Co sites, the effect of reduction temperature, H2 pressure, and reaction temperature were studied. Optimum reaction conditions were: 150 °C, 1.5 h, 2.0 MPa of H2 . The catalyst was recyclable, and furfuryl alcohol was recovered with a purity higher than 90 %. The effect of the solvent concentration was also studied. With a minimum of 50 wt % of solvent, the selectivity to furfuryl alcohol and the conversion of furfural remained high (both over 80 %). Likewise, the activity of the catalyst is maintained even in pure furfural, which confirms the real potential of the proposed catalytic system. This catalyst was also used in the hydrogenation of levulinic acid to produce γ-valerolactone selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts. (United States)

    McManus, Iain J; Daly, Helen; Manyar, Haresh G; Taylor, S F Rebecca; Thompson, Jillian M; Hardacre, Christopher


    Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

  1. An investigation of alumina-supported catalysts for the selective catalytic oxidation of ammonia in biomass gasification

    Energy Technology Data Exchange (ETDEWEB)

    Darvell, L.I.; Jones, J.M.; Ross, A.B.; Williams, A. [Department of Fuel and Energy, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); Heiskanen, K.; Simell, P. [VTT Processes, P.O. Box 1601, FIN-02044 VTT (Finland)


    Alumina-supported catalysts containing different transition metals (Ni, Cu, Cr, Mn, Fe and Co) were prepared and tested for their activity in the selective oxidation of ammonia reaction at high temperatures (between 700 and 900C) using a synthetic gasification gas mixture. The catalysts were also characterised for their acidic properties by infrared studies of pyridine and ammonia adsorption and reaction/desorption. The Ni/Al{sub 2}O{sub 3} and Cr/Al{sub 2}O{sub 3} catalyst displayed the highest selective catalytic oxidation (SCO) activity in that temperature range with excellent N{sub 2} selectivities. FT-IR studies of adsorbed pyridine and NH{sub 3} indicate that Lewis acid sites dominate and that NH{sub 3} adsorption on these sites is likely to be the first step in the SCO reaction. FT-IR studies on less active catalysts, particularly on Cu/Al{sub 2}O{sub 3} allowed the detection of oxidation intermediates, amide (NH{sub 2}), and possibly hydrazine and imido and nitroxyl species. The amide and hydrazine intermediate gives credence to a proposed SCO mechanism involving a hydrazine intermediate, while the proposed imide, =N-H, and/or nitroxyl, HNO species could be intermediates in incomplete oxidation of NH{sub 3} to N{sub 2}O.

  2. Supported nano gold as a recyclable catalyst for green, selective and efficient oxidation of alcohol using molecular oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Dar


    Full Text Available The myth that gold cannot act as a catalyst has been discarded in view of recent studies, which have demonstrated the high catalytic efficiency of pure nano-gold and supported nano-gold catalysts. In recent years, numerous papers have described the use of supported nano-gold particles for catalysis in view of their action on CO and O2 to form CO2, as well as a variety of other reactions. Special emphasis is placed on the oxidation studies undertaken on model nano-Au systems. In this work a solvent free oxidation of 1-phenyl ethanol was carried out using gold supported on ceria-silica, ceria-titania, ceria- zirconia and ceria-alumina at 160 0C. Almost 88-97% conversion was obtained with >99% selectivity. Temperature screening was done from 70 to 160 0C.Catalysts were prepared by deposition co-precipitation method and deposition was determined by EDEX analysis.

  3. Design and Use of Nanostructured Single-Site Heterogeneous Catalysts for the Selective Transformation of Fine Chemicals

    Directory of Open Access Journals (Sweden)

    Vladimiro Dal Santo


    Full Text Available Nanostructured single-site heterogeneous catalysts possess the advantages of classical solid catalysts, in terms of easy recovery and recycling, together with a defined tailored chemical and steric environment around the catalytically active metal site. The use of inorganic oxide supports with selected shape and porosity at a nanometric level may have a relevant impact on the regio- and stereochemistry of the catalytic reaction. Analogously, by choosing the optimal preparation techniques to obtain spatially isolated and well-characterised active sites, it is possible to achieve performances that are comparable to (or, in the most favourable cases, better than those obtained with homogeneous systems. Such catalysts are therefore particularly suitable for the transformation of highly-functionalised fine chemicals and some relevant examples where high chemo-, regio- and stereoselectivity are crucial will be described.

  4. Direct and selective production of propene from bio-ethanol on Sc-loaded IN2O3 catalysts. (United States)

    Iwamoto, Masakazu; Mizuno, Shouta; Tanaka, Masashi


    Propene, one of key building blocks for manufacturing plastics and chemicals, could be directly and stably produced from ethanol in good yields. The conversion degree of ethanol to propene reached approximately 60 mol% by using a 3 atom% scandium-loaded indium oxide catalyst at 823 K in the presence of water and hydrogen. The introduction of Sc prevented the reduction of In2O3 to In metal during the reaction, and that of water decreased the coke formation. Both additions resulted in longer lifetimes of the catalysts. The hydrogen addition increased the conversion of acetone to propene. The reaction pathways are also suggested on the basis of the product distributions and the pulse experiments, ethanol→acetaldehyde→acetone→propene, which is quite different from the shape-selective catalysis on zeolites and the dimerization-metathesis of ethene on nickel ion-loaded silica catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2. (United States)

    Ju, Wen; Bagger, Alexander; Hao, Guang-Ping; Varela, Ana Sofia; Sinev, Ilya; Bon, Volodymyr; Roldan Cuenya, Beatriz; Kaskel, Stefan; Rossmeisl, Jan; Strasser, Peter


    Direct electrochemical reduction of CO 2 to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO 2 -consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO 2 to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N x moieties (M = Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N x moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N x moieties and it provides predictive guidelines for the rational design of selective carbon-based CO 2 reduction catalysts.Inexpensive and selective electrocatalysts for CO 2 reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO 2 to CO conversion.

  6. High performance vanadia-anatase nanoparticle catalysts for the selective catalytic reduction of NO by ammonia

    DEFF Research Database (Denmark)

    Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas; Riisager, Anders


    Highly active nanoparticle SCR deNO(x) catalysts composed of amorphous vanadia on crystalline anatase have been prepared by a sol-gel, co-precipitation method using decomposable crystallization seeds. The catalysts were characterized by means of XRPD, TEM/SEM, FT-IR, nitrogen physisorption and NH(3...

  7. Selective growth of silica nanowires using an Au catalyst for optical recognition of interleukin-10

    Energy Technology Data Exchange (ETDEWEB)

    Sekhar, Praveen K; Ramgir, Niranjan S; Joshi, Rakesh K; Bhansali, Shekhar [Bio-MEMS and Microfabrication Laboratory, Department of Electrical Engineering, University of South Florida, 4202 E Fowler Avenue, ENB 118, Tampa, FL 33620 (United States)], E-mail:


    The vapor-liquid-solid (VLS) growth procedure has been extended for the selective growth of silica nanowires on SiO{sub 2} layer by using Au as a catalyst. The nanowires were grown in an open tube furnace at 1100 deg. C for 60 min using Ar as a carrier gas. The average diameter of these bottom-up nucleated wires was found to be 200 nm. Transmission electron microscopy analysis indicates the amorphous nature of these nanoscale wires and suggests an Si-silica heterostructure. The localized silica nanowires have been used as an immunoassay template in the detection of interleukin-10 which is a lung cancer biomarker. Such a nanostructured platform offered a tenfold enhancement in the optical response, aiding the recognition of IL-10 in comparison to a bare silica substrate. The role of nanowires in the immunoassay was verified through the quenching behavior in the photoluminescence (PL) spectra. Two orders of reduction in PL intensity have been observed after completion of the immunoassay with significant quenching after executing every step of the protocol. The potential of this site-specific growth of silica nanowires on SiO{sub 2} as a multi-modal biosensing platform has been discussed.

  8. Selective Dehydration of Sorbitol to Isosorbide over Sulfonated Activated Carbon Catalyst

    International Nuclear Information System (INIS)

    Kang, Hyo Yoon; Hwang, Dong Won; Hwang, Young Kyu; Hwang, Jin-Soo; Chang, Jong-San


    A sulfonated activated carbon (AC-SO 3 H) was used as a solid acid catalyst for dehydration of sorbitol to isosorbide and its catalytic performance was compared with the commercial solid acid such as acidic ion exchange resin, Amberlyst-36, and sulfated copper oxide. The catalytic performance with 100% sorbitol conversion and 52% isosorbide selectivity was obtained over AC-SO 3 H at 423.15 K. Although AC-SO 3 H possessed only 0.5 mmol/g of sulfur content, it showed the similar dehydration activity of sorbitol to isosorbide with Amberlyst-36 (5.4 mmol/g) at 423.15 K. Based on the high thermal and chemical stability of AC-SO 3 H, one-step reactive distillation, where isosorbide separation can be carried out simultaneously with sorbitol dehydration, was tried to increase the recovery yield of isosorbide from sorbitol. The reactive distillation process using AC-SO 3 H, the turnover number of AC-SO 3 H was 4 times higher than the conventional two-step process using sulfuric acid

  9. Stable feature selection for clinical prediction: exploiting ICD tree structure using Tree-Lasso. (United States)

    Kamkar, Iman; Gupta, Sunil Kumar; Phung, Dinh; Venkatesh, Svetha


    Modern healthcare is getting reshaped by growing Electronic Medical Records (EMR). Recently, these records have been shown of great value towards building clinical prediction models. In EMR data, patients' diseases and hospital interventions are captured through a set of diagnoses and procedures codes. These codes are usually represented in a tree form (e.g. ICD-10 tree) and the codes within a tree branch may be highly correlated. These codes can be used as features to build a prediction model and an appropriate feature selection can inform a clinician about important risk factors for a disease. Traditional feature selection methods (e.g. Information Gain, T-test, etc.) consider each variable independently and usually end up having a long feature list. Recently, Lasso and related l1-penalty based feature selection methods have become popular due to their joint feature selection property. However, Lasso is known to have problems of selecting one feature of many correlated features randomly. This hinders the clinicians to arrive at a stable feature set, which is crucial for clinical decision making process. In this paper, we solve this problem by using a recently proposed Tree-Lasso model. Since, the stability behavior of Tree-Lasso is not well understood, we study the stability behavior of Tree-Lasso and compare it with other feature selection methods. Using a synthetic and two real-world datasets (Cancer and Acute Myocardial Infarction), we show that Tree-Lasso based feature selection is significantly more stable than Lasso and comparable to other methods e.g. Information Gain, ReliefF and T-test. We further show that, using different types of classifiers such as logistic regression, naive Bayes, support vector machines, decision trees and Random Forest, the classification performance of Tree-Lasso is comparable to Lasso and better than other methods. Our result has implications in identifying stable risk factors for many healthcare problems and therefore can

  10. Selective catalytic reduction of nitric oxide with acetaldehyde over NaY zeolite catalyst in lean exhaust feed

    International Nuclear Information System (INIS)

    Schmieg, Steven J.; Cho, Byong K.; Oh, Se H.


    Steady-state selective catalytic reduction (SCR) of nitric oxide (NO) was investigated under simulated lean-burn conditions using acetaldehyde (CH 3 CHO) as the reductant. This work describes the influence of catalyst space velocity and the impact of nitric oxide, acetaldehyde, oxygen, sulfur dioxide, and water on NO x reduction activity over NaY zeolite catalyst. Results indicate that with sufficient catalyst volume 90% NO x conversion can be achieved at temperatures relevant to light-duty diesel exhaust (150-350C). Nitric oxide and acetaldehyde react to form N 2 , HCN, and CO 2 . Oxygen is necessary in the exhaust feed stream to oxidize NO to NO 2 over the catalyst prior to reduction, and water is required to prevent catalyst deactivation. Under conditions of excess acetaldehyde (C 1 :N>6:1) and low temperature ( x conversion is apparently very high; however, the NO x conversion steadily declines with time due to catalytic oxidation of some of the stored (adsorbed) NO to NO 2 , which can have a significant impact on steady-state NO x conversion. With 250ppm NO in the exhaust feed stream, maximum NO x conversion at 200C can be achieved with =400ppm of acetaldehyde, with higher acetaldehyde concentrations resulting in production of acetic acid and breakthrough of NO 2 causing lower NO x conversion levels. Less acetaldehyde is necessary at lower NO concentrations, while more acetaldehyde is required at higher temperatures. Sulfur in the exhaust feed stream as SO 2 can cause slow deactivation of the catalyst by poisoning the adsorption and subsequent reaction of nitric oxide and acetaldehyde, particularly at low temperature

  11. Preparation and Performance of Modified Red Mud-Based Catalysts for Selective Catalytic Reduction of NOx with NH3

    Directory of Open Access Journals (Sweden)

    Jingkun Wu


    Full Text Available Bayer red mud was selected, and the NH3-SCR activity was tested in a fixed bed in which the typical flue gas atmosphere was simulated. Combined with XRF, XRD, BET, SEM, TG and NH3-Temperature Programmed Desorption (TPD characterization, the denitration characteristics of Ce-doped red mud catalysts were studied on the basis of alkali-removed red mud. The results showed that typical red mud was a feasible material for denitration catalyst. Acid washing and calcining comprised the best treatment process for raw red mud, which reduced the content of alkaline substances, cleared the catalyst pore and optimized the particle morphology with dispersion. In the temperature range of 300–400 °C, the denitrification efficiency of calcined acid washing of red mud catalyst (ARM was more than 70%. The doping of Ce significantly enhanced NH3 adsorption from weak, medium and strong acid sites, reduced the crystallinity of α-Fe2O3 in ARM, optimized the specific surface area and broadened the active temperature window, which increased the NOx conversion rate by an average of nearly 20% points from 250–350 °C. The denitration efficiency of Ce0.3/ARM at 300 °C was as high as 88%. The optimum conditions for the denitration reaction of the Ce0.3/ARM catalyst were controlled as follows: Gas Hourly Space Velocity (GHSV of 30,000 h−1, O2 volume fraction of 3.5–4% and the NH3/NO molar ratio ([NH3/NO] of 1.0. The presence of SO2 in the feed had an irreversible negative effect on the activity of the Ce0.3/ARM catalyst.

  12. Effects of γ- and x-irradiation upon activity and selectivity of a supported silver catalyst in the oxidation of ethylene and carbon monoxide

    International Nuclear Information System (INIS)

    Mora Vallejo, R.J.


    Effects of γ and x-radiation on catalytic selectivity of supported silver catalysts for production of ethylene oxide via ethylene oxidation were compared by determination of radio-induced changes in conversion-yield profiles. Influence of photon energy on the kinetics of the irradiation process was studied by determination of conversion-yield profiles, using samples of catalyst exposed to x-rays of different mean photon energy and γ-rays for different cumulative periods of time. The effect of γ-radiation on catalytic activity of the same silver catalysts for carbon monoxide oxidation was analyzed by determination of the reaction kinetics before and after catalyst irradiation

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

    International Nuclear Information System (INIS)

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


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

  14. Plasmodium vinckei: selection of a strain exhibiting stable resistance to arteether. (United States)

    Puri, S K; Chandra, Ramesh


    A strain of rodent malaria parasite Plasmodium vinckei showing >12-fold resistance to arteether has been selected after exposure to sub-curative doses of drug in 44 sequential passages over a period of 700 days. Experimentally induced resistance was found to be stable after drug free maintenance of parasites for 11 serial passages over a period of 100 days. Cross-sensitivity studies have shown that apart form resistance to related derivatives like artemether and artesunic acid, the derived parasites also show resistance to quinine and mefloquine.

  15. Selective hydrodechlorination of 1,2-dichloroethane catalyzed by trace Pd decorated Ag/Al2O3 catalysts prepared by galvanic replacement (United States)

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


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

  16. Gallium Modified HUSY Zeolite as an Effective Co-support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity. (United States)

    Zhou, Wenwu; Zhou, Yasong; Wei, Qiang; Du, Lin; Ding, Sijia; Jiang, Shujiao; Zhang, Yanan; Zhang, Qing


    The effects of metal-modified acidic co-supports on the hydrodesulfurization (HDS) activity and isomerization selectivity of highly refractory organosulfur compounds such as 4,6-dimethyldibenzothiophene have been investigated. Y zeolite crystals with high Si/Al ratios and small crystallite sizes were successfully synthesized by a new hydrothermal synthesis approach. The synthesized Y zeolite crystals were ion-exchanged and stabilized. The prepared samples were then modified with different gallium contents using an impregnation method to adjust their acidity properties, and these modified samples were used as co-supports for NiMo sulfide HDS catalysts. The catalyst containing 10 wt.% zeolite Y modified by 2 wt.% gallium (NiMo/2GaY-ASA-A) exhibited the highest HDS activity, with 4,6-dimethyldibenzothiophene (4,6-DMDBT) conversion nearly double the rate of the catalyst without zeolite at 563 K, 4.0 MPa and liquid hourly space velocity (LHSV) of 40 h -1 . NiMo/2GaY-ASA-A also exhibited superior isomerization ability, with 3,4'-DMBP, 4,4'DMBP, and 3,6-DMDBT as the main products, indicating that the isomerization pathway was the main reaction route over NiMo/2GaY-ASA-A. The superior catalytic performance is related to the synergistic effect of the proper amount of medium and strong Brønsted acid sites. The compounds 3,6-DMDBT and 3,7-DMDBT (isomers of 4,6-DMDBT) and 3,4,6-TMDBT and tetra-methyl-DBT (transmethyl products) were detected simultaneously in the HDS product of 4,6-DMDBT for the first time over NiMo/GaY-ASA-A catalysts. Finally, a new reaction network over NiMo/2GaY-ASA-A was proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Ni–Sn-Supported ZrO2 Catalysts Modified by Indium for Selective CO2 Hydrogenation to Methanol

    KAUST Repository

    Hengne, Amol Mahalingappa


    Ni and NiSn supported on zirconia (ZrO2) and on indium (In)-incorporated zirconia (InZrO2) catalysts were prepared by a wet chemical reduction route and tested for hydrogenation of CO2 to methanol in a fixed-bed isothermal flow reactor at 250 °C. The mono-metallic Ni (5%Ni/ZrO2) catalysts showed a very high selectivity for methane (99%) during CO2 hydrogenation. Introduction of Sn to this material with the following formulation 5Ni5Sn/ZrO2 (5% Ni-5% Sn/ZrO2) showed the rate of methanol formation to be 0.0417 μmol/(gcat·s) with 54% selectivity. Furthermore, the combination NiSn supported on InZrO2 (5Ni5Sn/10InZrO2) exhibited a rate of methanol formation 10 times higher than that on 5Ni/ZrO2 (0.1043 μmol/(gcat·s)) with 99% selectivity for methanol. All of these catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy, CO2-temperature-programmed desorption, and density functional theory (DFT) studies. Addition of Sn to Ni catalysts resulted in the formation of a NiSn alloy. The NiSn alloy particle size was kept in the range of 10–15 nm, which was evidenced by HRTEM study. DFT analysis was carried out to identify the surface composition as well as the structural location of each element on the surface in three compositions investigated, namely, Ni28Sn27, Ni18Sn37, and Ni37Sn18 bimetallic nanoclusters, and results were in agreement with the STEM and electron energy-loss spectroscopy results. Also, the introduction of “Sn” and “In” helped improve the reducibility of Ni oxide and the basic strength of catalysts. Considerable details of the catalytic and structural properties of the Ni, NiSn, and NiSnIn catalyst systems were elucidated. These observations were decisive for achieving a highly efficient formation rate of methanol via CO2 by the H2 reduction process with high methanol selectivity.

  18. The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds. (United States)

    Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno


    The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

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

    KAUST Repository

    Zwaschka, Gregor


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

  20. Using soluble polymers to enforce catalyst-phase-selective solubility and as antileaching agents to facilitate homogeneous catalysis. (United States)

    Liang, Yannan; Harrell, Mary L; Bergbreiter, David E


    The enforced phase-selective solubility of polyisobutylene (PIB)-bound Rh(II) catalysts in biphasic heptane/acetonitrile mixtures can be used not only to recycle these catalysts but also to minimize bimolecular reactions with ethyl diazoacetate. When cyclopropanation and O-H insertion reactions are carried out with PIB-bound Rh(II) catalysts either with or without addition of an unfunctionalized hydrocarbon polymer cosolvent, dimer by-product formation is suppressed even without slow syringe pump addition of the ethyl diazoacetate. This suppression of by-product formation is shown to be due to increased phase segregation of the soluble polymer-bound catalyst and the ethyl diazoacetate reactant. These studies also reveal that added hydrocarbon polymer cosolvents can function as antileaching agents, decreasing the already small amount of a soluble polymer-bound species that leaches into a polar phase in a biphasic mixture during a liquid/liquid separation step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Superior catalysts for selective catalytic reduction of nitric oxide. Annual technical report, September 30, 1993--September 29, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Chen, J.P.; Hausladen, M.C.; Yang, R.T.


    A delaminated Fe{sub 2}O{sub 3}-pillared clay catalyst was prepared for the selective catalytic reduction (SCR) of NO by NH{sub 3} at above 300{degrees}C. The delaminated pillard clay was characterized by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy) chemical analysis, XRD (X-ray diffraction) structure and line broadening analyses, micropore size probing, and Moessbauer analysis. These analyses showed that the catalyst contained fragmented Fe{sub 2}O{sub 3}-pillared clay forming {open_quotes}house-of-cards{close_quotes} structure with dispersed Fe{sub 2}O{sub 3} particles approximately 170 {angstrom} in size. The SCR activity of the delaminated pillard clay was higher than the commercial-type V{sub 2}O{sub 5} + WO{sub 3}/TiO{sub 2} catalyst, and also higher than the undelaminated pillard clay and supported Fe{sub 2}O{sub 3} catalysts, under conditions with SO{sub 2}. Infrared measurements of adsorbed NH{sub 3} showed strong Bronsted acidity which was caused possibly by interactions between Fe{sub 2}O{sub 3} and clay.

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

    DEFF Research Database (Denmark)

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


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

  3. A Membrane-Free Neutral pH Formate Fuel Cell Enabled by a Selective Nickel Sulfide Oxygen Reduction Catalyst. (United States)

    Yan, Bing; Concannon, Nolan M; Milshtein, Jarrod D; Brushett, Fikile R; Surendranath, Yogesh


    Polymer electrolyte membranes employed in contemporary fuel cells severely limit device design and restrict catalyst choice, but are essential for preventing short-circuiting reactions at unselective anode and cathode catalysts. Herein, we report that nickel sulfide Ni 3 S 2 is a highly selective catalyst for the oxygen reduction reaction in the presence of 1.0 m formate. We combine this selective cathode with a carbon-supported palladium (Pd/C) anode to establish a membrane-free, room-temperature formate fuel cell that operates under benign neutral pH conditions. Proof-of-concept cells display open circuit voltages of approximately 0.7 V and peak power values greater than 1 mW cm -2 , significantly outperforming the identical device employing an unselective platinum (Pt) cathode. The work establishes the power of selective catalysis to enable versatile membrane-free fuel cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Cu/MgAl(2)O(4) as bifunctional catalyst for aldol condensation of 5-hydroxymethylfurfural and selective transfer hydrogenation. (United States)

    Pupovac, Kristina; Palkovits, Regina


    Copper supported on mesoporous magnesium aluminate has been prepared as noble-metal-free solid catalyst for aldol condensation of 5-hydroxymethylfurfural with acetone, followed by hydrogenation of the aldol condensation products. The investigated mesoporous spinels possess high activity as solid-base catalysts. Magnesium aluminate exhibits superior activity compared to zinc and cobalt-based aluminates, reaching full conversion and up to 81 % yield of the 1:1 aldol product. The high activity can be correlated to a higher concentration of basic surface sites on magnesium aluminate. Applying continuous regeneration, the catalysts can be recycled without loss of activity. Focusing on the subsequent hydrogenation of aldol condensation products, Cu/MgAl2 O4 allows a selective hydrogenation and CO bond cleavage, delivering 3-hydroxybutyl-5-methylfuran as the main product with up to 84 % selectivity avoiding ring saturation. Analysis of the hydrogenation activity reveals that the reaction proceeds in the following order: CC>CO>CO cleavage>ring hydrogenation. Comparable activity and selectivity can be also achieved utilizing 2-propanol as solvent in the transfer hydrogenation, providing the possibility for partial recycling of acetone and optimization of the hydrogen management. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Sarfraz, Saad


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Richard M. Crooks


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

  7. Miniaturizable Ion-Selective Arrays Based on Highly Stable Polymer Membranes for Biomedical Applications

    Directory of Open Access Journals (Sweden)

    Mònica Mir


    Full Text Available Poly(vinylchloride (PVC is the most common polymer matrix used in the fabrication of ion-selective electrodes (ISEs. However, the surfaces of PVC-based sensors have been reported to show membrane instability. In an attempt to overcome this limitation, here we developed two alternative methods for the preparation of highly stable and robust ion-selective sensors. These platforms are based on the selective electropolymerization of poly(3,4-ethylenedioxythiophene (PEDOT, where the sulfur atoms contained in the polymer covalently interact with the gold electrode, also permitting controlled selective attachment on a miniaturized electrode in an array format. This platform sensor was improved with the crosslinking of the membrane compounds with poly(ethyleneglycol diglycidyl ether (PEG, thus also increasing the biocompatibility of the sensor. The resulting ISE membranes showed faster signal stabilization of the sensor response compared with that of the PVC matrix and also better reproducibility and stability, thus making these platforms highly suitable candidates for the manufacture of robust implantable sensors.

  8. Selective Degradation of Organic Pollutants Using an Efficient Metal-Free Catalyst Derived from Carbonized Polypyrrole via Peroxymonosulfate Activation. (United States)

    Hu, Peidong; Su, Hanrui; Chen, Zhenyu; Yu, Chunyang; Li, Qilin; Zhou, Baoxue; Alvarez, Pedro J J; Long, Mingce


    Metal-free carbonaceous materials, including nitrogen-doped graphene and carbon nanotubes, are emerging as alternative catalysts for peroxymonosulfate (PMS) activation to avoid drawbacks of conventional transition metal-containing catalysts, such as the leaching of toxic metal ions. However, these novel carbocatalysts face relatively high cost and complex syntheses, and their activation mechanisms have not been well-understood. Herein, we developed a novel nitrogen-doped carbonaceous nanosphere catalyst by carbonization of polypyrrole, which was prepared through a scalable chemical oxidative polymerization. The defective degree of carbon substrate and amount of nitrogen dopants (i.e., graphitic nitrogen) were modulated by the calcination temperature. The product carbonized at 800 °C (CPPy-F-8) exhibited the best catalytic performance for PMS activation, with 97% phenol degradation efficiency in 120 min. The catalytic system was efficient over a wide pH range (2-9), and the reaction of phenol degradation had a relatively low activation energy (18.4 ± 2.7 kJ mol -1 ). The nitrogen-doped carbocatalyst activated PMS through a nonradical pathway. A two-step catalytic mechanism was extrapolated: the catalyst transfers electrons to PMS through active nitrogen species and becomes a metastable state of the catalyst (State I); next, organic substrates are oxidized and degraded by serving as electron donors to reduce State I. The catalytic process was selective toward degradation of various aromatic compounds with different substituents, probably depending on the oxidation state of State I and the ionization potential (IP) of the organics; that is, only those organics with an IP value lower than ca. 9.0 eV can be oxidized in the CPPy-F-8/PMS system.

  9. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide. (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan


    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  10. Magnetic and dendritic catalysts. (United States)

    Wang, Dong; Deraedt, Christophe; Ruiz, Jaime; Astruc, Didier


    recyclability. In other words, the dendritic catalysts were more efficient and more stable than their nondendritic γ-Fe2O3@SiO2 analogues. The bulk at the dendritic periphery helps to localize the metal nanoparticles at the SPION core surface, which confers these advantages. We could also use sonification as a remarkably simple and efficient method to impregnate the SPIONs with dendrimer-encapsulated PdNPs. Catalysis within the hydrophobic dendrimer pockets that include ligands leads to rapid turnover with or without a γ-Fe2O3@SiO2 core. In addition, catalytically active metal nanoparticles are more robust when they are loaded onto the surface of a γ-Fe2O3@SiO2 dendritic core. Herein, we illustrate this chemistry with examples including olefin metathesis, click chemistry, cross carbon-carbon bond forming reactions, and selective alcohol oxidation.

  11. Gold Nanoparticles on Polymer-Wrapped Carbon Nanotubes: An Efficient and Selective Catalyst for the Electroreduction of CO2. (United States)

    Jhong, Huei-Ru Molly; Tornow, Claire E; Kim, Chaerin; Verma, Sumit; Oberst, Justin L; Anderson, Paul S; Gewirth, Andrew A; Fujigaya, Tsuyohiko; Nakashima, Naotoshi; Kenis, Paul J A


    Multiple approaches will be needed to reduce the atmospheric CO 2 levels, which have been linked to the undesirable effects of global climate change. The electroreduction of CO 2 driven by renewable energy is one approach to reduce CO 2 emissions while producing chemical building blocks, but current electrocatalysts exhibit low activity and selectivity. Here, we report the structural and electrochemical characterization of a promising catalyst for the electroreduction of CO 2 to CO: Au nanoparticles supported on polymer-wrapped multiwall carbon nanotubes. This catalyst exhibits high selectivity for CO over H 2 : 80-92 % CO, as well as high activity: partial current density for CO as high as 160 mA cm -2 . The observed high activity, originating from a high electrochemically active surface area (23 m 2  g -1 Au), in combination with the low loading (0.17 mg cm -2 ) of the highly dispersed Au nanoparticles underscores the promise of this catalyst for efficient electroreduction of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method

    International Nuclear Information System (INIS)

    Park, Kyung Ho; Mohapatra, D.; Reddy, B. Ramachandra


    The petroleum refining industry makes extensive use of hydroprocessing catalysts. These catalysts contain environmentally critical and economically valuable metals such as Mo, V, Ni and Co. In the present study, a simple hydrometallurgical processing of spent hydrodesulphurization (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixture was investigated. Recovery of molybdenum was largely dependent on the concentrations of Na 2 CO 3 and H 2 O 2 in the reaction medium, which in turn controls the pH of leach liquor and the presence of Al and Ni as impurities. Under the optimum leaching conditions (40 g L -1 Na 2 CO 3 , 6 vol.% H 2 O 2 , room temperature, 1 h) about 85% recovery of Mo was achieved. The leach liquor was processed by the carbon adsorption method, which selectively adsorbs Mo at pH around 0.75. Desorption of Mo was selective at 15 vol.% NH 4 OH. With a single stage contact, it was found possible to achieve >99%, adsorption and desorption efficiency. Using this method, recovery of molybdenum as MoO 3 product of 99.4% purity was achieved

  13. Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts. (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M


    Carbon-nitrogen (C-N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C-N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene can either add across a C═C bond to form an aziridine or insert into a C-H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh 2 L n and Ru 2 L n complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands. A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for flexible installation of new C-N bonds into hydrocarbons, natural product-inspired scaffolds, existing pharmaceuticals or biorenewable building blocks. Silver-catalyzed nitrene transfer enables flexible control over the position at which a new C-N bond is introduced. Ag(I) supported by simple N-donor ligands accommodates a diverse range of coordination geometries, from linear to tetrahedral to seesaw, enabling the electronic and steric parameters of the catalyst to be tuned independently. In addition, the ligand, Ag salt counteranion, Ag/ligand ratio and the solvent all influence the fluxional and dynamic behavior of Ag(I) complexes in solution. Understanding the interplay of these parameters to manipulate the behavior of Ag-nitrenes in a predictable manner is a key design feature of our work. In this Account, we describe successful applications of a variety of design principles to tunable, Ag-catalyzed aminations, including (1) changing Ag/ligand ratios to influence

  14. Acid Activation of Natural Zeolite with High Content of Iron Oxides in Creation of Selective Sorbents and Catalysts

    Directory of Open Access Journals (Sweden)

    Kadirbekov Kairat


    Full Text Available The paper studies the influence of the nature of modifying acids (mineral, organic and heteropolyacids, and their combination on the composition and structure of the iron oxide rich clinoptilolit from Shankanay field in Kazakhstan for creation of selective catalysts in hydracarbon processing and sorbents for extracting ions of lanthanide and actinide elements. It is shown that sequential processing of natural zeolite in optimal conditions, by hydrochloric and sulfosalicylic acids lead to intensive decationization and dealumination, as well as maximum removal of iron ions from the zeolite framework without destroying it. It is found that the combination of activated clinoptilolite with hydrochloric acid and phosphotungstic heteropolyacid contributes to obtain catalyst system with high surface area and acidity.

  15. Microwave-Assisted Synthesis of Nanoporous Aluminum-Based Coordination Polymers as Catalysts for Selective Sulfoxidation Reaction

    Directory of Open Access Journals (Sweden)

    Madhan Vinu


    Full Text Available A series of aluminum-based coordination polymers or metal–organic frameworks (Al–MOFs, i.e., DUT-4, DUT-5, MIL-53, NH2-MIL-53, and MIL-100, have been facile prepared by microwave (MW-assisted reactions and used as catalysts for selective sulfoxidation reactions. The MW-assisted synthesis drastically reduced the reaction time from few days to hours. The prepared MOFs have smaller and uniform particle sizes and better yield compared to conventional hydrothermal method. Furthermore, the Al–MOFs have been successfully demonstrated as catalysts in oxidation reaction of methyl phenyl sulfide with H2O2 as oxidant, even under mild conditions, with more than 95% conversion.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  17. A predictive tool for selective oxidation of hydrocarbons: optical basicity of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Moriceau, P.; Lebouteiller, A.; Bordes, E.; Courtine, P. [Universite de Technologie de Compiegne, 60 (France). Dept. de Genie Chimique


    Whatever the composition of the catalyst (promoted, supported, multicomponent, etc.) is, it is possible to calculate its electron donor capacity {Lambda}. However, one important question remains: How are the surface and the bulk values of {Lambda} related? Most oxidation catalysts exhibit either a layered structure as V{sub 2}O{sub 5}, and approximately {Lambda}{sub th}{proportional_to}{Lambda}{sub surf}, or a molecular structure as polyoxometallates, and no correction seems to be needed. Work is in progress on that point. Of great importance is also the actual oxidation and coordination states of cations at the stedy state: {Lambda}s have been calculated from the composition determined by XANES and XPS. Finally, the model is able to discriminate between `paraffins` and olefins as reactants. These calibration curves should help to find new catalysts. (orig.)

  18. Highly stable antibacterial silver nanoparticles as selective fluorescent sensor for Fe³⁺ ions. (United States)

    Makwana, Bharat A; Vyas, Disha J; Bhatt, Keyur D; Jain, Vinod K; Agrawal, Yadvendra K


    Calix[4]resorcinarene polyhydrazide (CPH) protected water dispersible fluorescent silver nanaoparticles (AgNps) were prepared by one-pot method using water soluble CPH and AgNO₃. (CPH) bearing hydrazide group on its periphery acts as a reducing agent and its web type of structure as a stabilizing agent for the formation of calix protected silver nanoparticles (CPH-AgNps). CPH-AgNps were found to be highly stable over 120 days at room temperature and at varied pH. CPH-AgNps were characterized by UV/Vis-spectroscopy, particle size analyzer (PSA), transmission electron microscopy (TEM) and Energy dispersive X-ray analysis (EDX). Duly characterized nanoparticles were explored for their application as sensitive and selective fluorescent chemosensors for various metal ions. It was found that nanoparticles were selective and sensitive only for Fe(3+) ions with the linear range of detection from 0.1 μM to 10 μM. CPH-AgNps were also found to exhibit good antimicrobial activity when compared with standard Chloramphenicol. The selectivity and antimicrobial activity of CPH-AgNps suggests its potential use as a sensor for Fe(III) ions in ecosystems prone to industrial pollution and as an antimicrobial agent in biological applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Highly stable antibacterial silver nanoparticles as selective fluorescent sensor for Fe3+ ions (United States)

    Makwana, Bharat A.; Vyas, Disha J.; Bhatt, Keyur D.; Jain, Vinod K.; Agrawal, Yadvendra K.


    Calix[4]resorcinarene polyhydrazide (CPH) protected water dispersible fluorescent silver nanaoparticles (AgNps) were prepared by one-pot method using water soluble CPH and AgNO3. (CPH) bearing hydrazide group on its periphery acts as a reducing agent and its web type of structure as a stabilizing agent for the formation of calix protected silver nanoparticles (CPH-AgNps). CPH-AgNps were found to be highly stable over 120 days at room temperature and at varied pH. CPH-AgNps were characterized by UV/Vis-spectroscopy, particle size analyzer (PSA), transmission electron microscopy (TEM) and Energy dispersive X-ray analysis (EDX). Duly characterized nanoparticles were explored for their application as sensitive and selective fluorescent chemosensors for various metal ions. It was found that nanoparticles were selective and sensitive only for Fe3+ ions with the linear range of detection from 0.1 μM to 10 μM. CPH-AgNps were also found to exhibit good antimicrobial activity when compared with standard Chloramphenicol. The selectivity and antimicrobial activity of CPH-AgNps suggests its potential use as a sensor for Fe(III) ions in ecosystems prone to industrial pollution and as an antimicrobial agent in biological applications.

  20. Robust and stable gene selection via Maximum-Minimum Correntropy Criterion. (United States)

    Mohammadi, Majid; Sharifi Noghabi, Hossein; Abed Hodtani, Ghosheh; Rajabi Mashhadi, Habib


    One of the central challenges in cancer research is identifying significant genes among thousands of others on a microarray. Since preventing outbreak and progression of cancer is the ultimate goal in bioinformatics and computational biology, detection of genes that are most involved is vital and crucial. In this article, we propose a Maximum-Minimum Correntropy Criterion (MMCC) approach for selection of informative genes from microarray data sets which is stable, fast and robust against diverse noise and outliers and competitively accurate in comparison with other algorithms. Moreover, via an evolutionary optimization process, the optimal number of features for each data set is determined. Through broad experimental evaluation, MMCC is proved to be significantly better compared to other well-known gene selection algorithms for 25 commonly used microarray data sets. Surprisingly, high accuracy in classification by Support Vector Machine (SVM) is achieved by less than 10 genes selected by MMCC in all of the cases. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Role of iron oxide catalysts in selective catalytic reduction of NOx and soot from vehicular emission

    International Nuclear Information System (INIS)

    Anjuman, S.; Tahira, S.; Hizbullah, K.; Hizbullah, K.


    This study deals with Iron containing catalysts i.e Iron oxide Fe/sub 2/O/sub 3/) Iron potassium oxide Fe/sub 1.9/K/sub 0.1/O/sub 3/, copper iron oxide Cu/sub 0.9/K/sub 0.1/, Fe/sub 2/O/sub 3/, nickel iron oxide Ni Fe/sub 2/O/sub 4/, and Nickel potassium iron oxide Ni/sub 0.95/K/sub 0.05/ Fe/sub 2/O/sub 4/ catalyst were synthesized by using PVA technique. By X-ray Diffraction technique these catalysts were characterized to ensure the formation of crystalline structure. Energy Dispersive X-rays analysis (EDX) was used for the confirmation of presence of different metals and Scanning Electron Microscopy (SEM) for Surface Morphology. Then the catalytic investigations of the prepared catalyst were carried out for their activity measurement toward simultaneous conversion of NOx and Soot from an engine exhaust. Some Iron containing oxide catalysts were partially modified by alkali metal potassium and were used for NOx -Soot reaction in a model exhaust gas. Fe/sub 1.9 K /sub 0.1/O/sub 3/ show high catalytic performance for N/sub 2/ formation in the prepared catalyst. Further studies have shown that Fe/sub 1.9/ K/sub 0.1/ O/sub 3/ was deactivated in a substantial way after about 20 Temperature. Temperature Programmed Reaction (TPR) experiments due to agglomeration of the promoter potassium. Experiments carried out over the aged Fe/sub 1.9/K/sub 0.1/O/sub 3/ catalyst have shown that NOx-soot reaction was suppressed at higher oxygen concentration, since O/sub 2/-soot conversion was kindly favored. More over nitrite species formed at the catalyst surface might play an important role in NOx-soot conversion. (author)

  2. Highly stable organic polymer field-effect transistor sensor for selective detection in the marine environment (United States)

    Knopfmacher, Oren; Hammock, Mallory L.; Appleton, Anthony L.; Schwartz, Gregor; Mei, Jianguo; Lei, Ting; Pei, Jian; Bao, Zhenan


    In recent decades, the susceptibility to degradation in both ambient and aqueous environments has prevented organic electronics from gaining rapid traction for sensing applications. Here we report an organic field-effect transistor sensor that overcomes this barrier using a solution-processable isoindigo-based polymer semiconductor. More importantly, these organic field-effect transistor sensors are stable in both freshwater and seawater environments over extended periods of time. The organic field-effect transistor sensors are further capable of selectively sensing heavy-metal ions in seawater. This discovery has potential for inexpensive, ink-jet printed, and large-scale environmental monitoring devices that can be deployed in areas once thought of as beyond the scope of organic materials.

  3. Nanostructured catalysts for organic transformations. (United States)

    Chng, Leng Leng; Erathodiyil, Nandanan; Ying, Jackie Y


    The development of green, sustainable and economical chemical processes is one of the major challenges in chemistry. Besides the traditional need for efficient and selective catalytic reactions that will transform raw materials into valuable chemicals, pharmaceuticals and fuels, green chemistry also strives for waste reduction, atomic efficiency and high rates of catalyst recovery. Nanostructured materials are attractive candidates as heterogeneous catalysts for various organic transformations, especially because they meet the goals of green chemistry. Researchers have made significant advances in the synthesis of well-defined nanostructured materials in recent years. Among these are novel approaches that have permitted the rational design and synthesis of highly active and selective nanostructured catalysts by controlling the structure and composition of the active nanoparticles (NPs) and by manipulating the interaction between the catalytically active NP species and their support. The ease of isolation and separation of the heterogeneous catalysts from the desired organic product and the recovery and reuse of these NPs further enhance their attractiveness as green and sustainable catalysts. This Account reviews recent advances in the use of nanostructured materials for catalytic organic transformations. We present a broad overview of nanostructured catalysts used in different types of organic transformations including chemoselective oxidations and reductions, asymmetric hydrogenations, coupling reactions, C-H activations, oxidative aminations, domino and tandem reactions, and more. We focus on recent research efforts towards the development of the following nanostructured materials: (i) nanostructured catalysts with controlled morphologies, (ii) magnetic nanocomposites, (iii) semiconductor-metal nanocomposites, and (iv) hybrid nanostructured catalysts. Selected examples showcase principles of nanoparticle design such as the enhancement of reactivity, selectivity

  4. Normalization Methods and Selection Strategies for Reference Materials in Stable Isotope Analyses - Review

    International Nuclear Information System (INIS)

    A stable isotope analyst has to make a number of important decisions regarding how to best determine the 'true' stable isotope composition of analysed samples in reference to an international scale. It has to be decided which reference materials should be used, the number of reference materials and how many repetitions of each standard is most appropriate for a desired level of precision, and what normalization procedure should be selected. In this paper we summarise what is known about propagation of uncertainties associated with normalization procedures and propagation of uncertainties associated with reference materials used as anchors for the determination of 'true' values for δ''1''3C and δ''1''8O. Normalization methods Several normalization methods transforming the 'raw' value obtained from mass spectrometers to one of the internationally recognized scales has been developed. However, as summarised by Paul et al. different normalization transforms alone may lead to inconsistencies between laboratories. The most common normalization procedures are: single-point anchoring (versus working gas and certified reference standard), modified single-point normalization, linear shift between the measured and the true isotopic composition of two certified reference standards, two-point and multipoint linear normalization methods. The accuracy of these various normalization methods has been compared by using analytical laboratory data by Paul et al., with the single-point and normalization versus tank calibrations resulting in the largest normalization errors, and that also exceed the analytical uncertainty recommended for δ 13 C. The normalization error depends greatly on the relative differences between the stable isotope composition of the reference material and the sample. On the other hand, the normalization methods using two or more certified reference standards produces a smaller normalization error, if the reference materials are bracketing the whole range of

  5. Mercury Oxidation over Selective Catalytic Reduction (SCR) Catalysts - Ph.d. thesis Karin Madsen

    DEFF Research Database (Denmark)

    Madsen, Karin

    The vanadium-based SCR catalyst used for NOx-control promotes the oxidation of elemental mercury Hg0 to Hg2+ in flue gases from coal-fired power plants. Hg2+ is water soluble and can effectively be captured in a wet scrubber. This means that the combination of an SCR with a wet FGD can offer an e...

  6. Selective oxidation of methane to ethane and ethylene over various oxide catalysts

    NARCIS (Netherlands)

    Roos, J.A.; Bakker, A.G.; Bosch, H.; van Ommen, J.G.; Ross, J.R.H.


    Preliminary results are reported for the oxidative coupling of methane to give ethane/ethylene mixtures over a series of different catalyst formulations; the temperature range studied is 650–850°C. A comparison is made of the behaviour of lead/alumina and lithium/magnesia materials. It is found that

  7. Combined Particle Filter and Selective Catalytic Reduction Catalyst for Diesel Engines

    DEFF Research Database (Denmark)

    Hvam, Jeanette

    oxidation of the silicon carbide crystals, ideal for catalyst adhesive layer. The silicon carbide filter, produced with trace amounts of copper, still fulfills the requirements for macroporosity and accessible porosity in excess of 50%, and is thus superior for the purpose of combined diesel particulate...

  8. Two stable, conducting conformations of the selectivity filter in Shaker K+ channels. (United States)

    Thompson, Jill; Begenisich, Ted


    We have examined the voltage dependence of external TEA block of Shaker K(+) channels over a range of internal K(+) concentrations from 2 to 135 mM. We found that the concentration dependence of external TEA block in low internal K(+) solutions could not be described by a single TEA binding affinity. The deviation from a single TEA binding isotherm was increased at more depolarized membrane voltages. The data were well described by a two-component binding scheme representing two, relatively stable populations of conducting channels that differ in their affinity for external TEA. The relative proportion of these two populations was not much affected by membrane voltage but did depend on the internal K(+) concentration. Low internal K(+) promoted an increase in the fraction of channels with a low TEA affinity. The voltage dependence of the apparent high-affinity TEA binding constant depended on the internal K(+) concentration, becoming almost voltage independent in 5 mM. The K(+) sensitivity of these low- and high-affinity TEA states suggests that they may represent one- and two-ion occupancy states of the selectivity filter, consistent with recent crystallographic results from the bacterial KcsA K(+) channel. We therefore analyzed these data in terms of such a model and found a large (almost 14-fold) difference between the intrinsic TEA affinity of the one-ion and two-ion modes. According to this analysis, the single ion in the one-ion mode (at 0 mV) prefers the inner end of the selectivity filter twofold more than the outer end. This distribution does not change with internal K(+). The two ions in the two-ion mode prefer to occupy the inner end of the selectivity filter at low K(+), but high internal K(+) promotes increased occupancy of the outer sites. Our analysis further suggests that the four K(+) sites in the selectivity filter are spaced between 20 and 25% of the membrane electric field.

  9. Bimetal catalysts

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. Stable Epigenetic Variants Selected from an Induced Hypomethylated Fragaria vesca Population

    Directory of Open Access Journals (Sweden)

    Jihua Xu


    Full Text Available Epigenetic inheritance was transmitted through selection over generations of extreme early, but not late flowering time phenotypic lines in F. vesca. Epigenetic variation was initially induced using the DNA demethylating reagent 5-azacytidine (5-azaC. It is the first report exploring epigenetic variant selection and phenotypic trait inheritance in strawberry, a model plant species for one of the most important temperate fruit crop families, Rosaceae. Transmission frequency of these traits was determined across generations. Early flowering (EF4 and late stolon (LS phenotypic traits were successfully transmitted through meiosis across at least five and two generations, respectively. Stable mitotic transmission of the early flowering phenotype was also demonstrated using clonal daughters derived from the 4th Generation (S4 mother plant. In order to further explore the DNA methylation patterns underlying the early flowering trait, the standard MSAP method using isoschizomers Hpa II / Msp I, and a newly modified MSAP method using isoschizomers Tfi I / Pfe I which detected DNA methylation at CG, CHG, CHH sites were used in two early flowering lines, EF4 lines 1 (P2 and EF4 lines 2 (P3, and control lines (P1. A significant reduction in the number of fully-methylated bands was detected in P2 and P3 when compared to P1 using the novel MSAP method. In the standard MSAP, the symmetric CG and CHG methylation was maintained over generations in the early flowering lines based on the clustering in P2 and P3, while the novel MSAP approach revealed the asymmetric CHH methylation pattern was not maintained over generations. This study provides evidence of stable selection of phenotypic traits, particularly the early flowering phenotype through both meiosis and mitosis, which is meaningful to both breeding programs and commercial horticulture. The maintenance in CG and CHG methylation over generations suggests the early flowering phenotype might be related to DNA

  11. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xinbo [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Wang, Danjun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Li, Kebin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Zhen, Yanzhong [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Hu, Huaiming [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Xue, Ganglin, E-mail: [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China)


    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.

  12. Green and selective synthesis of N-substituted amides using water soluble porphyrazinato copper(II) catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ghodsinia, Sara S.E.; Akhlaghinia, Batool; Eshghi, Hossein, E-mail: [Ferdowsi University of Mashhad (Iran, Islamic Republic of). Faculty of Sciences. Department of Chemistry; Safaei, Elham [Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of). Department of Chemistry


    N, N',N{sup ,} N{sup '}-Tetramethyl tetra-2,3-pyridinoporphyrazinato copper(II) methyl sulfate ([Cu(2,3-tmtppa)](MeSO{sub 4}){sub 4}) efficiently catalyzed the direct conversion of nitriles to N-substituted amides. The one pot selective synthesis of the N-substituted amides from nitriles and primary amines was performed in refluxing H{sub 2}O. The catalyst was recovered and reused at least four times, maintaining its efficiency. (author)

  13. Hafnium(IV) triflate as a potent catalyst for selective 1-O-deacetylation of peracetylated saccharides. (United States)

    Wang, Rui; Chen, Ji-Zong; Zheng, Xiu-An; Kong, Rui; Gong, Shan-Shan; Sun, Qi


    An efficient method for selective anomeric deacetylation of peracetylated mono-, di-, and trisaccharides has been developed by using 2 mol% Hf(OTf) 4 as catalyst in acetonitrile. Employment of ultrasonic irradiation could significantly accelerate the reaction rate. Mechanistic study confirmed the hydrolysis nature of this reaction, and NMR experimental data suggested that multiple peracetylated saccharide molecules may ligate to Hf(IV) cation primarily via the anomeric acetate to promote its specific hydrolysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Evaluation of NiFe2O4 spinel, synthesized by combustion reaction, as a catalyst for selective CO oxidation

    International Nuclear Information System (INIS)

    Santos, P.T.A.; Lira, H.L.; Costa, A.C.F.M.; Gama, L.; Argolo, F.; Andrade, H.M.C.


    The selective reaction of CO oxidation (PROX) was named as the most attractive way to reduce the CO concentration, thereby purifying the hydrogen. The aim of this work is to make the structural and morphologic characterization of the NiFe 2 O 4 spinel synthesized by combustion reaction, using glycine as fuel, and to evaluate as catalyst in the reaction of selective oxidation of carbon monoxide in the presence of hydrogen, oxygen and carbon monoxide. The powder was prepared by using a vitreous silica crucible on a hot plate at 480 deg C and according to stoichiometry established by theory of propellants and explosive. The powder was characterized by X-ray diffraction (XRD), FTIR, textural analyses, transmission electron microscopy (TEM) and catalytic measurements. The results from XRD show characteristic peaks of spinel phase without presence of secondary phases. The morphologic results show surface area of 3.1 m 2 /g and particle size calculated by TEM of 21.72 nm. The catalyst was active and selective for O 2 , reaching 100% of conversion. (author)

  15. Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment. (United States)

    Grigoropoulos, Alexios; McKay, Alasdair I; Katsoulidis, Alexandros P; Davies, Robert P; Haynes, Anthony; Brammer, Lee; Xiao, Jianliang; Weller, Andrew S; Rosseinsky, Matthew J


    Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL-101(Cr) metal-organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non-functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well-defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  16. About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

    Directory of Open Access Journals (Sweden)

    Hatice Mutlu


    Full Text Available We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS.

  17. MnAPO-5 as an efficient heterogeneous catalyst for selective liquid phase partial oxidation reactions. (United States)

    Chatterjee, Sauvik; Bhanja, Piyali; Paul, Luna; Ali, Mahammad; Bhaumik, Asim


    Heterogeneous catalysts play a key role in addressing the economic and environmental issues of the chemical industry due to their several advantages, like ease of product separation, work-up and high recycling efficiency. Herein, we report the synthesis of a robust manganese(iv)-containing aluminophosphate material (MnAPO-5), with an AFI framework topology. This material has been characterized thoroughly by powder XRD, XPS, UHR TEM, FE SEM, 31 P CP MAS NMR, atomic absorption spectroscopy, UV-visible spectroscopy and TGA. The Mn-containing microporous material has been employed as a heterogeneous catalyst for the oxidation of styrene and the synthesis of adipic acid from cyclohexanone in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant in air and it displayed very high recycling efficiency.

  18. Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf3 catalyst in the reaction selectivity

    Directory of Open Access Journals (Sweden)

    Natividad Herrera Cano


    Full Text Available An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from o-phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively obtained when Er(OTf3 was used as the catalyst in the presence of electron-rich aldehydes. Conversely, the formation of mono-condensation products was the preferred path in absence of this catalyst. One of the major advantages of these reactions was the formation of a single product, avoiding extensive isolation and purification of products, which is frequently associated with these reactions.Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron-rich aldehydes better coordinate to the catalyst, which favours the addition of the amine group to the carbonyl group, therefore facilitating the formation of double-condensation products.Reactions with aliphatic or aromatic aldehydes were possible, without using organic solvents and in a one-pot procedure with short reaction time (2–5 min, affording single products in excellent yields (75–99%. This convenient and eco-friendly methodology offers numerous benefits with respect to other protocols reported for similar compounds.

  19. Criteria for selection of dolomites and catalysts for tar elimination from biomass gasification gas. Kinetic constants

    Energy Technology Data Exchange (ETDEWEB)

    Corella, J.; Narvaez, I.; Orio, A. [Madrid Univ. (Spain). Dept. of Chem. Eng.


    Calcined dolomites and commercial steam reforming catalysts are used downstream biomass gasifiers for hot catalytic raw gas cleaning. To further compare these solids under a rigorous basis, a reaction network and a kinetic model are presented. The apparent kinetic constant for the tar reduction is here proposed as a basis of comparison. Tar sampling and analysis, and the units used for the space-time in the catalytic reactor affect the kinetic constants observed. (author) (2 refs.)

  20. Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

    International Nuclear Information System (INIS)

    Patel, B.M.; Price, G.L.


    This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with 18 O 2 have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C 3 D 6 reaction. No isotope effect is observed for carbon dioxide formation from C 3 D 6 suggesting that CO 2 is formed by parallel, not consecutive, oxidation of propylene

  1. Ambient Temperature Hydrocarbon Selective Catalytic Reduction of NOx Using Atmospheric Pressure Nonthermal Plasma Activation of a Ag/Al2O3 Catalyst


    Stere, Cristina E.; Adress, Wameedh; Burch, Robbie; Chansai, Sarayute; Goguet, Alexandre; Graham, William G.; De Rosa, Fabio; Palma, Vincenzo; Hardacre, Christopher


    Atmospheric pressure nonthermal-plasma-activated catalysis for the removal of NOx using hydrocarbon selective catalytic reduction has been studied utilizing toluene and n-octane as the hydrocarbon reductant. When the plasma was combined with a Ag/Al2O3 catalyst, a strong enhancement in activity was observed when compared with conventional thermal activation with high conversions of both. NOx and hydrocarbons obtained at temperature at temperature ≤250 °C, where the silver catalyst is normally...

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yanjun; Chen, Jixiang, E-mail:


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

  3. Pseudoliquid behavior of heteropoly compound catalysts. Unusual pressure dependencies of the rate and selectivity for ethanol dehydration

    International Nuclear Information System (INIS)

    Misono, M.; Okuhara, T.; Ichiki, T.; Arai, T.; Kanda, Y.


    Heteropoly compounds arenow utilized as industrial catalysts for olefin hydration and aldehyde oxidation and as interesting cluster models of mixed oxide catalysts. Certain heteropoly acids, like H 3 PW 12 O 40 and H 3 PMo 12 O 40 , easily absorb a large amount of water, alchols, and ethers in the solid state, although their surface areas are very low. This is not adsorption in micropores; rather molecules are absorbed between the lattice polyanions, sometimes expanding the lattice. The expansion can be seen visually as well as by x-ray diffraction. The authors showed that in some cases catalytic reactions take place in this novel bulk phase. Presumably due to this behavior, very high catalytic activity and unique selectivity as well as unusual reactivity order have been observed. They called this state the pseudoliquid phase. However, in only one case was the amount of absorbed reactant measured under the working conditions. They report here unusual pressure dependencies of the rate and selectivity of ethanol dehydration over heteropoly compounds. The dependency can only be explained by the formation of a pseudoliquid phase, i.e., a phase where the amount of absorbed ethanol has changed as a function of ethanol pressure

  4. Heterophase-structured nanocrystals as superior supports for Ru-based catalysts in selective hydrogenation of benzene (United States)

    Peng, Zhikun; Liu, Xu; Li, Shuaihui; Li, Zhongjun; Li, Baojun; Liu, Zhongyi; Liu, Shouchang


    ZrO2 heterophase structure nanocrystals (HSNCs) were synthesized with tunable ratios of monoclinic ZrO2 (m-ZrO2) to tetragonal ZrO2 (t-ZrO2). The phase mole ratio of m-ZrO2 versus t-ZrO2 in ZrO2 HSNCs was tuned from 40% to 100%. The concentration of the surface hydroxyl groups on m-ZrO2 is higher than that on t-ZrO2. ZrO2 HSNCs have different surface hydroxyl groups on two crystalline phases. This creates more intimate synergistic effects than their single-phase counterparts. The ZrO2 HSNCs were used as effective supports to fabricate heterophase-structured Ru/ZrO2 catalysts for benzene-selective hydrogenation. The excellent catalytic performance including high activity and selectivity is attributed to the heterogeneous strong/weak hydrophilic interface and water layer formed at the m-ZrO2/t-ZrO2 catalyst junction. PMID:28057914

  5. Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method (United States)

    Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi


    Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.

  6. A study of Cu/ZnO/Al2O3 methanol catalysts prepared by flame combustion synthesis

    DEFF Research Database (Denmark)

    Jensen, Joakim Reimer; Johannessen, Tue; Wedel, Stig


    The flame combustion synthesis of Cu/ZnO/Al2O3 catalysts for the synthesis of methanol from CO, CO2 and H2 is investigated. The oxides are generated in a premixed flame from the acetyl-acetonate vapours of Cu, Zn and Al mixed with the fuel and air prior to combustion. The flame-generated powder.......1 %. A ternary catalyst with the composition of Cu:Zn:Al=45:45:10 has the highest catalytic activity of all samples tested. This catalyst is also very selective and stable towards thermal deactivation. The role of the individual catalyst components in the optimal catalyst is discussed....


    A selective hydrogenation of maleic anhydride to either y-butyrolactone or succinic anhydride over simple Pd/Al(2)O(3) catalyst under supercritical CO(2) medium is described for the first time which has considerable promise for obht lab-scale as well as industrial selective hydro...

  8. Microwave-Assisted Selective Hydrogenation of Furfural to Furfuryl Alcohol Employing a Green and Noble Metal-Free Copper Catalyst. (United States)

    Romano, Pedro N; de Almeida, João M A R; Carvalho, Yuri; Priecel, Peter; Falabella Sousa-Aguiar, Eduardo; Lopez-Sanchez, Jose A


    Green, inexpensive, and robust copper-based heterogeneous catalysts achieve 100 % conversion and 99 % selectivity in the conversion of furfural to furfuryl alcohol when using cyclopentyl-methyl ether as green solvent and microwave reactors at low H 2 pressures and mild temperatures. The utilization of pressurized microwave reactors produces a 3-4 fold increase in conversion and an unexpected enhancement in selectivity as compared to the reaction carried out at the same conditions using conventional autoclave reactors. The enhancement in catalytic rate produced by microwave irradiation is temperature dependent. This work highlights that using microwave irradiation in the catalytic hydrogenation of biomass-derived compounds is a very strong tool for biomass upgrade that offers immense potential in a large number of transformations where it could be a determining factor for commercial exploitation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

    Directory of Open Access Journals (Sweden)

    Ting Ma


    Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

  10. Correlating ultrasonic impulse and addition of ZnO promoter with CO2conversion and methanol selectivity of CuO/ZrO2catalysts. (United States)

    Ezeh, Collins I; Yang, Xiaogang; He, Jun; Snape, Colin; Cheng, Xiao Min


    The thermal characteristics of Cu-based catalysts for CO 2 utilization towards the synthesis of methanol were analysed and discussed in this study. The preparation process were varied by adopting ultrasonic irradiation at various impulses for the co-precipitation route and also, by introducing ZnO promoters using the solid-state reaction route. Prepared catalysts were characterised using XRD, TPR, TPD, SEM, BET and TG-DTA-DSC. In addition, the CO 2 conversion and CH 3 OH selectivity of these samples were assessed. Calcination of the catalysts facilitated the interaction of the Cu catalyst with the respective support bolstering the thermal stability of the catalysts. The characterisation analysis clearly reveals that the thermal performance of the catalysts was directly related to the sonication impulse and heating rate. Surface morphology and chemistry was enhanced with the aid of sonication and introduction of promoters. However, the impact of the promoter outweighs that of the sonication process. CO 2 conversion and methanol selectivity showed a significant improvement with a 270% increase in methanol yield. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Ethanol-selective catalytic reduction of NO by Ag/Al2O3 catalysts: Activity and deactivation by alkali salts

    DEFF Research Database (Denmark)

    Schill, Leonhard; Putluru, Siva Sankar Reddy; Jacobsen, Casper Funk


    Ag/Al2O3 catalysts with and without potassium doping were prepared by incipient wetness impregnation and characterized by N2 physisorption, XRPD, NH3-TPD and SEM. The influence of the Ag content from 1 to 5 wt.% was investigated for the selective catalytic reduction (SCR) of NO with ethanol. The 3...... wt.% Ag/Al2O3 catalyst was found to be the most active and CO2 selective over a wide temperature window (300–500 ◦C). Addition of 500 ppm of H2 has a mild promotional effect on the activity while SO2 has a strong negative influence on the SCR activity. Furthermore, the Ag/Al2O3 ethanol-SCR catalyst......3 ethanol-SCR catalyst compared to the conventional NH3-SCR catalyst. The still low potassium resistance, in combination with the high sensitivity to SO2, seems not to make these catalysts a real option for biomass fired boilers....

  12. Heat Transfer Processes in the Selective Microwave Heating of Heterogeneous Catalysts (United States)

    Serniak, Kyle; Crosswhite, Mark; Stiegman, A. E.


    Experimental evidence has shown an unexplained increase in reaction rates during catalytic processes when heated by microwave irradiation relative to traditional thermal processes. We believe this is due to a difference in temperature between the bulk solvent and catalytic sites. In a reaction system that has a small amount of catalyst with a high absorption cross section relative to a large amount of weakly absorbing solvent, traditional measurement techniques, which take an average, will greatly underestimate the temperature on the catalytic sites. In order to correct this, we have solved a system of differential equations which describes the rate of heat transfer between each constituent in the system. Along with these solutions, data from heating experiments lets us estimate the various heat transfer constants inherent to the system as well as absorption cross sections of all components. These solutions predict a higher temperature on the catalytic sites than reported by the thermometer in the microwave system, as well as a very low heat transfer coefficient, which implies the formation of an insulating vapor barrier around the catalyst. In addition, thermal imaging data support the notion that the temperature of the catalytic sites are much higher than that of the solvent.


    Directory of Open Access Journals (Sweden)



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

  14. Oxidation selectivity between n-hexane and sulfur dioxide in diesel simulated exhaust gas over platinum-supported zirconia catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Nagai, Yasutaka; Shinjoh, Hirofumi; Yokota, Koji [Toyota Central R and D Labs. Inc., Aichi 480-1192 Nagakute (Japan)


    We examined the oxidation reaction of n-C{sub 6}H{sub 14} and SO{sub 2} over two types of Pt/ZrO{sub 2} catalysts with low (8m{sup 2}/g) and high (75m{sup 2}/g) surface areas of the ZrO{sub 2} supports (referred to as ZrO{sub 2}-8 and ZrO{sub 2}-75, respectively). The catalytic activity was evaluated under simulated diesel exhaust gas which simultaneously contained n-C{sub 6}H{sub 14} and SO{sub 2}. The Pt/ZrO{sub 2}-75 exhibited a desirably higher selectivity for the complete oxidation of n-C{sub 6}H{sub 14} than that of SO{sub 2}, as compared with the Pt/ZrO{sub 2}-8. In order to clarify the cause of this selective oxidation, we investigated the Arrhenius parameter for these oxidation reactions and characterized these catalysts using X-ray photoelectron spectra (XPS), X-ray diffraction (XRD), Transmission electron micrograph (TEM), IR and CO{sub 2} temperature-programmed desorption (CO{sub 2}-TPD) methods. The amount of Pt{sup 0} (metal) in the Pt/ZrO{sub 2}-75 was significantly lower than that in Pt/ZrO{sub 2}-8, because the high basicity of the ZrO{sub 2}-75 support stabilized the high oxidation state of Pt such as Pt{sup 2+} and Pt{sup 4+}. It was concluded that the difference in the number of Pt{sup 0} sites as catalytic active sites causes the apparent selectivity to change due to the much slower reaction rate for the SO{sub 2} oxidation than that for the n-C{sub 6}H{sub 14} oxidation.

  15. Structural Evolution under Reaction Conditions of Supported (NH43HPMo11VO40 Catalysts for the Selective Oxidation of Isobutane

    Directory of Open Access Journals (Sweden)

    Fangli Jing


    Full Text Available When using heteropolycompounds in the selective oxidation of isobutane to methacrolein and methacrylic acid, both the keeping of the primary structure (Keggin units and the presence of acidic sites are necessary to obtain the desired products. The structural evolution of supported (NH43HPMo11VO40 (APMV catalysts under preliminary thermal oxidizing and reducing treatments was investigated. Various techniques, such as TGA/DTG (Thermo-Gravimetric Analysis/Derivative Thermo-Gravimetry, H2-TPR (Temperature Programed Reduction, in situ XRD (X-Ray Diffraction and XPS (X-ray Photoelectron Spectroscopy, were applied. It was clearly evidenced that the thermal stability and the reducibility of the Keggin units are improved by supporting 40% APMV active phase on Cs3PMo12O40 (CPM. The partial degradation of APMV takes place depending on temperature and reaction conditions. The decomposition of ammonium cations (releasing NH3 leads to the formation of vacancies favoring cationic exchanges between vanadium coming from the active phase and cesium coming from the support. In addition, the vanadium expelled from the Keggin structure is further reduced to V4+, species, which contributes (with Mo5+ to activate isobutane. The increase in reducibility of the supported catalyst is assumed to improve the catalytic performance in comparison with those of unsupported APMV.

  16. Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems (United States)

    Park, Paul W.


    A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

  17. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L. [Colorado School of Mines, Golden, CO (United States)


    The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has the potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.

  18. Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

    NARCIS (Netherlands)

    Filiz, B.C.; Gnanakumar, E.S.; Martinez-Arias, A.; Gengler, R.; Rudolf, P.; Rothenberg, G.; Shiju, N.R.

    We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrOx(OH)4−2x and ZrO2). Although the final compositions of the catalysts are the

  19. Highly Selective Hydrogenation of Levulinic Acid to gamma-Valerolactone Over Ru/ZrO2 Catalysts

    NARCIS (Netherlands)

    Filiz, Bilge Coskuner; Gnanakumar, Edwin S.; Martinez-Arias, Arturo; Gengler, Regis; Rudolf, Petra; Rothenberg, Gadi; Shiju, N. Raveendran

    We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrOx(OH)(4-2x) and ZrO2). Although the final compositions of the catalysts are the

  20. Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen (United States)

    Qian, Linping; Wang, Zhen; Beletskiy, Evgeny V.; Liu, Jingyue; Dos Santos, Haroldo J.; Li, Tiehu; Rangel, Maria Do C.; Kung, Mayfair C.; Kung, Harold H.


    The ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml-1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s-1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participation in the cycle. Spectroscopic characterization suggests that 7-8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.

  1. Assessing permethrin resistance in the stable fly (Diptera: Muscidae) in Florida by using laboratory selections and field evaluations. (United States)

    Pitzer, Jimmy B; Kaufman, Phillip E; Tenbroeck, Saundra H


    Insecticide resistance in the stable fly, Stomoxys calcitrans (L.) (Diptera: Muscidae),has been demonstrated previously, but mostly with insecticides that are no longer used, such as the organochlorines. Resistance to commonly used pyrethroids has been evaluated twice, but only in the midwestern United States. Stable fly susceptibility to a commonly used pyrethroid, permethrin, was determined in Florida to assess the possibility of resistance development. Diagnostic concentration evaluations of three stable fly field strains demonstrated a maximum of 57 and 21% survival to permethrin residues of 3x and 10x the LC99 of a susceptible strain, respectively. Stable flies from an equine facility with no reported insecticide use demonstrated approximately 20% survival with a 3x diagnostic concentration. Despite a distance of 91-km between field collection sites, survival profiles of field-collected stable fly strains were similar. Although an established stable fly colony collected from a local dairy previously expressed low level resistance to permethrin residues, five generations of laboratory permethrin selection increased resistance 15-fold.

  2. From the Lindlar catalyst to supported ligand-modified palladium nanoparticles: selectivity patterns and accessibility constraints in the continuous-flow three-phase hydrogenation of acetylenic compounds. (United States)

    Vilé, Gianvito; Almora-Barrios, Neyvis; Mitchell, Sharon; López, Núria; Pérez-Ramírez, Javier


    Site modification and isolation through selective poisoning comprise an effective strategy to enhance the selectivity of palladium catalysts in the partial hydrogenation of triple bonds in acetylenic compounds. The recent emergence of supported hybrid materials matching the stereo- and chemoselectivity of the classical Lindlar catalyst holds promise to revolutionize palladium-catalyzed hydrogenations, and will benefit from an in-depth understanding of these new materials. In this work, we compare the performance of bare, lead-poisoned, and ligand-modified palladium catalysts in the hydrogenation of diverse alkynes. Catalytic tests, conducted in a continuous-flow three-phase reactor, coupled with theoretical calculations and characterization methods, enable elucidation of the structural origins of the observed selectivity patterns. Distinctions in the catalytic performance are correlated with the relative accessibility of the active site to the organic substrate, and with the adsorption configuration and strength, depending on the ensemble size and surface potentials. This explains the role of the ligand in the colloidally prepared catalysts in promoting superior performance in the hydrogenation of terminal and internal alkynes, and short-chain alkynols. In contrast, the greater accessibility of the active surface of the Pd-Pb alloy and the absence of polar groups are shown to be favorable in the conversion of alkynes containing long aliphatic chains and/or ketone groups. These findings provide detailed insights for the advanced design of supported nanostructured catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The selective catalytic reduction of NO with NH3 over a novel Ce-Sn-Ti mixed oxides catalyst: Promotional effect of SnO2 (United States)

    Yu, Ming'e.; Li, Caiting; Zeng, Guangming; Zhou, Yang; Zhang, Xunan; Xie, Yin'e.


    A series of novel catalysts (CexSny) for the selective catalytic reduction of NO by NH3 were prepared by the inverse co-precipitation method. The aim of this novel design was to improve the NO removal efficiency of CeTi by the introduction of SnO2. It was found that the Ce-Sn-Ti catalyst was much more active than Ce-Ti and the best Ce:Sn molar ratio was 2:1. Ce2Sn1 possessed a satisfied NO removal efficiency at low temperature (160-280 °C), while over 90% NO removal efficiency maintained in the temperature range of 280-400 °C at the gas hourly space velocity (GHSV) of 50,000 h-1. Besides, Ce2Sn1 kept a stable NO removal efficiency within a wide range of GHSV and a long period of reacting time. Meanwhile, Ce2Sn1 exhibited remarkable resistance to both respectively and simultaneously H2O and SO2 poisoning due to the introduction of SnO2. The promotional effect of SnO2 was studied by N2 adsorption-desorption, X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR) for detail information. The characterization results revealed that the excellent catalytic performance of Ce2Sn1 was associated with the higher specific surface area, larger pore volume and poorer crystallization. Besides, the introduction of SnO2 could result in not only greater conversion of Ce4+ to Ce3+ but also the increase amount of chemisorbed oxygen, which are beneficial to improve the SCR activity. More importantly, a novel peak appearing at lower temperatures through the new redox equilibrium of 2Ce4+ + Sn2+ ↔ 2Ce3+ + Sn4+ and higher total H2 consumption can be obtained by the addition of SnO2. Finally, the possible reaction mechanism of the selective catalytic reduction over Ce2Sn1 was also proposed.

  4. NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil (United States)

    Liu, Jing; He, Jing; Wang, Luying; Li, Rong; Chen, Pan; Rao, Xin; Deng, Lihong; Rong, Long; Lei, Jiandu


    Nickel oxide (NiO) and phosphotungstic acid (PTA) supported on a ZIF-8 (NiO-PTA/ZIF-8) catalyst was first synthesized and it showed high activity and good selectivity for the hydrocracking of Jatropha oil. The catalyst was characterized by SEM, SEM-EDS, TEM, N2 adsorption, FT-IR, XRD and XPS. Compared with the NiO-PTA/Al2O3 catalyst, the selectivity of C15-C18 hydrocarbon increased over 36%, and catalytic efficiency increased 10 times over the NiO-PTA/ZIF-8 catalyst. The prepared NiO-PTA/ZIF-8 catalyst was stable for a reaction time of 104 h and the kinetic behavior was also analyzed. This catalyst was found to bypass the presulfurization process, showing promise as an alternative to sulfided catalysts for green diesel production.

  5. NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil (United States)

    Liu, Jing; He, Jing; Wang, Luying; Li, Rong; Chen, Pan; Rao, Xin; Deng, Lihong; Rong, Long; Lei, Jiandu


    Nickel oxide (NiO) and phosphotungstic acid (PTA) supported on a ZIF-8 (NiO-PTA/ZIF-8) catalyst was first synthesized and it showed high activity and good selectivity for the hydrocracking of Jatropha oil. The catalyst was characterized by SEM, SEM-EDS, TEM, N2 adsorption, FT-IR, XRD and XPS. Compared with the NiO-PTA/Al2O3 catalyst, the selectivity of C15-C18 hydrocarbon increased over 36%, and catalytic efficiency increased 10 times over the NiO-PTA/ZIF-8 catalyst. The prepared NiO-PTA/ZIF-8 catalyst was stable for a reaction time of 104 h and the kinetic behavior was also analyzed. This catalyst was found to bypass the presulfurization process, showing promise as an alternative to sulfided catalysts for green diesel production. PMID:27020579

  6. Coal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kroenig, W.


    Some considerations in the selection of a catalyst for the liquid phase of coal hydrogenation are discussed. Some of the previous history of such selections is mentioned. At one stage of the development, the principal catalyst had been iron sulfate (FeSO/sub 4/.7H/sub 2/O). Later, for reasons of cost and availability of large supplies, selections had turned to mixtures of iron sulfate and one or another of some iron oxide- and aluminum oxide-containing byproducts of aluminum manufacture, namely Bayermasse, Luxamsse, or Lautamasse. Much of the discussion centered on optimal proportions for such mixtures, particularly as related to pH values of resulting coal pastes. Upper Silesian coal was more alkaline than Ruhr coal, and Bayermasse, etc., were quite alkaline. Thus, since the iron sulfate served as a partial neutralizer for the coal as well as a catalyst, it seemed necessary to increase the proportions of iron sulfate in the catalyst mixture when processing coal of greater alkalinity. A further reason for a greater proportion of iron sulfate seemed to be that most of the catalytic activity of the iron came from the ferrous iron of iron sulfate rather than from the ferric iron of the other materials. Ferrous-ferric ratios also seemed to indicate that Luxmasse or Lautamasse might be better catalyst components than Bayermasse but their water content sometimes caused handling problems, so Bayermasse had been more widely used. Formation of deposits in the preheater was more likely due to the Bayermasse than to the iron sulfate; sodium sulfide could help to prevent them.

  7. Role of K3-xHxPW12O40 as a Catalyst in Selective Catalysis of Methylamine Synthesis from Ammonia and Methanol

    Directory of Open Access Journals (Sweden)

    Mohammad Nasikin


    Full Text Available Synthesize of methylamine from methanol and ammonia was studied in this research work using a partially potassium heteropoly salt (K3-xHxPW12O40 abbreviated as KPW as a catalyst. KPW was prepared from heteropoly salt and potassium carbonate by using ion exchange method. The reaction was conducted at 600 ~ 800K and at the atmospheric pressure. Reactor used was a continue flow reactor with W/F=0,1~0,9g-kat.mnt./cc.Concentration of reactants and products were analyzed by gas chromathography while catalyst structure was observed by XRD (X-ray diffraction. Isothermal adsorption method was used for determining catalyst pore size. The result showed that ion exchange between H ion in zeolit with K ion produced potassium heteropoly salt that caused the change of interstitial space. The change of interstitial space was observed by the change of the lattice constant of the catalyst crystal. Trimethylamine(TMA has molecule size smaller than catalyst pore size but bigger than molecular size of Dimethylamine (DMA and Monimethylamine (MMA. This phenomenon caused the suppression of TMA formation. KPW has a rigid crystal structure and stabil during reaction. On the other hand, crystal structure of a non selective catalyst (NH43PW12O40 was not rigid and its pore size is easy to change depending on the product molecule size.

  8. Novel nano-semiconductor film layer supported nano-Pd Complex Nanostructured Catalyst Pd/Ⓕ-MeOx/AC for High Efficient Selective Hydrogenation of Phenol to Cyclohexanone. (United States)

    Si, Jiaqi; Ouyang, Wenbing; Zhang, Yanji; Xu, Wentao; Zhou, Jicheng


    Supported metal as a type of heterogeneous catalysts are the most widely used in industrial processes. High dispersion of the metal particles of supported catalyst is a key factor in determining the performance of such catalysts. Here we report a novel catalyst Pd/Ⓕ-MeO x /AC with complex nanostructured, Pd nanoparticles supported on the platelike nano-semiconductor film/activated carbon, prepared by the photocatalytic reduction method, which exhibited high efficient catalytic performance for selective hydrogenation of phenol to cyclohexanone. Conversion of phenol achieved up to more than 99% with a lower mole ratio (0.5%) of active components Pd and phenol within 2 h at 70 °C. The synergistic effect of metal nanoparticles and nano-semiconductors support layer and the greatly increasing of contact interface of nano-metal-semiconductors may be responsible for the high efficiency. This work provides a clear demonstration that complex nanostructured catalysts with nano-metal and nano-semiconductor film layer supported on high specific surface AC can yield enhanced catalytic activity and can afford promising approach for developing new supported catalyst.

  9. Total oxidation of naphthalene with high selectivity using a ceria catalyst prepared by a combustion method employing ethylene glycol

    International Nuclear Information System (INIS)

    Aranda, Asuncion; Lopez, Jose M.; Murillo, Ramon; Mastral, Ana M.; Dejoz, Ana; Vazquez, Isabel; Solsona, Benjamin; Taylor, Stuart H.; Garcia, Tomas


    During the catalytic combustion of naphthalene, compounds other than CO 2 are often obtained. These products, as polymerized polycyclic aromatic hydrocarbons, oxygenated aromatic compounds and benzene derivate compounds, are usually more toxic than naphthalene. At the present work it is shown a nanocrystalline cerium oxide prepared by a combustion method employing a proper ethylene glycol concentration that exhibits very high activity in the decomposition of naphthalene in the presence of air and, most importantly, a selectivity value towards CO 2 of 100% for any range of conversions and/or temperatures used. In addition, it has been demonstrated that the amount of ethylene glycol employed in the synthesis of the catalyst is determinant to achieve the optimal catalytic performance. The catalytic results have been explained in terms of the amount of cerium oxide defects.

  10. Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, William David [Iowa State Univ., Ames, IA (United States)


    The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m2/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO3/(MoO3 + V2O5). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V+4 and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V2O5-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V2O5, solid solutions of Mo in V2O5, V9Mo6O40, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO3/(V2O5 + MoO3), determined by EDS analysis.

  11. Selective debenzylation of 1-benzyloxy-4-methoxy benzene over 5-sulfosalicylic acid-functionalized ordered mesoporous silica (SBA-15/SFSA) catalyst (United States)

    Verma, Savita; Dubey, Amit


    5-Sulfosalicylic acid (SFSA) functionalized mesoporous silica nanocomposites (SBA/APTS/SFSA) were synthesized by post grafting technique for selective debenzylation of 1-benzyloxy-4-methoxy benzene. The uniform incorporation of SFSA inside the mesoporous SBA-15 framework was confirmed by standard characterization techniques (PXRD, adsorption studies, FT-IR, etc.). Total surface area, pore size and pore volume of the SBA/APTS/SFSA catalysts decreased with increase in the concentration of SFSA confirming the uniform insertion of SFSA into mesoporous SBA-15 matrix. Catalytic activity studies showed highest conversion and selectivity of the desired product on SBA/APTS/SFSA catalyst compared to homogeneous SFSA and other solid support (Al2O3 and SiO2). All the reaction parameters such as reaction time, reaction temperature and catalyst weight were optimized under environmental friendly conditions. Finally, the possible mechanism of the reaction was explained.

  12. Critical advancements in achieving high power and stable nonprecious metal catalyst-based MEAs for real-world proton exchange membrane fuel cell applications. (United States)

    Banham, Dustin; Kishimoto, Takeaki; Zhou, Yingjie; Sato, Tetsutaro; Bai, Kyoung; Ozaki, Jun-Ichi; Imashiro, Yasuo; Ye, Siyu


    Despite great progress in the development of nonprecious metal catalysts (NPMCs) over the past several decades, the performance and stability of these promising catalysts have not yet achieved commercial readiness for proton exchange membrane fuel cells (PEMFCs). Through rational design of the cathode catalyst layer (CCL), we demonstrate the highest reported performance for an NPMC-based membrane electrode assembly (MEA), achieving a peak power of 570 mW/cm 2 under air. This record performance is achieved using a precommercial catalyst for which nearly all pores are <3 nm in diameter, challenging previous beliefs regarding the need for larger catalyst pores to achieve high current densities. This advance is achieved at industrially relevant scales (50 cm 2 MEA) using a precommercial NPMC. In situ electrochemical analysis of the CCLs is also used to help gain insight into the degradation mechanism observed during galvanostatic testing. Overall, the performance of this NPMC-based MEA has achieved commercial readiness and will be introduced into an NPMC-based product for portable power applications.

  13. Highly selective luminescent sensing of picric acid based on a water-stable europium metal-organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Tifeng; Zhu, Fengliang; Cui, Yuanjing, E-mail:; Yang, Yu; Wang, Zhiyu; Qian, Guodong, E-mail:


    A water-stable metal-organic framework (MOF) EuNDC has been synthesized for selective detection of the well-known contaminant and toxicant picric acid (PA) in aqueous solution. Due to the photo-induced electron transfer and self-absorption mechanism, EuNDC displayed rapid, selective and sensitive detection of PA with a detection limit of 37.6 ppb. Recyclability experiments revealed that EuNDC retains its initial luminescent intensity and same quenching efficiency in each cycle, suggesting high photostability and reusability for long-term sensing applications. The excellent detection performance of EuNDC makes it a promising PA sensing material for practical applications. - Graphical abstract: A water-stable europium-based metal-organic framework has been reported for highly selective sensing of picric acid (PA) with a detection limit of 37.6 ppb in aqueous solution. - Highlights: • A water-stable metal-organic framework (MOF) EuNDC was synthesized. • The highly selective detection of picric acid with a detection limit of 37.6 ppb was realized. • The detection mechanism were also presented and discussed.

  14. Selective oxidation of isobutane on V–Mo–O mixed oxide catalysts

    Directory of Open Access Journals (Sweden)



    Full Text Available Four V–Mo–O mixed metal oxides were prepared, characterized and tested for the selective oxidation of isobutane in the temperature range 350–550 °C, at atmospheric pressure. Isobutane was mainly oxidized to iso-butene and carbon oxides. The systems with low vanadium contents showed low activities but high isobutene selectivities, while the systems with high vanadium contents showed high activities with high carbon oxides selectivities. The effects of temperature, contact time and the molar ratio iso-butane to oxygen on the conversion of isobutane and the selectivity of the oxidation were studied.


    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov


    catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.


    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov


    catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.

  17. A Mild and Green Route for Regio-selective Amination of Oxiranes Using Nanomagnetic Supported Ferrous Ion as a Solid Lewis Acid Catalyst in Water

    Directory of Open Access Journals (Sweden)

    Fariborz Mansouri


    Full Text Available A mild, green and highly efficient route for regio-selective amination of oxiranes was developed via incorporation of Mn(II, Fe(II, Co(II, Ni(II, Cu(II and Zn(II cations onto the surface of hydroxyapatite-encapsulated γ-Fe2O3 nanoparticles (γ-Fe2O3@HAp. Among six magnetically recoverable catalytic systems denoted as [γ-Fe2O3@HAp-MII], the catalyst in which M designated as Fe(II showed the best efficiency as well as regio-selectivity in amination of oxiranes under an ambient reaction condition. A wide variety of aromatic and aliphatic amines were reacted with epoxides using magnetically separable iron catalyst to give the corresponding amino alcohols in excellent yields and selectivities in water as solvent at room temperature. In addition, recovery of the catalyst was successfully carried out in subsequent runs without any decrease in activity even after 5 runs. High regio-selectivity toward terminal ring-opening, efficient catalyst reusability using simple magnetic separation, high yields, simplicity in operation and diversity for various substrates are of advantages of this study.

  18. La-doped Al2O3 supported Au nanoparticles: highly active and selective catalysts for PROX under PEMFC operation conditions. (United States)

    Lin, Qingquan; Qiao, Botao; Huang, Yanqiang; Li, Lin; Lin, Jian; Liu, Xiao Yan; Wang, Aiqin; Li, Wen-Cui; Zhang, Tao


    La-doped γ-Al2O3 supported Au catalysts show high activity and selectivity for the PROX reaction under PEMFC operation conditions. The superior performance is attributed to the formation of LaAlO3, which suppresses H2 oxidation and strengthens CO adsorption on Au sites, thereby improving competitive oxidation of CO at elevated temperature.

  19. Low-temperature synthesis of Mn-based mixed metal oxides with novel fluffy structures as efficient catalysts for selective reduction of nitrogen oxides by ammonia. (United States)

    Meng, Bo; Zhao, Zongbin; Chen, Yongsheng; Wang, Xuzhen; Li, Yong; Qiu, Jieshan


    A series of Mn-based mixed metal oxide catalysts (Co-Mn-O, Fe-Mn-O, Ni-Mn-O) with high surface areas were prepared via low temperature crystal splitting and exhibited extremely high catalytic activity for the low-temperature selective catalytic reduction of nitrogen oxides with ammonia.

  20. A unique heterogeneous nucleophilic catalyst comprising methylated nitrogen-substituted porous silica provides high product selectivity for the Morita-Baylis-Hillman reaction. (United States)

    Furukawa, Yutaro; Ogura, Masaru


    Methylated nitrogen-substituted microporous and mesoporous silica exhibited almost the same catalytic performance as that of a conventional homogeneous base catalyst. They also demonstrated unexpectedly high product selectivity for the Morita-Baylis-Hillman reaction of formaldehyde with methyl acrylate at high temperatures.

  1. Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems (United States)

    Catalytic destruction of benzene (C6H6), a surrogate for organic hazardous air pollutants (HAPs) produced from coal combustion, was investigated using a commercial selective catalytic reduction (SCR) catalyst for evaluating the potential co-benefit of the SCR technology for reduc...

  2. The reaction mechanism and selectivity of acetylene hydrogenation over Ni-Ga intermetallic compound catalysts: a density functional theory study. (United States)

    Rao, De-Ming; Zhang, Shi-Tong; Li, Chang-Ming; Chen, Yu-Di; Pu, Min; Yan, Hong; Wei, Min


    Intermetallic compounds (IMCs) have shown excellent catalytic performance toward the selective hydrogenation of acetylene, but the theoretical understanding on this reaction over Ni-based IMCs is rather limited. In this work, the adsorptions of the C 2 species, Bader charge, projected density of states (PDOS) and the reaction pathways were calculated by the density functional theory (DFT) method to investigate the mechanism and selectivity for the acetylene hydrogenation on the (111) surface of Ni n Ga (n = 1, 3) IMCs, with a comparative study on the pristine Ni(111) surface. The results indicate that the adsorption energy of acetylene increased along with the Ni/Ga ratio, therefore a feasible acetylene adsorption on the Ga-rich surface guaranteed a low effective barrier, leading to the best activity for the NiGa(111) surface among three surfaces. Bader charge analysis shows that electrons transferred from Ga atoms to Ni atoms and further delivered to C 2 species, decreasing the adsorption capacity of C 2 species on NiGa(111) in comparison with those on Ni(111) and Ni 3 Ga(111). The reaction pathway of acetylene hydrogenation to ethylene via vinyl or even over-hydrogenation to ethane via ethyl is more favorable than the pathway involving the ethylidene intermediate on all surfaces. Moreover, the ethylene selectivity has a positive correlation with the gallium content by comparing the desorption barrier with the hydrogenation barrier of ethylene, thus the NiGa(111) surface also exhibits the best selectivity. Therefore, the NiGa(111) surface demonstrates to be an excellent reaction facet for the semihydrogenation of acetylene, which agreed with the experimental findings, and would provide helpful instructions for designing and preparing highly-selective and noble-substitute catalysts of alkyne semihydrogenation.

  3. Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Hansen, T. W.; Kustova, Marina


    Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH3. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents......, the activity of the mesoporous samples in NO SCR with NH3 is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite...

  4. Graphitic Carbon Nitride Supported Ultrafine Pd and Pd-Cu Catalysts: Enhanced Reactivity, Selectivity, and Longevity for Nitrite and Nitrate Hydrogenation. (United States)

    Ye, Tao; Durkin, David P; Banek, Nathan A; Wagner, Michael J; Shuai, Danmeng


    Novel Pd-based catalysts (i.e., Pd and Pd-Cu) supported on graphitic carbon nitride (g-C 3 N 4 ) were prepared for nitrite and nitrate hydrogenation. The catalysts prepared by ethylene glycol reduction exhibited ultrafine Pd and Pd-Cu nanoparticles (∼2 nm), and they showed high reactivity, high selectivity toward nitrogen gas over byproduct ammonium, and excellent stability over multiple reaction cycles. The unique nitrogen-abundant surface, porous structure, and hydrophilic nature of g-C 3 N 4 facilitates metal nanoparticle dispersion, mass transfer of reactants, and nitrogen coupling for nitrogen gas production to improve catalytic performance.

  5. Nitro-Grela-type complexes containing iodides - robust and selective catalysts for olefin metathesis under challenging conditions. (United States)

    Tracz, Andrzej; Matczak, Mateusz; Urbaniak, Katarzyna; Skowerski, Krzysztof


    Iodide-containing nitro-Grela-type catalysts have been synthesized and applied to ring closing metathesis (RCM) and cross metathesis (CM) reactions. These new catalysts have exhibited improved efficiency in the transformation of sterically, non-demanding alkenes. Additional steric hindrance in the vicinity of ruthenium related to the presence of iodides ensures enhanced catalyst stability. The benefits are most apparent under challenging conditions, such as very low reaction concentrations, protic solvents or with the occurrence of impurities.

  6. Nitro-Grela-type complexes containing iodides – robust and selective catalysts for olefin metathesis under challenging conditions

    Directory of Open Access Journals (Sweden)

    Andrzej Tracz


    Full Text Available Iodide-containing nitro-Grela-type catalysts have been synthesized and applied to ring closing metathesis (RCM and cross metathesis (CM reactions. These new catalysts have exhibited improved efficiency in the transformation of sterically, non-demanding alkenes. Additional steric hindrance in the vicinity of ruthenium related to the presence of iodides ensures enhanced catalyst stability. The benefits are most apparent under challenging conditions, such as very low reaction concentrations, protic solvents or with the occurrence of impurities.

  7. Single-Atom Pd₁/Graphene Catalyst Achieved by Atomic Layer Deposition: Remarkable Performance in Selective Hydrogenation of 1,3-Butadiene. (United States)

    Yan, Huan; Cheng, Hao; Yi, Hong; Lin, Yue; Yao, Tao; Wang, Chunlei; Li, Junjie; Wei, Shiqiang; Lu, Junling


    We reported that atomically dispersed Pd on graphene can be fabricated using the atomic layer deposition technique. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy both confirmed that isolated Pd single atoms dominantly existed on the graphene support. In selective hydrogenation of 1,3-butadiene, the single-atom Pd1/graphene catalyst showed about 100% butenes selectivity at 95% conversion at a mild reaction condition of about 50 °C, which is likely due to the changes of 1,3-butadiene adsorption mode and enhanced steric effect on the isolated Pd atoms. More importantly, excellent durability against deactivation via either aggregation of metal atoms or carbonaceous deposits during a total 100 h of reaction time on stream was achieved. Therefore, the single-atom catalysts may open up more opportunities to optimize the activity, selectivity, and durability in selective hydrogenation reactions.

  8. Highly active and stable ion-exchanged Fe–Ferrierite catalyst for N2O decomposition under nitric acid tail gas conditions

    NARCIS (Netherlands)

    Melián-Cabrera, I.; Mentruit, C.; Pieterse, J.A.Z.; Brink, R.W. van den; Mul, G.; Kapteijn, F.; Moulijn, J.A.


    This communication reports on the excellent performance and durability of a wet ion-exchanged Fe–Ferrierite catalysts for N2O decomposition under conditions of nitric acid plants, especially in the presence of water (0.5% vol) and at a high space time W/F0(N2O) = 900 kgcat s mol-1. In contrast to

  9. Sustaining high-energy orbits of bi-stable energy harvesters by attractor selection (United States)

    Udani, Janav P.; Arrieta, Andres F.


    Nonlinear energy harvesters have the potential to efficiently convert energy over a wide frequency range; however, difficulties in attaining and sustaining high-energy oscillations restrict their applicability in practical scenarios. In this letter, we propose an actuation methodology to switch the state of bi-stable harvesters from the low-energy intra-well configuration to the coexisting high-energy inter-well configuration by controlled phase shift perturbations. The strategy is designed to introduce a change in the system state without creating distinct metastable attractors by exploiting the basins of attraction of the coexisting stable attractors. Experimental results indicate that the proposed switching strategy yields a significant improvement in energy transduction capabilities, is highly economical, enabling the rapid recovery of energy spent in the disturbance, and can be practically implemented with widely used low-strain piezoelectric transducers.

  10. Selecting Sources that Define a Stable Celestial Reference Frame with the Allan Variance (United States)

    Le Bail, Karine; Gordon, David; Ma, Chopo


    The ICRF2 was adopted by the IAU in 2009 and was based on the positions of 3,414 radio sources determined by VLBI. Discussions on the next realization of the ICRF (ICRF3) have been underway within the IAU and IVS since 2012. VLBI has made significant advances since ICRF2. From the latest GSFC solution, we extract a set of sources that defines a stable celestial reference frame, as shown by Feissel-Vernier 2003 te{Feissel-Vernier2003} using tools such as the Allan variance and the drift of the position time series. This method also allows us to highlight a set of the least stable sources that may need special handling.

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

    KAUST Repository

    Shaikh Ali, Anaam


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

  12. Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    International Nuclear Information System (INIS)

    Mahdavi, Vahid; Soleimani, Shima


    Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V 2 O 5 /OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V 2 O 5 /OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V 2 O 5 /K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V 2 O 5 /K-OMS-2 catalyst. • V 2 O 5 /K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V 2 O 5 /K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V 2 O 5 species. Oxidation of various alcohols was studied in the liquid phase over the V 2 O 5 /K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H 2 O 2 as the oxidant. Activity of the V 2 O 5 /K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V 2 O 5 . The kinetic of benzyl alcohol oxidation using excess TBHP over V 2 O 5 /K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated

  13. The use of stable isotope compositions of selected elements in food origin control

    International Nuclear Information System (INIS)

    Wierzchnicki, R.


    Stable isotope ratios have been used widely for authentication of foodstuffs especially for detection of added water and sugar in fruit juices and wines. Hydrogen and oxygen composition are particularly interesting probes for geographical origin and authenticity identification. Carbon and nitrogen composition of fruits contains the finger-print of their metabolism and growing condition. Exemplary data are presented which demonstrated the usefulness of the Isotope Ratio Mass Spectrometry (IRMS) methods for authenticating wines and fruits (juice and pulp). (author)

  14. Hybrid selective noncatalytic reduction (SNCR)/selective catalytic reduction (SCR) for NOx removal using low-temperature SCR with Mn-V2O5/TiO2 catalyst. (United States)

    Choi, Sung-Woo; Choi, Sang-Ki; Bae, Hun-Kyun


    A hybrid selective noncatalytic reduction/selective catalytic reduction (SNCR/SCR) system that uses two types of technology, low-temperature SCR process and SNCR process, was designed to develop nitrogen oxide (NOx) reduction technology. SCR was conducted with space velocity (SV)=2400 hr(-1) and hybrid SNCR/SCR with SV=6000 hr(-1), since the study focused on reducing the amount of catalyst and both achieved 98% NOx reduction efficiency. Characteristics of NOx reduction by NH3 were studied for low-temperature SCR system at 150 °C using Mn-V2O5/TiO2 catalyst. Mn-added V2O5/TiO2 catalyst was produced, and selective catalyst reduction of NOx by NH3 was experimented. NOx reduction rate according to added Mn content in Mn-V2O5/TiO2 catalyst was studied with varying conditions of reaction temperature, normalized stoichiometric ratio (NSR), SV, and O2 concentration. In the catalyst experiment according to V2O5 concentration, 1 wt.% V2O5 catalyst showed the highest NOx reduction rate: 98% reduction at temperature window of 200~250 °C. As a promoter of the V2O5 catalyst, 5 wt.% Mn was added, and the catalyst showed 47~90% higher efficiency even with low temperatures, 100~200 °C. Mn-V2O5/TiO2 catalyst, prepared by adding 5 wt.% Mn in V2O5/TiO2 catalyst, showed increments of catalyst activation at 150 °C as well as NOx reduction. Mn-V2O5/TiO2 catalyst showed 8% higher rate for NOx reduction compared with V2O5/TiO2 catalyst in 150 °C SCR. Thus, (5 wt.%)Mn-(1 wt.%)V2O5/TiO2 catalyst was applied in SCR of hybrid SNCR/SCR system of low temperature at 150 °C. Low-temperature SCR hybrid SNCR/SCR (150 °C) system and hybrid SNCR/SCR (350 °C) showed 91~95% total reduction rate with conditions of SV=2400~6000 hr(-1) SCR and 850~1050 °C SNCR, NSR=1.5~2.0, and 5% O2. Hybrid SNCR/SCR (150 °C) system proved to be more effective than the hybrid SNCR/SCR (350 °C) system at low temperature. NOx control is very important, since they are the part of greenhouse gases as well as the

  15. Concentrations of radionuclides and selected stable elements in fruits and vegetables

    International Nuclear Information System (INIS)

    Oakes, T.W.; Shank, K.E.


    Twenty-two types of fruits and vegetables collected from two commercial supermarkets have been analyzed for their radionuclidic and stable-element composition. A specific gamma-emitting isotope analysis was performed on each sample for 40 K, 60 Co, 95 Zr-Nb, 106 Ru, 137 Cs, 226 Ra, and 232 Th. The concentration of the stable elements in each sample were determined using multi-element neutron-activation analysis (Al, Ag, Au, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Cu, Eu, Fe, Hf, I, K, La, Mn, Mo, Mg, Na, Rb, Sb, Sc, Se, Sr, Ta, Te, Th, Ti, Zn, Zr) and atomic absorption (Cd, Ni, Pb). Information on the composition of a typical diet is used to estimate the radiological dose to man subsequent to ingestion of these fruits and vegetables. The stable-elemental compositions of the foodstuffs analyzed were compared with estimated values assuming foliar deposition and long-term buildup of effluents from a large modern coal-fired steam plant. It is tentatively concluded that for the general case of a precipitator-equipped, coal-fired steam plant, no toxic levels of trace elements in foodstuffs are expected as a result of the plant operation

  16. Concentrations of radionuclides and selected stable elements in fruits and vegetables

    Energy Technology Data Exchange (ETDEWEB)

    Oakes, T W; Shank, K E


    Twenty-two types of fruits and vegetables collected from two commercial supermarkets have been analyzed for their radionuclidic and stable-element composition. A specific gamma-emitting isotope analysis was performed on each sample for /sup 40/K, /sup 60/Co, /sup 95/Zr-Nb, /sup 106/Ru, /sup 137/Cs, /sup 226/Ra, and /sup 232/Th. The concentration of the stable elements in each sample were determined using multi-element neutron-activation analysis (Al, Ag, Au, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Cu, Eu, Fe, Hf, I, K, La, Mn, Mo, Mg, Na, Rb, Sb, Sc, Se, Sr, Ta, Te, Th, Ti, Zn, Zr) and atomic absorption (Cd, Ni, Pb). Information on the composition of a typical diet is used to estimate the radiological dose to man subsequent to ingestion of these fruits and vegetables. The stable-elemental compositions of the foodstuffs analyzed were compared with estimated values assuming foliar deposition and long-term buildup of effluents from a large modern coal-fired steam plant. It is tentatively concluded that for the general case of a precipitator-equipped, coal-fired steam plant, no toxic levels of trace elements in foodstuffs are expected as a result of the plant operation.

  17. Stable Reference Gene Selection for RT-qPCR Analysis in Nonviruliferous and Viruliferous Frankliniella occidentalis.

    Directory of Open Access Journals (Sweden)

    Chunxiao Yang

    Full Text Available Reverse transcriptase-quantitative polymerase chain reaction (RT-qPCR is a reliable technique for measuring and evaluating gene expression during variable biological processes. To facilitate gene expression studies, normalization of genes of interest relative to stable reference genes is crucial. The western flower thrips Frankliniella occidentalis (Pergande (Thysanoptera: Thripidae, the main vector of tomato spotted wilt virus (TSWV, is a destructive invasive species. In this study, the expression profiles of 11 candidate reference genes from nonviruliferous and viruliferous F. occidentalis were investigated. Five distinct algorithms, geNorm, NormFinder, BestKeeper, the ΔCt method, and RefFinder, were used to determine the performance of these genes. geNorm, NormFinder, BestKeeper, and RefFinder identified heat shock protein 70 (HSP70, heat shock protein 60 (HSP60, elongation factor 1 α, and ribosomal protein l32 (RPL32 as the most stable reference genes, and the ΔCt method identified HSP60, HSP70, RPL32, and heat shock protein 90 as the most stable reference genes. Additionally, two reference genes were sufficient for reliable normalization in nonviruliferous and viruliferous F. occidentalis. This work provides a foundation for investigating the molecular mechanisms of TSWV and F. occidentalis interactions.

  18. Stable Reference Gene Selection for RT-qPCR Analysis in Nonviruliferous and Viruliferous Frankliniella occidentalis. (United States)

    Yang, Chunxiao; Li, Hui; Pan, Huipeng; Ma, Yabin; Zhang, Deyong; Liu, Yong; Zhang, Zhanhong; Zheng, Changying; Chu, Dong


    Reverse transcriptase-quantitative polymerase chain reaction (RT-qPCR) is a reliable technique for measuring and evaluating gene expression during variable biological processes. To facilitate gene expression studies, normalization of genes of interest relative to stable reference genes is crucial. The western flower thrips Frankliniella occidentalis (Pergande) (Thysanoptera: Thripidae), the main vector of tomato spotted wilt virus (TSWV), is a destructive invasive species. In this study, the expression profiles of 11 candidate reference genes from nonviruliferous and viruliferous F. occidentalis were investigated. Five distinct algorithms, geNorm, NormFinder, BestKeeper, the ΔCt method, and RefFinder, were used to determine the performance of these genes. geNorm, NormFinder, BestKeeper, and RefFinder identified heat shock protein 70 (HSP70), heat shock protein 60 (HSP60), elongation factor 1 α, and ribosomal protein l32 (RPL32) as the most stable reference genes, and the ΔCt method identified HSP60, HSP70, RPL32, and heat shock protein 90 as the most stable reference genes. Additionally, two reference genes were sufficient for reliable normalization in nonviruliferous and viruliferous F. occidentalis. This work provides a foundation for investigating the molecular mechanisms of TSWV and F. occidentalis interactions.

  19. The effect of the central donor in bis(benzimidazole)-based cobalt catalysts for the selective cis-1,4-polymerisation of butadiene. (United States)

    Cariou, Renan; Chirinos, Juan J; Gibson, Vernon C; Jacobsen, Grant; Tomov, Atanas K; Britovsek, George J P; White, Andrew J P


    A series of bis(benzimidazole)-based cobalt(II) dichloride complexes containing a range of different central donors has been synthesized and characterized. The nature of the central donor affects the binding of the ligand to the cobalt centre and determines the coordination geometry of the metal complexes. All complexes have been shown to catalyse the polymerization of butadiene, in combination with MAO as the co-catalyst, to give cis-1,4-polybutadiene with high selectivity. The nature of the central donor has a marked influence on the polymerization activity of the catalysts, but does not affect the polymer microstructure. The addition of PPh(3) generally increases the polymerization activity of these cobalt catalysts and results in predominantly (60-70%) 1,2-vinyl-polybutadiene.

  20. Oxidation catalyst (United States)

    Ceyer, Sylvia T.; Lahr, David L.


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

  1. A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide. (United States)

    Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin


    Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

  2. Supported Molten Metal Catalysis. A New Class of Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ravindra Datta; Ajeet Singh; Manuela Serban; Istvan Halasz


    We describe a new class of heterogeneous catalysts called supported molten metal catalysis (SMMC), in which molten metal catalysts are dispersed as nanodroplets on the surface of porous supports, allowing much larger active surface area than is possible in conventional contacting techniques for catalytic metals that are molten under reaction conditions, thus greatly enhancing their activity and potential utility. Specific examples of different types of reactions are provided to demonstrate the broad applicability of the technique in designing active, selective, and stable new catalysts. It is shown that dispersing the molten metal on a support in the suggested manner can enhance the rate of a reaction by three to four orders of magnitude as a result of the concomitant increase in the active surface area. New reaction examples include {gamma}-Al{sub 2}O{sub 3} supported molten Te (melting point 450 C) and Ga (MP 30 C) catalysts for bifunctional methylcyclohexane dehydrogenation. These catalysts provide activity similar to conventional Pt-based catalysts for this with better resistance to coking. In addition, results are described for a controlled pore glass supported molten In (MP 157 C) catalyst for the selective catalytic reduction of NO with ethanol in the presence of water, demonstrating activities superior to conventional catalysts for this reaction. A discussion is also provided on the characterization of the active surface area and dispersion of these novel supported catalysts. It is clear based on the results described that the development of new active and selective supported molten metal catalysts for practical applications is entirely plausible.

  3. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

    KAUST Repository

    Szeto, Kaï Chung


    We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product is unprecedented, asymmetrically distributed towards heavier alkanes. This journal is © 2012 The Royal Society of Chemistry.

  4. Lithium-Vanadium bronzes as model catalysts for the selective reduction of nitric oxide

    NARCIS (Netherlands)

    Bosch, H.; Bongers, Annemie; Enoch, Gert; Snel, Ruud; Ross, Julian R.H.


    The effect of alkali metals on the selective reduction of nitric oxide with ammonia has been studied on bulk iron oxide and bulk vanadium oxide. The influence of additions of LiOH, NaOH and KOH on the activity was screened by pulse experiments carried out in the absence of gaseous oxygen; FTIR

  5. Carbon nanotube diameter selection by pretreatment of metal catalysts on surfaces (United States)

    Hauge, Robert H [Houston, TX; Xu, Ya-Qiong [Houston, TX; Shan, Hongwei [Houston, TX; Nicholas, Nolan Walker [South Charleston, WV; Kim, Myung Jong [Houston, TX; Schmidt, Howard K [Cypress, TX; Kittrell, W Carter [Houston, TX


    A new and useful nanotube growth substrate conditioning processes is herein disclosed that allows the growth of vertical arrays of carbon nanotubes where the average diameter of the nanotubes can be selected and/or controlled as compared to the prior art.

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

    Directory of Open Access Journals (Sweden)

    Juliana Cristina Tristão


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

  7. Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2. (United States)

    DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip


    Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

  8. Immobilized triazacyclononane derivatives as selective oxidation catalysts. Final technical report of DOE Award No. DE-FG02-99ER14968 with the University of Munich [Encapsulation of metal chelate and oxocatalysts in nanoporous hosts

    Energy Technology Data Exchange (ETDEWEB)

    Bein, Thomas


    This project deals with the covalent anchoring of various derivatives of triazacyclononane (TACN)ligands in the channels of period mesoporous materials and the catalytic activity of the corresponding metal complexes. Catalyst preparation, ligand immobilization, catalyst characterization, and catalyst performance in selective oxidation are discussed. A wide range of pendant variations on the TACN ligand can be synthesized, and ligands can be covalently bound to high surface area, pseudo-crystalline, silicate solids, before or after pendant addition.

  9. Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst. (United States)

    Adam, Rosa; Bheeter, Charles Beromeo; Cabrero-Antonino, Jose R; Junge, Kathrin; Jackstell, Ralf; Beller, Matthias


    A general procedure for the catalytic hydrogenation of nitriles to primary amines by using a non-noble metal-based system is presented. Co(acac) 3 in combination with tris[2-(dicyclohexylphosphino)ethyl]phosphine efficiently catalyzes the selective hydrogenation of a wide range of (hetero)aromatic and aliphatic nitriles to give the corresponding amines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Regeneration of sulfur-fouled bimetallic Pd-based catalysts. (United States)

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


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

  11. Determination of Trophic Structure in Selected Freshwater Ecosystems by using Stable Isotope Analysis. (United States)

    Zainordin, 'Amila Faqhira; Ab Hamid, Suhaila


    Stable isotope analysis has been used extensively to establish trophic relationships in many ecosystems. Present study utilised stable isotope signatures of carbon and nitrogen to identify trophic structure of aquatic food web in river and rice field ecosystems in Perak, northern peninsular Malaysia. The mean δ 13 C values of all producers ranged from -35.29 ± 0.21 to -26.00 ± 0.050‰. The greatest δ 15 N values noted was in zenarchopterid fish with 9.68 ± 0.020‰. The δ 15 N values of aquatic insects ranged between 2.59 ± 0.107 in Elmidae (Coleoptera) and 8.11 ± 0.022‰ in Nepidae (Hemiptera). Correspondingly, with all the δ 13 C and δ 15 N values recorded, it can be deduced that there are four trophic levels existed in the freshwater ecosystems which started with the producer (plants), followed by primary consumer (aquatic insects and non-predatory fish), secondary consumer (invertebrate predators) and lastly tertiary consumer (vertebrate predators).

  12. Selective liquid-phase oxidation of alcohols catalyzed by a silver-based catalyst promoted by the presence of ceria

    DEFF Research Database (Denmark)

    Beier, Matthias Josef; Hansen, Thomas Willum; Grunwaldt, Jan-Dierk


    simultaneously. When a high catalytic conversion (>30% over 2 h) was found the number of catalyst components was reduced in the following tests. Thereby, a collaborative effect between a physical mixture of ceria nanoparticles and silver-impregnated silica (10 wt.% Ag–SiO2) was found. The catalytic activity...... by in situ XAS experiments. Oxygen species incorporated in the silver lattice appear to be important for the catalytic oxidation of the alcohol for which a preliminary mechanism is presented. The application of the catalyst was extended to the oxidation of a wide range of primary and secondary alcohols....... Compared to palladium and gold catalysts, the new silver catalyst performed similarly or even superior in the presence of CeO2. In addition, the presence of ceria increased the catalytic activity of all investigated catalysts....

  13. Design of slurry bubble column reactors: novel technique for optimum catalyst size selection contractual origin of the invention (United States)

    Gamwo, Isaac K [Murrysville, PA; Gidaspow, Dimitri [Northbrook, IL; Jung, Jonghwun [Naperville, IL


    A method for determining optimum catalyst particle size for a gas-solid, liquid-solid, or gas-liquid-solid fluidized bed reactor such as a slurry bubble column reactor (SBCR) for converting synthesis gas into liquid fuels considers the complete granular temperature balance based on the kinetic theory of granular flow, the effect of a volumetric mass transfer coefficient between the liquid and the gas, and the water gas shift reaction. The granular temperature of the catalyst particles representing the kinetic energy of the catalyst particles is measured and the volumetric mass transfer coefficient between the gas and liquid phases is calculated using the granular temperature. Catalyst particle size is varied from 20 .mu.m to 120 .mu.m and a maximum mass transfer coefficient corresponding to optimum liquid hydrocarbon fuel production is determined. Optimum catalyst particle size for maximum methanol production in a SBCR was determined to be in the range of 60-70 .mu.m.

  14. Selecting the best stable isotope mixing model to estimate grizzly bear diets in the Greater Yellowstone Ecosystem.

    Directory of Open Access Journals (Sweden)

    John B Hopkins

    Full Text Available Past research indicates that whitebark pine seeds are a critical food source for Threatened grizzly bears (Ursus arctos in the Greater Yellowstone Ecosystem (GYE. In recent decades, whitebark pine forests have declined markedly due to pine beetle infestation, invasive blister rust, and landscape-level fires. To date, no study has reliably estimated the contribution of whitebark pine seeds to the diets of grizzlies through time. We used stable isotope ratios (expressed as δ13C, δ15N, and δ34S values measured in grizzly bear hair and their major food sources to estimate the diets of grizzlies sampled in Cooke City Basin, Montana. We found that stable isotope mixing models that included different combinations of stable isotope values for bears and their foods generated similar proportional dietary contributions. Estimates generated by our top model suggest that whitebark pine seeds (35±10% and other plant foods (56±10% were more important than meat (9±8% to grizzly bears sampled in the study area. Stable isotope values measured in bear hair collected elsewhere in the GYE and North America support our conclusions about plant-based foraging. We recommend that researchers consider model selection when estimating the diets of animals using stable isotope mixing models. We also urge researchers to use the new statistical framework described here to estimate the dietary responses of grizzlies to declines in whitebark pine seeds and other important food sources through time in the GYE (e.g., cutthroat trout, as such information could be useful in predicting how the population will adapt to future environmental change.

  15. Performance of Ru/La2O3–ZnO Catalyst for the Selective Hydrogenation of Benzene to Cyclohexene

    Directory of Open Access Journals (Sweden)

    Hendrik Spod


    Full Text Available Cyclohexene is an important intermediate product for a highly efficient and greener formation of major end products like adipic acid, nylon 6, and nylon 6.6. By using a complex tetra-phase system (g/l/l/s including hydrogen (g, water (l, an organic phase, i.e., benzene (l, and a supported ruthenium catalyst (s it is possible to get the desired intermediate cyclohexene based on benzene. We prepared an oxide-supported ruthenium catalyst that was applied together with minimal amounts of the additive NaDCA (sodium dicyanamide in a batch and continuous apparatus for the selective benzene hydrogenation. We compared these two processes and reached by an optimization of the reaction parameters in continuous process selectivities up to 50% at conversions of 36%. This corresponds to cyclohexene yields of 18% over a period of 100 h. Finally, the catalyst was characterized using X-ray diffraction (XRD, transmission electron spectroscopy (TEM, inductively coupled plasma optical emission spectrometry (ICP-OES, and laser scattering to understand the performance of the catalyst and the effect of the small deactivation.

  16. Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Thornburg, Nicholas E.; Notestein, Justin M. (NWU)


    Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions. Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.

  17. Selection criterion of stable dendritic growth at arbitrary Péclet numbers with convection. (United States)

    Alexandrov, Dmitri V; Galenko, Peter K


    A free dendrite growth under forced fluid flow is analyzed for solidification of a nonisothermal binary system. Using an approach to dendrite growth developed by Bouissou and Pelcé [Phys. Rev. A 40, 6673 (1989)], the analysis is presented for the parabolic dendrite interface with small anisotropy of surface energy growing at arbitrary Péclet numbers. The stable growth mode is obtained from the solvability condition giving the stability criterion for the dendrite tip velocity V and dendrite tip radius ρ as a function of the growth Péclet number, flow Péclet number, and Reynolds number. In limiting cases, the obtained stability criterion presents known criteria for small and high growth Péclet numbers of the solidifying system with and without convective fluid flow.

  18. Selection of energy source and evolutionary stable strategies for power plants under financial intervention of government (United States)

    Hafezalkotob, Ashkan; Mahmoudi, Reza


    Currently, many socially responsible governments adopt economic incentives and deterrents to manage environmental impacts of electricity suppliers. Considering the Stackelberg leadership of the government, the government's role in the competition of power plants in an electricity market is investigated. A one-population evolutionary game model of power plants is developed to study how their production strategy depends on tariffs levied by the government. We establish that a unique evolutionary stable strategy (ESS) for the population exists. Numerical examples demonstrate that revenue maximization and environment protection policies of the government significantly affect the production ESS of competitive power plants. The results reveal that the government can introduce a green energy source as an ESS of the competitive power plants by imposing appropriate tariffs.

  19. Catalyst for hydrocarbon conversion

    International Nuclear Information System (INIS)

    Duhaut, P.; Miquel, J.


    A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

  20. Nonstop Selection for High and Stable Crop Yield by Two Prognostic Equations to Reduce Yield Losses

    Directory of Open Access Journals (Sweden)

    Dionysia A. Fasoula


    Full Text Available Yield losses occurring at the field level, whether due to plant diseases or abiotic stresses, reveal reduced stability of the crop yield potential. The paper argues that the stability of crop yield potential is a trait with a clear genetic component, which can be successfully selected for at the single-plant level and incorporated into high-yielding cultivars. Two novel selection equations with prognostic power are presented, capable to objectively phenotype and evaluate individual plants in real field conditions in the absence of the masking effects of interplant competition and soil heterogeneity. The equations predict performance at the crop stand through the key concept of coefficient of homeostasis and are equally useful for early generation selection and for nonstop selection within finished cultivars in order to continuously incorporate the adaptive (genetic or epigenetic responses of plants. Exploitation of adaptive responses acquires particular importance in view of the climate change effects on crop productivity and the changing biotic or abiotic micro-environments. Cotton is used as a case study to highlight the potential of nonstop selection for increasing crop yield and for the gradual build-up of disease resistance. In addition, the paper envisions and proposes the formation of international networks of researchers focusing on specific diseases as, for example, the cereal root-rot or the cotton Verticillium wilt that will concurrently use the proposed strategy in their respective environments to select for resistant genotypes, while gaining a deeper understanding of the nature of the genetic or epigenetic changes at the phenotypic and genomic levels.

  1. In-situ characterization of heterogeneous catalysts

    CERN Document Server

    Rodriguez, Jose A; Chupas, Peter J


    Helps researchers develop new catalysts for sustainable fuel and chemical production Reviewing the latest developments in the field, this book explores the in-situ characterization of heterogeneous catalysts, enabling readers to take full advantage of the sophisticated techniques used to study heterogeneous catalysts and reaction mechanisms. In using these techniques, readers can learn to improve the selectivity and the performance of catalysts and how to prepare catalysts as efficiently as possible, with minimum waste. In-situ Characterization of Heterogeneous Catalysts feat

  2. Stable maintenance of multiple plasmids in E. coli using a single selective marker. (United States)

    Schmidt, Calvin M; Shis, David L; Nguyen-Huu, Truong D; Bennett, Matthew R


    Plasmid-based genetic systems in Escherichia coli are a staple of synthetic biology. However, the use of plasmids imposes limitations on the size of synthetic gene circuits and the ease with which they can be placed into bacterial hosts. For instance, unique selective markers must be used for each plasmid to ensure their maintenance in the host. These selective markers are most often genes encoding resistance to antibiotics such as ampicillin or kanamycin. However, the simultaneous use of multiple antibiotics to retain different plasmids can place undue stress on the host and increase the cost of growth media. To address this problem, we have developed a method for stably transforming three different plasmids in E. coli using a single antibiotic selective marker. To do this, we first examined two different systems with which two plasmids may be maintained. These systems make use of either T7 RNA polymerase-specific regulation of the resistance gene or split antibiotic resistance enzymes encoded on separate plasmids. Finally, we combined the two methods to create a system with which three plasmids can be transformed and stably maintained using a single selective marker. This work shows that large-scale plasmid-based synthetic gene circuits need not be limited by the use of multiple antibiotic resistance genes.

  3. Carrier-selective p- and n-contacts for efficient and stable photocatalytic water reduction

    DEFF Research Database (Denmark)

    Bae, Dowon; Pedersen, Thomas; Seger, Brian


    The successful realization of carrier-selective contacts for crystalline silicon (c-Si) based device for pho-tocatalytic hydrogen production has been demonstrated. The proposed TiO2protected carrier-selectivecontacts resemble a metal-oxide-semiconductor configuration, including a highly-doped nan...

  4. Green synthesis of Pd@graphene nanocomposite: Catalyst for the selective oxidation of alco

    Directory of Open Access Journals (Sweden)

    Abdulhadi H. Al-Marri


    Full Text Available Due to their excellent physicochemical properties and synergistic effect, graphene metallic NPs based nanocomposites have gained significant attention in various technological fields including catalysis. Here we demonstrate a single pot, facile and environmental friendly synthesis of catalytically active palladium(Pd@graphene nanocomposites (SP-HRG-Pd by the simultaneous reduction of graphene oxide (GRO and PdCl2 using Salvadora persica L. (miswak root extract (RE as bioreductant. The synthesis of SP-HRG-Pd was confirmed by various spectroscopic and microscopic techniques, including ultraviolet–visible (UV–vis, Fourier-transform infrared (FT-IR, Raman and X-ray photoelectron (XPS spectroscopy, X-ray powder diffraction (XRD and transmission electron microscopy (TEM. The polyphenolic (flavonoids and terpenoids rich contents of the miswak RE not only facilitated the reduction of graphene oxide and PdCl2 but also ensured the homogeneous binding of the Pd NPs on graphene, and through stabilization of the surface of SP-HRG-Pd nanocomposites. This also led to the enhanced dispersibility of as synthesized nanocomposites in aqueous solutions. The as-prepared SP-HRG-Pd nanocomposites also demonstrated excellent catalytic activity toward the selective oxidation of aromatic alcohols. Furthermore, in order to study the effect of calcination temperature and concentration of Pd NPs on the catalytic activities of nanocomposites, different samples of SP-HRG-Pd nanocomposites containing different amounts of Pd using various concentrations of Pd precursor were prepared and calcined at various temperatures.

  5. Ni- and Mn-Promoted Mesoporous Co3O4: A Stable Bifunctional Catalyst with Surface-Structure-Dependent Activity for Oxygen Reduction Reaction and Oxygen Evolution Reaction. (United States)

    Song, Wenqiao; Ren, Zheng; Chen, Sheng-Yu; Meng, Yongtao; Biswas, Sourav; Nandi, Partha; Elsen, Heather A; Gao, Pu-Xian; Suib, Steven L


    Efficient bifunctional catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable due to their wide applications in fuel cells and rechargeable metal air batteries. However, the development of nonprecious metal catalysts with comparable activities to noble metals is still challenging. Here we report a one-step wet-chemical synthesis of Ni-/Mn-promoted mesoporous cobalt oxides through an inverse micelle process. Various characterization techniques including powder X-ray diffraction (PXRD), N2 sorption, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) confirm the successful incorporation of Ni and Mn leading to the formation of Co-Ni(Mn)-O solid solutions with retained mesoporosity. Among these catalysts, cobalt oxide with 5% Ni doping demonstrates promising activities for both ORR and OER, with an overpotential of 399 mV for ORR (at -3 mA/cm(2)) and 381 mV (at 10 mA/cm(2)) for OER. Furthermore, it shows better durability than precious metals featuring little activity decay throughout 24 h continuous operation. Analyses of cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), Raman, and O2-temperature-programmed desorption (O2-TPD) reveal that redox activity of Co(3+) to Co(4+) is crucial for OER performance, while the population of surface oxygen vacancies and surface area determine ORR activities. The comprehensive investigation of the intrinsic active sites for ORR and OER by correlating different physicochemical properties to the electrochemical activities is believed to provide important insight toward the rational design of high-performance electrocatalysts for ORR and OER reactions.

  6. Stable Aluminum Metal-Organic Frameworks (Al-MOFs) for Balanced CO2 and Water Selectivity. (United States)

    Li, Haiwei; Feng, Xiao; Ma, Dou; Zhang, Mengxi; Zhang, Yuanyuan; Liu, Yi; Zhang, Jinwei; Wang, Bo


    Three new Al-MOFs in the formation of [Al 4 (OH) 2 (OCH 3 ) 4 (OH-BDC) 3 ]·xH 2 O (BIT-72), [Al 4 (OH) 2 (OCH 3 ) 4 (CH 3 -BDC) 3 ]·xH 2 O (BIT-73) and {Al 4 (OH) 2 (OCH 3 ) 4 [(CH 3 ) 2 -BDC] 3 }·xH 2 O (BIT-74) have been synthesized by assembling Al 3+ ion with terephthalic acid ions decorated with monohydroxyl, monomethyl or dimethyl groups, respectively. All of these three MOFs exhibit high stability in boiling water and acidic conditions. Among them, BIT-72 shows the highest surface area of 1618 m 2 ·g -1 and IAST CO 2 /N 2 selectivity of 48, while BIT-73 and BIT-74 present moderate IAST CO 2 /N 2 selectivity and much lower H 2 O capacity below P/P 0 = 0.3. The high CO 2 /N 2 selectivity together with alleviative H 2 O sorption at low water relative pressure may provide promising potential in postcombustion CO 2 capture.

  7. In-line localized monitoring of catalyst activity in selective catalytic NO.sub.x reduction systems (United States)

    Muzio, Lawrence J [Laguna Niguel, CA; Smith, Randall A [Huntington Beach, CA


    Localized catalyst activity in an SCR unit for controlling emissions from a boiler, power plant, or any facility that generates NO.sub.x-containing flue gases is monitored by one or more modules that operate on-line without disrupting the normal operation of the facility. Each module is positioned over a designated lateral area of one of the catalyst beds in the SCR unit, and supplies ammonia, urea, or other suitable reductant to the catalyst in the designated area at a rate that produces an excess of the reductant over NO.sub.x on a molar basis through the designated area. Sampling probes upstream and downstream of the designated area draw samples of the gas stream for NO.sub.x analysis, and the catalyst activity is determined from the difference in NO.sub.x levels between the two probes.

  8. Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts. (United States)

    Ye, Rong; Zhukhovitskiy, Aleksandr V; Deraedt, Christophe V; Toste, F Dean; Somorjai, Gabor A


    demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl 2 ) or reduced (e.g., with H 2 ) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. In this Account, we will briefly introduce metal clusters and describe the synthesis and characterizations of supported DEMCs. We will present the catalysis studies of supported DEMCs in both the batch and flow modes. Lastly, we will summarize the current state of heterogenizing homogeneous catalysis and provide future directions for this area of research.

  9. A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide. (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan


    Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

  10. Ruthenium meso-Tetrakis(2,6-dichlorophenyl)porphyrin Complex Immobilized in Mesoporous MCM-41 as a Heterogeneous Catalyst for Selective Alkene Epoxidations. (United States)

    Liu, Chun-Jing; Yu, Wing-Yiu; Li, Shou-Gui; Che, Chi-Ming


    A ruthenium complex of meso-tetrakis(2,6-dichlorophenyl)porphyrin, [Ru(II)(TDCPP)(CO)(EtOH)], is immobilized into mesoporous MCM-41 molecular sieves; the supported Ru catalyst can effect highly selective heterogeneous alkene epoxidations using 2,6-dichloropyridine N-oxide as terminal oxidant. Aromatic and aliphatic alkenes can be efficiently converted to their epoxides in good yields and selectivities, and cis-alkenes such as cis-stilbene, cis-beta-methylstyrene, and cis-beta-deuteriostyrene are epoxidized stereospecifically. Oxidation of cycloalkenes, e.g., norbornene and cyclooctene, can be carried out effectively using the heterogeneous Ru-catalyzed reaction while these alkenes are unreactive in the zeolite-based titanium silicate (TS-1)-catalyzed conditions (Murugavel, R.; Roesky, H. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 477). On the other hand, the Ru/M-41(m) catalyst displays size selectivity in the (+)-limonene oxidation where the terminal C=C bond (vs internal trisubstituted C=C bond) becomes more readily oxidized. Bulky 3,4,6-tri-O-benzyl-D-glucal has failed to react under the heterogeneous Ru-catalyzed conditions, whereas the smaller acetyl derivative is converted to a 3:1 mixture of alpha- and beta-glycal epoxides. The Ru/M-41(m) catalyst can be used repeatedly, and 67% of its initial activity is retained after 11 691 turnovers (three runs). The loss of activity is attributed to catalyst leaching and/or deactivation. On the basis of Hammett correlation (rho(+) = -0.72, R = 0.997) and product studies (cyclohexene and cis-alkenes as the substrates), a reactive dioxoruthenium(VI) porphyrin intermediate is not favored. An oxoruthenium(V) complex or oxoruthenium(IV) porphyrin cation radical could be the key intermediate for this highly selective epoxidation reaction.

  11. 2D-QSPR/DFT studies of aryl-substituted PNP-Cr-based catalyst systems for highly selective ethylene oligomerization. (United States)

    Tang, Siyang; Liu, Zhen; Zhan, Xingwen; Cheng, Ruihua; He, Xuelian; Liu, Boping


    1-Hexene and 1-octene are important comonomers for the synthesis of high performance polyolefins. Recently, various N-substituted Cr-bis(diphenylphosphino)amine (PNP-Cr) catalysts show the potential as excellent candidates for highly selective ethylene trimerization/tetramerization. In this work, a series of aryl-substituted PNP-Cr catalysts were studied by two-dimensional quantitative structure-property relationship (QSPR) method based on density functional theory (DFT) calculations. The heuristic method (HM) and best multi-linear regression (BMLR) were used to establish the best linear regression models to describe the relationship between selectivities and catalyst structures. Both Cr(I) and Cr(II) active site models for ethylene trimerization/tetramerization were considered. It was found that 1) the relativity and stability of the models were increased by using self-defined descriptors based on DFT calculations; 2) Cr(I)/Cr(III) centers were the most plausible active sites for ethylene trimerization, while Cr(II)/Cr(IV) active sites were most possibly responsible for ethylene tetramerization; and 3) the skeleton structures of the PNP-Cr system with good complanation and symmetry were crucial for achieving excellent catalytic selectivity of 1-octene, while the PNP-Cr backbone with a large steric effect on N atom would benefit ethylene trimerization. Six new PNP ligands with high selectivity toward ethylene trimerization/tetramerization were predicted based on descriptor analysis and the best linear regression models providing a good basis for further development of novel catalyst systems with better performance.

  12. Selective Heart Rate Reduction With Ivabradine Increases Central Blood Pressure in Stable Coronary Artery Disease. (United States)

    Rimoldi, Stefano F; Messerli, Franz H; Cerny, David; Gloekler, Steffen; Traupe, Tobias; Laurent, Stéphane; Seiler, Christian


    Heart rate (HR) lowering by β-blockade was shown to be beneficial after myocardial infarction. In contrast, HR lowering with ivabradine was found to confer no benefits in 2 prospective randomized trials in patients with coronary artery disease. We hypothesized that this inefficacy could be in part related to ivabradine's effect on central (aortic) pressure. Our study included 46 patients with chronic stable coronary artery disease who were randomly allocated to placebo (n=23) or ivabradine (n=23) in a single-blinded fashion for 6 months. Concomitant baseline medication was continued unchanged throughout the study except for β-blockers, which were stopped during the study period. Central blood pressure and stroke volume were measured directly by left heart catheterization at baseline and after 6 months. For the determination of resting HR at baseline and at follow-up, 24-hour ECG monitoring was performed. Patients on ivabradine showed an increase of 11 mm Hg in central systolic pressure from 129±22 mm Hg to 140±26 mm Hg (P=0.02) and in stroke volume by 86±21.8 to 107.2±30.0 mL (P=0.002). In the placebo group, central systolic pressure and stroke volume remained unchanged. Estimates of myocardial oxygen consumption (HR×systolic pressure and time-tension index) remained unchanged with ivabradine.The decrease in HR from baseline to follow-up correlated with the concomitant increase in central systolic pressure (r=-0.41, P=0.009) and in stroke volume (r=-0.61, Pcoronary artery disease patients. CLINICAL TRIALSURL: Unique identifier NCT01039389. © 2016 American Heart Association, Inc.

  13. Controlled Polymerization of Isoprene with Chromium-Based Metal-Organic Framework Catalysts: Switching from Cyclic to cis-1,4-Selectivity Depending on Activator. (United States)

    Gao, Fei; Zhang, Li; Yu, Chao; Yan, Xinwen; Zhang, Shaowen; Li, Xiaofang


    Chromium-based metal-organic framework (MOF) Cr-MIL-100/101 activated by activator and aluminum trialkyl compound serve as unique, highly efficient heterogeneous single-site catalysts for the controlled polymerization of isoprene, which not only exhibit quasi-living nature in isoprene polymerization but also unprecedentedly switch from cyclic to cis-1,4-selectivity depending on the activator used to yield low molecular weight cyclic PIPs or extremely high molecular weight cis-1,4-PIPs. Such heterogeneous Cr-MOF catalysts can be recycled approximately five times. Based on nitrogen sorption isotherm tests and powder X-ray diffraction, a cationic mechanism is suggested, in which the polymerization takes place inside the open nanochannels of MOF catalysts and the space confinement effect of narrow open nanochannels originated from the coordination of PhNMe 2 from activator [PhNHMe 2 ][B(C 6 F 5 ) 4 ] with the multiple metal centers of MOF catalysts might give a rational explanation for such controlled adjustment on the PIP's structure and properties. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. MnFe/Al2O3 Catalyst Synthesized by Deposition Precipitation for Low-Temperature Selective Catalytic Reduction of NO with NH3

    DEFF Research Database (Denmark)

    Schill, Leonhard; Putluru, Siva Sankar Reddy; Jensen, Anker Degn


    to a gas containing 20 vol% H2O at temperatures between 140 and 200 A degrees C and compared to an industrial V2O5-WO3/TiO2 catalyst tested at 220 °C. Both homemade catalysts were severely inhibited by 20 vol% H2O. However, used at 180 °C they match the activity of the industrial reference at 220 °C.......Mn-Fe/Al2O3 and Mn-Fe/TiO2 catalysts have been prepared by impregnation (IMP) and deposition precipitation (DP) and characterized with several techniques including: XRDP, N2-physisorption, NH3-TPD, H2-TPR, TGA and XPS. 40 wt% Mn0.75Fe0.25/Al2O3 prepared with ammonia carbamate as precipitating agent...... showed the same superior low temperature selective catalytic reduction of NO with NH3 as did 25 wt% Mn0.75Fe0.25/TiO2 prepared in the same way. Both catalysts were much more active when prepared by DP instead of IMP. 25 wt% Mn0.75Fe0.25/TiO2 and 40 wt% Mn0.75Fe0.25/Al2O3 prepared by DP were exposed...

  15. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

    International Nuclear Information System (INIS)

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo


    Highlights: • Nano-ceria was successfully encapsulated into MIL-100(Fe) for the SCR of NO x . • The incorporated ceria in MIL-100(Fe) showed high content of chemisorbed oxygen. • The added ceria into MIL-100(Fe) improved the formation of adsorbed NO 2 species. • The addition of ceria into MIL-100(Fe) enhanced SCR activity at low temperature. - Abstract: The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO 2 and H 2 O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO 2 /MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NO x conversion ranges from 196 to 300 °C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO 2 species responsible for fast SCR reactions.

  16. The Poisoning Effect of Na Doping over Mn-Ce/TiO2 Catalyst for Low-Temperature Selective Catalytic Reduction of NO by NH3

    Directory of Open Access Journals (Sweden)

    Liu Yang


    Full Text Available Sodium carbonate (Na2CO3, sodium nitrate (NaNO3, and sodium chloride (NaCl were chosen as the precursors to prepare the Na salts deposited Mn-Ce/TiO2 catalysts through an impregnation method. The influence of Na on the performance of the Mn-Ce/TiO2 catalyst for low-temperature selective catalytic reduction of NOx by NH3 was investigated. Experimental results showed that Na salts had negative effects on the activity of Mn-Ce/TiO2 and the precursors of Na salts also affected the catalytic activity. The precursor Na2CO3 had a greater impact on the catalytic activity, while NaNO3 had minimal effect. The characterization results indicated that the significant changes in physical and chemical properties of Mn-Ce/TiO2 were observed after Na was doped on the catalysts. The significant decreases in surface areas and NH3 adsorption amounts were observed after Na was doped on the catalysts, which could be considered as the main reasons for the deactivation of Na deposited Mn-Ce/TiO2.

  17. Stable acetate production in extreme-thermophilic (70°C) mixed culture fermentation by selective enrichment of hydrogenotrophic methanogens (United States)

    Zhang, Fang; Zhang, Yan; Ding, Jing; Dai, Kun; van Loosdrecht, Mark C. M.; Zeng, Raymond J.


    The control of metabolite production is difficult in mixed culture fermentation. This is particularly related to hydrogen inhibition. In this work, hydrogenotrophic methanogens were selectively enriched to reduce the hydrogen partial pressure and to realize efficient acetate production in extreme-thermophilic (70°C) mixed culture fermentation. The continuous stirred tank reactor (CSTR) was stable operated during 100 days, in which acetate accounted for more than 90% of metabolites in liquid solutions. The yields of acetate, methane and biomass in CSTR were 1.5 +/- 0.06, 1.0 +/- 0.13 and 0.4 +/- 0.05 mol/mol glucose, respectively, close to the theoretical expected values. The CSTR effluent was stable and no further conversion occurred when incubated for 14 days in a batch reactor. In fed-batch experiments, acetate could be produced up to 34.4 g/L, significantly higher than observed in common hydrogen producing fermentations. Acetate also accounted for more than 90% of soluble products formed in these fed-batch fermentations. The microbial community analysis revealed hydrogenotrophic methanogens (mainly Methanothermobacter thermautotrophicus and Methanobacterium thermoaggregans) as 98% of Archaea, confirming that high temperature will select hydrogenotrophic methanogens over aceticlastic methanogens effectively. This work demonstrated a potential application to effectively produce acetate as a value chemical and methane as an energy gas together via mixed culture fermentation.

  18. Microfluidic preparation of a highly active and stable catalyst by high performance of encapsulation of polyvinylpyrrolidone (PVP)-Pt nanoparticles in microcapsules. (United States)

    Nam, Jin-Oh; Kim, Jongmin; Jin, Si Hyung; Chung, Young-Min; Lee, Chang-Soo


    The encapsulation of active metals in microcapsules would be highly advantageous in maintaining or improving the reaction performance of an array of widely used chemical reactions. However, conventional methods suffer from low uniformity, complicated fabrication steps, sintering, leaching, decline of catalytic activity, and/or poor reusability. Here, we report an efficient microfluidic approach to encapsulate Pt nanoparticle stabilized by polyvinylpyrrolidone (PVP) in photocurable double-emulsion droplets with semipermeable thin shells. The encapsulated catalysts are prepared by the in situ photopolymerization of a double emulsion. The rapid and exquisite microfluidics-based fabrication process successfully generates monodisperse microcapsules without loss of the PVP-Pt nanoparticles, which is the first demonstration of the microfluidic encapsulation of active metal with promising catalytic activity. Specifically, compared to quasi-homogeneous catalysis of PVP-Pt nanoparticles for 4-nitrophenol hydrogenation, the encapsulated PVP-Pt nanoparticles demonstrate excellent catalytic activity, a leaching-proof nature, and high reusability under the same reaction conditions. We envision that the approach described here may be an example of elegant catalyst design to efficiently overcome difficult problems in active-metal encapsulation and to dramatically enhance catalytic activity by taking advantage of the unique aspects of microfluidic methods. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Methyl Esters Selectivity of Transesterification Reaction with Homogenous Alkaline Catalyst to Produce Biodiesel in Batch, Plug Flow, and Continuous Stirred Tank Reactors

    Directory of Open Access Journals (Sweden)

    N. F. Nasir


    Full Text Available Selectivity concept is essential in establishing the best operating conditions for attaining maximum production of the desired product. For complex reaction such as biodiesel fuel synthesis, kinetic studies of transesterification reaction have revealed the mechanism of the reaction and rate constants. The objectives of this research are to develop the kinetic parameters for determination of methyl esters and glycerol selectivity, evaluate the significance of the reverse reaction in transesterification reaction, and examine the influence of reaction characteristics (reaction temperature, methanol to oil molar ratio, and the amount of catalyst on selectivity. For this study, published reaction rate constants of transesterification reaction were used to develop mathematical expressions for selectivities. In order to examine the base case and reversible transesterification, two calculation schemes (Case  1 and Case  2 were established. An enhanced selectivity was found in the base case of transesterification reaction. The selectivity was greatly improved at optimum reaction temperature (60°C, molar ratio (9 : 1, catalyst concentration (1.5 wt.%, and low free fatty acid feedstock. Further research might explore the application of selectivity for specifying reactor configurations.

  20. Toward Annealing-Stable Molybdenum-Oxide-Based Hole-Selective Contacts For Silicon Photovoltaics

    KAUST Repository

    Essig, Stephanie


    Molybdenum oxide (MoOX) combines a high work function with broadband optical transparency. Sandwiched between a hydrogenated intrinsic amorphous silicon passivation layer and a transparent conductive oxide, this material allows a highly efficient hole-selective front contact stack for crystalline silicon solar cells. However, hole extraction from the Si wafer and transport through this stack degrades upon annealing at 190 °C, which is needed to cure the screen-printed Ag metallization applied to typical Si solar cells. Here, we show that effusion of hydrogen from the adjacent layers is a likely cause for this degradation, highlighting the need for hydrogen-lean passivation layers when using such metal-oxide-based carrier-selective contacts. Pre-MoOX-deposition annealing of the passivating a-Si:H layer is shown to be a straightforward approach to manufacturing MoOX-based devices with high fill factors using screen-printed metallization cured at 190 °C.

  1. A novel metamaterial filter with stable passband performance based on frequency selective surface

    Directory of Open Access Journals (Sweden)

    C. Y. Fang


    Full Text Available In this paper, a novel metamaterial filter based on frequency selective surface (FSS is proposed. Using the mode matching method, we theoretically studied the transmission performance of the structure. Results show that, by rotating its neighboring elements 90 degree, the novel filter has a better stability to angle of incidence than traditional structures for TE and TM polarization. As the incident angles vary from 0 to 50 degrees, the metamaterial filter exhibits a transmittance higher than 0.98 and the center frequency slightly shifts downward (from 10 GHz to 0.96 GHz for TE polarization. For TM polarization, a transmittance of 0.98 is achieved and the center frequency retains 0.96 GHz with the varying of the incident angles. Furthermore, an experimental prototype fabricated was tested in a microwave chamber, and the measured results show good agreement with the simulated ones.

  2. Carbon dioxide selective adsorption within a highly stable mixed-ligand Zeolitic Imidazolate Framework

    KAUST Repository

    Huang, Lin


    A new mixed-ligand Zeolitic Imidazolate Framework Zn4(2-mbIm) 3(bIm)5·4H2O (named JUC-160, 2-mbIm = 2-methylbenzimidazole, bIm = benzimidazole and JUC = Jilin University China) was synthesized with a solvothermal reaction of Zn(NO3) 2·6H2O, bIm and 2-mbIm in DMF solution at 180 °C. Topological analysis indicated that JUC-160 has a zeolite GIS (gismondine) topology. Study of the gas adsorption and thermal and chemical stability of JUC-160 demonstrated its selective adsorption property for carbon dioxide, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvent for up to one week. © 2014 Elsevier B.V.

  3. A New Dynamic Injection System of Urea-Water Solution for a Vehicular Select Catalyst Reduction System

    Directory of Open Access Journals (Sweden)

    Long Li


    Full Text Available Since the Euro-ІІІ standard was adopted, the main methods to inhibit NOx production in diesel engines are exhaust gas recirculation (EGR and select catalyst reduction (SCR. On these methods SCR offers great fuel economy, so it has received wide attention. However, there also exists a trade-off law between NOx conversion efficiency and NH3 slip under dynamic conditions. To inhibit NH3 slip with high NOx conversion efficiency, a dynamic control method for a urea water solution (UWS injection was investigated. The variation phenomena of SCR conversion efficiency with respect to the cross-sensitivity characteristics of the NOx sensor to NH3 have been thoroughly analyzed. The methodology of “uncertain conversion efficiency curve tangent analysis” has been applied to estimate the concentration of the slipped NH3. The correction factor “φ” of UWS injection is obtained by a comparative calculation of the NOx conversion ability and subsequent NH3 slip. It also includes methods of flow compensation and flow reduction. The proposed control method has been authenticated under dynamic conditions. In low frequency dynamic experiments, this control method has accurately justified the NH3 slip process and inhibits the NH3 emission to a lower level thereby improving the conversion efficiency to a value closer to the target value. The results of European transient cycle (ETC experiments indicate that NH3 emissions are reduced by 90.8% and the emission level of NOx is close to the Euro-Ѵ standard.

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

    KAUST Repository

    Al-ShaikhAli, Anaam H.


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

  5. Structure-property relationship of bifunctional MnO2 nanostructures: highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media. (United States)

    Meng, Yongtao; Song, Wenqiao; Huang, Hui; Ren, Zheng; Chen, Sheng-Yu; Suib, Steven L


    Manganese oxides of various structures (α-, β-, and δ-MnO2 and amorphous) were synthesized by facile methods. The electrocatalytic properties of these materials were systematically investigated for catalyzing both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in alkaline media. Extensive characterization was correlated with the activity study by investigating the crystal structures (XRD, HRTEM), morphologies (SEM), porosities (BET), surfaces (XPS, O2-TPD/MS), and electrochemical properties (Tafel analysis, Koutechy-Levich plots, and constant-current electrolysis). These combined results show that the electrocatalytic activities are strongly dependent on the crystallographic structures, and follow an order of α-MnO2 > AMO > β-MnO2 > δ-MnO2. Both OER studies and ORR studies reveal similar structure-determined activity trends in alkaline media. In the OER studies, α-MnO2 displays an overpotential of 490 mV compared to 380 mV shown by an Ir/C catalyst in reaching 10 mA cm(-2). Meanwhile, α-MnO2 also exhibits stability for 3 h when supplying a constant current density of 5 mA cm(-2). This was further improved by adding Ni(2+) dopants (ca. 8 h). The superior OER activity was attributed to several factors, including abundant di-μ-oxo bridges existing in α-MnO2 as the protonation sites, analogous to the OEC in PS-II of the natural water oxidation system; the mixed valencies (AOS = 3.7); and the lowest charge transfer resistances (91.8 Ω, η = 430 mV) as revealed from in situ electrochemical impedance spectroscopy (EIS). In the ORR studies, when reaching 3 mA cm(-2), α-MnO2 shows 760 mV close to 860 mV for the best ORR catalyst (20% Pt/C). The outstanding ORR activity was due to the strongest O2 adsorption capability of α-MnO2 suggested by temperature-programmed desorption. As a result, this discovery of the structure-related electrocatalytic activities could provide guidance in the further development of easily prepared, scalable, and low

  6. Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production

    Energy Technology Data Exchange (ETDEWEB)

    Volli, Vikranth; Purkait, M.K., E-mail:


    Highlights: • Flyash was utilized for zeolites preparation for transesterification. • Single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio of 1:1.2. • Si/Al ratio of 2 resulted in the formation of zeolite X. • At 5 wt% of catalyst loading conversion was 84.6%. • The biodiesel obtained has a calorific value of 37.5 MJ/Kg. - Abstract: This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12 h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity.

  7. A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds. (United States)

    Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M


    The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

  8. Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water (United States)

    Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong


    Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction. PMID:27328834

  9. Use of Maximum Likelihood-Mixed Models to select stable reference genes: a case of heat stress response in sheep

    Directory of Open Access Journals (Sweden)

    Salces Judit


    Full Text Available Abstract Background Reference genes with stable expression are required to normalize expression differences of target genes in qPCR experiments. Several procedures and companion software have been proposed to find the most stable genes. Model based procedures are attractive because they provide a solid statistical framework. NormFinder, a widely used software, uses a model based method. The pairwise comparison procedure implemented in GeNorm is a simpler procedure but one of the most extensively used. In the present work a statistical approach based in Maximum Likelihood estimation under mixed models was tested and compared with NormFinder and geNorm softwares. Sixteen candidate genes were tested in whole blood samples from control and heat stressed sheep. Results A model including gene and treatment as fixed effects, sample (animal, gene by treatment, gene by sample and treatment by sample interactions as random effects with heteroskedastic residual variance in gene by treatment levels was selected using goodness of fit and predictive ability criteria among a variety of models. Mean Square Error obtained under the selected model was used as indicator of gene expression stability. Genes top and bottom ranked by the three approaches were similar; however, notable differences for the best pair of genes selected for each method and the remaining genes of the rankings were shown. Differences among the expression values of normalized targets for each statistical approach were also found. Conclusions Optimal statistical properties of Maximum Likelihood estimation joined to mixed model flexibility allow for more accurate estimation of expression stability of genes under many different situations. Accurate selection of reference genes has a direct impact over the normalized expression values of a given target gene. This may be critical when the aim of the study is to compare expression rate differences among samples under different environmental

  10. Unexpected effect of catalyst concentration on photochemical CO2reduction bytrans(Cl)-Ru(bpy)(CO)2Cl2: new mechanistic insight into the CO/HCOO-selectivity. (United States)

    Kuramochi, Yusuke; Itabashi, Jun; Fukaya, Kyohei; Enomoto, Akito; Yoshida, Makoto; Ishida, Hitoshi


    Photochemical CO 2 reduction catalysed by trans (Cl)-Ru(bpy)(CO) 2 Cl 2 (bpy = 2,2'-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO - ) in N , N -dimethylacetamide (DMA)/water containing [Ru(bpy) 3 ] 2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO - ) in the photochemical CO 2 reduction: the ratio of CO/HCOO - decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO - is selectively produced by the formation of a Ru(i)-Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru-Ru bond dissociates in the reaction of the dimer with CO 2 , and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO - . The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO - in the photochemical CO 2 reduction catalysed by [Ru(bpy)(CO) 2 Cl] 2 (0.05 mM) are very similar to those of the reduction catalysed by trans (Cl)-Ru(bpy)(CO) 2 Cl 2 (0.10 mM), and that HCOO - formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO 2 reduction using [Ru(4dmbpy) 3 ] 2+ (4dmbpy = 4,4'-dimethyl-2,2'-bipyridine) instead of [Ru(bpy) 3 ] 2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy) 3 ] 2+ by BNAH than that of excited [Ru(bpy) 3 ] 2+ . We have further synthesized trans (Cl)-Ru(6Mes-bpy)(CO) 2 Cl 2 (6Mes-bpy = 6,6'-dimesityl-2,2'-bipyridine), which bears bulky substituents at the 6,6'-positions in the 2,2'-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the

  11. Pt/YSZ electrochemical catalysts prepared by electrostatic spray deposition for selective catalytic reduction of NO by C{sub 3}H{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Lintanf, A.; Djurado, E. [Laboratoire d' Electrochimie et de Physico-Chimie des Materiaux et des Interfaces (LEPMI), ENSEEG/INPG/UJF/CNRS Institut National Polytechnique de Grenoble Domaine Universitaire, BP 75, 1130 rue de la Piscine, 38402 St Martin d' Heres Cedex (France); Vernoux, P. [Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon, UMR 5256, CNRS, Universite Claude Bernard Lyon 1, 2 avenue A. Einstein, 69626 Villeurbanne (France)


    Due to the great importance of automotive exhaust gas treatment, the catalytic activity was investigated in selective catalytic reduction of NO by propene on Pt films - with controlled microstructure - deposited on YSZ (8 mol% Y{sub 2}O{sub 3}-doped ZrO{sub 2}) by electrostatic spray deposition. This technique requires low Pt loadings in order to reduce costs and also to achieve high Pt particles dispersion with good reproducibility. This kind of electrochemical catalysts was found to be effective for NO reduction by propene in the presence of oxygen. A dense Pt film was found to be the most suitable. Furthermore, we have demonstrated that these electrochemical catalysts can implement the concept of electrochemical promotion of catalysis (EPOC). (author)

  12. Fe–Co/sulfonated polystyrene as an efficient and selective catalyst in heterogeneous Baeyer–Villiger oxidation reaction of cyclic ketones

    Directory of Open Access Journals (Sweden)

    Yingting Wang


    Full Text Available A highly efficient catalyst Fe–Co/sulfonated polystyrene (Fe–Co/SPS was introduced and synthesized, which catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield and selectivity. Solid acid catalyst of Fe–Co/SPS has been prepared by using the 98-wt% sulfuric acid as the sulfonating agent and CoCl2 combined FeCl3 as sources of metal ions. Various physical–chemical characterizations including FT-IR, XRD, SEM and TGA, revealed that bimetallic ions Fe3+–Co2+ species in the sulfonated polystyrene framework were responsible for the catalytic activities. The BV reaction catalyzed by Fe–Co/SPS highlighted the special effects between metal ions and protonic acids as well as solvent-free heterogeneous catalytic oxidation with excellent conversion.

  13. Fischer-Tropsch synthesis over cobalt catalysts supported on mesoporous metallo-silicates

    Energy Technology Data Exchange (ETDEWEB)

    Kiyomi Okabe; Mingdeng Wei; Hironori Arakawa [National Institute of Advanced Industrial Science and Technology (AIST), Ibaraki (Japan)


    Fischer-Tropsch synthesis was carried out in slurry phase over cobalt-based catalysts supported on mesoporous metallo-silicates prepared by the rapid room-temperature synthesis method. The incorporation of Al and Ti into the silica framework was confirmed by NMR, FT-IR, and UV. Although the catalyst supported on mesoporous silica (MPS) was deactivated during the reaction, the catalysts supported on mesoporous Al- and Ti-silicates (MPAS and MPTS) showed high and stable activity. The selectivity for higher hydrocarbons ({alpha}) increased with the amount of tetrahedral Al incorporated into the silica framework. 26 refs., 11 figs., 3 tabs.

  14. Highly stable aptamers selected from a 2'-fully modified fGmH RNA library for targeting biomaterials. (United States)

    Friedman, Adam D; Kim, Dongwook; Liu, Rihe


    When developed as targeting ligands for the in vivo delivery of biomaterials to biological systems, RNA aptamers immediately face numerous obstacles, in particular nuclease degradation and post-selection 2' modification. This study aims to develop a novel class of highly stable, 2'-fully modified RNA aptamers that are ideal for the targeted delivery of biomaterials. We demonstrated the facile transcription of a fGmH (2'-F-dG, 2'-OMe-dA/dC/dU) RNA library with unexpected hydrophobicity, the direct selection of aptamers from a fGmH RNA library that bind Staphylococcus aureus Protein A (SpA) as a model target, and the superior nuclease and serum stability of these aptamers compared to 2'-partially modified RNA variants. Characterizations of fGmH RNA aptamers binding to purified SpA and to endogenous SpA present on the surface of S. aureus cells demonstrate fGmH RNA aptamer selectivity and stability. Significantly, fGmH RNA aptamers were able to functionalize, stabilize, and specifically deliver aggregation-prone silver nanoparticles (AgNPs) to S. aureus with SpA-dependent antimicrobial effects. This study describes a novel aptamer class with considerable potential to improve the in vivo applicability of nucleic acid-based affinity molecules to biomaterials.

  15. Highly Selective and Stable Reduction of CO2 to CO by a Graphitic Carbon Nitride/Carbon Nanotube Composite Electrocatalyst. (United States)

    Lu, Xunyu; Tan, Tze Hao; Ng, Yun Hau; Amal, Rose


    A stable and selective electrocatalyst for CO2 reduction was fabricated by covalently attaching graphitic carbon nitride onto multiwall carbon nanotubes (g-C3 N4 /MWCNTs). The as-prepared composite is able to reduce CO2 exclusively to CO with a maximum Faraday efficiency of 60 %, and no decay in the catalytic activity was observed even after 50 h of reaction. The enhanced catalytic activity towards CO2 reduction is attributed to the formation of active carbon-nitrogen bonds, high specific surface area, and improved material conductivity of the g-C3 N4 /MWCNT composite. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A tailored catalyst for the sustainable conversion of glycerol to acrolein: mechanistic aspect of sequential dehydration. (United States)

    Yun, Danim; Kim, Tae Yong; Park, Dae Sung; Yun, Yang Sik; Han, Jeong Woo; Yi, Jongheop


    Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. An open-macropore-structured and Brønsted-acidic catalyst (Marigold-like silica functionalized with sulfonic acid groups, MS-FS) was synthesized for the stable and selective production of acrolein from glycerol. A high acrolein yield of 73% was achieved and maintained for 50 h in the presence of the MS-FS catalyst. The hierarchical structure of the catalyst with macropores was found to have an important effect on the stability of the catalyst because coke polymerization and pore blocking caused by coke deposition were inhibited. In addition, the behavior of 3-hydroxypropionaldehyde (3-HPA) during the sequential dehydration was studied using density functional theory (DFT) calculations because 3-HPA conversion is one of the main causes for coke formation. We found that the easily reproducible Brønsted acid sites in MS-FS permit the selective and stable production of acrolein. This is because the reactive intermediate (3-HPA) is readily adsorbed on the regenerated acid sites, which is essential for the selective production of acrolein during the sequential dehydration. The regeneration ability of the acid sites is related not only to the selective production of acrolein but also to the retardation of catalyst deactivation by suppressing the formation of coke precursors originating from 3-HPA degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Selective aerobic oxidation of 5-(hydroxymethyl)furfural to 2,5-diformylfuran or 2-formyl-5-furancarboxylic acid in water using MgO·CeO2 mixed oxides as catalysts. (United States)

    Dibenedetto, Angela; Ventura, Maria; Lobefaro, Francesco; de Giglio, Elvira; Distaso, Monica; Nocito, Francesco


    Mixed oxides based on MgO·CeO2 were used, as efficient catalysts, in the aerobic oxidation of 5-(hydroxymethyl)furfural (5-HMF) to afford, with very high selectivity, either 2,5-diformylfuran (DFF, 99%) or 2-formyl-5-furancarboxylic acid (FFCA, 90%) depending on the reaction conditions. 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA, 57-90%) was formed only at low concentration of 5-HMF (catalysts gave important information about their acid-base properties, which drive the selectivity of the reaction towards DFF. FFCA was formed from DFF for longer reaction times. Catalysts were studied by XPS and XRD before and after catalytic runs to identify the reason why they undergo reversible deactivation. XRD has clearly shown that MgO is hydrated to Mg(OH)2 which, even if not leached out, changes the basic properties of the catalyst that becomes less active after some time. Calcination of the recovered catalyst allows recovering their initial activity. The catalyst is, thus, recoverable (>99%) and reusable. The use of mixed oxides allows tune the basicity of catalysts, avoiding external bases for efficient and selective conversion of 5-HMF and waste formation, resulting in an environmentally friendly, sustainable process. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders


    (FDA), a possible plastics precursor. The novel catalyst systems were characterized by nitrogen physisorption, XRPD, TEM and EDS analysis, and applied for the oxidation with no added base at moderate to high pressures of dioxygen and elevated temperatures. The effects of support, temperature...... and oxidant pressure were studied and optimized to allow a quantitative yield of FDA to be obtained....

  19. Bismuth molybdate catalysts prepared by mild hydrothermal synthesis: Influence of pH on the selective oxidation of propylene

    DEFF Research Database (Denmark)

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin


    A series of bismuth molybdate catalysts with relatively high surface area was prepared via mild hydrothermal synthesis. Variation of the pH value and Bi/Mo ratio during the synthesis allowed tuning of the crystalline Bi-Mo oxide phases, as determined by X-ray diffraction (XRD) and Raman spectrosc...

  20. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides

    NARCIS (Netherlands)

    Hereijgers, B.P.C.; Weckhuysen, B.M.


    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with

  1. Spatial Distribution of Zeolite ZSM-5 within Catalyst Bodies Affects Selectivity and Stability of Methanol-to-Hydrocarbons Conversion

    NARCIS (Netherlands)

    Castaño, P.; Ruiz-Martinez, J.; Epelde, E.; Gayubo, A.G.; Weckhuysen, B.M.


    Solid acids, such as zeolites, are used as catalyst materials in a wide variety of important crude oil refinery, bulk chemical synthesis, and green processes. Examples include fluid catalytic cracking (FCC),[1] methanol-to-hydrocarbons (MTH) conversion,[ 2] plastic waste valorization,[3] and biomass

  2. Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction. (United States)

    Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding


    A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Biomass gasification with air in fluidized bed. Hot gas cleanup with selected commercial and full-size nickel-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Caballero, M.A.; Corella, J.; Aznar, M.P.; Gil, J.


    Three selected commercial, full-size steam-reforming catalysts for naphthas, BASF G1-50, ICI 46-1, and Topsoee R-67, are tested at pilot-scale level for hot gas cleanup in biomass gasification in a fluidized bed. Gas composition and tar content in the flue gas are measured before and after the catalytic bed. Variations of the catalytic bed in H{sub 2}, CO, CO{sub 2}, CH{sub 4}, and H{sub 2}O contents are reported for different operating conditions. Tar conversions and an apparent first-order kinetics constant for the overall tar removal reaction are calculated. Tar contents at the exit of the catalytic reactor as low as 10 mg/m{sub n}{sup 3} are obtained in a test of 50 h-on-stream without noticeable catalyst deactivation. Important variations in tar conversion with space time in the catalytic bed, with H{sub 2}O/C* in the flue gas, and with the equivalence ratio in the upstream gasifier are observed. These results obtained at the pilot-scale level and with the use of full-sized commercial catalysts are an important forward step in demonstrating the technical feasibility of the overall biomass gasification process.

  4. Selective catalytic reduction of nitric oxide with carbon monoxide over alumina-pellet-supported catalysts in the presence of excess oxygen. (United States)

    Liu, Kaijie; Yu, Qingbo; Qin, Qin; Wang, Chunpeng


    Selective catalytic reduction of nitrogen oxides with carbon monoxide (CO-SCR) is a promising technology to remove NO x and CO simultaneously from flue gas. The thermodynamic analyses of catalytic process were performed toward four kinds of active metal oxides (Cu x O y , Co x O y , Mn x O y and Ce x O y ). According to the standard Gibbs free-energy changes calculated, Mn had better resistance to oxygen than Cu, Co and Ce, while Cu and Ce had better resistance to water vapor poisoning, as active metals. Then, a series of binary- and ternary-preformed catalysts with different metal ratios were prepared by the impregnation method using Al 2 O 3 pellets as support and tested in excess oxygen (16 vol%) atmosphere with or without SO 2 . The results of experiment were analyzed based on thermodynamic analyses. Results indicated that the NO conversions of Cu-Co/Al 2 O 3 catalysts increased with the rise of reaction temperature; however, the tendency changed at 160°C for Cu-Mn/Al 2 O 3 . Besides, the NO conversions of Cu-Mn/Al 2 O 3 were better than Cu-Co/Al 2 O 3 . The catalysts with the metal ratio of 1.5 had the best denitrification performance. Among various binary catalysts, Cu-Mn/Al 2 O 3 with the metal ratio Cu:Mn of 1.5 showed promising activity for CO-SCR, giving nearly 90% NO conversion. Besides, the doping of Ce could inhibit the sulfur poisoning and promote the oxide of CO under experimental conditions.

  5. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard


    on titania (V2O5-WO3/TiO2) as the example catalyst. The main photocatalysts examined for mineralization of organic compounds were TiO2 and MoS2. It is important to obtain insight into the catalyst structure-to-activity relationship in order to understand and locate the active site(s). In this chapter......The properties of catalysts used in environmental remediation are described here through specific examples in heterogeneous catalysis and photocatalysis. In the area of heterogeneous catalysis, selective catalytic reduction (SCR) of NOx was used as an example reaction with vanadia and tungsta...

  6. Impact of SCILL catalysts for the S-S coupling of thiols to disulfides. (United States)

    Pavel, Octavian D; Podolean, Iunia; Parvulescu, Vasile I; Taylor, S F Rebecca; Manyar, Haresh G; Ralphs, Kathryn; Goodrich, Peter; Hardacre, Christopher


    This study reports the behaviour of SCILL based catalysts in the oxidative S-S coupling of aliphatic and aromatic thiols, namely 1-butanethiol and thiophenol, to dibutyl disulfide and diphenyl disulfide. A range of ionic liquids (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide) and metal supported catalysts (5% Pt/SiO 2 ; 5% Ru/SiO 2 ; 5% Ru/C; 5% Pt/OMS-2) were used to prepare the SCILL catalysts and all were found to be active for the reaction following the trend 5% Pt-OMS-2 > 5% Pt/SiO 2 > 5% Ru/C > 5% Ru/SiO 2 . The presence of SCILL catalysts afforded high selectivity to the disulfide, and the activity of the SCILL catalyst was dependent on the ionic liquid used. A significant increase in the stability of all the supported metal catalysts was found in the presence of the ionic liquid, and there was no change in the selectivity towards disulfides. This demonstrated that the ionic liquids protect the active sites of the catalyst against sulfation, thus providing more stable and active catalysts.

  7. Synthesis of novel macrocycles carrying pincer-type ligands as future candidates for potential applications in size-selective, stereochemical and recyclable catalysts (United States)

    Khan, Burhan; Shah, Muhammad Raza; Rabnawaz, Muhammad


    Macrocycles with ultra dense functionalities are very useful but are difficult to synthesize. In this study, we report six novel macrocycles bearing a pincer ligand alone or a combination of pincer-calixarenes, and pincer-fluorene moieties. Click chemistry was utilized to synthesize the desired macrocycles in good yields. These macrocycles were fully characterized using mass spectrometry (EI-MS, ESI-MS, and MALDI-TOF MS), and NMR spectroscopy. These macrocycles are under investigations as size-selective and recyclable catalysts for various chemical transformations.

  8. Selective and regular localization of accessible Pt nanoparticles inside the walls of an ordered silica: Application as a highly active and well-defined heterogeneous catalyst for propene and styrene hydrogenation reactions

    KAUST Repository

    Boualleg, Malika


    We describe here an original methodology related to the "build-the-bottle-around-the-ship" approach yielding a highly ordered silica matrix containing regularly distributed Pt nanoparticles (NPs) located inside the silica walls, Pt@{walls}SiO2. The starting colloidal solution of crystalline Pt nanoparticles was obtained from Pt(dba)2 (dba = dibenzylidene acetone) and 3-chloropropylsilane. The resulting nanoparticles (diameter: 2.0 ± 0.4 nm determined by HRTEM) resulted hydrophilic. The NPs present in the THF colloidal solution were incorporated inside the walls of a highly ordered 2D hexagonal mesoporous silica matrix via sol-gel process using a templating route with tetraethylorthosilicate, TEOS, as the silica source, and block copolymer (EthyleneOxide) 20(PropyleneOxide)70(EthyleneOxide)20 (Pluronic P123) as the structure-directing agent. Low-temperature calcination of the crude material at 593 K led to the final solid Pt@{walls}SiO2. Characterization by IR, HRTEM, BF-STEM and HAADF-STEM, SAXS, WAXS, XRD, XPS, H2 chemisorption, etc. of Pt@{walls}SiO2 confirmed the 2D hexagonal structuration and high mesoporosity (870 m2/g) of the material as well as the presence of stable 2-nm-sized crystalline Pt(0) NPs embedded inside the walls of the silica matrix. The material displayed no tendency to NPs sintering or leaching (Pt loading 0.3 wt.%) during its preparation. Pt@{walls}SiO2 was found to be a stable, selective and highly active hydrogenation catalyst. The catalytic performances in propene hydrogenation were tested under chemical regime conditions in a tubular flow reactor (278 K, propene/H2/He = 20/16/1.09 cm3/min, P tot = 1 bar) and were found superior to those of an homologous solid containing Pt NPs along its pore channels Pt@{pores}SiO2 and to those of a classical industrial catalysts Pt/Al2O3, (TOF = 2.3 s-1 vs. TOF = 0.90 and 0.92 s-1, respectively, calculated per surface platinum atoms). Pt@{walls}SiO2 also catalyzes fast and selective styrene

  9. In situ photoactivated plasmonic Ag{sub 3}PO{sub 4}@silver as a stable catalyst with enhanced photocatalytic activity under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Dongfang; Wang, Jiaxun, E-mail: [College of Science, Huazhong Agricultural University, Wuhan (China)


    Silver orthophosphate (Ag{sub 3}PO{sub 4}) had been reported as an excellent candidate to split water or decompose pollutants with high efficiency in visible light region, yet is not stable due to the reduction of silver ion. In this work, an easy-fabricated method (in situ photoinduced reduction) was provided to enhance the stability of Ag{sub 3}PO{sub 4} for its possible application as a visible-light sensitive photocatalyst. The as-prepared samples were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, photoluminescence spectra (PL) and Photoelectrochemical measurements. The Ag{sub 3}PO{sub 4}/Ag photocatalysts showed strong photocatalytic activity for decomposition of RhB dye or phenol-X-3B mixture under visible light irradiation (λ> 420 nm) and can be used repeatedly. The possible mechanism for the enhanced photocatalytic properties of the Ag{sub 3}PO{sub 4} /Ag hybrid was also discussed. It was found that •OH and holes take priority over •O{sub 2}{sup -} radicals in serving as the main oxidant in the Ag{sub 3}PO{sub 4}/Ag photocatalytic system. Especially, the experimental results indicate that the surface plasmon resonance of Ag nanoparticles and a large negative charge of PO{sub 4}{sup 3-} ions as well as high separation efficiency of {sup e-} --h{sup +} pairs, facilitated the enhancement of the photocatalytic activity of the Ag{sub 3} PO{sub 4} /Ag composite. The results indicated that Ag{sub 3} PO{sub 4} /Ag is an efficient and stable visible-light-driven photocatalyst. (author)

  10. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G


    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with

  11. Graphene-supported Pd catalyst for highly selective hydrogenation of resorcinol to 1, 3-cyclohexanedione through giant π-conjugate interactions (United States)

    Wei, Zuojun; Pan, Ruofei; Hou, Yaxin; Yang, Yao; Liu, Yingxin


    The selective hydrogenation of resorcinol (RES) to 1, 3-cyclohexanedione (1,3-CHD) without the addition of alkali is a big challenge. In this article, a novel reduced graphene oxide (rGO) supported Pd catalyst was prepared through co-reduction method, over which we obtained 99.9% of resorcinol conversion and 94.2% of the ever-reported highest 1,3-cyclohexanedione selectivity at 25 °C in only CH2Cl2 solvent. The excellent selectivity was contributed to the strong π-π and p-π interactions between the graphene nanosheet and the benzene ring as well as hydroxyl in RES molecule. The followed adsorption experiment and Raman analysis also showed the existence of aromatic graphite structures in rGO, which exhibited stronger adsorption towards RES than towards 1,3-CHD. PMID:26494123

  12. Graphene-supported Pd catalyst for highly selective hydrogenation of resorcinol to 1, 3-cyclohexanedione through giant π-conjugate interactions (United States)

    Wei, Zuojun; Pan, Ruofei; Hou, Yaxin; Yang, Yao; Liu, Yingxin


    The selective hydrogenation of resorcinol (RES) to 1, 3-cyclohexanedione (1,3-CHD) without the addition of alkali is a big challenge. In this article, a novel reduced graphene oxide (rGO) supported Pd catalyst was prepared through co-reduction method, over which we obtained 99.9% of resorcinol conversion and 94.2% of the ever-reported highest 1,3-cyclohexanedione selectivity at 25 °C in only CH2Cl2 solvent. The excellent selectivity was contributed to the strong π-π and p-π interactions between the graphene nanosheet and the benzene ring as well as hydroxyl in RES molecule. The followed adsorption experiment and Raman analysis also showed the existence of aromatic graphite structures in rGO, which exhibited stronger adsorption towards RES than towards 1,3-CHD.

  13. Hydrolytically Stable Luminescent Cationic Metal Organic Framework for Highly Sensitive and Selective Sensing of Chromate Anions in Natural Water Systems. (United States)

    Liu, Wei; Wang, Yanlong; Bai, Zhuanling; Li, Yuxiang; Wang, Yaxing; Chen, Lanhua; Xu, Lin; Diwu, Juan; Chai, Zhifang; Wang, Shuao


    Effective detection of chromate anions in aqueous solution is highly desirable because of their high solubility, environmental mobility, carcinogenicity, and bioaccumulation effect. A new strategy for precise detection of chromate anions in the presence of a large excess of other anions, such as Cl - , NO 3 - , and HCO 3 - , in drinking water and natural water systems remains a challenge. Herein, a hydrolytically stable cationic luminescent europium(III)-based metal organic framework (MOF), 1, was successfully synthesized and investigated as a luminescent sensor that exhibits instant and selective luminescence quenching properties toward chromate ions in aqueous solutions. Moreover, 1 can be introduced into high-ionic-strength water system (e.g., seawater) for chromate detection as a consequence of the excellent sensing selectivity. The real environmental application of 1 as a chromate probe is studied in deionized water, lake water, and seawater. The detection limits in these aqueous media are calculated to be 0.56, 2.88, and 1.75 ppb, respectively. All of these values are far below the maximum contamination standard of Cr(VI) in drinking water of 100 ppb, defined by the U.S. Environmental Protection Agency. This excellent chromate sensing capability originates from the fast enrichment of chromate ions in solids of 1 from solutions, followed by efficient energy transfer from the MOF skeleton to the chromate anion, as demonstrated by solution absorption spectroscopy, X-ray diffraction, and chromate uptake kinetics and isotherm investigations. To the best of our knowledge, 1 possesses the lowest chromate detection limit among all reported MOFs up to date and is the only MOF material reported for chromate sensing application under environmentally relevant conditions with high ionic strengths.

  14. Selective extinction of marine plankton at the end of the Mesozoic era: The fossil and stable isotope record (United States)

    Herman, Y.; Bhattacharya, S. K.


    Floral, faunal and stable isotope evidence in a continuous sequence of latest Cretaceous and earliest Tertiary shallow water marine deposits in the Mangyshlak Peninsula, USSR suggest severe environmental changes at the Cretaceous/Tertiary (K/T) boundary. Time frame is provided by nanno, micro and macrofossils as well as by magnetic stratigraphy and an iridium spike. Oxygen isotopic analyses of the bulk sediments, composed of nanno and microplankton skeletal remains, show a sharp positive spike at the K/T boundary. This shift is primarily attributed to severe cooling possibly accompanied by increased salinities of the surface mixed layer. Floral and faunal extinctions were selective, affecting approximately 90 percent of the warm water calcareous phyto and zooplankton genera in the Tethyan-Paratethyan regions. These highly diverse taxa with many endemic representatives were at the peak of their evolutionary development. Geologic evidence indicates that the terminal Cretaceous temperature decline was coeval with widespread and intense volcanic activity which reached a peak at the close of the Mesozoic Era. Increased acidity temporarily prohibited calcite nucleation of the surface dwelling warm-water plankton. Superimposed upon decreased alkalinity, severe and rapid climatic changes caused the extinction of calcareous phyto and zooplankton.

  15. Tailored cationic palladium(II) compounds as catalysts for highly selective dimerization and polymerization of vinylic monomers: Synthetic and mechanistic aspects

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Z.; Sen, A. (Pennsylvania State Univ., University Park (United States))


    The electrophilic palladium(II)compounds Pd(2,6-di-tert-butylpyridine)[sub 2](CH[sub 3]NO[sub 2])[sub 2](BF[sub 4])[sub 2] (1), Pd(PPh[sub 3])[sub 2](BF[sub 4])[sub 2] (2), and Pd(Ph[sub 2]PCH[sub 2]CH[sub 2]PPh[sub 2])(BF[sub 4])[sub 2] (3) were found to be highly selective catalysts for the acyclic dimerization of vinyl monomers (styrene, ethylene, and propylene) and the linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. One manifestation of the high selectivity was the ability to catalyze the dimerization of ethylene in the presence of propylene and styrene in the presence of [alpha]-methylstyrene even though the second member of each pair was normally significantly more reactive in reactions involving carbocationic intermediates. The linear polymerization of p-divinylbenzene involved in step-growth mechanism. The synthesis of a telechelic polymer through cross-coupling between the terminal vinyl groups of linear poly(p-divinylbenzene) and the vinyl group of a functionalized styrene derivative was also achieved. The reaction rates for the linear dimerization of styrene and the linear polymerization of p-divinylbenzene were found to be first order in the monomer concentration and fractional order in the catalyst concentration. Mathematical modeling indicated that the fractional order in the catalyst concentration was due to preequilibria involving anion dissociation from the metal center, and actually, the catalytic species in the case of 2 was found to be the dication, Pd(PPh[sub 3])[sub 2][sup 2+]. 17 refs., 6 figs., 4 tabs.

  16. Mixed Alcohol Synthesis Catalyst Screening

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; White, James F.; Stevens, Don J.


    National Renewable Energy Laboratory (NREL) and Pacific Northwest National Laboratory (PNNL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. From the standpoint of producing C2+ alcohols as the major product, it appears that the rhodium catalyst is the best choice in terms of both selectivity and space-time yield (STY). However, unless the rhodium catalyst can be improved to provide minimally acceptable STYs for commercial operation, mixed alcohol synthesis will involve significant production of other liquid coproducts. The modified Fischer-Tropsch catalyst shows the most promise for providing both an acceptable selectivity to C2+ alcohols and total liquid STY. However, further optimization of the Fischer-Tropsch catalysts to improve selectivity to higher alcohols is highly desired. Selection of a preferred catalyst will likely entail a decision on the preferred coproduct slate. No other catalysts tested appear amenable to the significant improvements needed for acceptable STYs.

  17. Well-dispersed Ni nanoclusters on the surfaces of MFI nanosheets as highly efficient and selective catalyst for the hydrogenation of naphthalene to tetralin (United States)

    Gong, Pengyu; Li, Baoshan; Kong, Xianglong; Liu, Jianjun; Zuo, Shengli


    One of the challenges in material science has been to design and prepare highly efficient and selective catalysts for target reactions. Here we demonstrate a one-pot hydrothermal synthesis of hierarchical MFI nanosheets with nickel species chemically bonded on the outer surfaces. It turns out that the growth and morphologies of self-pillared MFI nanosheets are affected by Ni content, and the thickness of MFI nanosheets are determined to be 2.3 nm or 3.0 nm. Specially, the bonded Ni on the outer surfaces can effectively prevent adjacent nanosheets from forming new Sisbnd Osbnd Si bonds, and in conjunction with the self-pillared structure, can hamper complete collapse of Ni-MFI-NSs during calcination. In naphthalene hydrogenation, the separated Ni species are previously reduced to highly-dispersed metallic Ni nanoclusters with size below 1.6 nm, which are highly active for hydrogenation. And the hierarchical porosity of Ni-MFI-NSs significantly enhances the diffusion of substrates and the accessibility of active sites. As a result, Ni-MFI-NSs achieve 100% selectivity for tetralin and 84.9% conversion of naphthalene with Ni content of only 4.2 wt%. Furthermore, the gradually enlarged Ni nanoparticles cause the decline of catalytic activities of catalysts.

  18. Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s as high-efficiency catalysts for carbonyl-group transformation reactions. (United States)

    Qiu, Renhua; Xu, Xinhua; Peng, Lifeng; Zhao, Yalei; Li, Ningbo; Yin, Shuangfeng


    Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s [M(Cp)(2)][OSO(2)C(8)F(17)](2)⋅nH(2)O⋅THF (M = Zr (2 a⋅3 H(2)O⋅THF), M = Ti (2 b⋅2 H(2)O⋅THF)) were synthesized by the reaction of [M(Cp)(2)]Cl(2) (M = Zr (1 a), M = Ti (1 b)) with nBuLi and C(8)F(17)SO(3)H (2 equiv) or with C(8)F(17)SO(3)Ag (2 equiv). The hydrate numbers (n) of these complexes were variable, changing from 0 to 4 depending on conditions. In contrast to well-known metallocene triflates, these complexes suffered no change in open air for a year. thermogravimetry-differential scanning calorimetry (TG-DSC) analysis showed that 2 a and 2 b were thermally stable at 300 and 180 °C, respectively. These complexes exhibited unusually high solubility in polar organic solvents. Conductivity measurement showed that the complexes (2 a and 2 b) were ionic dissociation in CH(3)CN solution. X-ray analysis result confirmed 2 a⋅3 H(2)O⋅THF was a cationic organometallic Lewis acid. UV/Vis spectra showed a significant red shift due to the strong complex formation between 10-methylacridone and 2 a. Fluorescence spectra showed that the Lewis acidity of 2 a fell between those of Sc(3+) (λ(em)=474 nm) and Fe(3+) (λ(em)=478 nm). ESR spectra showed the Lewis acidity of 2 a (0.91 eV) was at the same level as that of Sc(3+) (1.00 eV) and Y(3+) (0.85 eV), while the Lewis acidity of 2 b (1.06 eV) was larger than that of Sc(3+) (1.00 eV) and Y(3+) (0.85 eV). They showed high catalytic ability in carbonyl-compound transformation reactions, such as the Mannich reaction, the Mukaiyama aldol reaction, allylation of aldehydes, the Friedel-Crafts acylation of alkyl aromatic ethers, and cyclotrimerization of ketones. Moreover, the complexes possessed good reusability. On account of their excellent catalytic efficiency, stability, and reusability, the complexes will find broad catalytic applications in organic synthesis. Copyright © 2012

  19. Computational Study of the Effect of Confinement within Microporous Structures on the Activity and Selectivity of Metallocene Catalysts for Ethylene Oligomerization

    KAUST Repository

    Toulhoat, Hervé


    The effect of confinement within some zeolitic structures on the activity and selectivity of metallocene catalysts for the ethylene oligomerization has been investigated using grand canonical Monte Carlo simulations (GCMC). The following zeolite (host) frameworks displaying different pore sizes, have been studied as solid hosts: mazzite (MAZ), AIPO-8 (AET), UTD-1F (DON), faujasite (FAU), and VPI-5 (VFI). Intermediates and transition states involved in the ethylene trimerization reaction catalyzed by a Ti-based catalyst [(η5-C5H4CMe2C6H 5)TiCl3/MAO] have been used as sorbates (guests). We have demonstrated linear correlations with slope aH,j between the adsorption enthalpy and the molecular volume Vm of the sorbates, each holding for a given microporous host below a host-specific threshold V mmax,j. Beyond this maximal molecular volume, the adsorption vanishes due to steric exclusion. aH,j increases, and Vmmax,j decreases with decreasing host pore size, in line with the confinement concept. We moreover showed that, in the limit of vanishing loading (Henry regime), the enthalpies and entropies of adsorption in a given host are linearly correlated. We have defined a host-specific confinement compensation temperature a j, which refers to a temperature where the stabilizing adsorption enthalpic interactions are canceled out against the loss in entropy. However, calculated aj are much larger than the operating temperatures. With a setup microkinetic model, we predict that the activity and selectivity of the confined Ti-catalyst in ethylene oligomerization can be significantly altered with respect to homogeneous phase conditions, since the adsorption free energies of transition states and intermediates also become functions of aH,j and Vm. We have applied this theory to predict the optimum host pore size to get maximum α-octene production, instead of α-hexene, which is primarily produced in the homogeneous phase. We also predict a significantly increased activity for

  20. Computational study of the effect of confinement within microporous structures on the activity and selectivity of metallocene catalysts for ethylene oligomerization. (United States)

    Toulhoat, Hervé; Fomena, Mireille Lontsi; de Bruin, Theodorus


    The effect of confinement within some zeolitic structures on the activity and selectivity of metallocene catalysts for the ethylene oligomerization has been investigated using grand canonical Monte Carlo simulations (GCMC). The following zeolite (host) frameworks displaying different pore sizes, have been studied as solid hosts: mazzite (MAZ), AIPO-8 (AET), UTD-1F (DON), faujasite (FAU), and VPI-5 (VFI). Intermediates and transition states involved in the ethylene trimerization reaction catalyzed by a Ti-based catalyst [(η(5)-C(5)H(4)CMe(2)C(6)H(5))TiCl(3)/MAO] have been used as sorbates (guests). We have demonstrated linear correlations with slope a(H,j) between the adsorption enthalpy and the molecular volume V(m) of the sorbates, each holding for a given microporous host below a host-specific threshold V(mmax,j). Beyond this maximal molecular volume, the adsorption vanishes due to steric exclusion. a(H,j) increases, and V(mmax,j) decreases with decreasing host pore size, in line with the confinement concept. We moreover showed that, in the limit of vanishing loading (Henry regime), the enthalpies and entropies of adsorption in a given host are linearly correlated. We have defined a host-specific confinement compensation temperature a(j), which refers to a temperature where the stabilizing adsorption enthalpic interactions are canceled out against the loss in entropy. However, calculated a(j) are much larger than the operating temperatures. With a setup microkinetic model, we predict that the activity and selectivity of the confined Ti-catalyst in ethylene oligomerization can be significantly altered with respect to homogeneous phase conditions, since the adsorption free energies of transition states and intermediates also become functions of a(H,j) and V(m). We have applied this theory to predict the optimum host pore size to get maximum α-octene production, instead of α-hexene, which is primarily produced in the homogeneous phase. We also predict a

  1. Epoxidation catalyst and process (United States)

    Linic, Suljo; Christopher, Phillip


    Disclosed herein is a catalytic method of converting alkenes to epoxides. This method generally includes reacting alkenes with oxygen in the presence of a specific silver catalyst under conditions suitable to produce a yield of the epoxides. The specific silver catalyst is a silver nanocrystal having a plurality of surface planes, a substantial portion of which is defined by Miller indices of (100). The reaction is performed by charging a suitable reactor with this silver catalyst and then feeding the reactants to the reactor under conditions to carry out the reaction. The reaction may be performed in batch, or as a continuous process that employs a recycle of any unreacted alkenes. The specific silver catalyst has unexpectedly high selectivity for epoxide products. Consequently, this general method (and its various embodiments) will result in extraordinarily high epoxide yields heretofore unattainable.

  2. Recyclable Earth-Abundant Metal Nanoparticle Catalysts for Selective Transfer Hydrogenation of Levulinic Acid to Produce γ-Valerolactone. (United States)

    Gowda, Ravikumar R; Chen, Eugene Y-X


    Nanoparticles (NPs) derived from earth-abundant metal(0) carbonyls catalyze conversion of bio-derived levulinic acid into γ-valerolactone in up to 93% isolated yield. This sustainable and green route uses non-precious metal catalysts and can be performed in aqueous or ethanol solution without using hydrogen gas as the hydrogen source. Generation of metal NPs using microwave irradiation greatly enhances the rate of the conversion, enables the use of ethanol as both solvent and hydrogen source without forming the undesired ethyl levulinate, and affords recyclable polymer-stabilized NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Gregory R.; Bell, Alexis T. (LBNL); (UCB)


    Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH4 and increase the selectivity toward C5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and

  4. Synthesis of CuNi/C and CuNi/γ-Al2O3 Catalysts for the Reverse Water Gas Shift Reaction

    Directory of Open Access Journals (Sweden)

    Maxime Lortie


    Full Text Available A new polyol synthesis method is described in which CuNi nanoparticles of different Cu/Ni atomic ratios were supported on both carbon and gamma-alumina and compared with Pt catalysts using the reverse water gas shift, RWGS, reaction. All catalysts were highly selective for CO formation. The concentration of CH4 was less than the detection limit. Cu was the most abundant metal on the CuNi alloy surfaces, as determined by X-ray photoelectron spectroscopy, XPS, measurements. Only one CuNi alloy catalyst, Cu50Ni50/C, appeared to be as thermally stable as the Pt/C catalysts. After three temperature cycles, from 400 to 700°C, the CO yield at 700°C obtained using the Cu50Ni50/C catalyst was comparable to that obtained using a Pt/C catalyst.

  5. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S.G.; Banks, R.L.


    A process is described for preparing a disproportionation catalyst comprising admixing a catalytically effective amount of a calcined and activated catalyst consisting essentially of at least one metal oxide selected from molybdenum oxide and tungsten oxide and a support containing a major proportion of silica or alumina with a promoting amount of a methylating agent selected from the group consisting of dimethyl sulfate, dimethylsulfoxide, trimethyloxonium tetrafluorborate, methyl iodide, and methyl bromide, and subjecting same to inert atmospheric conditions for the methylating agent to promote the activity of the calcined molybdenum and tungsten oxides for the disproportionation of olefins.

  6. Nano Catalysts for Diesel Engine Emission Remediation

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya Kumar [ORNL; Yang, Xiaofan [ORNL; Debusk, Melanie Moses [ORNL; Mullins, David R [ORNL; Mahurin, Shannon Mark [ORNL; Wu, Zili [ORNL


    conditions were provided by our collaborators at John Deere Power Systems. Among various zeolites reported here, CuFe-SSZ-13 offers the best NO{sub x} conversion activity in 150-650 C range and is hydrothermally stable when tested under accelerated aging conditions. It is important to note that Cu-SSZ-13 is now a commercial catalyst for NO{sub x} treatment on diesel passenger vehicles. Thus, our catalyst performs better than the commercial catalyst under fast SCR conditions. We initially focused on fast SCR tests to enable us to screen catalysts rapidly. Only the catalysts that exhibit high NO{sub x} conversion at low temperatures are selected for screening under varying NO{sub 2}:NO{sub x} ratio. The detailed tests of CuFe-SSZ-13 show that CuFe-SSZ-13 is more effective than commercial Cu-SSZ-13 even at NO{sub 2}:NO{sub x} ratio of 0.1. The mechanistic studies, employing stop-flow diffuse reflectance FTIR spectroscopy (DRIFTS), suggest that high concentration of NO{sup +}, generated by heterobimetallic zeolites, is probably responsible for their superior low temperature NO{sub x} activity. The results described in this report clearly show that we have successfully completed the first step in a new emission treatment catalyst which is synthesis and laboratory testing employing simulated exhaust. The next step in the catalyst development is engine testing. Efforts are in progress to obtain follow-on funding to carry out scale-up and engine testing to facilitate commercialization of this technology.

  7. Kinetic Study of Oxygen Adsorption over Nanosized Au/γ-Al2O3 Supported Catalysts under Selective CO Oxidation Conditions

    Directory of Open Access Journals (Sweden)

    George Karaiskakis


    Full Text Available O2 adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO on gold catalysts. Rate constants related to the elementary steps of O2 adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al2O3 catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC. The present study, carried-out in a wide temperature range (50–300 °C, both in excess as well as in the absence of H2, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H2, the rate of O2 binding, over Au/γ-Al2O3, drastically changes with rising temperature, indicating possible O2 dissociation at elevated temperatures. H2 facilitates stronger O2 bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H2 rich conditions, can be correlated to O2 dissociation after hydrogenation. Although, H2 enhances both selective CO reactant’s desorption, O2 desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant’s at lower temperatures. The experimentally observed drastic change in the strength of CO and O2 binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.

  8. Kinetic Study of Oxygen Adsorption over Nanosized Au/γ-Al2O3 Supported Catalysts under Selective CO Oxidation Conditions

    Directory of Open Access Journals (Sweden)

    George Karaiskakis


    Full Text Available O2 adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO on gold catalysts. Rate constants related to the elementary steps of O2 adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al2O3 catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC. The present study, carried-out in a wide temperature range (50–300 °C, both in excess as well as in the absence of H2, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H2, the rate of O2 binding, over Au/γ-Al2O3, drastically changes with rising temperature, indicating possible O2 dissociation at elevated temperatures. H2 facilitates stronger O2 bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H2 rich conditions, can be correlated to O2 dissociation after hydrogenation. Although, H2 enhances both selective CO reactant’s desorption, O2 desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant’s at lower temperatures. The experimentally observed drastic change in the strength of CO and O2 binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.

  9. Design, Synthesis, Characterization of Novel Ruthenium(II Catalysts: Highly Efficient and Selective Hydrogenation of Cinnamaldehyde to (E-3-Phenylprop-2-en-1-ol

    Directory of Open Access Journals (Sweden)

    Hany W. Darwish


    Full Text Available In this contribution, two novel supported and non-supported ruthenium(II complexes of type [RuCl2(dppme(NN] where [dppme is H2C=C(CH2PPh22 and NN is N1-(3-(trimethoxysilylpropylethane-1,2-diamine] were prepared. The NN co-ligand caused release of one of the dppme ligands from [RuCl2(dppme2] precursor to yield complex 1. The process of substitution of dppme by NN was monitored by 31P{1H}-NMR. Taking advantage of the presence of trimethoxysilane group in the backbone of complex 1, polysiloxane xerogel counterpart, X1, was prepared via sol-gel immobilization using tetraethoxysilane as cross-linker. Both complexes 1 and X1 have been characterized via elemental analysis, CV and a number of spectroscopic techniques including FT-IR, 1H-, 13C-, and 31P-NMR, and mass spectrometry. Importantly, carbonyl selective hydrogenation was successfully accomplished under mild conditions using complex 1 as a homogenous catalyst and X1 as a heterogeneous catalyst, respectively.

  10. Preparative treatment with NaOH to selectively concentrate iron oxides of a Chilean volcanic soil material to produce effective heterogeneous Fenton catalyst

    International Nuclear Information System (INIS)

    Manzo, Valentina; Pizarro, Carmen; Rubio, María Angélica; Cavalcante, Luis Carlos Duarte; Garg, Vijayendra Kumar; Fabris, José Domingos


    A Chilean volcanic Ultisol material was first size-fractionated so as to obtain the fraction with mean particle sizes φ   − 1 NaOH, in an attempt to evaluate the effectiveness of the selective chemical dissolution to concentrate iron oxides, as a preparation procedure before using the materials as heterogeneous Fenton catalysts. The effects of those treatments on the iron oxides mineralogy were monitored with Mössbauer spectroscopy. The NaOH-treated samples were tested as catalysts towards the H 2 O 2 decomposition. Three or five sequential NaOH treatments were found to be comparably effective, by concentrating nearly the same proportion of iron oxides in the remaining solid phase (25.1 ± 0.4 and 23.3 ± 0.2 mass%, respectively). 298 K-Mössbauer patterns were similar for both samples, with a central (super)paramagnetic Fe 3 +  doublet and a broad sextet, assignable to several closely coexisting magnetically ordered forms of iron oxides. Despite of this nearly similar effect of the two treatments, the Ultisol material treated three times with NaOH presents higher heterogeneous catalytic efficiency and is more suitable to decompose H 2 O 2 than that with five treatments.

  11. Technical characterisation of different catalysts for the selective reduction of nitrogen oxides in fluegas. Reaktionstechnische Charakterisierung unterschiedlicher Katalysatoren zur selektiven Reduktion von Stickoxiden in Rauchgasen

    Energy Technology Data Exchange (ETDEWEB)

    Dembele, C.


    In the context of this work, experimental investigations were made on the kinetics of the selective catalytic reduction of nitrogen monoxide with ammonia on catalysts of industrial origin. The aim of the work was to examine the effect of NO, NH[sub 3], H[sub 2]O and SO[sub 2] concentrations and the temperature on the speed of material quantity change of NO. The measurements with water proved difficult, as with high water contents, there was a drift of the measured values of NO concentration, the cause of which could not be cleared up. By repeated calibration of the NO concentrations to be set in the waste gas during a series of measurements, success was achieved in compensating for this drift and in obtaining reproducible results. The addition of SO[sub 2] to the reaction mixture brings the simulated fluegas closer to real powerstation fluegas. In determining the NO and NH[sub 3] concentration, the 'quenching' effect occurred and the calibration of the chemi-luminescence equipment frequently had to be repeated. The limited partial step of the reduction of NO is the transports of the educts into the pores of the catalyst grain to the active centres. (orig./EF)

  12. The development of precipitated iron catalysts with improved stability; Final report, September 1987--September 1992

    Energy Technology Data Exchange (ETDEWEB)

    Abrevaya, H.


    Precipitated iron catalysts are expected to be used in next generation slurry reactors for large-scale production of transportation fuels from synthesis gas. These reactors are expected to operate at higher temperatures and lower H{sub 2}:CO ratios relative to the Sasol Arge reactor (Table 1A). The feasibility of using iron catalysts has been demonstrated under relatively mild Arge-type conditions but not under more severe slurry conditions. Possibly, an improvement in catalytic stability will be needed to make iron catalysts suitable for slurry operation. This program was aimed at identifying the chemical principles governing the deactivation of precipitated iron catalysts during Fischer-Tropsch synthesis and use of these chemical principles in the design of more stable catalysts. A new precipitated Fe catalyst was developed in this program for slurry reactor operation. The new Fe catalyst is predicted to perform slightly below the performance targets for slurry bubble column operation. Stability targets appear to be achievable. This catalyst did not noticeably deactivate during 1,740 hours on-stream. Compared to the selectivity target, an excess of 2% C{sub 1} + C{sub 2} was formed at 265{degrees}C. Based on the initial catalyst inventory in the autoclave, the catalyst seems to be short of the activity target by a factor of 1.8 at 265{degrees}C and 1.3 at 275{degrees}C. However, actual specific activities are likely to be closer to target because of catalyst inventory loss across the filter during the run and because catalytic activities were underestimated at low conversions.

  13. Fischer-Tropsch Synthesis: Influence of CO Conversion on Selectivities H2/CO Usage Ratios and Catalyst Stability for a 0.27 percent Ru 25 percent Co/Al2O3 using a Slurry Phase Reactor

    Energy Technology Data Exchange (ETDEWEB)

    W Ma; G Jacobs; Y Ji; T Bhatelia; D Bukur; S Khalid; B Davis


    The effect of CO conversion on hydrocarbon selectivities (i.e., CH{sub 4}, C{sub 5+}, olefin and paraffin), H{sub 2}/CO usage ratios, CO{sub 2} selectivity, and catalyst stability over a wide range of CO conversion (12-94%) on 0.27%Ru-25%Co/Al{sub 2}O{sub 3} catalyst was studied under the conditions of 220 C, 1.5 MPa, H{sub 2}/CO feed ratio of 2.1 and gas space velocities of 0.3-15 NL/g-cat/h in a 1-L continuously stirred tank reactor (CSTR). Catalyst samples were withdrawn from the CSTR at different CO conversion levels, and Co phases (Co, CoO) in the slurry samples were characterized by XANES, and in the case of the fresh catalysts, EXAFS as well. Ru was responsible for increasing the extent of Co reduction, thus boosting the active site density. At 1%Ru loading, EXAFS indicates that coordination of Ru at the atomic level was virtually solely with Co. It was found that the selectivities to CH{sub 4}, C{sub 5+}, and CO{sub 2} on the Co catalyst are functions of CO conversion. At high CO conversions, i.e. above 80%, CH{sub 4} selectivity experienced a change in the trend, and began to increase, and CO{sub 2} selectivity experienced a rapid increase. H{sub 2}/CO usage ratio and olefin content were found to decrease with increasing CO conversion in the range of 12-94%. The observed results are consistent with water reoxidation of Co during FTS at high conversion. XANES spectroscopy of used catalyst samples displayed spectra consistent with the presence of more CoO at higher CO conversion levels.

  14. Catalysts and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil


    The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

  15. Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol

    DEFF Research Database (Denmark)

    Studt, Felix; Sharafutdinov, Irek; Abild-Pedersen, Frank


    The use of methanol as a fuel and chemical feedstock could become very important in the development of a more sustainable society if methanol could be efficiently obtained from the direct reduction of CO 2 using solar-generated hydrogen. If hydrogen production is to be decentralized, small-scale CO...... 2 reduction devices are required that operate at low pressures. Here, we report the discovery of a Ni-Ga catalyst that reduces CO 2 to methanol at ambient pressure. The catalyst was identified through a descriptor-based analysis of the process and the use of computational methods to identify Ni......-Ga intermetallic compounds as stable candidates with good activity. We synthesized and tested a series of catalysts and found that Ni 5 Ga 3 is particularly active and selective. Comparison with conventional Cu/ZnO/Al 2 O 3 catalysts revealed the same or better methanol synthesis activity, as well as considerably...

  16. Promoted V2O5/TiO2 catalysts for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Godiksen, Anita


    The influence of varying the V2O5 content (3–6 wt.%) was studied for the selective catalytic reduction (SCR) of nitrogen oxides by ammonia on heteropoly acid (HPA)- and tungsten oxide (WO3)-promoted V2O5/TiO2 catalysts. The SCR activity and alkali deactivation resistance of HPA-promoted V2O5/TiO2...... catalysts was found to be much higher than for WO3-promoted catalysts. By increasing the vanadium content from 3 to 5 wt.% the catalysts displayed a two fold increase in activity at 225 °C and retained their initial activity after alkali doping at a molar K/V ratio of 0.181. Furthermore, the catalysts were...... not cause increased N2O formation or unselective oxidation of NH3. NH3-TPD showed that promotion by HPA instead of WO3 causes the catalysts to possess a higher number of acid sites, both in fresh and alkali poisoned form, which might explain their higher potassium tolerance. Ex-situ EPR spectroscopy...

  17. A peroxotungstate-ionic liquid brush assembly: an efficient and reusable catalyst for selectively oxidizing sulfides with aqueous H{sub 2}O{sub 2} solution in neat water

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Xianying; Ma, Wenjuan; Ou, Hui; Han, Xiaoyan; Lu, Congmin; Chen, Yan; Wei, Junfa, E-mail:, E-mail: [School of Chemistry and Chemical Engineering, Shaanxi Normal University and Key Laboratory for Macromolecular Science of Shaanxi Province, Xian (China)


    An efficient and reusable heterogeneous catalytic assembly of peroxotungstate held in a ionic liquid (IL) brush was synthesized and an environmentally-friendly procedure was developed for selective oxidation of sulfides at room temperature using 30 wt.% hydrogen peroxide as the terminal oxidant and water as a sole solvent. No organic co-solvent or other additive was needed. A 1.5-2.0 mol% (based on W atom) loading catalyst was found to be sufficient for a smooth and clean reaction. Both aliphatic and aromatic sulfides were efficiently and selectively transformed into their respective sulfoxides or sulfones by simply controlling of equivalents of hydrogen peroxide. In addition to the high catalytic activity, the catalyst exhibits excellent chemoselectivity. Sensitive functional groups, such as double bond and hydroxyl, remained under the oxidation conditions the reaction even with an excess hydrogen peroxide. The catalyst was easily recovered (via simple filtration) and reused at least eight times without a noticeable loss of activity. (author)

  18. Towards ALD thin film stabilized single-atom Pd1 catalysts. (United States)

    Piernavieja-Hermida, Mar; Lu, Zheng; White, Anderson; Low, Ke-Bin; Wu, Tianpin; Elam, Jeffrey W; Wu, Zili; Lei, Yu


    Supported precious metal single-atom catalysts have shown interesting activity and selectivity in recent studies. However, agglomeration of these highly mobile mononuclear surface species can eliminate their unique catalytic properties. Here we study a strategy for synthesizing thin film stabilized single-atom Pd1 catalysts using atomic layer deposition (ALD). The thermal stability of the Pd1 catalysts is significantly enhanced by creating a nanocavity thin film structure. In situ infrared spectroscopy and Pd K-edge X-ray absorption spectroscopy (XAS) revealed that the Pd1 was anchored on the surface through chlorine sites. The thin film stabilized Pd1 catalysts were thermally stable under both oxidation and reduction conditions. The catalytic performance in the methanol decomposition reaction is found to depend on the thickness of protecting layers. While Pd1 catalysts showed promising activity at low temperature in a methanol decomposition reaction, 14 cycle TiO2 protected Pd1 was less active at high temperature. Pd L3 edge XAS indicated that the low reactivity compared with Pd nanoparticles is due to the strong adsorption of carbon monoxide even at 250 °C. These results clearly show that the ALD nanocavities provide a basis for future design of single-atom catalysts that are highly efficient and stable.

  19. Light Absorbers and Catalysts for Solar to Fuel Conversion (United States)

    Kornienko, Nikolay I.

    Increasing fossil fuel consumption and the resulting consequences to the environment has propelled research into means of utilizing alternative, clean energy sources. Solar power is among the most promising of renewable energy sources but must be converted into an energy dense medium such as chemical bonds to render it useful for transport and energy storage. Photoelectrochemistry (PEC), the splitting of water into oxygen and hydrogen fuel or reducing CO 2 to hydrocarbon fuels via sunlight is a promising approach towards this goal. Photoelectrochemical systems are comprised of several components, including light absorbers and catalysts. These parts must all synergistically function in a working device. Therefore, the continual development of each component is crucial for the overall goal. For PEC systems to be practical for large scale use, the must be efficient, stable, and composed of cost effective components. To this end, my work focused on the development of light absorbing and catalyst components of PEC solar to fuel converting systems. In the direction of light absorbers, I focused of utilizing Indium Phosphide (InP) nanowires (NWs) as photocathodes. I first developed synthetic techniques for InP NW solution phase and vapor phase growth. Next, I developed light absorbing photocathodes from my InP NWs towards PEC water splitting cells. I studied cobalt sulfide (CoSx) as an earth abundant catalyst for the reductive hydrogen evolution half reaction. Using in situ spectroscopic techniques, I elucidated the active structure of this catalyst and offered clues to its high activity. In addition to hydrogen evolution catalysts, I established a new generation of earth abundant catalysts for CO2 reduction to CO fuel/chemical feedstock. I first worked with molecularly tunable homogeneous catalysts that exhibited high selectivity for CO2 reduction in non-aqueous media. Next, in order to retain molecular tunability while achieving stability and efficiency in aqueous

  20. Unraveling the role of support surface hydroxyls and its effect on the selectivity of C2 species over Rh/γ-Al2O3 catalyst in syngas conversion: A theoretical study (United States)

    Zhang, Riguang; Duan, Tian; Wang, Baojun; Ling, Lixia


    The supported Rh-based catalysts exhibit the excellent catalytic performances for syngas conversion to C2 species. In this study, all possible elementary steps leading to C2 species from syngas have been explored to identify the role of support and its surface hydroxyls over Rh/γ-Al2O3 catalyst; Here, the results are obtained using density functional theory (DFT) method. Two models: Rh4 cluster supported on the dry γ-Al2O3(110) surface, D(Rh4), and on the hydroxylated γ-Al2O3(110) surface, H(Rh4), have been used to model Rh/γ-Al2O3 catalyst. Our results show that CO prefers to be hydrogenated to CHO, subsequently, starting from CHO species, CH and CH2 species are the dominate monomers among CHx(x = 1-3) species rather than CH3 and CH3OH on D(Rh4) and H(Rh4) surfaces, suggesting that γ-Al2O3-supported Rh catalyst exhibits the high selectivity towards CHx formation compared to the pure Rh catalyst. On the other hand, D(Rh4) is more favorable for C2 hydrocarbon (C2H2) formation, whereas H(Rh4) surface easily produces C2 hydrocarbon (C2H2) and C2 oxygenates (CHCO,CH2CHO), indicating that the surface hydroxyls of support can affect the selectivity of C2 species over Rh/γ-Al2O3 catalyst in syngas conversion. Moreover, compared to the pure Rh(111) surface, Rh/γ-Al2O3 catalyst can achieve the excellent catalytic performances for syngas conversion to C2 species.

  1. Supported Catalysts for CO2 Methanation: A Review

    Directory of Open Access Journals (Sweden)

    Patrizia Frontera


    Full Text Available CO2 methanation is a well-known reaction that is of interest as a capture and storage (CCS process and as a renewable energy storage system based on a power-to-gas conversion process by substitute or synthetic natural gas (SNG production. Integrating water electrolysis and CO2 methanation is a highly effective way to store energy produced by renewables sources. The conversion of electricity into methane takes place via two steps: hydrogen is produced by electrolysis and converted to methane by CO2 methanation. The effectiveness and efficiency of power-to-gas plants strongly depend on the CO2 methanation process. For this reason, research on CO2 methanation has intensified over the last 10 years. The rise of active, selective, and stable catalysts is the core of the CO2 methanation process. Novel, heterogeneous catalysts have been tested and tuned such that the CO2 methanation process increases their productivity. The present work aims to give a critical overview of CO2 methanation catalyst production and research carried out in the last 50 years. The fundamentals of reaction mechanism, catalyst deactivation, and catalyst promoters, as well as a discussion of current and future developments in CO2 methanation, are also included.

  2. Highly active thermally stable nanoporous gold catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Biener, Juergen; Wittstock, Arne; Biener, Monika M.; Bagge-Hansen, Michael; Baeumer, Marcus; Wichmann, Andre; Neuman, Bjoern


    In one embodiment, a system includes a nanoporous gold structure and a plurality of oxide particles deposited on the nanoporous gold structure; the oxide particles are characterized by a crystalline phase. In another embodiment, a method includes depositing oxide nanoparticles on a nanoporous gold support to form an active structure and functionalizing the deposited oxide nanoparticles.


    DEFF Research Database (Denmark)


    of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  4. Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst. (United States)

    Dai, Lei; Qin, Qing; Zhao, Xiaojing; Xu, Chaofa; Hu, Chengyi; Mo, Shiguang; Wang, Yu Olivia; Lin, Shuichao; Tang, Zichao; Zheng, Nanfeng


    Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni-Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources.

  5. Catalysts preparing

    International Nuclear Information System (INIS)

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


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

  6. Lunar CATALYST (United States)

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

  7. Photo-oxidation catalysts (United States)

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


    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  8. The preparation and activity of Cu-Fe-Zr-Ce based catalysts for water gas shift (United States)

    Wu, H. D.; Liu, T. S.; Liu, H. Z.


    CeO2-ZrO2 composite oxide was synthesized with precipitation method as support and CuaFeb(ZrCe4)8Ox catalysts were prepared by impregnation; X-ray diffraction, H2 temperature program reduction, and scanning electron microscope techniques were jointly used to characterize the crystal phases and reduction properties of catalysts. Then the activity of catalysts in water gas shift was studied, thus investigated how catalyst composition impacted the water gas shift. Conclusions drew from the results can be briefly stated. CuaFeb(ZrCe4)8Ox was provided with stable cubic crystalline framework and Cu and Fe, as the active components, was highly dispersed on the surface of supports in the form of CuO and Fe2O3 respectively. The strong interactions between copper and iron component enhanced the reducing capacity of CuO and Fe2O3. CuaFeb(ZrCe4)8Ox catalysts exhibited high catalytic activity and selectivity while the main active components were Cu and Fe3O4. The CO conversion rate reached 96% when Cu7Fe3(ZrCe4)8Ox catalysts was used in water gas shift at 623K and the only products were H2 and CO2. The activity was still desirable even the catalysts was applied at 723K.

  9. An alternative mechanistic concept for homogeneous selective ethylene oligomerization of chromium-based catalysts: binuclear metallacycles as a reason for 1-octene selectivity? (United States)

    Peitz, Stephan; Aluri, Bhaskar R; Peulecke, Normen; Müller, Bernd H; Wöhl, Anina; Müller, Wolfgang; Al-Hazmi, Mohammed H; Mosa, Fuad M; Rosenthal, Uwe


    An alternative concept for the selective catalytic formation of 1-octene from ethylene via dimeric catalytic centers is proposed. The selectivity of the tetramerization systems depends on the capability of ligands to form binuclear complexes that subsequently build up and couple two separate metallacyclopentanes to form 1-octene selectively. Comparison of existing catalytic processes, the ability of the bis(diarylphosphino)amine (PNP) ligand to bridge two metal centers, and the experimental background support the proposed binuclear mechanism for ethylene tetramerization.

  10. Selective Fischer-Tropsch synthesis over an Al{sub 2}O{sub 3} supported cobalt catalyst in supercritical hexane

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xiwen; Roberts, Christopher B. [Chemical Engineering Department, Auburn University, 230 Ross Hall, Auburn, AL 36849 (United States)


    Supercritical fluids (SCFs) offer several advantages as reaction media for catalytic reactions. These advantages include the ability to manipulate the reaction environment through simple changes in pressure to enhance solubility of reactants and products, to eliminate interphase transport limitations, and to integrate reaction and separation unit operations. Benefits derived from the SCF-phase Fischer-Tropsch synthesis (SCF-FTS) involve the gas-like diffusivities and liquid-like solubilities, which together combine the desirable features of the gas- and liquid-phase FT synthesis routes. In this paper, FT synthesis under SCF hexane conditions is examined in a continuous, high-pressure reactor by employing a traditional Co catalyst (15% Co-0.5% Pt/Al{sub 2}O{sub 3}). Steady-state operation was quickly achieved under SCF conditions and the SCF-FT process has a marked effect on the hydrocarbon product distribution with a shift to higher carbon number products owing to enhanced heat and mass transfer from the catalyst surface. In addition, an obvious difference in the olefin content was observed where the 1-olefin content in the SCF phase was always higher than in the gas phase. Based on the experimental observations, a mechanistic explanation is provided for the difference of the reaction behavior under supercritical and gas-phase environments. Enhanced olefins readsorption and increased availability of active sites in the supercritical state contribute to the increased olefin selectivity and chain growth probability in the supercritical phase. In addition, the effect of pressure tuning in the supercritical phase reaction was investigated as well as the effect of the supercritical medium on heat transfer and temperature distribution within the reactor.

  11. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry


    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  12. The ability of selected pupal parasitoids (Hymenoptera: Pteromalidae) to locate stable fly hosts in a soiled equine bedding substrate. (United States)

    Pitzer, Jimmy B; Kaufman, Phillip E; Geden, Christopher J; Hogsette, Jerome A


    The ability of Spalangia cameroni Perkins, Spalangia endius Walker, and Muscidifurax raptorellus Kogan and Legner to locate and attack stable fly hosts was evaluated under laboratory conditions. Postfeeding third-instar stable fly larvae were released and allowed to pupate in two arena types: large 4.8 liter chambers containing a field-collected, soiled equine bedding substrate; or 120-ml plastic cups containing wood chips. At the time of fly pupariation, parasitoids were released and permitted 72 h to locate and attack hosts. On average, parasitism rates of freely accessible stable fly pupae in cups were not significantly different between parasitoid species. However, parasitism rates in chambers containing either Spalangia spp. were ≈50-fold more than M. raptorellus. Additional intraspecies analysis revealed that parasitism rates both by S. cameroni and S. endius were not significantly different when pupae were freely accessible or within bedding, whereas M. raptorellus attacked significantly more pupae in cups than in the larger chambers where hosts were distributed within bedding. These results suggest that Spalangia spp. are more suited to successfully locate and attack hosts in habitats created by equine husbandry in Florida. Therefore, commercially available parasitoid mixtures containing Muscidifurax spp. may be ineffective if used as a control measure at Florida equine facilities. © 2011 Entomological Society of America

  13. A new kinetic model based on the remote control mechanism to fit experimental data in the selective oxidation of propene into acrolein on biphasic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Abdeldayem, H.M.; Ruiz, P.; Delmon, B. [Unite de Catalyse et Chimie des Materiaux Divises, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Thyrion, F.C. [Unite des Procedes Faculte des Sciences Appliquees, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium)


    A new kinetic model for a more accurate and detailed fitting of the experimental data is proposed. The model is based on the remote control mechanism (RCM). The RCM assumes that some oxides (called `donors`) are able to activate molecular oxygen transforming it to very active mobile species (spillover oxygen (O{sub OS})). O{sub OS} migrates onto the surface of the other oxide (called `acceptor`) where it creates and/or regenerates the active sites during the reaction. The model contains tow terms, one considering the creation of selective sites and the other the catalytic reaction at each site. The model has been tested in the selective oxidation of propene into acrolein (T=380, 400, 420 C; oxygen and propene partial pressures between 38 and 152 Torr). Catalysts were prepared as pure MoO{sub 3} (acceptor) and their mechanical mixtures with {alpha}-Sb{sub 2}O{sub 4} (donor) in different proportions. The presence of {alpha}-Sb{sub 2}O{sub 4} changes the reaction order, the activation energy of the reaction and the number of active sites of MoO{sub 3} produced by oxygen spillover. These changes are consistent with a modification in the degree of irrigation of the surface by oxygen spillover. The fitting of the model to experimental results shows that the number of sites created by O{sub SO} increases with the amount of {alpha}-Sb{sub 2}O{sub 4}. (orig.)

  14. Selective Hydrogenolysis of Glycerol and Crude Glycerol (a By-Product or Waste Stream from the Biodiesel Industry to 1,2-Propanediol over B2O3 Promoted Cu/Al2O3 Catalysts

    Directory of Open Access Journals (Sweden)

    Malaya R. Nanda


    Full Text Available The performance of boron oxide (B2O3-promoted Cu/Al2O3 catalyst in the selective hydrogenolysis of glycerol and crude glycerol (a by-product or waste stream from the biodiesel industry to produce 1,2-propanediol (1,2-PDO was investigated. The catalysts were characterized using N2-adsorption-desorption isotherm, Inductively coupled plasma atomic emission spectroscopy (ICP-AES, X-ray diffraction (XRD, ammonia temperature programmed desorption (NH3-TPD, thermogravimetric analysis (TGA, temperature programmed reduction (TPR, and transmission electron microscopy (TEM. Incorporation of B2O3 to Cu/Al2O3 was found to enhance the catalytic activity. At the optimum condition (250 °C, 6 MPa H2 pressure, 0.1 h−1 WHSV (weight hourly space velocity, and 5Cu-B/Al2O3 catalyst, 10 wt% aqueous solution of glycerol was converted into 1,2-PDO at 98 ± 2% glycerol conversion and 98 ± 2% selectivity. The effects of temperature, pressure, boron addition amount, and liquid hourly space velocity were studied. Different grades of glycerol (pharmaceutical, technical, or crude glycerol were used in the process to investigate the stability and resistance to deactivation of the selected 5Cu-B/Al2O3 catalyst.

  15. Noble metal catalysts in the production of biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, A.


    -based pyrolysis oil, and in the ATR of simulated gasoline and diesel, low sulfur diesel and ethanol for the production of hydrogen-rich mixture for fuel cells. In hydrotreatment and ATR, rhodium-containing catalysts were the most active, selective, and stable. (orig.)

  16. Highly dispersed metal catalyst (United States)

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


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


    International Nuclear Information System (INIS)

    Andrew W. Wang


    The Liquid Phase Dimethyl Ether (LPDME(trademark)) process converts synthesis gas to dimethyl ether in a single slurry bubble column reactor. A mixed slurry of methanol synthesis catalyst and methanol dehydration catalyst in a neutral mineral oil simultaneously synthesizes methanol from syngas and converts some of it to dimethyl ether and water. The reaction scheme is shown below: 2H(sub 2)+ CO= CH(sub 3)OH; 2CH(sub 3)OH= CH(sub 3)OCH(sub 3)+ H(sub 2)O; H(sub 2)O+ CO= CO(sub 2)+ H(sub 2). Most of the water produced in this reaction is converted to hydrogen by reduction with carbon monoxide (water gas shift reaction). This synergy permits higher per pass conversion than methanol synthesis alone. The enhancement in conversion occurs because dehydration of the methanol circumvents the equilibrium constraint of the syngas-to-methanol step. The slurry bubble column reactor provides the necessary heat transfer capacity to handle the greater heat duty associated with high conversion. In order to improve the stability of the catalyst system, non-stoichiometric aluminum phosphate was proposed as the dehydration catalyst for the LPDME(trademark) process. This aluminum phosphate material is a proprietary catalyst. This catalyst system of a standard methanol catalyst and the aluminum phosphate provided stable process performance that met the program targets under our standard test process conditions in the laboratory. These targets are (1) an initial methanol equivalent productivity of 28 gmol/kg/hr, (2) a CO(sub 2)-free, carbon selectivity of 80% to dimethyl ether and (3) stability of both catalysts equivalent to that of the methanol catalyst in the absence of the aluminum phosphate. A pilot plant trial of the LPDME(trademark) process using the aluminum phosphate catalyst was originally planned for March 1998 at the DOE-owned, Air Products (APCI)-operated facility at LaPorte, Texas. Because the aluminum phosphate catalyst is not commercially available, we initiated a scaleup

  18. Synergy effects between bismuth molybdate catalyst phases (Bi/Mo from 0.57 to 2) for the selective oxidation of propylene to arcrolein

    DEFF Research Database (Denmark)

    Le, Minh Thang; Well, Willy van; Stoltze, Per


    In this work, the synergy effect between different phases of bismuth molybdate catalysts was investigated systematically. The catalysts were prepared by spray drying and had a Bi/Mo atomic between 0.57 and 2. It is found that the synergy effect is only observed in mixtures containing γ...

  19. Stable acetate production in extreme-thermophilic (70ºC) mixed culture fermentation by selective enrichment of hydrogenotrophic methanogens

    NARCIS (Netherlands)

    Zhang, F.; Zhang, Y.; Ding, J.; Dai, K.; Van Loosdrecht, M.C.M.; Zeng, R.J.


    The control of metabolite production is difficult in mixed culture fermentation. This is particularly related to hydrogen inhibition. In this work, hydrogenotrophic methanogens were selectively enriched to reduce the hydrogen partial pressure and to realize efficient acetate production in

  20. Inducing Stable α + β Microstructures during Selective Laser Melting of Ti-6Al-4V Using Intensified Intrinsic Heat Treatments. (United States)

    Barriobero-Vila, Pere; Gussone, Joachim; Haubrich, Jan; Sandlöbes, Stefanie; Da Silva, Julio Cesar; Cloetens, Peter; Schell, Norbert; Requena, Guillermo


    Selective laser melting is a promising powder-bed-based additive manufacturing technique for titanium alloys: near net-shaped metallic components can be produced with high resource-efficiency and cost savings [...].

  1. Inducing Stable α + β Microstructures during Selective Laser Melting of Ti-6Al-4V Using Intensified Intrinsic Heat Treatments

    Directory of Open Access Journals (Sweden)

    Pere Barriobero-Vila


    Full Text Available Selective laser melting is a promising powder-bed-based additive manufacturing technique for titanium alloys: near net-shaped metallic components can be produced with high resource-efficiency and cost savings [...

  2. Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, Gabor A.; Park, Jeong Y.


    Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-path reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.

  3. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal


    How can architecture promote the enriching experiences of the tolerant, the democratic, and the learning city - a city worth living in, worth supporting and worth investing in? Catalyst Architecture comprises architectural projects, which, by virtue of their location, context and their combination...... of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city development...

  4. Dual catalyst bed concept for catalytic partial oxidation of methane to synthesis gas

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus


    A system with two catalyst beds instead of one single metal catalyst bed is proposed for catalytic partial oxidation of methane (CPOM) to synthesis gas. In this dual catalyst bed system, an irreducible stable oxide, such as yttrium-stabilized zirconia (YSZ), is used in the first catalyst bed to

  5. Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements. (United States)

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


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

  6. Preparative characteristics of hydrophobic polymer catalyst for the tritium removal

    International Nuclear Information System (INIS)

    Kang, Hee Suk; Choi, H. J.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Paek, S. W.; Paek, S. W.; Kim, J. G.; Chung, H. S.


    The optimum method for the fabrication of hydrophobic catalyst was selected and the apparatuses for the preparation of catalyst support with high yield was developed for the large scale production. Also, we summarized the method of improving the physical property of the catalyst support, the loading characteristics of Pt metal as a catalyst, and the characteristics of the apparatus for the fabrication of the catalysts on a large scale

  7. Catalyst-free selective-area epitaxy of GaAs nanowires by metal-organic chemical vapor deposition using triethylgallium (United States)

    Kim, Hyunseok; Ren, Dingkun; Farrell, Alan C.; Huffaker, Diana L.


    We demonstrate catalyst-free growth of GaAs nanowires by selective-area metal-organic chemical vapor deposition (MOCVD) on GaAs and silicon substrates using a triethylgallium (TEGa) precursor. Two-temperature growth of GaAs nanowires—nucleation at low temperature followed by nanowire elongation at high temperature—almost completely suppresses the radial overgrowth of nanowires on GaAs substrates while exhibiting a vertical growth yield of almost 100%. A 100% growth yield is also achieved on silicon substrates by terminating Si(111) surfaces by arsenic prior to the nanowire growth and optimizing the growth temperature. Compared with trimethylgallium (TMGa) which has been exclusively employed in the vapor–solid phase growth of GaAs nanowires by MOCVD, the proposed growth technique using TEGa is advantageous because of lower growth temperature and fully suppressed radial overgrowth. It is also known that GaAs grown by TEGa induce less impurity incorporation compared with TMGa, and therefore the proposed method could be a building block for GaAs nanowire-based high-performance optoelectronic and nanoelectronic devices on both III–V and silicon platforms.

  8. Biomass processing over gold catalysts

    CERN Document Server

    Simakova, Olga A; Murzin, Dmitry Yu


    The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries.  In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds derived from cellulose, hemicelluloses, and woody biomass extractives. Since gold catalysts possess high stability under oxidative conditions, selective oxidation reactions were discussed more thoroughly than other critical reactions such as partial hydrogenation, acetalization, and isomerization. The influence of reaction conditions, the role of the catalyst, and the advantages and disadvantages of using gold are pre...

  9. Effect of metal ions doping (M = Ti4+, Sn4+) on the catalytic performance of MnOx/CeO2 catalyst for low temperature selective catalytic reduction of NO with NH3 (United States)

    Xiong, Yan; Tang, Changjin; Dong, Lin


    Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China The abatement of nitrogen oxides (NOx) emission from exhaust gases of diesel and stationary sources is a significant challenge for economic and social development. Ceria-based solid solutions were synthesized and used as supports to prepare MnOx/Ce0.8Ti0.2O2 and MnOx/Ce0.8Sn0.2O2 catalysts (Mn/CeTi and Mn/CeSn) for low temperature selective catalytic reduction of NO by NH3 (NH3-SCR). The effects of Ti or Sn doping on the catalytic performance of MnOx/CeO2 catalyst were investigated. Experimental results show that doping of Ti or Sn increases the NO removal efficiency of MnOx/CeO2. The NO conversion of Mn/CeTi catalyst is more than 90 % at temperature window of 175 ~ 300 °C under a gas hour space velocity of 60,000 mL.g-1.h-1. Modified catalysts are also found to exhibit greatly improved resistance to sulfur-poisoning. NH3-TPD results suggest that NH3 desorption on the catalysts is observed over a wide temperature range, due to the variability of adsorbed NH3 species with different thermal stabilities. Doping of Ti and Sn into Mn/CeO2 greatly increased the NH3 adsorption ability of the composites which could promote the SCR reaction. Characterization results also indicate that doping of Ti or Sn brings about catalysts with higher BET surface area, enhanced oxygen storage capacity and increased surface acidity.

  10. Promotional effect of fluorine on the selective catalytic reduction of NO with NH{sub 3} over CeO{sub 2}-TiO{sub 2} catalyst at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Rui; Zhong, Qin, E-mail:; Zhao, Wei; Yu, Lemeng; Qu, Hongxia


    In order to investigate the effect of F on CeO{sub 2}-TiO{sub 2} catalyst for the selective catalytic reduction (SCR) of NO with NH{sub 3}, a series of F-doped CeO{sub 2}-TiO{sub 2} catalysts were prepared by co-precipitation method. Compared with Ce0.3TiF0 catalyst, Ce0.3TiF1.5 catalyst exhibited the best catalytic activity, yielding 92.19% NO conversion at 180 °C. The catalysts were characterized by Brunauer–Emmett–Teller (BET) surface area, X-ray powder diffraction (XRD), photoluminescence (PL) spectra, Raman spectra, X-ray photoelectron spectroscopy (XPS) and Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) techniques. It was found that the enhanced catalytic activity was ascribed to several beneficial effects produced by the introduction of F: inhibition of the crystallization, decrease of the particle size, increase of the oxygen vacancies (F+ centers) and lattice defects. Raman measurements disclosed the formation of superoxide (O{sub 2}{sup −}) ions in chemisorbed oxygen which was crucial for the formation of reaction intermediates (NO{sub 2}{sup −}, NO{sub 3}{sup −}). The study of DRIFTS proved that the addition of F could bring more ad-NO{sub x} and reaction intermediates. The NH{sub 3}-TPD studies confirmed that the right amount of F could improve the number of acid sites over CeO{sub 2}-TiO{sub 2} catalyst, especially the Lewis acid sites. These factors simultaneously enhanced the catalytic activity for NH{sub 3}-SCR of NO. The effect of H{sub 2}O and SO{sub 2} on the NO conversion was also investigated in our work.

  11. A codon-optimized bacterial antibiotic gene used as selection marker for stable nuclear transformation in the marine red alga Pyropia yezoensis. (United States)

    Uji, Toshiki; Hirata, Ryo; Fukuda, Satoru; Mizuta, Hiroyuki; Saga, Naotsune


    Marine macroalgae play an important role in marine coastal ecosystems and are widely used as sea vegetation foodstuffs and for industrial purposes. Therefore, there have been increased demands for useful species and varieties of these macroalgae. However, genetic transformation in macroalgae has not yet been established. We have developed a dominant selection marker for stable nuclear transformation in the red macroalga Pyropia yezoensis. We engineered the coding region of the aminoglycoside phosphotransferase gene aph7″ from Streptomyces hygroscopicus to adapt codon usage of the nuclear genes of P. yezoensis. We designated this codon-optimized aph7″ gene as PyAph7. After bombarding P. yezoensis cells with plasmids containing PyAph7 under the control of their endogenous promoter, 1.9 thalli (or individuals) of hygromycin-resistant strains were isolated from a 10-mm square piece of the bombarded thallus. These transformants were stably maintained throughout the asexual life cycle. Stable expression of PyAph7was verified using Southern blot analysis and genomic PCR and RT-PCR analyses. PyAph7 proved to be a new versatile tool for stable nuclear transformation in P. yezoensis.

  12. Selective Growth of Single-, Double-, and Triple-Walled Carbon Nanotubes through Precise Control of Catalyst Diameter by Radiation-Heated Chemical Vapor Deposition (United States)

    Taki, Yusuke; Shinohara, Kiyoaki; Kikuchi, Makiko; Tanaka, Akira


    Radiation-heated chemical vapor deposition (RHCVD) is a newly developed process which enables the maintenance of narrow catalyst diameter distributions until carbon nanotubes (CNTs) start growing and the synthesis of single-walled carbon nanotube (SWCNT), double-walled carbon nanotube (DWCNT), and triple-walled carbon nanotube (TWCNT) films by changing catalyst diameters. The proportions of specific walled CNTs/as-grown CNTs are as follows: SWCNT/CNT ratio of 100%, DWCNT/CNT ratio of 88% and TWCNT/CNT ratio of 76%. It is clarified that CNT diameter and the number of graphene walls of CNTs are proportional to catalyst diameter.

  13. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.


    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory material containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one treating agent selected from chlorinated silicon compounds, thionyl chloride, and sulfuryl chloride under conditions suitable for the treating agent to promote the activity of tungsten and molybdenum oxides for the disporoportionation reaction.

  14. Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis (United States)

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


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

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

    Directory of Open Access Journals (Sweden)

    Magda Blosi


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

  16. Walkable new urban LEED_Neighborhood-Development (LEED-ND) community design and children's physical activity: selection, environmental, or catalyst effects? (United States)


    Background Interest is growing in physical activity-friendly community designs, but few tests exist of communities explicitly designed to be walkable. We test whether students living in a new urbanist community that is also a pilot LEED_ND (Leadership in Energy and Environmental Design-Neighborhood Development) community have greater accelerometer-measured moderate-to-vigorous physical activity (MVPA) across particular time periods compared to students from other communities. We test various time/place periods to see if the data best conform to one of three explanations for MVPA. Environmental effects suggest that MVPA occurs when individuals are exposed to activity-friendly settings; selection effects suggest that walkable community residents prefer MVPA, which leads to both their choice of a walkable community and their high levels of MVPA; catalyst effects occur when walking to school creates more MVPA, beyond the school commute, on schooldays but not weekends. Methods Fifth graders (n = 187) were sampled from two schools representing three communities: (1) a walkable community, Daybreak, designed with new urbanist and LEED-ND pilot design standards; (2) a mixed community (where students lived in a less walkable community but attended the walkable school so that part of the route to school was walkable), and (3) a less walkable community. Selection threats were addressed through controlling for parental preferences for their child to walk to school as well as comparing in-school MVPA for the walkable and mixed groups. Results Minutes of MVPA were tested with 3 × 2 (Community by Gender) analyses of covariance (ANCOVAs). Community walkability related to more MVPA during the half hour before and after school and, among boys only, more MVPA after school. Boys were more active than girls, except during the half hour after school. Students from the mixed and walkable communities--who attended the same school--had similar in-school MVPA levels, and community groups

  17. Bifunctional cobalt F-T catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.G.; Coughlin, P.K.; Yang, C.L.; Rabo, J.A.


    Results on the catalytic screening of Fischer-Tropsch catalysts containing shape selective components are reported. Catalysts consist of promoted cobalt intimately contacted with Union Carbide molecular sieves and were tested using a Berty type internally recycled reactor. Methods of preparation, promoters and shape selective components were varied and aimed at improving catalyst performance. Catalysts were developed demonstrating high C/sub 5/ + yields with high olefin content and low methane production while maintaining stability under both low and high H/sub 2/:CO ratio conditions.

  18. Catalysts based on PdO_ZrO2 in the hydrodechlorination reaction of chlorobenzene (United States)

    Otroshchenko, T. P.; Turakulova, A. O.; Lokteva, E. S.; Golubina, E. V.; Lunin, V. V.


    The possibility of using mixed oxides of palladium and zirconium obtained with biotemplates (cellulose and wood pulp) as the precursor of catalysts for the hydrodechlorination of chlorobenzene is analyzed. The properties of the samples are studied by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method, and temperature-programmed reduction (TPR). They are then compared to the properties of a supported analogue. The biomorphic precursors are characterized by high porosity and include micropores, mesopores, and macropores; the results from TPR reveal the presence in the precursors of several forms of PdO that differ by reduction temperature. It is shown that the distribution of palladium in the catalysts obtained by reducing the precursors with hydrogen depends on the method used in synthesizing the precursor. It is shown that the studied catalysts ensure 100% conversion of chlorobenzene at temperatures of 100 to 250°C. It is established that cyclohexane is the principal product in the presence of the supported catalyst across the range of temperatures, while cyclohexane and benzene are detected among the products in the presence of biomorphous samples at temperatures above 130°C. The effect the presence of an admixture of alkaline and alkaline-earth metals in the catalyst has on the selectivity of the process is noted. It is established that the catalysts operate in a stable manner for at least 27 h of use under experimental conditions.

  19. Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions. (United States)

    Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D


    Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin


    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.