WorldWideScience

Sample records for bifunctional sulfide catalysts

  1. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Final technical progress report, September 12, 1991--December 11, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.; Deemer, M.; Richards-Babb, M.; Carr, T.

    1995-07-01

    The objective of this research was to investigate sulfur-resistant catalysts for the conversion of synthesis gas having H{sub 2}/CO {le} 1 into C{sub 1}--C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway, while also promoting the water gas shift reaction (WGSR). The catalysts chosen are bifunctional, base-hydrogenation, sulfur-tolerant transition metal sulfides with heavy alkali, e.g. Cs{sup +}, promoter dispersed on their surfaces. The modes of activation of H{sub 2} and CO on MoS{sub 2} and alkali-doped MoS{sub 2} were considered, and computational analyses of the thermodynamic stability of transition metal sulfides and of the electronic structure of these sulfide catalysts were carried out. In the preparation of the cesium-promoted MoS{sub 2} catalysts, a variety of preparation methods using CsOOCH were examined. In all cases, doping with CsOOCH led to a lost of surface area. The undoped molybdenum disulfide catalyst only produced hydrocarbons. Cs-doped MoS{sub 2} catalysts all produced linear alcohols, along with smaller amounts of hydrocarbons. With a 20 wt% CsOOCH/MoS{sub 2} catalyst, temperature, pressure, and flow rate dependences of the synthesis reactions were investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 synthesis gas during short term testing experiments. It was shown that with a carefully prepared 10 wt% CsOOCH/MoS{sub 2} catalyst, reproducible and high alcohol synthesis activity could be obtained. For example, at 295 C with H{sub 2}/CO = 1 synthesis gas at 8.3 MPa and with GHSV = 7,760 l/kg cat/hr, the total alcohol space time yield was ca 300 g/kg cat/hr (accompanied with a hydrocarbon space time yield of ca 60 g/kg cat/hr). Over a testing period of ca 130 hr, no net deactivation of the catalyst was observed. 90 refs., 82 figs., 14 tabs.

  2. Molybdenum sulfide/carbide catalysts

    Science.gov (United States)

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda

    2007-05-29

    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

  3. Bifunctional Catalysts for Upgrading of Biomass-Derived Oxygenates: A Review

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

    2016-08-05

    Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the different types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. These studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.

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

    NARCIS (Netherlands)

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

    2015-01-01

    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 source

  5. Environmentally Benign Bifunctional Solid Acid and Base Catalysts

    NARCIS (Netherlands)

    Elmekawy, A.; Shiju, N.R.; Rothenberg, G.; Brown, D.R.

    2014-01-01

    Solid bifunctional acid-​base catalysts were prepd. in two ways on an amorphous silica support: (1) by grafting mercaptopropyl units (followed by oxidn. to propylsulfonic acid) and aminopropyl groups to the silica surface (NH2-​SiO2-​SO3H)​, and (2) by grafting only aminopropyl groups and then parti

  6. A bifunctional perovskite catalyst for oxygen reduction and evolution.

    Science.gov (United States)

    Jung, Jae-Il; Jeong, Hu Young; Lee, Jang-Soo; Kim, Min Gyu; Cho, Jaephil

    2014-04-25

    La0.3(Ba0.5Sr0.5)0.7Co0.8Fe0.2O3d is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm-scale rhombohedral LaCoO3 cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A-site cations with La3+ and local stress on Cosite sub-lattice with the cubic perovskite structure.

  7. Bifunctional Catalysts for CO2 Reduction

    Science.gov (United States)

    2014-09-30

    dioxide reduction catalysis . (SA 1 – Catalyst candidate synthesis) As outlined in the original proposal, ligand platforms have been synthesized to...was limited to outer-sphere electron transfer (necessary oxidation potentials for catalysis > –2.1 V vs. [Cp2Fe] +/0). Thus, we pursued two...to heterogeneous Fischer-Tropsch13 catalysts. This reactivity must also be compared with mononuclear early transition metal ligands that require

  8. Bifunctional catalysts for the direct production of liquid fuels from syngas

    NARCIS (Netherlands)

    Sartipi, S.

    2014-01-01

    Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve th

  9. Novel bifunctional double-layer catalysts for application in microreactors for direct DME synthesis

    OpenAIRE

    Lee, Seungcheol

    2016-01-01

    This thesis describes experimental research toward the selective and efficient DME production from syngas in microstructured reactors using bifunctional catalysts. Two catalysts, Cu/ZnO/Al2O3 and ZSM-5, catalyze syngas conversion to methanol and methanol conversion to DME, respectively. The catalysts were prepared and successfully introduced in microchannel reactor for direct DME synthesis.

  10. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold–titania c...... new and environmentally benign routes to caprolactam and cyclohexanone oxime, both of which are precursors for nylon-6....

  11. Increasing round trip efficiency of hybrid Li-air battery with bifunctional catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Huang, K; Li, YF; Xing, YC

    2013-07-30

    Previously it was shown that Pt as cathode catalyst ha's a large overpotential during charge in rechargeable hybrid Li-air battery with sulfuric acid catholyte. This article demonstrates that a bifunctional catalyst composed of Pt and IrO2 supported on carbon nanotubes can address this problem. The specially designed and synthesized bifunctional catalyst showed significant overpotential reduction and achieved a round trip energy efficiency of 81% after 10 cycles, higher than many achieved in aprotic Li-O-2 batteries. The hybrid Li-air battery was discharged and recharged for 20 cycles at 0.2 mA/cm(2), showing a fairly stable cell performance. A specific capacity of 306 mAh/g and a specific energy of 1110 Wh/kg were obtained for the hybrid Li-air battery in terms of acid weight. (c) 2013 Elsevier Ltd. All rights reserved.

  12. Bifunctional heterogeneous catalysts from oil palm empty fruit bunches ash and alum for biodiesel synthesis simultaneously

    Science.gov (United States)

    Astar, Ismail; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Alimuddin, Andi Hairil

    2017-03-01

    Free fatty acids (FFA) contained in crude palm oil (CPO) and sludge oil has been used as the base material of biodiesel with the aid of a catalyst in the transesterification and esterification reactions. This study aims to synthesize and characterize bifunctional catalysts were synthesized from the ashes of palm empty fruit bunches (EFB) and alum based on the analysis of XRD, XRF and acidity test. Bifunctional catalyst obtained was used as a catalyst to production of biodiesel with different levels of FFA. The optimum ratio alum added was 0.2 mol at 3 hours of reaction time and 3% of catalyst by the FFA samples were used 67,40%. The catalyst with optimum alum mole variations subsequently used on samples with varying levels of FFA, namely 1.29%, 4.98%, 29.21%, 67.40% and 74.47%. Optimum conversion of methyl ester in the esterification reaction occurs in the sample with 67.40% FFA content, which reached 86.17%, while the conversion of methyl ester transesterification process optimum amounted to 45.70% in the samples with 4.98% FFA content. Methyl ester produced has a refractive index of 1.448 (29.8 ° C), density of 0.883 g / mL (25 °C) and a viscosity of 8.933 cSt (25 ° C). The results of GC-MS analysis showed that the main composition of methyl ester result of esterification of sludge oil methyl palmitate (36.84%), while the CPO transesterification shows the main composition of methyl ester is methyl oleic (38.87%). Based on the research results, the catalyst synthesized from alum and EFB ash can be used as a Bifunctional catalysts for biodiesel synthesis.

  13. Extraction of Nanosized Cobalt Sulfide from Spent Hydrocracking Catalyst

    Directory of Open Access Journals (Sweden)

    Samia A. Kosa

    2013-01-01

    Full Text Available The processes used for the extraction of metals (Co, Mo, and Al from spent hydrotreating catalysts were investigated in this study. A detailed mechanism of the metal extraction process is described. Additionally, a simulation study was performed to understand the sulfidizing mechanism. The suggested separation procedure was effective and achieved an extraction of approximately 80–90%. In addition, the sulfidization mechanism was identified. This sulfidizing process for Co was found to involve an intermediate, the structure of which was proposed. This proposed intermediate was confirmed through simulations. Moreover, the activities of the spent and the regenerated catalyst were examined in the cracking of toluene. The modification of the spent catalyst through the use of different iron oxide loadings improved the catalytic activity.

  14. Bifunctional Nanostructured Base Catalysts: Opportunities for BioFuels

    Energy Technology Data Exchange (ETDEWEB)

    Connor, William

    2010-12-30

    ABSTRACT This research studied and develop novel basic catalysts for production of renewable chemicals and fuels from biomass. We will focus on the development of unique porous structural-base catalysts formed by two techniques: from (mixed) metal-oxide bases and by nitrogen substitution for oxygen in zeolites. These catalysts will be compared to conventional solid base materials for aldol condensation, catalytic fast pyrolysis, and transesterification reactions. These reactions are important in processes that are currently being commercialized for production of fuels from biomass and will be pivotal in future biomass conversion to fuels and chemicals. Specifically, we have studied the aldol-condensation of acetone with furfural over oxides and zeolites, the conversion of sugars by rapid pyrolysis over zeolites and the trans-esterification of vegetable oil with methanol over mixed oxide catalysts. Our previous research has indicated that the base strength of framework nitrogen in nitrogen-substituted zeolites (NH-zeolites) is nearly twice as strong as in standard zeolites. Nitrogen substituted catalysts have been synthesized from several zeolites (including FAU, MFI, BEA, and LTL) using NH3 treatment.

  15. Bifunctional anode catalysts for direct methanol fuel cells

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios

    2012-01-01

    Using the binding energy of OH* and CO* on close-packed surfaces as reactivity descriptors, we screen bulk and surface alloy catalysts for methanol electro-oxidation activity. Using these two descriptors, we illustrate that a good methanol electro-oxidation catalyst must have three key properties......: (1) the ability to activate methanol, (2) the ability to activate water, and (3) the ability to react off surface intermediates (such as CO* and OH*). Based on this analysis, an alloy catalyst made up of Cu and Pt should have a synergistic effect facilitating the activity towards methanol electro....... Adding Cu to a Pt(111) surface increases the methanol oxidation current by more than a factor of three, supporting our theoretical predictions for improved electrocatalysts....

  16. Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

    Science.gov (United States)

    Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

    2015-09-01

    Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

  17. Scaffolding Catalysis: Expanding the Repertoire of Bifunctional Catalysts.

    Science.gov (United States)

    Tan, Kian L; Sun, Xixi; Worthy, Amanda D

    2012-02-01

    Inducing an intramolecular reaction is a powerful means of accelerating reactions. Though this mechanism of catalysis is common in enzymes, it is underutilized in synthetic catalysts. This article outlines our group's recent efforts to use reversible covalent bonding to induce an intramolecular reaction, allowing for rate acceleration as well as control of the selectivity in the desymmetrization of 1,2-diols.

  18. Ternary NiCoP nanosheet arrays: An excellent bifunctional catalyst for alkaline overall water splitting

    Institute of Scientific and Technical Information of China (English)

    Yingjie Li; Haichuan Zhang; Ming Jiang; Yun Kuang; Xiaoming Sun; Xue Duan

    2016-01-01

    Exploring bifunctional catalysts for the hydrogen and oxygen evolution reactions (HER and OER) with high efficiency,low cost,and easy integration is extremely crucial for future renewable energy systems.Herein,ternary NiCoP nanosheet arrays (NSAs) were fabricated on 3D Ni foam by a facile hydrothermal method followed by phosphorization.These arrays serve as bifunctional alkaline catalysts,exhibiting excellent electrocatalytic performance and good working stability for both the HER and OER.The overpotentials of the NiCoP NSA electrode required to drive a current density of 50 mA/cm2 for the HER and OER are as low as 133 and 308 mV,respectively,which is ascribed to excellent intrinsic electrocatalytic activity,fast electron transport,and a unique superaerophobic structure.When NiCoP was integrated as both anodic and cathodic material,the electrolyzer required a potential as low as ~1.77 V to drive a current density of 50 mA/cm2 for overall water splitting,which is much smaller than a reported electrolyzer using the same kind of phosphide-based material and is even better than the combination of Pt/C and Ir/C,the best known noble metal-based electrodes.Combining satisfactory working stability and high activity,this NiCoP electrode paves the way for exploring overall water splitting catalysts.

  19. The Sulfidation of gamma-Alumina and Titania Supported (Cobalt) Molybdenum Oxide Catalysts Monitored by EXAFS.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Leliveld, R.G.; Dillen, A.J. van; Geus, John W.

    1997-01-01

    The sulfidation of @c-alumina- and titania-supported(cobalt)molybdenum oxide catalysts has been studied with X-rayabsorption spectroscopy and temperature programmed sulfidation (TPS).The catalysts were stepwise sulfided at temperatures between 298 and673 K and their structure was determined with EXA

  20. Bifunctional Nanoparticle-SILP Catalysts (NPs@SILP) for the Selective Deoxygenation of Biomass Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Luska, Kylie L. [RWTH Aachen Univ. (Germany); Julis, Jennifer [RWTH Aachen Univ. (Germany); Evonik Industries AG, Marl (Germany); Stavitski, Eli [Brookhaven National Lab. (BNL), Upton, NY (United States); Zakharov, Dmitri N. [Brookhaven National Lab. (BNL), Upton, NY (United States); Adams, Alina [RWTH Aachen Univ. (Germany); Leitner, Walter [RWTH Aachen Univ. (Germany); Max Planck Inst. for Coal Research, Ruhr (Germany)

    2014-08-27

    We immobilized ruthenium nanoparticles onto an acidic supported ionic liquid phase (RuNPs@SILP) in the development of bifunctional catalysts for the selective deoxygenation of biomass substrates. RuNPs@SILPs possessed high catalytic activities, selectivities and recyclabilities in the hydrogenolytic deoxygenation and ring opening of C8- and C9-substrates derived from furfural or 5-hydroxymethylfurfural and acetone. When we tailor the acidity of the SILP through the ionic liquid loading provided a molecular parameter by which the catalytic activity and selectivity of the RuNPs@SILPs were controlled to provide a flexible catalyst system toward the formation of different classes of value-added products: cyclic ethers, primary alcohols or aliphatic ethers.

  1. L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

    KAUST Repository

    Zhong, Fangrui

    2011-03-18

    A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

  2. Hydroisomerization of Ethylbenzene on Mordenite-Based Bifunctional Catalysts with Different Platinum Contents

    Directory of Open Access Journals (Sweden)

    Fernandes L.D.

    1998-01-01

    Full Text Available A commercial Na-mordenite sample underwent ion exchange with HCl. The ion-exchanged sample was sequentially submitted to hydrothermal treatments at 823, 873 and 923 K, each followed by acid leaching of the extraframework alumina (EFAL generated. Six mordenite samples, presenting different framework and extraframework compositions, were obtained. These samples were used to prepare bifunctional catalysts by mixing them with Pt/Al2O3 in different proportions. The generated samples presented distinct platinum contents and were tested in the hydroisomerization reaction of ethylbenzene. A maximum xylene selectivity at about 0.45 wt% of platinum was observed. Normally, the total activity increased as the platinum content increased; this effect was more pronounced in the samples which presented lower mesoporosity. The most dealuminated sample, which presented a high mesoporosity, did not show any change in activity with the increase in platinum content.

  3. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide.

    Science.gov (United States)

    Hasegawa, Jun-Ya; Miyazaki, Ray; Maeda, Chihiro; Ema, Tadashi

    2016-10-01

    Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

  4. Catalytic characterization of bi-functional catalysts derived from Pd–Mg–Al layered double hydroxides

    Indian Academy of Sciences (India)

    N N Das; S C Srivastava

    2002-08-01

    Hydrotalcite like precursors containing PdII–MgII–AlIII with varying molar ratios, (Pd + Mg)/Al ≈ 3 and Mg/Pd ≈ 750 to 35, were prepared by coprecipitation of metal nitrates at constant pH. Characterization of samples as synthesized and their calcined products by elemental analyses, powder XRD, TG–DTA, FT–IR spectroscopy, TPR and N2 physisorption indicated a well crystalline hydrotalcite like structure with incorporation of Pd2+ in the brucite layers. Thermal decomposition of hydrotalcite precursors at intermediate temperatures led to amorphous mixed oxides, Pd/MgAl(O), which on reduction yielded bi-functional catalyst, Pd°/MgAl(O). The resultant catalysts with acid, base and hydrogenating sites, were highly active and selective for one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen. The results showed an optimal balance between acid-base and metallic sites were required to increase the selectivity of MIBK and stability of the catalysts.

  5. Synergistic bifunctional catalyst design based on perovskite oxide nanoparticles and intertwined carbon nanotubes for rechargeable zinc-air battery applications.

    Science.gov (United States)

    Lee, Dong Un; Park, Hey Woong; Park, Moon Gyu; Ismayilov, Vugar; Chen, Zhongwei

    2015-01-14

    Advanced morphology of intertwined core-corona structured bifunctional catalyst (IT-CCBC) is introduced where perovskite lanthanum nickel oxide nanoparticles (LaNiO3 NP) are encapsulated by high surface area network of nitrogen-doped carbon nanotubes (NCNT) to produce highly active and durable bifunctional catalyst for rechargeable metal-air battery applications. The unique composite morphology of IT-CCBC not only enhances the charge transport property by providing rapid electron-conduction pathway but also facilitates in diffusion of hydroxyl and oxygen reactants through the highly porous framework. Confirmed by electrochemical half-cell testing, IT-CCBC in fact exhibits very strong synergy between LaNiO3 NP and NCNT demonstrating bifunctionality with significantly improved catalytic activities of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, when compared to the state-of-art catalysts, IT-CCBC outperforms Pt/C and Ir/C in terms of ORR and OER, respectively, and shows improved electrochemical stability compared to them after cycle degradation testing. The practicality of the catalyst is corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where IT-CCBC demonstrates superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. These improved electrochemical properties of the catalyst are attributed to the nanosized dimensions of LaNiO3 NP controlled by simple hydrothermal technique, which enables prolific growth of and encapsulation by highly porous NCNT network. The excellent electrochemical results presented in this study highlight IT-CCBC as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery applications.

  6. XAFS characterization of industrial catalysts: in situ study of phase transformation of nickel sulfide

    Science.gov (United States)

    Wang, J.; Jia, Z.; Wang, Q.; Zhao, S.; Xu, Z.; Yang, W.; Frenkel, A. I.

    2016-05-01

    The online sulfiding process for nickel-contained catalyst often ends up with a nickel sulfide mixture in refinery plant. To elucidate the local environment of nickel and its corresponding sulfur species, a model catalyst (nickel sulfide) and model thermal process were employed to explore the possibilities for characterization of real catalysts in industrial conditions. The present investigation shows effectiveness of in situ XANES and EXAFS measurements for studying the phase stability and phase composition in these systems, which could be used to simulate real sulfiding process in industrial reactions, such as hydrodesulfurizations of oil.

  7. Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application.

    Science.gov (United States)

    Chen, Zhu; Yu, Aiping; Higgins, Drew; Li, Hui; Wang, Haijiang; Chen, Zhongwei

    2012-04-11

    A new class of core-corona structured bifunctional catalyst (CCBC) consisting of lanthanum nickelate centers supporting nitrogen-doped carbon nanotubes (NCNT) has been developed for rechargeable metal-air battery application. The nanostructured design of the catalyst allows the core and corona to catalyze the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), respectively. These materials displayed exemplary OER and ORR activity through half-cell testing, comparable to state of the art commercial lanthanum nickelate (LaNiO(3)) and carbon-supported platinum (Pt/C), with added bifunctional capabilities allowing metal-air battery rechargeability. LaNiO(3) and Pt/C are currently the most accepted benchmark electrocatalyst materials for the OER and ORR, respectively; thus with comparable activity toward both of these reactions, CCBC are presented as a novel, inexpensive catalyst component for the cathode of rechargeable metal-air batteries. Moreover, after full-range degradation testing (FDT) CCBC retained excellent activity, retaining 3 and 13 times greater ORR and OER current upon comparison to state of the art Pt/C. Zinc-air battery performances of CCBC is in good agreement with the half-cell experiments with this bifunctional electrocatalyst displaying high activity and stability during battery discharge, charge, and cycling processes. Owing to its outstanding performance toward both the OER and ORR, comparable with the highest performing commercial catalysts to date for each of the respective reaction, coupled with high stability and rechargeability, CCBC is presented as a novel class of bifunctional catalyst material that is very applicable to future generation rechargeable metal-air batteries.

  8. Preparation of IrO2 nanoparticles with SBA-15 template and its supported Pt nanocomposite as bifunctional oxygen catalyst

    Science.gov (United States)

    Kong, Fan-Dong; Liu, Jing; Ling, Ai-Xia; Xu, Zhi-Qiang; Wang, Hui-Yun; Kong, Qing-Sheng

    2015-12-01

    In the present work, we report the syntheses of IrO2 nanoparticles with SBA-15 template (s-IrO2), and s-IrO2 supported Pt nanocomposite (Pt/s-IrO2) as bifunctional oxygen catalyst. Physical characterizations including X-ray diffraction and transmission electron microscopy demonstrate that s-IrO2 catalyst has excellent uniformity and regularity in particle shape and much ordered distribution in geometric space, and Pt/s-IrO2 catalyst shows a uniform Pt dispersion on the surface of the s-IrO2 particles. Electrochemical analyses prove that s-IrO2 catalyst possesses superior OER activity at operating potentials; and that Pt/s-IrO2 catalyst, in comparison to Pt/commercial IrO2, has higher ESA value and ORR catalytic performance with a mechanism of four-electron pathway and a high ORR efficiency. And as a bifunctional oxygen catalyst, Pt/s-IrO2 also exhibits more remarkable OER performance than the commercial one. The s-IrO2 nanoparticles will be a promising active component (for OER), and suitable for Pt support (for ORR).

  9. A bifunctional palladium-acid solid catalyst performs the direct synthesis of cyclohexylanilines and dicyclohexylamines from nitrobenzenes

    OpenAIRE

    Rubio Marqués, Paula; Leyva Perez, Antonio; Corma Canós, Avelino

    2013-01-01

    Nitroderivatives are transformed to cyclohexylanilines at room temperature in good yields and selectivity via a hydrogenation-amine coupling cascade reaction using Pd nanoparticles on carbon as a catalyst and a Bronsted acid. Consolider-Ingenio MULTICAT subprograma de Apoyo a Centros y Universidades de Excelencia Severo Ochoa SEV 2012 0267 MICINN MAT2009-00889 FPU contract ITQ Rubio Marqués, P.; Leyva Perez, A.; Corma Canós, A. (2013). A bifunctional palladium-acid solid ca...

  10. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    Science.gov (United States)

    Yik, Edwin Shyn-Lo

    The presence of heteroatoms (e.g. S, N) in crude oil poses formidable challenges in petroleum refining processes as a result of their irreversible binding on catalytically active sites at industrially relevant conditions. With increasing pressures from legislation that continues to lower the permissible levels of sulfur content in fuels, hydrodesulfurization (HDS), the aptly named reaction for removing heteroatoms from organosulfur compounds, has become an essential feedstock pretreatment step to remove deleterious species from affecting downstream processing. Extensive research in the area has identified the paradigm catalysts for desulfurization; MoSx or WSx, promoted with Co or Ni metal; however, despite the vast library of both empirical and fundamental studies, a clear understanding of site requirements, the elementary steps of C-S hydrogenolysis, and the properties that govern HDS reactivity and selectivity have been elusive. While such a lack of rigorous assessments has not prevented technological advancements in the field of HDS catalysis, fundamental interpretations can inform rational catalyst and process design, particularly in light of new requirements for "deep" desulfurization and in the absence of significant hydrotreatment catalyst developments in recent decades. We report HDS rates of thiophene, which belongs to a class of compounds that are most resistant to sulfur removal (i.e. substituted alkyldibenzothiophenes), over a range of industrially relevant temperatures and pressures, measured at differential conditions and therefore revealing their true kinetic origins. These rates, normalized by the number of exposed metal atoms, on various SiO 2-supported, monometallic transition metals (Re, Ru, Pt), range several orders of magnitude. Under relevant HDS conditions, Pt and Ru catalysts form a layer of chemisorbed sulfur on surfaces of a metallic bulk, challenging reports that assume the latter exists as its pyrite sulfide phase during reaction. While

  11. Bifunctional carbohydrate biopolymers entrapped lipase as catalyst for the two consecutive conversions of α-pinene to oxy-derivatives.

    Science.gov (United States)

    Tudorache, Madalina; Gheorghe, Andreea; Negoi, Alina; Enache, Madalin; Maria, Gabriel-Mihai; Parvulescu, Vasile I

    2016-11-01

    Bifunctional catalysts designed as carbohydrate biopolymers entrapping lipase have been investigated for the biotransformation of a natural compound (α-pinene) to oxy-derivatives. Lipases assisted the epoxidation of α-pinene using H2O2 as oxidation reagent and ethyl acetate as both acetate-supplier and solvent affording α-pinene oxide as the main product. Further, the biopolymer promoted the isomerization of α-pinene oxide to campholenic aldehyde and trans-carenol. In this case, the biopolymers played double roles of the support and also active part of the bifunctional catalyst. Screening of enzymes and their entrapping in a biopolymeric matrix (e.g. Ca-alginate and κ-carrageenan) indicated the lipase extracted from Aspergillus niger as the most efficient. In addition, the presence of biopolymers enhanced the catalytic activity of the immobilized lipase (i.e. 13.39×10(3), 19.76×10(3)and 26.46×10(3) for the free lipase, lipase-carrageenan and lipase-alginate, respectively). The catalysts stability and reusability were confirmed in eight consecutively reaction runs.

  12. Efficient bifunctional catalyst lipase/organophosphonic acid-functionalized silica for biodiesel synthesis by esterification of oleic acid with ethanol.

    Science.gov (United States)

    Yin, Ping; Chen, Wen; Liu, Wei; Chen, Hou; Qu, Rongjun; Liu, Xiguang; Tang, Qinghua; Xu, Qiang

    2013-07-01

    An efficient bifunctional catalyst lipase/organophosphonic acid-functionalized silica (SG-T-P-LS) has been successfully developed, and biodiesel production of fatty acid ethyl ester (FAEE) from free fatty acid (FFA) oleic acid with short-chain alcohol ethanol catalyzed by SG-T-P-LS was investigated. The process optimization using response surface methodology (RSM) was performed and the interactions between the operational variables were elucidated, and it was found that the molar ratio of alcohol to acid was the most significant factor. The optimum values for maximum conversion ratio can be obtained by using a Box-Behnken center-united design, and the conversion ratio could reach 89.94 ± 0.42% under the conditions that ethanol/acid molar ratio was 1.05:1 and SG-T-P-LS to FFA weight ratio was 14.9 wt.% at 28.6°C. The research results show that SG-T-P and LS-20 could work cooperatively to promote the esterification reaction, and the bifunctional catalyst SG-T-P-LS is a potential catalyst for biodiesel production.

  13. QEXAFS study of the sulfidation of NiMo/Al2O3 hydrotreating catalysts.

    Science.gov (United States)

    Cattaneo, R; Shido, T; Prins, R

    2001-03-01

    Quick-scanning extended X-ray absorption fine structure (QEXAFS) spectroscopy was employed to investigate in situ the sulfidation of Mo and Ni in y-AI2O3-supported hydrotreating catalysts modified with chelating ligands. Mo K-edge QEXAFS enabled the detection of an intermediate product in the sulfidation of Mo. The parameters obtained from the fits of the QEXAFS spectra showed that this product consists of compounds similar to Mo2S2-(12) or Mo3S2-(13). QEXAFS also demonstrated that the sulfidation of Ni is strongly influenced by the presence of chelating ligands. Classical EXAFS spectra of the sulfided catalysts showed that Ni forms small sulfided clusters, the size of which is influenced by the presence or absence of the chelating agents.

  14. Zinc Oxide Hydrogen Sulfide Removal Catalyst/ Preparation, Activity Test and Kinetic Study

    Directory of Open Access Journals (Sweden)

    Ameel. M. Rahman

    2008-01-01

    Full Text Available Hydrogen sulfide removal catalyst was prepared chemically by precipitation of zinc bicarbonate at a controlled pH. The physical and chemical catalyst characterization properties were investigated. The catalyst was tested for its activity in adsorption of H2S using a plant that generates the H2S from naphtha hydrodesulphurization and a unit for the adsorption of H2S. The results comparison between the prepared and commercial catalysts revealed that the chemical method can be used to prepare the catalyst with a very good activity.It has observed that the hydrogen sulfide removal over zinc oxide catalyst follows first order reaction kinetics with activation energy of 19.26 kJ/mole and enthalpy and entropy of activation of 14.49 kJ/mole and -220.41 J/mole respectively.

  15. Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals.

    Science.gov (United States)

    Luo, Rongchang; Chen, Yaju; He, Qian; Lin, Xiaowei; Xu, Qihang; He, Xiaohui; Zhang, Wuying; Zhou, Xiantai; Ji, Hongbing

    2016-12-31

    A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO2 /N2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO2 /epoxides cycloaddition and Nformylation of amines from CO2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO2 near the catalytic centers in the CO2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts.

  16. 3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Park, Moon Gyu; Lee, Dong Un; Seo, Min Ho; Cano, Zachary Paul; Chen, Zhongwei

    2016-05-01

    To enhance energy efficiency and durability, a highly active and durable 3D ordered mesoporous cobalt oxide framework has been developed for rechargeable zinc-air batteries. The bifunctional air electrode consisting of 3DOM Co3 O4 having high active surface area and robust structure, results in superior charge and discharge battery voltages, and durable performance for electrically rechargeable zinc-air batteries.

  17. Synthesis and characterization of bifunctional transition-metal/silica-alumina catalysts for the chloromethane conversion to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Sousa, J.F. [Universidade Federal de Rio de Grande do Norte (UFRN), Natal, RN (Brazil). Programa de Pos-Graduacao em Engenharia Quimica; Rojas, L.O.A.; Nascimento, J.C. [Universidade Federal de Rio de Grande do Norte (UFRN), Natal, RN (Brazil). Programa de Pos-Graduacao em Engenharia Quimica; Centro de Tecnologias do Gas (CTGAS), Natal, RN (Brazil)], E-mail: leopoldo@ctgas.com.br; Ruiz, J.A.C. [Centro de Tecnologias do Gas (CTGAS), Natal, RN (Brazil); Benachour, M. [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Programa de Pos-Graduacao em Engenharia Quimica

    2008-10-15

    In this work bifunctional (metal-acid) catalysts of Fe, Ni, Fe{sub 2}O{sub 3} and NiO over amorphous silica alumina support were characterized (acidity) and evaluated for the conversion of chloromethane in a fixed bed reactor. Temperature program tests TPD (Temperature Programmed Desorption) and TPR (Temperature Programmed Reduction) were performed to characterize the chemisorption sites for the impregnated and unimpregnated support. New adsorption sites were created on the metal supported catalysts. The conversion yield of chloromethane was evaluated for the five materials. The highest conversion conversion (85%) was observed for the unmodified support (SiAl) after 6 of reaction at 860 K and a WHSV (Weight Hourly Space Velocity) of 4,5 h{sup -1}. The best selectivity toward desirable hydrocarbons (C{sup 3}, C{sup 4}) was found for the Fe-SiAl catalyst. C{sup 3} was also found in the products stream when Ni/SiAl and NiO/SiAl catalysts were tested. Ni catalysts were the most favorable to methane production. The catalytic tests showed coke formation in all materials. For the SiAl support the desorption energy of chloromethane, determined by TPD runs, was 101,9 KJ/mol. The metals presented lower desorption energies (75,2 KJ/mol for Ni and 133,4 KJ/mol for Fe) than the oxides (190,1 KJ/mol for Fe{sub 2}O{sub 3} and 322,4 KJ/mol for NiO). (author)

  18. Influence of Metal Sulfides as Anode Catalysts on Performance of H2S SOFC

    Institute of Scientific and Technical Information of China (English)

    钟理; 刘曼; 韩国林; CHUANGKar

    2003-01-01

    Two anode catalysts with Pt, MoS2 and composite metal sulfides (MoS2+NiS), are investigated for electrochemical oxidation of hydrogen sulfide in solid oxide fuel cell (SOFC) at temperatures 750-850℃. The catalysts comprising MoS2 and MoS2+NiS exhibited good electrical conductivity and catalytic activity. MoS2 and composite catalysts were found to be more active than Pt, a widely used catalyst for high temperature H2S/O2 fuel cell at 750-850℃. However, MoS2 itself sublimes above 450℃. In contrast, composite catalysts containing both Mo and transition metal (Ni) are shown to be stable and effective in promoting the oxidation of H2S in SOFC up to 850℃. However, electric contact is poor between the platinum current collecting layer and the composite metal sulfide layer, so that the cell performance becomes worse. This problem is overcome by adding conductive Ag powder into the anode layer (forming MoS2+NiS+Ag anode material) to increase anode electrical conductance instead of applying a thin laver of platinum on the top of anode.

  19. Bifunctional catalysts based on m-phenylene-bridged porphyrin dimer and trimer platforms: synthesis of cyclic carbonates from carbon dioxide and epoxides.

    Science.gov (United States)

    Maeda, Chihiro; Taniguchi, Tomoya; Ogawa, Kanae; Ema, Tadashi

    2015-01-01

    Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO2 with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220 000 and 46 000 h(-1) , respectively, for the magnesium catalyst, and 310 000 and 40 000 h(-1) , respectively, for the zinc catalyst. Results obtained with a zinc/free-base hybrid diporphyrin catalyst demonstrated that the Br(-) ions on the adjacent porphyrin moiety also function as nucleophiles.

  20. Self-assembly of cobalt-centered metal organic framework and multiwalled carbon nanotubes hybrids as a highly active and corrosion-resistant bifunctional oxygen catalyst

    Science.gov (United States)

    Fang, Yiyun; Li, Xinzhe; Li, Feng; Lin, Xiaoqing; Tian, Min; Long, Xuefeng; An, Xingcai; Fu, Yan; Jin, Jun; Ma, Jiantai

    2016-09-01

    Metal organic frameworks (MOF) derived carbonaceous materials have emerged as promising bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts for electrochemical energy conversion and storage. But previous attempts to overcome the poor electrical conductivity of MOFs hybrids involve a harsh high-template pyrolytic process to in situ form carbon, which suffer from extremely complex operation and inevitable carbon corrosion at high positive potentials when OER is operated. Herein, a self-assembly approach is presented to synthesize a non-precious metal-based, high active and strong durable Co-MOF@CNTs bifunctional catalyst for OER and ORR. CNTs not only improve the transportation of the electrons but also can sustain the harsh oxidative environment of OER without carbon corrosion. Meanwhile, the unique 3D hierarchical structure offers a large surface area and stable anchoring sites for active centers and CNTs, which enables the superior durability of hybrid. Moreover, a synergistic catalysis of Co(II), organic ligands and CNTs will enhance the bifunctional electrocatalytic performance. Impressively, the hybrid exhibits comparable OER and ORR catalytic activity to RuO2 and 20 wt% Pt/C catalysts and superior stability. This facile and versatile strategy to fabricating MOF-based hybrids may be extended to other electrode materials for fuel cell and water splitting applications.

  1. Vibrational Spectroscopic Studies of Hydrogen, Carbon-Monoxide and Thiophene Adsorption on Ruthenium-Sulfide and Sulfided Ruthenium Catalysts.

    Science.gov (United States)

    Heise, William Herbert

    The "working surface" of ruthenium hydrodesulfurization (HDS) catalysts has been modeled by preadsorption of sulfur, carbon and carbon plus sulfur on Ru(0001). Adsorption and decomposition of thiophene over these surfaces have been investigated using TDS/TPRS, XPS and EELS. Thiophene is proposed to decompose via a three-step mechanism involving: (i) initial thiophene cracking at 120 K yielding surface sulfur and hydrocarbon species, (ii) hydrogen desorption near 230 K providing additional decomposition ensembles and (iii) continued decomposition to form "metallocycle -like" intermediates which retain EELS features similar to thiophene. Preadsorbed carbon or carbon plus sulfur are not as effective for passivation of the surface toward metallocycle formation as preadsorbed sulfur alone. This result is attributed to the fact that carbon deposited from butadiene annealed and decomposed at 700 K forms islands, while sulfur establishes a well-ordered superlattice on the surface. The decrease in metallocycle formation with increasing poison levels appears to explain HDS selectivity and specific activity trends observed in our laboratory from mildly sulfided (10% H_2S/H_2 , 673 K, 2h) ruthenium catalysts retaining submonolayers of sulfur. Incoherent inelastic neutron scattering (IINS) has been used to characterize hydrogen adsorption sites on ruthenium sulfide. Hydrogen resides on sulfur anions to form SH groups, yielding two non-degenerate bending modes at 600 and 710 cm^{-1}. Complementary hydrogen adsorption and H_2/D _2 exchange data suggest that the active sites for hydrogen adsorption may be coordinatively unsaturated S-S anion pairs. Comparison of CO adsorption on sulfided Ru/Al _2O_3 to sulfur precovered Ru(0001) reveals an adsorption site related to edge/corner atoms directly perturbed by sulfur, consistent with previous kinetic studies demonstrating higher specific activity for thiophene HDS over smaller ruthenium crystallites.

  2. Sulfiding behavior of iron based coal liquefaction catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ikenaga, N.; Taniguchi, H.; Watanabe, A.; Suzuki, T. [Kansai University, Osaka (Japan). Dept. of Chemical Engineering

    2000-03-01

    In order to understand the transformation mechanisms of iron-sulfur catalyst systems to pyrrhotite, the iron catalysts ({gamma}-FeOOH, {alpha}-FeOOH, Fe(CO){sub 5} and Fe{sub 3}(CO){sub 12}) and sulfur compounds (S and H{sub 2}S) were treated at 150-420{degree}C with or without an activated carbon, and then subjected to XRD and XPS analyses. Pyrrhotite (Fe{sub 1-x}S) was the major phase above 200{degree}C in the XRD profiles of all iron-sulfur catalyst systems. However, the formation of pyrite (FeS{sub 2}) from {gamma}-FeOOH and {gamma}-FeOOH on the catalyst surface was observed at 150-325{degree}C by XPS analyses. This result seems to indicate that active species (Fe{sub 1-x}S) would be transformed through FeS{sub 2} as an intermediate, but iron carbonyl complexes were directly transformed into pyrrhotite without the formation of FeS{sub 2}. 28 refs., 8 figs., 1 tab.

  3. Preparation, structural characterization of a novel egg-shell palladium sulfide catalyst and its application in selective reductive alkylation reaction

    Institute of Scientific and Technical Information of China (English)

    Qun Feng Zhang; Xiao Nian Li; Jia Chun Wu; Chang Su; Feng Feng; Qiao Ling Ding; Zhao Lian Yuan; Hong Wang; Lei Ma; Chun Shan Lu

    2012-01-01

    A novel egg-shell Pd-S catalyst with palladium metal as the core and a membrane of palladium sulfide as the surface has been prepared by sulphidizing Pd/C with H2S.This catalyst is effective for the reductive alkylation of p-amino diphenylamine (PADPA)and methylisobutyl ketone (MIBK) to afford N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenedianine (DBPPD) with conversion up to 99.42% and selectivity to 97.46%.Comparing with the other common palladium sulfide catalysts,the membrane of palladium sulfide on the surface and the core of palladium metal cause the Pd on the surface of the new catalyst in a lower sulfur coordination,which improves its activity.Our result indicates that this new egg-shell Pd-S/C is an efficient hydrogenation catalyst.

  4. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    Science.gov (United States)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  5. Asymmetric α-amination of 3-substituted oxindoles using chiral bifunctional phosphine catalysts

    Directory of Open Access Journals (Sweden)

    Qiao-Wen Jin

    2016-04-01

    Full Text Available A highly enantioselective α-amination of 3-substituted oxindoles with azodicarboxylates catalyzed by amino acids-derived chiral phosphine catalysts is reported. The corresponding products containing a tetrasubstituted carbon center attached to a nitrogen atom at the C-3 position of the oxindole were obtained in high yields and with up to 98% ee.

  6. Influence of Gas Components on the Formation of Carbonyl Sulfide over Water-Gas Shift Catalyst B303Q

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Water-gas shift reaction catalyst at lower temperature (200-400 ℃) may improve the conversion of carbon monoxide. But carbonyl sulfide was found to be present over the sulfided cobaltmolybdenum/alumina catalyst for water-gas shift reaction. The influences of temperature, space velocity,and gas components on the formation of carbonyl sulfide over sulfided cobalt-molybdenum/alumina catalyst B303Q at 200-400 ℃ were studied in a tubular fixed-bed quartz-glass reactor under simulated water-gas shift conditions. The experimental results showed that the yield of carbonyl sulfide over B303Q catalyst reached a maximum at 220 ℃ with the increase in temperature, sharply decreased with the increase in space velocity and the content of water vapor, increased with the increase in the content of carbon monoxide and carbon dioxide, and its yield increased and then reached a stable value with the increase in the content of hydrogen and hydrogen sulfide. The formation mechanism of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was discussed on the basis of how these factors influence the formation of COS. The yield of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was the combined result of two reactions, that is, COS was first produced by the reaction of carbon monoxide with hydrogen sulfide,and then the as-produced COS was converted to hydrogen sulfide and carbon dioxide by hydrolysis. The mechanism of COS formation is assumed as follows: sulfur atoms in the Co9Ss-MoS2/Al2O3 crystal lattice were easily removed and formed carbonyl sulfide with CO, and then hydrogen sulfide in the water-gas shift gas reacted with the crystal lattice oxygen atoms in CoO-MoO3/Al2O3 to form Co9Ss-MoS2/Al2O3.This mechanism for the formation of COS over water-gas shift catalyst B303Q is in accordance with the Mars-Van Krevelen's redox mechanism over metal sulfide.

  7. Silver-Copper Nanoalloy Catalyst Layer for Bifunctional Air Electrodes in Alkaline Media.

    Science.gov (United States)

    Wu, Xiaoqiang; Chen, Fuyi; Jin, Yachao; Zhang, Nan; Johnston, Roy L

    2015-08-19

    A carbon-free and binder-free catalyst layer composed of a Ag-Cu nanoalloy on Ni foam was used as the air cathode in a zinc-air battery for the first time. The Ag-Cu catalyst was prepared using pulsed laser deposition. The structures of the catalysts were found to consist of crystalline Ag-Cu nanoalloy particles with an average size of 2.58 nm embedded in amorphous Cu films. As observed in the X-ray photoelectron spectra, the Ag 3d core levels shifted to higher binding energies, whereas the Cu 2p core levels shifted to lower binding energies, indicating alloying of the silver and copper. Rotating disk electrode measurements indicated that the oxygen reduction reaction (ORR) proceeded through a four-electron pathway on the Ag50Cu50 and Ag90Cu10 nanoalloy catalysts in alkaline solution. Moreover, the catalytic activity of Ag50Cu50 in the ORR is more efficient than that of Ag90Cu10. By performing charge and discharge cycling measurements, the Ag50Cu50 catalyst layer was confirmed to have a maximum power density of approximately 86.3 mW cm(-2) and an acceptable cell voltage at 0.863 V for current densities up to 100 mA cm(-2) in primary zinc-air batteries. In addition, a round-trip efficiency of approximately 50% at a current density of 20 mA cm(-2) was also obtained in the test.

  8. Synthesis of Ni-Mo-W sulfide nanorods as catalyst for hydrodesulfurization of dibenzothiophene.

    Science.gov (United States)

    Paraguay-Delgado, F; García-Alamilla, R; Lumbreras, J A; Cizniega, E; Alonso-Núñez, G

    2008-12-01

    Two trimetallic sulfurs, MoWNiS and MoWSNi, were synthesized to be used as a catalyst in hydrodesulfurization reactions. The mixed oxide mesoporous nanostructured MoO3 -WO3 with an Mo:W atomic ratio of 1:1 was used as the precursor. The first catalyst was prepared by impregnating nickel in the oxide precursor and then subsequent sulfiding with an H2S/H2 mix at 400 degrees C for 2 hours. The second catalyst was prepared by sulfiding the precursor and then impregnating the nickel, and finally reducing the material with a H2/N2 at 350 degrees C. In both catalysts the Mo:W:Ni atomic ratio was maintained at 1:1:0.5. The materials obtained were characterized by physical adsorption of nitrogen, X-ray diffraction, scanning electron microscopy, transmission electron microscopy. Furthermore, the materials obtained were evaluated by a dibenzothiophene hydrodesulfuration reaction. The diffraction patterns show that both materials are polycrystalline and mainly of MoS2 and WS2 phases.

  9. Characterization of the active site structure of Pd and Pd-promoted Mo sulfide catalysts by means of XAFS.

    Science.gov (United States)

    Kubota, T; Okamoto, Y

    2001-03-01

    Recently, noble metal catalysts are noted as promising candidates for new super-deep-hydrodesulfurization (HDS) catalysts. In this study, we investigated the structure of Pd particles supported on zeolite and Al2O3 under a sulfidation or reduction condition. From EXAFS analysis, it was found for sulfided Pd catalysts that small Pd sulfide clusters are formed without sintering. It was also revealed that no extensive growth of metal Pd particles occurs in Pd/NaY sulfide catalysts even after a treatment with H2 at 673 K. The dispersion of Pd metal particles is improved by H2/H2S treatment. These results indicate that in the presence of H2S, Pd shows high resistance against particle growth. A comparison of the Mo and Pd K-edge EXAFS spectra for MoS(x)/Pd-NaY and Pd-NaY catalysts revealed the existence of Mo-Pd bondings by the addition of Mo sulfide, indicating a direct interaction between Mo and Pd sulfides.

  10. Sulfide catalysts made of cobalt and hydroxyapatite; Catalyseurs sulfures a base de cobalt et d`hydroxyapatite

    Energy Technology Data Exchange (ETDEWEB)

    El Ouassouli, A.; Ezzemouri, S.; Ezzamarty, A.; Lakhdar, M. [Faculte des Sciences Hassan 2, Casablanca (Morocco). Lab. de Catalyse Heterogene; Leglise, J. [Centre National de la Recherche Scientifique (CNRS-ISMRA) Lab. de Catalyse et Spectrochimie, 14 - Caen (France)

    1999-07-01

    We have prepared a series of catalysts combining cobalt and a hydroxyapatite by coprecipitation in a basic medium. These sulfided solids catalyze the hydro-desulfurization of dimethyl-disulfide at 360 deg C and its hydrogenolysis int CH{sub 3}SH at 200 deg C. The coprecipitated solids are found more active than the impregnated catalysts because they exhibit a better dispersion of the active Co-S phase at higher Co content. With the precipitated catalysts, Co ions substitute for Ca ions into the apatite structure. The formation of large sulfide particles is thus more difficult as a result of sulfiding because the Co ions have to move to the surface. The apatite catalysts are intrinsically as active as their homologous Co/Al{sub 2}O{sub 3} (used in gas oils desulfurization. (authors) 20 refs.

  11. In situ sulfiding of Ni-W hydrocracking catalysts : differentiation of different preparation procedures using EXAFS and HRTEM.

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, S. D.; Yang, N.; Mickelson, G. E.; Greenlay, N.; Karapetrova, E.; Sinkler, W.; Bare, S. R.; UOP LLC; EXAFS Analysis

    2009-01-01

    The detailed structural characterization of the metal function of two fully formulated Ni-W hydrocracking catalysts was investigated by time resolved in situ X-ray absorption spectroscopy (EXAFS and XANES) at both the Ni K-edge and W L{sub 3}-edge, and by high resolution transmission electron microscopy. These two hydrocracking catalysts (designated as HCA and HCB) contained the same wt% of Ni and W, the same wt% of the other constituents ({gamma}-Al{sub 2}O{sub 3}/silico-aluminate), and were calcined at the same temperature, but were prepared by different methods in order to highlight the sensitivity of the characterization techniques to the structural differences. The morphology of the WS{sub 2} particles in the sulfided catalyst is substantially different between the two catalysts: in the HCA catalyst there are many more particles with multiple WS{sub 2} layers whereas in HCB there are more single layers. The average diameter of the WS{sub 2} plates is similar in both. The catalysts show a difference in the amount of W sulfidation after the 410 C sulfidation treatment in 10% H{sub 2}S/H{sub 2}. The W of HCA catalyst was completely sulfided whereas 16% W of HCB catalyst was unsulfided. Similarly there is a difference in the amount of sulfided Ni: 16% Ni in HCA and 60% Ni in HCB remain unsulfided. In the sulfided form of both catalysts the Ni exists in three different morphologies: oxidized Ni (six-fold coordinate as a nickel aluminate), nanoparticulate Ni{sub 3}S{sub 2}, and Ni decorating the edge sites of the WS{sub 2}. In both the Ni{sub 3}S{sub 2}, and Ni decorating the edge sites of the WS{sub 2}, the Ni is in a tetrahedral coordination with sulfur. In both catalysts the sulfidation of the Ni and W occurs essentially simultaneously over most of the temperature range and the sulfidation of the W proceeds through the same tungsten oxysulfide in both samples. The characterization methodology presented here is a powerful one for elucidating the structural

  12. Molecular metal sulfide cluster model for substrate binding to oil-refinery hydrodesulfurization catalysts.

    Science.gov (United States)

    Herbst, Konrad; Monari, Magda; Brorson, Michael

    2002-03-25

    Reaction between [(eta5-Cp')3Mo3S4]+ and [Ni(1,5-cod)2] (Cp' = methylcyclopentadienyl; 1,5-cod = 1,5-cyclooctadiene) in THF at ambient temperature yielded a coordinatively unsaturated cubane-like cluster cation, [(eta5-Cp')3Mo3S4Ni]+. The ligand sphere at the Ni atom could be saturated by coordinating dimethyl sulfide, diethyl sulfide, di(tert-butyl) sulfide, tetrahydrothiophene, thiochroman-4-ol, 1,4-dithiane, pyridine, quinoline, or 4,4'-bipyridine. The products structurally model a mode of substrate coordination on proposed binding sites of heterogeneous MoNi sulfide hydrotreating catalysts. No stable coordination compounds could be isolated for thiophene derivatives. X-ray crystal structures are reported for the ligand-bridged dicluster compounds [[(eta5-Cp')3Mo3S4Ni]2(mu-C4H4S2)][pts]2 (C4H8S2 = 1,4-dithiane) and [[(eta5-Cp')3Mo3S4Ni]2(mu-bipy)][pts]2 (bipy = 4,4'-bipyridine).

  13. Cobalt Nanoparticle-Embedded Porous Carbon Nanofibers with Inherent N- and F-Doping as Binder-Free Bifunctional Catalysts for Oxygen Reduction and Evolution Reactions.

    Science.gov (United States)

    Singhal, Richa; Kalra, Vibha

    2017-01-18

    Efficient, low-cost, non-precious metal-based, and stable bifunctional electrocatalysts are key to various energy storage and conversion devices such as regenerative fuel cells and metal-air batteries. In this work, we report cobalt nanoparticle-embedded porous carbon nanofibers with inherent N- and F-doping as binder-free bifunctional electrocatalysts with excellent activity for both the oxygen reduction and oxygen evolution reaction (ORR/OER) in an alkaline medium. Single-step electrospinning of a solution of the polymer mixture (carbon precursor) and the cobalt precursor followed by controlled pyrolysis with an intermediate reduction step in H2 (to reduce cobalt oxides to cobalt) was utilized to synthesize an integrated freestanding catalyst. The fabricated catalyst with effective structural and electronic interaction between the cobalt metal nanoparticles and the N- and F-doped carbon defect sites showed enhanced catalytic properties compared to the benchmark catalysts for ORR and OER (Pt, Ir, and Ru). The ORR potential at the current density of -3 mA cm(-2) was 0.81 VRHE and the OER potential at a current density of 10 mA cm(-2) was 1.595 VRHE , resulting in a ΔE of only 0.785 V.

  14. Operando study of iridium acetylacetonate decomposition on amorphous silica-alumina for bifunctional catalyst preparation.

    Science.gov (United States)

    Nassreddine, Salim; Bergeret, Gérard; Jouguet, Bernadette; Geantet, Christophe; Piccolo, Laurent

    2010-07-28

    The decomposition of iridium acetylacetonate Ir(acac)(3) impregnated on amorphous silica-alumina (ASA) has been investigated by combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS) and by in situ X-ray diffraction (XRD). The resulting Ir/ASA hydrotreating catalysts have also been characterized by transmission electron microscopy (TEM). The effects of heating treatments under oxidative, reductive or inert gas flows are compared with each other and with similar experiments on ASA-supported acetylacetone (acacH). It is shown that Ir(acac)(3) undergoes exothermic combustion during calcination in air, leading to agglomerated IrO(2) particles. Conversely, direct reduction involves hydrogenolysis of the acac followed by hydrogenation of the ligand residues to alkanes and water. These two processes are catalyzed by Ir clusters, the gradual growth of which is followed in situ by XRD. The resulting nanoparticles are highly and homogeneously dispersed.

  15. Practical selective hydrogenation of α-fluorinated esters with bifunctional pincer-type ruthenium(II) catalysts leading to fluorinated alcohols or fluoral hemiacetals.

    Science.gov (United States)

    Otsuka, Takashi; Ishii, Akihiro; Dub, Pavel A; Ikariya, Takao

    2013-07-01

    Selective hydrogenation of fluorinated esters with pincer-type bifunctional catalysts RuHCl(CO)(dpa) 1a, trans-RuH2(CO)(dpa) 1b, and trans-RuCl2(CO)(dpa) 1c under mild conditions proceeds rapidly to give the corresponding fluorinated alcohols or hemiacetals in good to excellent yields. Under the optimized conditions, the hydrogenation of chiral (R)-2-fluoropropionate proceeds smoothly to give the corresponding chiral alcohol without any serious decrease of the ee value.

  16. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  17. 3D-modelling of bifunctional core-shell catalysts for the production of fuels from biomass-based synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Wenjin; Lee, Seung Cheol; Li, Hui; Pfeifer, Peter; Dittmeyer, Roland [Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen (Germany). Inst. for Micro Process Engineering (IMVT)

    2013-09-01

    Until now, the main route for the production of DME from synthesis gas in industry is methanol synthesis on a metallic catalyst and subsequent dehydration of methanol on an acid catalyst (two-step process). A single-step process using bifunctional catalysts to perform the two steps simultaneously would be preferred e.g. due to thermodynamic considerations; but this is impeded by the higher volumetric heat release which may cause deactivation of the methanol synthesis catalyst function. Thus we propose to conduct the reaction in a microchannel reactor. However, in order to increase the productivity of the microchannel reactor and to lower the investment costs, we aim at a high selectivity and activity of the catalyst. The continuously removal of methanol by dehydration on an acidic ZSM-5 catalyst as shell improves the thermodynamic conditions of methanol synthesis in the CuO/ZnO/Al{sub 2}O{sub 3} core; thus, the synthesis gas conversion can be higher than that determined by the thermodynamics of pure methanol synthesis. The molecular sieving in the zeolite layer can further lead to higher selectivity of DME at milder reaction conditions. However, mass transport limitation of the synthesis gas to the catalyst core should not hinder the reaction, and therefore a more detailed investigation is required. In order to computer-aided optimize the catalyst structure and the operating conditions for core-shell catalysts, a simulation model should be developed to study the coupled reaction and transport processes in core-shell catalysts. In this simulation model the complicated interaction of diffusion and reaction in the zeolite layer (shell) must be detailed by a network model to describe its structure and the mechanisms effectively. In addition, suitable diffusion and kinetic models are required to describe the mass transport and reactions in the layer. Suitable networks, diffusion and kinetic models are discussed for 3D simulations in this contribution. (orig.)

  18. An ethylene glycol intercalated monometallic layered double hydroxide based on iron as an efficient bifunctional catalyst.

    Science.gov (United States)

    Nagarajan, Rajamani; Gupta, Pankaj; Singh, Poonam; Chakraborty, Pinki

    2016-11-01

    Given the fact that the literature describing the intercalation of organic molecules in monometallic LDH systems is scarce, the present investigation is aimed at the generation of ethylene glycol intercalated Fe(II)-Fe(III) LDH with the objective of enhancing the surface area for further catalytic applications of industrially important and environmentally harmful organics. The solvothermal reaction of FeCl3 with urea in an ethylene glycol medium yielded a brown colored powder which was characterized employing a wide range of analytical techniques including high resolution powder X-ray diffraction (PXRD), scanning electron microscopy, thermal analysis, X-ray photo electron spectroscopy (XPS), elemental (C, H, N and S) analysis, UV-visible, photoluminescence spectroscopy measurements, BET surface area and pore-size analysis. The observed reflections in the PXRD pattern were indexed in a rhombohedral symmetry with a = 3.175 and c = 31.9 Å. Combining the results from the Fe 2p core level analysis and anion contents from elemental and thermogravimetric analysis, a formula of Fe(2+)1.06 Fe(3+)0.94 (O2C2H4) (OH)4 was deduced for the sample. The intercalation of EG in the interlayer was confirmed from FTIR and Raman spectroscopy measurements. The d-d transitions of the Fe(3+)-ion and the charge transfer transition of the Fe(ii)-Fe(iii) lattice were evident in the UV-visible spectrum. Blue indigoid emission bands arising from the transitions present in the Fe(3+)-ion were noticed in the photoluminescence spectrum. The measured BET surface area and pore diameter of the sample were 144 m(2) g(-1) and 12.5 nm, respectively. Almost instant decolourisation of the Xylenol Orange (XO) dye occurred in the presence of H2O2 and the LDH sample as catalyst. Similar observations were encountered for Methyl Orange (MO) and Methylene Blue (MB) dyes. All these reactions followed pseudo first-order kinetics. The industrially important reductive conversion of nitro aromatics was catalyzed

  19. Co3O4 nanoparticle-modified MnO2 nanotube bifunctional oxygen cathode catalysts for rechargeable zinc-air batteries

    Science.gov (United States)

    Du, Guojun; Liu, Xiaogang; Zong, Yun; Hor, T. S. Andy; Yu, Aishui; Liu, Zhaolin

    2013-05-01

    We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone.We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone. Electronic supplementary information (ESI) available: Zinc-air cell device, XPS survey scan and power density of the cell. See DOI: 10.1039/c3nr00300k

  20. Ionic Polymer Microspheres Bearing a Co(III) -Salen Moiety as a Bifunctional Heterogeneous Catalyst for the Efficient Cycloaddition of CO2 and Epoxides.

    Science.gov (United States)

    Leng, Yan; Lu, Dan; Zhang, Chenjun; Jiang, Pingping; Zhang, Weijie; Wang, Jun

    2016-06-01

    We report a unique strategy to obtain the bifunctional heterogeneous catalyst TBB-Bpy@Salen-Co (TBB=1,2,4,5-tetrakis(bromomethyl)benzene, Bpy=4,4'-bipyridine, Salen-Co=N,N'-bis({4-dimethylamino}salicylidene)ethylenediamino cobalt(III) acetate) by combining a cross-linked ionic polymer with a Co(III) -salen Schiff base. The catalyst showed extra high activity for CO2 fixation under mild, solvent-free reaction conditions with no requirement for a co-catalyst. The synthesized catalyst possessed distinctive spherical structural features, abundant halogen Br(-) anions with good leaving group ability, and accessible Lewis acidic Co metal centers. These unique features, together with the synergistic role of the Co and Br(-) functional sites, allowed TBB-Bpy@Salen-Co to exhibit enhanced catalytic conversion of CO2 into cyclic carbonates relative to the corresponding monofunctional analogues. This catalyst can be easily recovered and recycled five times without significant leaching of Co or loss of activity. Moreover, based on our experimental results and previous work, a synergistic cycloaddition reaction mechanism was proposed.

  1. MnCo2O4 nanowires anchored on reduced graphene oxide sheets as effective bifunctional catalysts for Li-O2 battery cathodes.

    Science.gov (United States)

    Kim, Jong Guk; Kim, Youngmin; Noh, Yuseong; Kim, Won Bae

    2015-05-22

    A hybrid composite system of MnCo2 O4 nanowires (MCO NWs) anchored on reduced graphene oxide (RGO) nanosheets was prepared as the bifunctional catalyst of a Li-O2 battery cathode. The catalysts can be obtained from the hybridization of one-dimensional MCO NWs and two-dimensional RGO nanosheets. As O2 -cathode catalysts for Li-O2 cells, the MCO@RGO composites showed a high initial discharge capacity (ca. 11092.1 mAh gcarbon (-1) ) with a high rate performance. The Li-O2 cells could run for more than 35 cycles with high reversibility under a limited specific capacity of 1000 mAh gcarbon (-1) with a low potential polarization of 1.36 V, as compared with those of pure Ketjenblack and MCO NWs. The high cycling stability, low potential polarization, and rate capability suggest that the MCO@RGO composites prepared here are promising catalyst candidates for highly reversible Li-O2 battery cathodes.

  2. Dimethyl ether synthesis from CO2 hydrogenation on La-modified CuO-ZnO-Al2O3/HZSM-5 bifunctional catalysts

    Institute of Scientific and Technical Information of China (English)

    GAO Wengui; WANG Hua; WANG Yuhao; GUO Wei; JIA Miaoyao

    2013-01-01

    A series of CuO-ZnO-A12O3-La2Oy/HZSM-5 bifunctional catalysts with various La loadings for dimethyl ether (DME) directly synthesized from CO2 hydrogenation were prepared.The catalysts were characterized with N2 adsorption-desorption,X-ray diffraction (XRD),H2 temperature-programmed reduction (H2-TPR),NH3 temperature-programmed desorption (NH3-TPD) and N2O titration techniques,and tested for the synthesis of DME directly from CO2 hydrogenation in a fixed-bed reactor.The results showed that the reducibility,dispersion ofbifunctional catalysts were strongly dependent on the addition of La.With the addition of appropriate amount of La,the crystallite size of CuO was decreased and the dispersion of Cu on the surface was enhanced,which resulted in the increased conversion of CO2.It was also found that the selectivity to DME was related to the intensity and amount of strong acid site on the catalyst surface.The presence of La favored the production of DME,and the optimum catalytic activity was obtained when the amount of La was 2.0 wt.%.

  3. The urchin-like sphere arrays Co3O4 as a bifunctional catalyst for hydrogen evolution reaction and oxygen evolution reaction

    Science.gov (United States)

    Li, Ruchun; Zhou, Dan; Luo, Jiaxian; Xu, Weiming; Li, Jingwei; Li, Shuoshuo; Cheng, Pengpeng; Yuan, Dingsheng

    2017-02-01

    Electrochemical water splitting has attracted great interest because of the growing demand for sustainable energy and increasing concerns for the environment. We present a facile strategy to design the three-dimensional (3D) urchin-like sphere arrays Co3O4 as an effective bifunctional catalyst for electrochemical water splitting. The 3D urchin-like Co3O4 was directly grown on Ni foam by a hydrothermal reaction and annealing treatment at a low temperature. This process offers several advantages including facile synthesis, binder-free, and low cost. The 3D urchin-like Co3O4 as a catalyst for hydrogen evolution reaction exhibits a low onset potential (-130 mV vs. RHE) and good cycling stability in an alkaline electrolyte. When urchin-like Co3O4 is used as a catalyst for oxygen evolution reaction, the onset potential is at 1.46 V (vs. RHE) with a low overpotential of only 230 mV. The good catalytic activity can be attributed to the unique urchin-like nanostructure, abundant mesopores, and low charge-transfer resistance (compared with Co3O4 NPs). In addition, H2 and O2 generation was performed using Co3O4 as both cathode and anode catalysts with a potential of 1.64 V to reach a current density of 10 mA cm-2.

  4. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECT OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    Science.gov (United States)

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and Cu, Mo, V, Cr and Mn metal oxides, and mixed metal oxides support on y-alumina as catalysts ov...

  5. Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent [2,3]-Sigmatropic Rearrangement

    Institute of Scientific and Technical Information of China (English)

    江玉波; 莫凡洋; 邱迪; 匡春香; 张艳; 王剑波

    2012-01-01

    A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and sub- sequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within 10 min, providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.

  6. Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    K. C. Kwon

    2007-09-30

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2}S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and

  7. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

    DEFF Research Database (Denmark)

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela Costinela

    2012-01-01

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen...... and that its overpotential is highly dependent on the stabilization of intermediates through hydrogen bonds with water molecules. We also determine that OER occurs through direct recombination mechanism and that its major source of overpotential is the scaling relationship between HOO* and HO* surface...... intermediates. Using a previously developed Sabatier model we show that the theoretical predictions of catalytic activities match the experimentally determined onset potentials for the ORR and the OER, both qualitatively and quantitatively. Consequently, the combination of first-principles theoretical analysis...

  8. Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries

    Science.gov (United States)

    Wu, Yixin; Wang, Taohuan; Zhang, Yidie; Xin, Sen; He, Xiaojun; Zhang, Dawei; Shui, Jianglan

    2016-04-01

    A low cost and non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a bifunctional electrocatalyst for the air electrode of lithium-oxygen (Li-O2) batteries. The composition strategy changed the electron structure of LaNiO3 and g-C3N4, ensures high Ni3+/Ni2+ ratio and more absorbed hydroxyl on the surface of CNL that can promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composite catalyst presents higher activities than the individual components g-C3N4 and LaNiO3 for both ORR and OER. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotentials and better cycling stability than XC-72 carbon and LaNiO3 catalysts. Our results suggest that CNL composite is a promising cathode catalyst for Li-O2 batteries.

  9. Bifunctional TiO2 Catalysts for Efficient Cr(Ⅵ) Photoreduction Under Solar Light Irradiation Without Addition of Acids

    Institute of Scientific and Technical Information of China (English)

    Fu-cheng Shi; Wen-dong Wang; Wei-xin Huang

    2012-01-01

    Bifunctional Ti02 photocatalysts co-doped with nitrogen and sulfur were prepared by the controlled thermal decomposition of ammonium titanyl sulfate precursor.They have both photocatalytic activity and Brφnsted acidity,and thus are active in the photoreduction of Cr(VI) under solar light irradiation without the addition of acids.The activity is superior to that of Degussa P25 in the acidified suspension at the same pH adjusted by H2SO4.

  10. Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    K. C. Kwon

    2006-09-30

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2} in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and

  11. Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    K. C. Kwon

    2007-09-30

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2}S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and

  12. Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    K. C. Kwon

    2006-09-30

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2} in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and

  13. Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2009-09-30

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2}S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and

  14. Aqueous-Phase Preparation of Model HDS Catalysts on Planar Alumina Substrates: Support Effect on Mo Adsorption and Sulfidation.

    Science.gov (United States)

    Bara, Cédric; Plais, Lucie; Larmier, Kim; Devers, Elodie; Digne, Mathieu; Lamic-Humblot, Anne-Félicie; Pirngruber, Gerhard D; Carrier, Xavier

    2015-12-23

    The role of the oxide support on the structure of the MoS2 active phase (size, morphology, orientation, sulfidation ratio, etc.) remains an open question in hydrotreating catalysis and biomass processing with important industrial implications for the design of improved catalytic formulations. The present work builds on an aqueous-phase surface-science approach using four well-defined α-alumina single crystal surfaces (C (0001), A (112̅0), M (101̅0), and R (11̅02) planes) as surrogates for γ-alumina (the industrial support) in order to discriminate the specific role of individual support facets. The reactivity of the various surface orientations toward molybdenum adsorption is controlled by the speciation of surface hydroxyls that determines the surface charge at the oxide/water interface. The C (0001) plane is inert, and the R (11̅02) plane has a limited Mo adsorption capacity while the A (112̅0) and M (101̅0) surfaces are highly reactive. Sulfidation of model catalysts reveals the highest sulfidation degree for the A (112̅0) and M (101̅0) planes suggesting weak metal/support interactions. Conversely, a low sulfidation rate and shorter MoS2 slabs are found for the R (11̅02) plane implying stronger Mo-O-Al bonds. These limiting cases are reminiscent of type I/type II MoS2 nanostructures. Structural analogies between α- and γ- alumina surfaces allow us to bridge the material gap with real Al2O3-supported catalysts. Hence, it can be proposed that Mo distribution and sulfidation rate are heterogeneous and surface-dependent on industrial γ-Al2O3-supported high-surface-area catalysts. These results demonstrate that a proper control of the γ-alumina morphology is a strategic lever for a molecular-scale design of hydrotreating catalysts.

  15. Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2009-09-30

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2}S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and

  16. 钼基加氢催化剂硫化研究进展%Research progress in sulfidation of Mo-based hydrotreating catalysts

    Institute of Scientific and Technical Information of China (English)

    王保伟; 蒋民宏; 丁国忠; 李振花; 马新宾

    2012-01-01

    The sulfidation process and extent of Mo-based hydrotreating catalyst have a crucial effect on catalyst activity. In this paper, the research status of the sulfidation of Mo-based hydrotreating catalysts, including sulfiding approach, sulfiding agents, sulfidation processes and sulfidation mechanism was summarized. The existing problems in sulfidation of Mo-based hydrotreating catalysts were pointed out. The development prospects of Mo-based hydrotreating catalysts in the future were also outlined.%钼基加氢催化剂的硫化过程和硫化程度对催化剂活性影响较大,从硫化方式、硫化剂、硫化过程和硫化机理等方面综述了钼基加氢催化剂的硫化研究状况,指出钼基加氢催化剂的硫化研究面临的问题,并对钼基加氢催化剂的发展前景进行展望.

  17. Bifunctional enhancement of oxygen reduction reaction activity on Ag catalysts due to water activation on LaMnO3 supports in alkaline media.

    Science.gov (United States)

    Park, Shin-Ae; Lee, Eun-Kyung; Song, Hannah; Kim, Yong-Tae

    2015-08-27

    Ag is considered to be one of the best candidates for oxygen reduction reaction electrocatalysts in alkaline media for application in various electrochemical energy devices. In this study, we demonstrate that water activation is a key factor in enhancing the ORR activity in alkaline media, unlike in acid environments. Ag supported on LaMnO3 having a high oxophilicity showed a markedly higher ORR activity than that on carbon with inert surfaces. Through various electrochemical tests, it was revealed that the origin of the enhanced ORR activity of Ag/LaMnO3 is the bifunctional effect mainly due to the water activation at the interface between Ag and LaMnO3. Furthermore, the ligand effect due to the charge transfer from Mn to Ag leads to the enhancement of both oxygen activation on Ag and water activation on Mn sites, and hence, an improvement in the ORR activity of Ag/LaMnO3. On the other hand, the strain effect based on the fine structure variation in the lattice was negligible. We therefore suggest that the employment of a co-catalyst or support with highly oxophilic nature and the maximization of the interface between catalyst and support should be considered in the design of electrocatalysts for the ORR in alkaline media.

  18. Hierarchical nanostructured NiCo2O4 as an efficient bifunctional non-precious metal catalyst for rechargeable zinc-air batteries

    Science.gov (United States)

    Prabu, Moni; Ketpang, Kriangsak; Shanmugam, Sangaraju

    2014-02-01

    A nickel-doped cobalt oxide spinel structure is a promising non-precious metal electrocatalyst for oxygen evolution and oxygen reduction in rechargeable metal-air batteries and water electrolyzers operating with alkaline electrolytes. One dimensional NiCo2O4 (NCO) nanostructures were prepared by using a simple electrospinning technique with two different metal precursors (metal nitrate/PAN and metal acetylacetonate/PAN). The effect of precursor concentration on the morphologies was investigated. Single-phase, NCO with an average diameter of 100 nm, porous interconnected fibrous morphology was revealed by FESEM and FETEM analysis. The hierarchical nanostructured 1D-spinel NiCo2O4 materials showed a remarkable electrocatalytic activity towards oxygen reduction and evolution in an aqueous alkaline medium. The extraordinary bi-functional catalytic activity towards both ORR and OER was observed by the low over potential (0.84 V), which is better than that of noble metal catalysts [Pt/C (1.16 V), Ru/C (1.01 V) and Ir/C (0.92 V)], making them promising cathode materials for metal-air batteries. Furthermore, the rechargeable zinc-air battery with NCO-A1 as a bifunctional electrocatalyst displays high activity and stability during battery discharge, charge, and cycling processes.A nickel-doped cobalt oxide spinel structure is a promising non-precious metal electrocatalyst for oxygen evolution and oxygen reduction in rechargeable metal-air batteries and water electrolyzers operating with alkaline electrolytes. One dimensional NiCo2O4 (NCO) nanostructures were prepared by using a simple electrospinning technique with two different metal precursors (metal nitrate/PAN and metal acetylacetonate/PAN). The effect of precursor concentration on the morphologies was investigated. Single-phase, NCO with an average diameter of 100 nm, porous interconnected fibrous morphology was revealed by FESEM and FETEM analysis. The hierarchical nanostructured 1D-spinel NiCo2O4 materials showed a

  19. Preparation and evaluation of sulfided NiMo/γ-Al2O3 hydrotreating catalysts

    OpenAIRE

    KAMYAB, ALI

    2016-01-01

      Four nickel-molybdenum catalysts were synthesized on gamma alumina with higher surface area and on NiMo catalyst was prepared using gamma alumina with lower surface area. Catalysts with higher-surface-area support were prepared by co-impregnation, sequential impregnation and adding phosphorous. Theses catalysts were calcined at 500  ͦC. Effect of higher calcination temperature was investigated by preparation of one catalyst calcined at 700 ͦC. Catalysts were thoroughly characterized via fou...

  20. Direct and Highly Selective Conversion of Synthesis Gas into Lower Olefins: Design of a Bifunctional Catalyst Combining Methanol Synthesis and Carbon-Carbon Coupling.

    Science.gov (United States)

    Cheng, Kang; Gu, Bang; Liu, Xiaoliang; Kang, Jincan; Zhang, Qinghong; Wang, Ye

    2016-04-01

    The direct synthesis of lower (C2 to C4) olefins, key building-block chemicals, from syngas (H2/CO), which can be derived from various nonpetroleum carbon resources, is highly attractive, but the selectivity for lower olefins is low because of the limitation of the Anderson-Schulz-Flory distribution. We report that the coupling of methanol-synthesis and methanol-to-olefins reactions with a bifunctional catalyst can realize the direct conversion of syngas to lower olefins with exceptionally high selectivity. We demonstrate that the choice of two active components and the integration manner of the components are crucial to lower olefin selectivity. The combination of a Zr-Zn binary oxide, which alone shows higher selectivity for methanol and dimethyl ether even at 673 K, and SAPO-34 with decreased acidity offers around 70% selectivity for C2-C4 olefins at about 10% CO conversion. The micro- to nanoscale proximity of the components favors the lower olefin selectivity.

  1. The Modification of Diphenyl Sulfide to Pd/C Catalyst and Its Application in Selective Hydrogenation of p-Chloronitrobenzene☆

    Institute of Scientific and Technical Information of China (English)

    Qunfeng Zhang; Chang Su; Jie Cen; Feng Feng; Lei Ma; Chunshan Lu; Xiaonian Li⁎

    2014-01-01

    In this study, diphenyl sulfide (Ph2S) was employed to prepare a series of Ph2S-modified Pd/C catalysts (Pd–Ph2S/C). Catalyst characterization carried out by Brunner–Emmet–Teller (BET), energy dispersive spectrom-eter (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and CO chemisorption uptake mea-surements suggested a chemical interaction between Ph2S and Pd. The ligand was preferably absorbed on the active site of Pd metal but after increasing the amount of Ph2S, the adsorption of Ph2S on Pd metal tended to be saturated and the excess of Ph2S partially adsorbed on the activated carbon. A part of Pd atoms without adsorbing any Ph2S stil existed, even for the saturated Pd–Ph2S/C catalyst. The Pd–Ph2S/C catalysts exhibited a good selectivity of p-chloroaniline (p-CAN) in the hydrogenation of p-chloronitrobenzene (p-CNB). However, the chemisorption between Ph2S and Pd was not so strong that part of Ph2S was leached from Pd–Ph2S/C catalyst during the hydrogenation, which caused the decline of the selectivity of p-CAN over the used Pd–Ph2S/C catalyst. Resulfidation of the used Pd–Ph2S/C catalyst was effective to resume its stability, and the regenerated Pd–Ph2S/C catalyst could be reused for at least ten runs with a stable catalytic performance.

  2. Epoxidation of alkenes through oxygen activation over a bifunctional CuO/Al2O3 catalyst.

    Science.gov (United States)

    Scotti, Nicola; Ravasio, Nicoletta; Zaccheria, Federica; Psaro, Rinaldo; Evangelisti, Claudio

    2013-03-07

    The epoxidation of alkenes was carried out over a CuO/Al(2)O(3) catalyst using cumene as an oxygen carrier, through a one-pot reaction, giving high conversion and selectivity with different substrates. Trans-β-methylstyrene gave the corresponding epoxide in 95% yield after 3 h.

  3. Design of an effective bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate (ATMP-FA) and optimization by Box-Behnken model for biodiesel esterification synthesis of oleic acid over ATMP-FA.

    Science.gov (United States)

    Liu, Wei; Yin, Ping; Liu, Xiguang; Qu, Rongjun

    2014-12-01

    Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0 °C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production.

  4. Bifunctional Ag/Fe/N/C Catalysts for Enhancing Oxygen Reduction via Cathodic Biofilm Inhibition in Microbial Fuel Cells.

    Science.gov (United States)

    Dai, Ying; Chan, Yingzi; Jiang, Baojiang; Wang, Lei; Zou, Jinlong; Pan, Kai; Fu, Honggang

    2016-03-23

    Limitation of the oxygen reduction reaction (ORR) in single-chamber microbial fuel cells (SC-MFCs) is considered an important hurdle in achieving their practical application. The cathodic catalysts faced with a liquid phase are easily primed with the electrolyte, which provides more surface area for bacterial overgrowth, resulting in the difficulty in transporting protons to active sites. Ag/Fe/N/C composites prepared from Ag and Fe-chelated melamine are used as antibacterial ORR catalysts for SC-MFCs. The structure-activity correlations for Ag/Fe/N/C are investigated by tuning the carbonization temperature (600-900 °C) to clarify how the active-constituents of Ag/Fe and N-species influence the antibacterial and ORR activities. A maximum power density of 1791 mW m(-2) is obtained by Ag/Fe/N/C (630 °C), which is far higher than that of Pt/C (1192 mW m(-2)), only having a decline of 16.14% after 90 days of running. The Fe-bonded N and the cooperation of pyridinic N and pyrrolic N in Ag/Fe/N/C contribute equally to the highly catalytic activity toward ORR. The ·OH or O2(-) species originating from the catalysis of O2 can suppress the biofilm growth on Ag/Fe/N/C cathodes. The synergistic effects between the Ag/Fe heterojunction and N-species substantially contribute to the high power output and Coulombic efficiency of Ag/Fe/N/C catalysts. These new antibacterial ORR catalysts show promise for application in MFCs.

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

    Science.gov (United States)

    Pupovac, Kristina; Palkovits, Regina

    2013-11-01

    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.

  6. Palladium on Nitrogen-Doped Mesoporous Carbon: A Bifunctional Catalyst for Formate-Based, Carbon-Neutral Hydrogen Storage.

    Science.gov (United States)

    Wang, Fanan; Xu, Jinming; Shao, Xianzhao; Su, Xiong; Huang, Yanqiang; Zhang, Tao

    2016-02-08

    The lack of safe, efficient, and economical hydrogen storage technologies is a hindrance to the realization of the hydrogen economy. Reported herein is a reversible formate-based carbon-neutral hydrogen storage system that is established over a novel catalyst comprising palladium nanoparticles supported on nitrogen-doped mesoporous carbon. The support was fabricated by a hard template method and nitridated under a flow of ammonia. Detailed analyses demonstrate that this bicarbonate/formate redox equilibrium is promoted by the cooperative role of the doped nitrogen functionalities and the well-dispersed, electron-enriched palladium nanoparticles.

  7. A Novel Sulfided Mo/C Catalyst for Direct Vapor Phase Carbonylation of Methanol at Atmospheric Pressure

    Institute of Scientific and Technical Information of China (English)

    Feng Peng

    2003-01-01

    The direct carbonylation of methanol, without any halide in the feed as a promoter, ispresented. A series of Mo catalysts supported on activated carbon, γ-Al2O3 and SiO2 were prepared.The results show that the support greatly affects the Mo catalyst in the direct vapor-phase carbonylationof methanol, and activated carbon is the best supports of the investigated supports. In addition, therelationships between adsorptions of NH3 and CO and carbonylation of methanol were investigated. A novelsulfided Mo/C catalyst had high activity and selectivity for the vapor phase carbonylation of methanol tomethyl acetate without the addition ofa CH3I promoter to the feed. The reaction conditions were optimizedat a reaction temperature of 573 K, a methanol concentration of 23 mol% and a carbon monoxide spacevelocity of 3,000 L/(kg.h). Under these optimal conditions a methanol conversion of 50%, carbonylationselectivity of 80 mol%, and space-time yield of 8.0 mol/(kg.h) were obtained. The active phase of thisnovel sulfided Mo/C catalyst is the non-crystalline phase, and the active component is present as MoS2.5on the surface of the activated carbon.

  8. Behavior of adsorbed diphenyl-sulfide on the Pd/C catalyst for o-chloronitrobenzene hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Chang Su; Xiao-Nian Li; Qun-Feng Zhang; Lei Ma; Chun-Shan Lu; Feng Feng

    2013-01-01

    A series of diphenyl-sulfide (Ph2S)-immobilized Pd/C catalysts (Pd-Ph2S(x)/C) were prepared using the wetness-impregnation and immobilization method.Pd-Ph2S(x)/C catalysts employed for the hydrogenation of o-chloronitrobenzene showed very high selectivity.The structure of Pd-Ph2S(x)/C with different molar ratio of ligand (x-values) was characterized by XPS and TG-DSC-MS.The results suggest a "saturated" surface ratio of Ph2S/Pd (about 0.3) was formed on the Pd-Ph2S(x)/C catalysts surface.The Ph2S immobilized on the Pd particle is quite stable,and the desorption of Ph2S or dissociative loss of phenyl group was only found at temperatures above 500 K.The possible catalytic mechanism of the Pd-Ph2S(x)/C catalyst was also discussed.

  9. Nitrogen-doped aligned carbon nanotube/graphene sandwiches: facile catalytic growth on bifunctional natural catalysts and their applications as scaffolds for high-rate lithium-sulfur batteries.

    Science.gov (United States)

    Tang, Cheng; Zhang, Qiang; Zhao, Meng-Qiang; Huang, Jia-Qi; Cheng, Xin-Bing; Tian, Gui-Li; Peng, Hong-Jie; Wei, Fei

    2014-09-17

    Nitrogen-doped aligned CNT/graphene sandwiches are rationally designed and in-situ fabricated by a facile catalytic growth on bifunctional natural catalysts that exhibit high-rate performances as scaffolds for lithium-sulfur batteries, with a high initial capacity of 1152 mA h g(-1) at 1.0 C. A remarkable capacity of 770 mA h g(-1) can be achieved at 5.0 C. Such a design strategy for materials opens up new perspectives to novel advanced functional composites, especially interface-modified hierarchical nanocarbons for broad applications.

  10. Electrochemical, spectroscopic and theoretical studies of a simple bifunctional cobalt corrole catalyst for oxygen evolution and hydrogen production.

    Science.gov (United States)

    Lei, Haitao; Han, Ali; Li, Fengwang; Zhang, Meining; Han, Yongzhen; Du, Pingwu; Lai, Wenzhen; Cao, Rui

    2014-02-07

    Six cobalt and manganese corrole complexes were synthesized and examined as single-site catalysts for water splitting. The simple cobalt corrole [Co(tpfc)(py)2] (1, tpfc = 5,10,15-tris(pentafluorophenyl)corrole, py = pyridine) catalyzed both water oxidation and proton reduction efficiently. By coating complex 1 onto indium tin oxide (ITO) electrodes, the turnover frequency for electrocatalytic water oxidation was 0.20 s(−1) at 1.4 V (vs. Ag/AgCl, pH = 7), and it was 1010 s(−1) for proton reduction at −1.0 V (vs. Ag/AgCl, pH = 0.5). The stability of 1 for catalytic oxygen evolution and hydrogen production was evaluated by electrochemical, UV-vis and mass measurements, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX), which confirmed that 1 was the real molecular catalyst. Titration and UV-vis experiments showed that the pyridine group on Co dissociated at the beginning of catalysis, which was critical to subsequent activation of water. A proton-coupled electron transfer process was involved based on the pH dependence of the water oxidation reaction catalyzed by 1. As for manganese corroles 2–6, although their oxidizing powers were comparable to that of 1, they were not as stable as 1 and underwent decomposition at the electrode. Density functional theory (DFT) calculations indicated that water oxidation by 1 was feasible through a proposed catalytic cycle. The formation of an O–O bond was suggested to be the rate-determining step, and the calculated activation barrier of 18.1 kcal mol(−1) was in good agreement with that obtained from experiments.

  11. High CO methanation activity on zirconia-supported molybdenum sulfide catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhenhua Li; Ye Tian; Jia He; Baowei Wang; Xinbin Ma

    2014-01-01

    In this study, different methods were used to prepare MoO3/ZrO2 catalysts for sulfur resistant methanation reaction. It was found that MoO3/ZrO2 catalyst prepared by one-step co-precipitation method achieved high methanation performance. CO conversion could reach up to 90%on 25 wt%MoO3/ZrO2 catalyst, much higher than that on the conventional 25 wt%MoO3/Al2O3 catalyst. The Mo-based catalysts were characterized by XRF, XRD, Raman, BET, TEM and H2-TPR etc. It was found that MoO3 particles were highly dispersed on ZrO2 support for 25 wt%MoO3/ZrO2 catalyst prepared at 65-85◦C because of its relatively larger pore size, which contributed to a high CO conversion. Meanwhile, when MoO3 loading exceeded the monolayer coverage, the formed crystalline MoO3 and ZrMo2 O8 might block the micropores of the catalyst and make the methanation activity declined. These results are useful for preparing highly efficient catalyst for CO methanation process.

  12. Study of the hydro-isomerization of paraffins with 7 and 8 carbon atoms on bifunctional catalysts; Etude de l'hydroisomerisation des paraffines a 7 et 8 atomes de carbone sur catalyseurs bifonctionnels

    Energy Technology Data Exchange (ETDEWEB)

    Patrigeon, A.

    2000-10-11

    Due to the suppression of lead additives and the trend to decrease the aromatic and olefinic content in gasoline, the interest for new octane enhancement processes has increased, particularly for isomerization of C{sub 7} and C{sub 8} linear paraffins into higher octane number multi-branched paraffins. Up to the present day, no industrial bifunctional catalyst exists due to the high tendency of the paraffins to be cracked limiting the amount of multi-branched products. The aim of this work is to study the possibility of isomerizing linear C{sub 7} and C{sub 8} paraffins in two steps in order to increase the amount of formed multi-branched paraffins. The first step converts linear paraffins into mono-branched paraffins (that step is supposed to be the slowest one) carried out using one bifunctional catalyst. The second step converts the formed mono-branched paraffins into multi-branched paraffins using a second bifunctional catalyst. The aim is to determine the characteristics of the two catalysts. To study the first step, Pt/zeolite or Pt/meso-porous solid catalysts, with different acidities and porosities, were tested in n-heptane and n-octane hydro-conversion. The role of solid porosity on selectivities was clearly established. Molecular modelling was utilised to explain the observed selectivities. To study the second step, the 2-methyl-hexane and 2-methyl-heptane hydro-conversion on Pt/H-beta and Pt/H-Y was carried out. This lead to maximum multi-branched yields similar to those obtained with the n-heptane and n-octane hydro-conversion. That result shows that the two steps isomerization process is not necessarily required because no more multi-branched products are formed. A kinetic study on the n-heptane hydro-conversion was performed. The decomposition of isomerization and cracking reactions into elementary steps has shown the major role of the paraffins physio-sorption step in the zeolite pores. (author)

  13. Highly efficient and selective photocatalytic oxidation of sulfide by a chromophore-catalyst dyad of ruthenium-based complexes.

    Science.gov (United States)

    Li, Ting-Ting; Li, Fu-Min; Zhao, Wei-Liang; Tian, Yong-Hua; Chen, Yong; Cai, Rong; Fu, Wen-Fu

    2015-01-05

    Electronic coupling across a bridging ligand between a chromophore and a catalyst center has an important influence on biological and synthetic photocatalytic processes. Structural and associated electronic modifications of ligands may improve the efficiency of photocatalytic transformations of organic substrates. Two ruthenium-based supramolecular assemblies based on a chromophore-catalyst dyad containing a Ru-aqua complex and its chloro form as the catalytic components were synthesized and structurally characterized, and their spectroscopic and electrochemical properties were investigated. Under visible light irradiation and in the presence of [Co(NH3)5Cl]Cl2 as a sacrificial electron acceptor, both complexes exhibited good photocatalytic activity toward oxidation of sulfide into the corresponding sulfoxide with high efficiency and >99% product selectivity in neutral aqueous solution. The Ru-aqua complex assembly was more efficient than the chloro complex. Isotopic labeling experiments using (18)O-labeled water demonstrated the oxygen atom transfer from the water to the organic substrate, likely through the formation of an active intermediate, Ru(IV)═O.

  14. XAFS study on the sulfidation mechanisms of Co-Mo catalysts supported on activated carbon and alumina: effect of complexing agent.

    Science.gov (United States)

    Tsuji, K; Umeki, T; Yokoyama, Y; Kitada, T; Iwanami, Y; Nonaka, O; Shimada, H; Matsubayashi, N; Nishijima, A; Nomura, M

    2001-03-01

    The effect of nitrilotriacetic acid (NTA) as a complexing agent on the sulfidation mechanisms of Co-Mo catalysts supported on activated carbon and alumina was examined by the XAFS technique. The XAFS results revealed that NTA interacted with Co atoms and formed the Co-NTA interaction, while it showed almost no influence on the local structures around Mo atoms. The Co-NTA interaction suppressed the aggregation of cobalt atoms and the interaction between cobalt and alumina during sulfiding, and consequently promoted the formation of the Co-Mo-S phase.

  15. "Smart poisoning" of Co/SiO2 catalysts by sulfidation for chirality-selective synthesis of (9,8) single-walled carbon nanotubes.

    Science.gov (United States)

    Yuan, Yang; Karahan, H Enis; Yıldırım, Cansu; Wei, Li; Birer, Özgür; Zhai, Shengli; Lau, Raymond; Chen, Yuan

    2016-10-14

    The chirality-selective synthesis of relatively large (diameter > 1 nm) single-walled carbon nanotubes (SWCNTs) is of great interest for a variety of practical applications, but only a few catalysts are available so far. Previous studies suggested that S (compounds) can enhance the chirality-selectivity of Co catalysts in SWCNT synthesis, however, the mechanism behind is not fully understood, and no tailorable methodology has yet been developed. Here, we demonstrate a facile approach to achieve the chirality-selective synthesis of SWCNTs by the sulfidation-based poisoning of silica-supported Co catalysts using a mixture of H2S and H2. The UV-vis-NIR, photoluminescence, and Raman spectroscopy results together show that the resulting SWCNTs have a narrow diameter distribution of around 1.2 nm, and (9,8) nanotubes have an abundance of ∼38% among the semiconducting species. More importantly, the carbon yield achieved by the sulfided catalyst (2.5 wt%) is similar to that of the nonsulfided one (2.7 wt%). The characterization of the catalysts by X-ray diffraction, X-ray photoelectron spectroscopy, X-ray fluorescence, and H2 temperature-programmed reduction shows that the sulfidation leads to the formation of Co9S8 nanoparticles. However, Co9S8 nanoparticles are reduced back to regenerate metallic Co nanoparticles during the synthesis of SWCNTs, which maintain a high carbon yield. In this process, Co9S8 nanoparticles seemingly intermediate the production of Co nanoparticles with narrow size distribution. Due to the fact that the poisoning step improves the quality of the end-product rather than hampering the growth process, we have coined the process developed as "smart poisoning". This study not only reveals the mechanism behind the beneficial role of S in the selective synthesis of relatively large SWCNTs but also presents a promising method to create chirality-selective catalysts with high activity for scalable synthesis.

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

    Science.gov (United States)

    Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-09-01

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

  17. Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery

    Science.gov (United States)

    Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

    2016-09-01

    α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm‑2. At 1.0 V of cell voltage, a current density of 324 mA cm‑2 is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm‑2, and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte.

  18. A Non-sulfided flower-like Ni-PTA Catalyst that Enhances the Hydrotreatment Efficiency of Plant Oil to Produce Green Diesel

    Science.gov (United States)

    Liu, Jing; Chen, Pan; Deng, Lihong; He, Jing; Wang, Luying; Rong, Long; Lei, Jiandu

    2015-10-01

    The development of a novel non-sulfided catalyst with high activity for the hydrotreatment processing of plant oils, is of high interest as a way to improve the efficient production of renewable diesel. To attempt to develop such a catalyst, we first synthesized a high activity flower-like Ni-PTA catalyst used in the hydrotreatment processes of plant oils. The obtained catalyst was characterized with SEM, EDX, HRTEM, BET, XRD, H2-TPR, XPS and TGA. A probable formation mechanism of flower-like Ni(OH)2 is proposed on the basis of a range of contrasting experiments. The results of GC showed that the conversion yield of Jatropha oil was 98.95%, and the selectivity of C11-C18 alkanes was 70.93% at 360 °C, 3 MPa, and 15 h-1. The activity of this flower-like Ni-PTA catalyst was more than 15 times higher than those of the conventional Ni-PTA/Al2O3 catalysts. Additionally, the flower-like Ni-PTA catalyst exhibited good stability during the process of plant oil hydrotreatment.

  19. A Non-sulfided flower-like Ni-PTA Catalyst that Enhances the Hydrotreatment Efficiency of Plant Oil to Produce Green Diesel.

    Science.gov (United States)

    Liu, Jing; Chen, Pan; Deng, Lihong; He, Jing; Wang, Luying; Rong, Long; Lei, Jiandu

    2015-10-27

    The development of a novel non-sulfided catalyst with high activity for the hydrotreatment processing of plant oils, is of high interest as a way to improve the efficient production of renewable diesel. To attempt to develop such a catalyst, we first synthesized a high activity flower-like Ni-PTA catalyst used in the hydrotreatment processes of plant oils. The obtained catalyst was characterized with SEM, EDX, HRTEM, BET, XRD, H2-TPR, XPS and TGA. A probable formation mechanism of flower-like Ni(OH)2 is proposed on the basis of a range of contrasting experiments. The results of GC showed that the conversion yield of Jatropha oil was 98.95%, and the selectivity of C11-C18 alkanes was 70.93% at 360 °C, 3 MPa, and 15 h(-1). The activity of this flower-like Ni-PTA catalyst was more than 15 times higher than those of the conventional Ni-PTA/Al2O3 catalysts. Additionally, the flower-like Ni-PTA catalyst exhibited good stability during the process of plant oil hydrotreatment.

  20. Hydrogen production for fuel cells by autothermal reforming of methane over sulfide nickel catalyst on a gamma alumina support

    Science.gov (United States)

    Hoang, D. L.; Chan, S. H.; Ding, O. L.

    Experimental and modelling studies have been conducted on catalytic autothermal reforming (ATR) of methane for hydrogen production over a sulfide nickel catalyst on a gamma alumina support. The experiments are performed with different feedstock under thermally neutral conditions. The results show that the performance of the reformer is dependent on the molar air-to-fuel ratio (A/F), the molar water-to-fuel ratio (W/F) and the flowrate of the feedstock mixture. The optimum conditions for high methane conversion and high hydrogen yield are A/F = 3-3.5, W/F = 2-2.5 and a fuel flowrate below 120-250 l h -1. Under these conditions, a methane conversion of 95-99% and a hydrogen yield of 39-41% on a dry basis can be achieved and 1 mole of methane can produce 1.8 moles of hydrogen at an equilibrium reactor temperature of not exceeding 850 °C. A two-dimensional reactor model is developed to simulate the conversion behaviour of the reactor for further study of the reforming process. The model includes all aspects of the major chemical kinetics and the heat and mass transfer phenomena in the reactor. The predicted results are successfully validated with experimental data.

  1. Hydrogen photoproduction from hydrogen sulfide on Bi{sub 2}S{sub 3} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Bessekhouad, Y.; Trari, M. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie, USTHB B.P. 32 Algiers (Algeria); Mohammedi, M. [Ecole Polytechnique EMP,BP 17 Algiers (Algeria)

    2002-07-01

    Films of polycrystalline Bi{sub 2}S{sub 3} have been prepared onto bismuth and platinum substrates by electrodeposition from an aqueous sulfide bath. The films were thin, uniform and well adhered. Bi{sub 2}S{sub 3} is a direct band gap semiconductor with a value of 1.28eV optimally matched with the solar spectrum. The photoelectrochemical study was undertaken for the generation of hydrogen by using illuminated n-Bi{sub 2}S{sub 3} particles; it was found that hydrogen evolution depends highly on the synthesis method of powder. Impregnation of platinum onto Bi{sub 2}S{sub 3} shows a production enhancement of about 25%. The most active photocatalyst, prepared by a solvent thermal process and loaded with Pt in 0.1MS{sup 2-} alkaline electrolyte, yields 2.13x10{sup -2}mlmg{sup -1} of H{sub 2} after 4h of irradiation with the visible output of a 500W halogen lamp.

  2. Influence of the sulfidation procedure on the performance and the selectivity of hydro-treating catalysts; Influence de la procedure de sulfuration sur la performance et la selectivite des catalyseurs d'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Texier, S.

    2004-10-15

    This work is part of a general effort to reduce the sulfur content of fuels to satisfy new European regulations. The objective was to determine the influence of several activating agents during sulfidation on the activity of hydro-desulfurization (HDS) catalysts. Indeed, sulfidation is a critical step to achieve a good level of HDS activity on sulfide catalysts. Under industrial conditions, the activation by organo-sulfide compounds would be more beneficial to obtain active catalysts than the use of hydrogen sulfide. A systematic study of the various operational parameters of the activation process was thus carried out by comparing precisely activation by H{sub 2}S or by organo-sulfides. This study reveals that the recognized advantage of organo-sulfides compounds has not a 'purely chemical origin' but would be more probably related to a heating and/or thermodynamic effect which depends on the processes and on the implementation of sulfidation under the industrial conditions. (author)

  3. EXAFS Study on Structure of Sulfided K—Co—Mo Catalysts

    Institute of Scientific and Technical Information of China (English)

    BaoJun; LiuTao; 等

    2001-01-01

    Mixed alcohol is of great promise as octane improver in automotive fuel,and hopeful to replace the MTBE to reduce the environmental pollution,In this field,alkali-promted molybdenum-based catalysts have been given special interest because of their excellent sulfur-tolerance for synthesis of mixed alcohol from CO+H2,It was reported that the coblat is a favorable promoter for enhancing alcohol production,especially for improving the selectivity for C2+ alcohol[1-3],moreover,strong interaction between Con and Mo is in favor of mixed alcohol synthesis[4].Recently,we prpared a kind of K-Co-Mo ultrafine particles by sol-gel method and it shows much smaller particle size but higher activty and selectivity toward alcohol formation than the one prepared by conventional method[5],The aim of the present work is to research the micostructures of the Mo and Co species in the K-Co-Mo samples prepared by different method.

  4. Comparison of P-containing {gamma}-Al{sub 2}O{sub 3} supported Ni-Mo bimetallic carbide, nitride and sulfide catalysts for HDN and HDS of gas oils derived from Athabasca bitumen

    Energy Technology Data Exchange (ETDEWEB)

    Sundaramurthy, V.; Dalai, A.K. [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, SK (Canada); Adjaye, J. [Syncrude Edmonton Research Centre, Edmonton, AB (Canada)

    2006-09-01

    Phosphorus containing {gamma}-Al{sub 2}O{sub 3} supported bimetallic Ni-Mo carbide, nitride and sulfide catalysts have been synthesized from an oxide precursor containing 12.73wt.% Mo, 2.54wt.% Ni and 2.38wt.% P and characterized by elemental analysis, pulsed CO chemisorption, surface area measurements, X-ray diffraction, temperature-programmed reduction and DRIFT spectroscopy of CO adsorption. DRIFT spectroscopy of adsorbed CO on activated catalysts showed that carbide and nitride catalysts have surface exposed sites of Mo{sup o+} (0sulfidation with H{sub 2}S/H{sub 2} mixture at 370{sup o}C. The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities of the bimetallic Ni-Mo carbide, nitride and sulfide catalysts were compared against commercial Ni-Mo/Al{sub 2}O{sub 3} catalyst in a trickle bed reactor using light gas oil and heavy gas oil derived from Athabasca bitumen in the temperature range 340-370 and 375-400{sup o}C respectively at 8.8MPa. The gradual transformation of Ni-Mo carbide and nitride phases into Ni-Mo sulfide phases was observed during precoking period, and the formed Ni-Mo sulfide phases enhanced the HDN and HDS activities of carbide and nitride catalysts. The {gamma}-Al{sub 2}O{sub 3} supported Ni-Mo bimetallic sulfide catalyst was found to be more active for HDN and HDS of light gas oil and heavy gas oil than the corresponding carbide and nitride catalysts on the basis of unit weight. (author)

  5. Synthesis, Characterization, and Catalytic Activity of Sulfided Silico-Alumino-Titanate (Si-Al-Ti) Mixed Oxides Xerogels Supported Ni-Mo Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Al-Adwani, H.A.; Anthony, R.G.; Gardner, T.J.; Thammachote, N.

    1999-02-24

    Layered semicrystalline silico-alumino-titanate (Si-Al-Ti) mixed oxides were synthesized by a modified sol-gel method with hydrothermal synthesis temperatures less than 200 C and autogenic pressure. The solid products are semicrystalline materials with a surface area of 136-367 m{sup 2}/g and a monomodal pore size distribution with an average pore diameter of 3.6-4.7 nrn. The catalytic activity for pyrene hydrogenation in a batch reactor at 300 C and 500 psig was determined for sulfided Ni-Mo supported on the Si-Al-Ti mixed oxide. The activity was a function of the support composition the heat treatment before and after loading the active metals, the addition of organic templates, and different methods of metal loading. The most active sulfided Ni-Mo/Si-Al-Ti catalyst has an activity in the same range as the commercial catalyst, Shell 324, but the metal loading is 37% less than the commercial catalyst.

  6. Oxidative dehydration reaction of glycerol into acrylic acid: A first-principles prediction of structural and thermodynamic parameters of a bifunctional catalyst

    Science.gov (United States)

    Lacerda, Lívia Clara T.; dos Santos Pires, Maíra; Corrêa, Silviana; Oliveira, Luiz Carlos A.; Ramalho, Teodorico C.

    2016-05-01

    The production of biodiesel generates crude glycerol as a byproduct. The search for glycerol conversion routes has attracted the attention of researchers and thus, this work evaluated the properties of the catalysts T-Nb2O5 and T-Nb2O5/V treated with H2O2 applied to the reaction of oxidative dehydration of glycerol. The peroxo groups from the treatment with H2O2 had a greater oxidation capacity in relation to those in the pure catalyst. Furthermore, the catalyst doped with vanadium presented lower energy costs during the process. Those results might be helpful for designing new catalysts for the production of strategic chemical products from glycerol.

  7. CuZnAl双功能催化剂上一步法合成二甲醚的工艺研究%Study on Single-step Synthesis of Dimethyl Ether over CuZnAl Bifunctional Catalyst

    Institute of Scientific and Technical Information of China (English)

    吴文炳; 倪建聪; 林顺华; 林志文; 宋建龙; 杨顺童

    2011-01-01

    探讨TC301/γ-Al2O3和C207/γ-Al2O3双功能催化剂上合成气一步法制取二甲醚的反应,考察了催化剂浓度、原料气氢碳比和搅拌转速对一氧化碳转化率和二甲醚收率的影响.结果表明:在浆态床反应器内,催化剂C301的催化效果优于C207,且催化剂最佳浓度为7.27%;在300r/min搅拌转速下,外扩散阻力的影响基本可以消除;当原料气氢碳比为1.0时,二甲醚收率最大,进而提出利用富碳合成气生产二甲醚是缓解能源问题和减少能源污染的一条新途径.%The direct conversion of syngas into dimethyl ether over CuZnAI bifunctional catalyst was studied. Effect of catalyst concentration, feed gas ratio and stirring speed on CO conversion and DME yield was investigated. The results showed that C301 catalyst exhibited better performance than C207 catalyst in a slurry reactor, and the optimum concentration of catalyst was 7.27%. The resistance of external diffusion was eliminated when stirring speed reaching 300 r/min. When feed gas ratio between hydrogen and carbon was 1:1, the DME yield reached the maximum, and the production of DME from rich CO syngas was put forward, which is a new approach of solving energy problems and reducing environmental pollution from fuel combustion.

  8. Optimizing acid-base bifunctional mesoporous catalysts for the henry reaction: effects of the surface density and site isolation of functional groups.

    Science.gov (United States)

    Sharma, Krishna K; Buckley, Robert P; Asefa, Tewodros

    2008-12-16

    We report on the effects of the surface density and the spacing between grafted organoamines (and residual ungrafted silanols) of amine-functionalized mesoporous materials on their (cooperative) catalytic activity in the Henry reaction. The spacing between the bifunctional groups (amines and silanols), their site isolation, and their surface density were controlled by one-step or two-step grafting of a series of organosilanes containing linear alkylamine, alkyldiamine, alkyltriamine, and meta- and para-substituted aromatic amines onto mesoporous silica in ethanol and/or toluene. The grafting in ethanol produced site-isolated, flexible alkylamines, alkyldiamines, and alkyltriamines of different tether lengths and rigid meta- and para-substituted aromatic amines and high surface area materials, whereas the grafting in toluene resulted in closely spaced organoamines and materials with lower surface areas. The spacing between the organoamine groups was probed by complexing cupric ions with the amines and by measuring the electronic spectra of the complexes. The materials' catalytic activities were dependent not only on the degree of site isolation of the amine groups and the surface areas of the materials, but also on the relative spacing between the functional groups and their surface density. Samples grafted with monoamine groups in ethanol and samples grafted with diamine or triamine groups in toluene for 5 h gave approximately 100% conversion in 16 min of the Henry reaction between p-hydroxybenzaldehyde and nitromethane. However, the corresponding monoamine-grafted sample in toluene and diamine- and triamine-grafted samples in ethanol gave approximately 100% conversion after 1 h. On the basis of turnover number (TON) and TON per surface area, the samples containing optimum concentrations of approximately 0.8 - 1.5 mmol of grafted organoamines/g, which we dubbed as the critical density of organic grafted groups, gave the highest catalytic efficiencies. These samples

  9. Nano-molybdenum carbide/carbon nanotubes composite as bifunctional anode catalyst for high-performance Escherichia coli-based microbial fuel cell.

    Science.gov (United States)

    Wang, Yaqiong; Li, Bin; Cui, Dan; Xiang, Xingde; Li, Weishan

    2014-01-15

    A novel electrode, carbon felt-supported nano-molybdenum carbide (Mo2C)/carbon nanotubes (CNTs) composite, was developed as platinum-free anode of high performance microbial fuel cell (MFC). The Mo2C/CNTs composite was synthesized by using the microwave-assisted method with Mo(CO)6 as a single source precursor and characterized by using X-ray diffraction and transmission electron microscopy. The activity of the composite as anode electrocatalyst of MFC based on Escherichia coli (E. coli) was investigated with cyclic voltammetry, chronoamperometry, and cell discharge test. It is found that the carbon felt electrode with 16.7 wt% Mo Mo2C/CNTs composite exhibits a comparable electrocatalytic activity to that with 20 wt% platinum as anode electrocatalyst. The superior performance of the developed platinum-free electrode can be ascribed to the bifunctional electrocatalysis of Mo2C/CNTs for the conversion of organic substrates into electricity through bacteria. The composite facilitates the formation of biofilm, which is necessary for the electron transfer via c-type cytochrome and nanowires. On the other hand, the composite exhibits the electrocatalytic activity towards the oxidation of hydrogen, which is the common metabolite of E. coli.

  10. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 磷改性双功能催化剂合成二甲醚性能研究%Study on performances of P-modified bifunctional catalyst for dimethyl ether synthesis

    Institute of Scientific and Technical Information of China (English)

    黄兵; 张世玲; 谢磊磊

    2011-01-01

    采用磷酸水溶液浸渍-焙烧法对甲醇脱水催化剂γ-Al2O3改性,得到磷改性甲醇脱水催化剂P-γ-Al2O3与C301甲醇合成催化剂以1:4的质量比混合制备成C301/p-γ-A12O3双功能催化剂用于一步法合成二甲醚,该改性双功能催化剂比未改性催化剂具有更高的催化活性.将该催化剂用于浆态床反应器,在p=3.7MPa,T=250℃,进料合成气n(H2)/n(CO)=2的条件下,CO转化率从93.11%提高到95.90%,DME选择性从34.61%提高到42.27%.改性催化剂经FT-IR、BET、XRD手段进行表征,发现在P-γ-Al2O3中增加了O=P-O键,使得脱水催化剂的表面总酸量和L酸中心数量同时增加,从而提高了双功能催化剂的活性.%Abifunctional catalyst (C301/P-γ-Al2O3) for one-step synthesis of dimethyl ether from syngas was prepared by the method as follows: γ-Al2O3 was modified by impregnation with phosphoric acid aqueous solution and calcination to obtain the P-γ-Al2O3, which was then mixed with the commercial methanol synthesis catalyst C301 in a mass ratio of 1:4. The P-modified catalyst had higher activity than the unmodified catalyst. The modified catalyst was used in a slurry bed reactor and the conversion of CO increased from 93.11% to 95.90% while the DME selectivity increased from 34.61% to 42.27% under pressure of 3.7MPa, temperature of 250°C and feed gas HVCO molar ratio of 2. The P-γ-Al2O3 catalyst was characterized by FT-IR, XRD and BET, and it was found that the 0=P-0 bond existed in the P-γ-Al2O3, which made the numbers of both total acid and L acid sites of the P-γ-A12O3 surface increased that resulted in the improvement of the activity of the prepared bifunctional catalyst.

  12. Ti3C2 MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production

    Science.gov (United States)

    Ran, Jingrun; Gao, Guoping; Li, Fa-Tang; Ma, Tian-Yi; Du, Aijun; Qiao, Shi-Zhang

    2017-01-01

    Scalable and sustainable solar hydrogen production through photocatalytic water splitting requires highly active and stable earth-abundant co-catalysts to replace expensive and rare platinum. Here we employ density functional theory calculations to direct atomic-level exploration, design and fabrication of a MXene material, Ti3C2 nanoparticles, as a highly efficient co-catalyst. Ti3C2 nanoparticles are rationally integrated with cadmium sulfide via a hydrothermal strategy to induce a super high visible-light photocatalytic hydrogen production activity of 14,342 μmol h-1 g-1 and an apparent quantum efficiency of 40.1% at 420 nm. This high performance arises from the favourable Fermi level position, electrical conductivity and hydrogen evolution capacity of Ti3C2 nanoparticles. Furthermore, Ti3C2 nanoparticles also serve as an efficient co-catalyst on ZnS or ZnxCd1-xS. This work demonstrates the potential of earth-abundant MXene family materials to construct numerous high performance and low-cost photocatalysts/photoelectrodes.

  13. Novel bifunctional catalysts based on crystalline multi-oxide matrices containing iron ions for CO2 hydrogenation to liquid fuels and chemicals.

    Science.gov (United States)

    Utsis, N; Vidruk-Nehemya, R; Landau, M V; Herskowitz, M

    2016-07-04

    Seven solid mono-, bi- and tri-metallic oxide matrices where Fe(2+,3+) ions are distributed in different chemical/spatial environments were synthesized and characterized by XRD, N2-adsorption and EDAX methods. After basification with potassium, all matrices were activated by carburization or reduction-carburization under conditions selected based on the TPC/TPR spectra, tailoring the carburization extent of iron. The performances of the activated Fe-based catalysts with respect to CO2 conversion and C5+ selectivity were measured in a fixed-bed reactor under standard conditions in transient and continuous operation modes in units containing one or three reactors in series with water separations between the reactors. The catalysts were characterized by XRD, N2-adsorption, HRTEM-EELS and XPS before and after steady-state operation in the reactors. It was found that the rate of CO2 conversion is not limited by thermodynamic equilibrium but is strongly restricted by water inhibition and it depends on the nature of the Fe-oxide precursor. The ratio between the FTS and RWGS rates, which determines the C5+ hydrocarbons productivity, is strongly affected by the nature of the Fe-oxide matrix. The catalysts derived from the Fe-Al-O spinel and Fe-Ba-hexaaluminate precursors displayed the best balance of the two functions RFTS/RRWGS = 0.77-0.78. They were followed by magnetite, CuFe-delafossite, K-ferrite, Fe-La-hexaaluminate and LaFe-perovskite with a gradual lowering of RFTS/RRWGS from 0.60 to 0.15 and a gradual decrease in the C5+ productivity. The active sites that enhance the RWGS reaction are located on the surface of the Fe-oxide phases, while the FTS and methanation reactions occur on the surface of the Fe-carbide phases.

  14. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECTS OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    Science.gov (United States)

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and activities of Cu, Mo, Cr and Mn oxides, and mixed metal oxides supported on -alumina, were tes...

  15. Hydrogen Production Using a Molybdenum Sulfide Catalyst on a Titanium-Protected n+p-Silicon Photocathode

    DEFF Research Database (Denmark)

    Seger, Brian; Laursen, Anders Bo; Vesborg, Peter Christian Kjærgaard

    2012-01-01

    A low-cost substitute: A titanium protection layer on silicon made it possible to use silicon under highly oxidizing conditions without oxidation of the silicon. Molybdenum sulfide was electrodeposited on the Ti-protected n+p-silicon electrode. This electrode was applied as a photocathode for water...

  16. The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H2S-Pt/C interaction products

    Science.gov (United States)

    Lopes, Thiago; Paganin, Valdecir A.; Gonzalez, Ernesto R.

    2011-08-01

    The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H2, ∼20% N2, and 8 ppm hydrogen sulfide (H2S). Cell performance losses are calculated by evaluating cell potential reduction due to H2S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H2S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H2S-contaminated anode feeding stream.

  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: shixy@snnu.edu.cn, E-mail: weijf@snnu.edu.cn [School of Chemistry and Chemical Engineering, Shaanxi Normal University and Key Laboratory for Macromolecular Science of Shaanxi Province, Xian (China)

    2012-08-15

    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. Zinc-air battery: understanding the structure and morphology changes of graphene-supported CoMn(2)O(4) bifunctional catalysts under practical rechargeable conditions.

    Science.gov (United States)

    Prabu, Moni; Ramakrishnan, Prakash; Nara, Hiroki; Momma, Toshiyuki; Osaka, Tetsuya; Shanmugam, Sangaraju

    2014-10-08

    Nitrogen-doped/undoped thermally reduced graphene oxide (N-rGO) decorated with CoMn2O4 (CMO) nanoparticles were synthesized using a simple one-step hydrothermal method. The activity and stability of this hybrid catalyst were evaluated by preparing air electrodes with both primary and rechargeable zinc-air batteries that consume ambient air. Further, we investigated the relationship between the physical properties and the electrochemical results for hybrid electrodes at various cycles using X-ray diffraction, scanning electron microscopy, galvanodynamic charge-discharging and electrochemical impedance spectroscopy. The structural, morphological and electrocatalytic performances confirm that CMO/N-rGO is a promising material for safe, reliable, and long-lasting air cathodes for both primary and rechargeable zinc-air batteries that consume air under ambient condition.

  19. Light straight-run gas oil hydrotreatment over sulfided CoMoP/Al{sub 2}O{sub 3}-USY zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Marin, C.; Escobar, J.; Galvan, E.; Murrieta, F.; Zarate, R.; Vaca, H. [Instituto Mexicano del Petroleo, Tratamiento de Crudo Maya, Eje Central Lazaro Cardenas 152, Col. San Bartolo Atepehuacan, Del. G.A. Madero (Mexico)

    2005-01-25

    Al{sub 2}O{sub 3} supports were modified by integrating USY zeolites (13.6 wt.%) of various nominal SiO{sub 2}/Al{sub 2}O{sub 3} molar ratios (30-80). The obtained hybrid solids calcined at 500 {sup o}C were impregnated at incipient wetness with a Co-Mo-P solution. After sulfiding with CS{sub 2}-spiked naphtha (at 230 {sup o}C, 5.5 MPa and LHSV=3 h{sup -1}) the corresponding catalysts were tested in light straight-run gas oil hydrotreatment at industrially relevant operating conditions. The catalyst containing zeolite of the highest SiO{sub 2}/Al{sub 2}O{sub 3} molar ratio (80) showed very high hydrodesulfurization activity. Operating at 360 {sup o}C, 5.5 MPa and LHSV=2.5 h{sup -1}, ultra-low sulfur diesel (circa 50 ppm S) could be obtained over that material, from a feedstock of 10,400 ppm S. Medium-strong acidity could be playing an important role on this behaviour by promoting isomerization of sterically hindered organo-sulfur compounds to more favorable configurations. Moreover, hydrodearomatization and hydrodenitrogenation were also enhanced by addition of that high-silica zeolite.

  20. Highly effective nickel sulfide counter electrode catalyst prepared by optimal hydrothermal treatment for quantum dot-sensitized solar cells

    Science.gov (United States)

    Gopi, Chandu V. V. M.; Srinivasa Rao, S.; Kim, Soo-Kyoung; Punnoose, Dinah; Kim, Hee-Je

    2015-02-01

    Nickel sulfide (NiS) thin film has been deposited on a fluorine-doped tin oxide substrate by a hydrothermal method using 3-mercaptopropionic acid and used as an efficient counter electrode (CE) for polysulfide redox reactions in quantum dot-sensitized solar cells (QDSSCs). NiS has low toxicity and environmental compatibility. In the present study, the size of the NiS nanoparticle increases with the hydrothermal deposition time. The performance of the QDSSCs is examined in detail using polysulfide electrolyte with the NiS CE. A TiO2/CdS/CdSe/ZnS-based QDSSC using the NiS CE shows enhanced photovoltaic performance with a power conversion efficiency (PCE) of 3.03%, which is superior to that of a cell with Pt CE (PCE 2.20%) under one sun illumination (AM 1.5, 100 mW cm-2). The improved photovoltaic performance of the NiS-based QDSSC may be attributed to a low charge transfer resistance (5.08 Ω) for the reduction of polysulfide on the CE, indicating greater electrocatalytic activity of the NiS. Electrochemical impedance spectroscopy, cyclic voltammetry, and Tafel-polarization measurements were used to investigate the electrocatalytic activity of the NiS and Pt CEs.

  1. Preparation methods of mixed metal sulfide catalysts for deep hydrogenation of crude oils%原油深度加氢复合多金属硫化物催化剂的制备方法

    Institute of Scientific and Technical Information of China (English)

    蒋丽娟; 李来平; 张文钲

    2014-01-01

    复合多金属硫化物( MMS)催化剂主要用于原油的深度加氢,用于生产高十六烷值、低硫和低芳族化合物柴油。MMS催化剂包含NiMoS、NiWS、NiMoO、NiWO、NiMoWS和ZnMoWS催化剂等。综述MMS催化剂中二元复合金属硫化物催化剂和三元复合金属硫化物催化剂的制备方法,采用二步法即添加有机物作孔成形剂先制得催化剂前驱体,再由前驱体制得的MMS催化剂结构更松散,具有较大的比表面积(90 m2·g-1)和大孔容(大于0.3 cm3·g-1),因而具有更好的催化活性。对比不同MMS催化剂对重质柴油、焦油等的加氢裂解、加氢脱硫和加氢脱氮性能,认为NiMoW三元复合金属硫化物催化剂(50%Ni25%Mo25%W)的活性最优。%Mixed metal sulfide catalyst( MMS)catalysts are mainly used for deep hydroprocessing of refractory crudes to produce diesel oil with higher cetane number,lower sulfur and lower aromatic compounds. MMS catalysts include NiMoS,NiWS,NiMoO,NiWO,NiMoWS and ZnMoWS,etc. The preparation methods of MMS catalysts,including bi-metallic sulfide catalysts and tri-metallic sulfide catalysts,were summarized in this paper. The catalyst precursors were prepared by adding organic compounds as pore forming agents,and then the catalysts were prepared. The catalysts prepared by the two-steps method possessed dispersive structure. The attained catalyst with BET specific surface area of 90 m2·g-1 and pore volume of 0. 3 cm3 ·g-1 exhibited better catalytic activity. Compared with other several MMS catalysts,the hydrocracking,hydrodesulfurization and hydrodenitrification activities of NiMoW(50mol%Ni,25mol%Mo,25mol%W)tri-metallic sulfide catalysts for processing heavy diesel oil and tar were the best.

  2. Hydrogen evolution reaction catalyst

    Science.gov (United States)

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  3. {gamma} alumina- and HY zeolite-supported molybdenum catalysts: characterisation of the oxidic and sulfided phases; Catalyseurs a base de molybdene supporte sur alumine {gamma} et zeolithe HY: caracterisation des phases oxydes et sulfures

    Energy Technology Data Exchange (ETDEWEB)

    Plazenet, G.

    2001-10-01

    Oxidic precursors of hydro-treatment catalysts (Co)Mo/alumina or zeolite were characterised by Raman spectroscopy, NMR and EXAFS at the Mo and Co K-edges. The formation of an Anderson-type alumino-molybdate compound upon impregnation of the support with an ammonium hepta-molybdate solution was confirmed for alumina, and also observed for the HY zeolitic support, with consumption of the amorphous alumina of the zeolite. In absence of the latter, ammonium hepta-molybdate precipitates. The species are conserved upon drying; upon calcination, the alumino-molybdate evolves into a surface aluminium molybdate type phase, whereas the hepta-molybdate transforms into MoO{sub 3}. The species formed upon impregnation are located in the inter-granular porosity whereas MoO{sub 3} vapor-condensation leads to formation of dimers located inside the zeolitic structure. The study of the cobalt-promoted precursors showed that the evolution of the molybdenum is the same in the case of co-impregnation preparation. Impregnation with cobalt-molybdate prevents the formation of the alumino-molybdate anion and thus enables the preservation of the Mo-Co interaction but, whatever the precursor, the leveling effect of the calcination-re-hydration steps was demonstrated. An EXAFS study at different sulfur coverages of the MoS{sub 2} platelets in the alumina-supported sulfided catalysts showed the limitations of EXAFS for size determination of MoS{sub 2} crystallites, a parameter that can be reached by AWAXS, which also conveys information about sheet-stacking. The EXAFS study of sulfided (Co)Mo/HY systems revealed incomplete sulfidation of the samples and the very high dispersion of the active phase. The absence of an observable Mo-Co interaction whatever the preparation of the promoted catalysts is consistent with the absence of promoting effect in toluene hydrogenation. (author)

  4. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    Science.gov (United States)

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

  5. Hydride mobility in trinuclear sulfido clusters with the core [Rh3(μ-H)(μ3-S)2]: molecular models for hydrogen migration on metal sulfide hydrotreating catalysts.

    Science.gov (United States)

    Jiménez, M Victoria; Lahoz, Fernando J; Lukešová, Lenka; Miranda, José R; Modrego, Francisco J; Nguyen, Duc H; Oro, Luis A; Pérez-Torrente, Jesús J

    2011-07-11

    The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts.

  6. STUDY OF HYDROGEN SULFIDE REMOVAL FROM GROUNDWATER

    Directory of Open Access Journals (Sweden)

    T. Lupascu

    2013-06-01

    Full Text Available The process of the hydrogen sulfide removal from the underground water of the Hancesti town has been investigated. By oxygen bubbling through the water containing hydrogen sulfide, from the Hancesti well tube, sulfur is deposited in the porous structure of studied catalysts, which decreases their catalytic activity. Concomitantly, the process of adsorption / oxidation of hydrogen sulfide to sulfate take place. The kinetic research of the hydrogen sulfide removal from the Hancesti underground water, after its treatment by hydrogen peroxide, proves greater efficiency than in the case of modified carbonic adsorbents. As a result of used treatment, hydrogen sulfide is completely oxidized to sulfates

  7. Electrochemical catalyst recovery method

    Science.gov (United States)

    Silva, Laura J.; Bray, Lane A.

    1995-01-01

    A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

  8. A Metal-Amino Acid Complex-Derived Bifunctional Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Ding, Yanjun; Niu, Yuchen; Yang, Jia; Ma, Liang; Liu, Jianguo; Xiong, Yujie; Xu, Hangxun

    2016-10-01

    Bifunctional oxygen electrocatalyst: A metal-amino acid complex is developed to prepare high-performance mesoporous carbon electrocatalyst for both oxygen reduction and oxygen evolution reactions. Such prepared catalyst can be used to assemble rechargeable zinc-air batteries with excellent durability. This work represents a new route toward low-cost, highly active, and durable bifunctional electrocatalysts for cutting-edge energy conversion devices.

  9. Exploring the main function of reduced graphene oxide nano-flakes in a nickel cobalt sulfide counter electrode for dye-sensitized solar cell

    Science.gov (United States)

    Lu, Man-Ning; Lin, Jeng-Yu; Wei, Tzu-Chien

    2016-11-01

    Addition of carbonaceous materials into transition metal sulfide counter electrode (CE) of a dye-sensitized solar cell (DSSC) is a common method to improve the performance of the CE and consequent photovoltaic performance. This improvement is almost without exception attributed to the improvement of overall conductivity after the carbonaceous material addition; however, the root function of these carbonaceous materials in promoting the solar cell efficiency is seldom discussed. In this study, highly crystallized nickel cobalt sulfide (NCS) micro-particles were mixed with a small portion of home-made reduced graphene oxide (rGO) nano-flakes. This NCS/rGO hybrid is subjected to extensive characterizations including X-ray diffraction, Raman spectroscopy, field emission scanning microscopy and electrochemical impedance spectroscopy. It is found that the rGO acts bi-functionally including a co-catalyst in accelerating the tri-iodide reduction for the main NCS catalysts, conductivity promotor to decrease the series resistance of the CE. Proved by electrochemical impedance spectroscopy, it is confirmed that the decrease in series resistance is less insignificant than that in charge transfer resistance, indicating rGO functions more profoundly as a co-catalyst than as a conductivity promotor. Moreover, an argument to highlight the requirement of a CE in a dim-light optimized DSSC is also proposed.

  10. Bifunctional redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Y.H. [Research Institute of Chemical Defense, Beijing 100083 (China)], E-mail: wen_yuehua@126.com; Cheng, J. [Research Institute of Chemical Defense, Beijing 100083 (China); Beijing Science and Technology University, Beijing 100083 (China); Xun, Y. [Research Institute of Chemical Defense, Beijing 100083 (China); Ma, P.H. [Full Cell R and D Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Yang, Y.S. [Research Institute of Chemical Defense, Beijing 100083 (China); Beijing Science and Technology University, Beijing 100083 (China)

    2008-08-20

    A new bifunctional redox flow battery (BRFB) system, V(III)/V(II)-L-cystine(O{sub 2}), was systematically investigated by using different separators. It is shown that during charge, water transfer is significantly restricted with increasing the concentration of HBr when the Nafion 115 cation exchange membrane is employed. The same result can be obtained when the gas diffusion layer (GDL) hot-pressed separator is used. The organic electro-synthesis is directly correlated with the crossover of vanadium. When employing the anion exchange membrane, the electro-synthesis efficiency is over 96% due to a minimal crossover of vanadium. When the GDL hot-pressed separator is applied, the crossover of vanadium and water transfer are noticeably prevented and the electro-synthesis efficiency of over 99% is obtained. Those impurities such as vanadium ions and bromine can be eliminated through the purification of organic electro-synthesized products. The purified product is identified to be L-cysteic acid by IR spectrum. The BRFB shows a favorable discharge performance at a current density of 20 mA cm{sup -2}. Best discharge performance is achieved by using the GDL hot-pressed separator. The coulombic efficiency of 87% and energy efficiency of about 58% can be obtained. The cause of major energy losses is mainly associated with the cross-contamination of anodic and cathodic active electrolytes.

  11. Enantioselective α-Chlorination of Aldehydes with Recyclable Fluorous (S)-Pyrrolidine-Thiourea Bifunctional Organocatalyst.

    Science.gov (United States)

    Wang, Liang; Cai, Chun; Curran, Dennis P; Zhang, Wei

    2010-01-01

    A novel fluorous (S)-pyrrolidine-thiourea bifunctional organocatalyst is prepared. The catalyst shows good activity and enantioselectivity for direct α-chlorination of aldehydes using N-chlorosuccinimide (NCS) as the chlorine source. It can be recovered from the reaction mixture by fluorous solid-phase extraction with excellent purity for direct reuse.

  12. Characterization of A Sulfided Mo/γ-Al2O3 Catalyst by Low Temperature FTIR Spectroscopy of Adsorbed CO and Its Thiophene HDS Activity%硫化态Mo/γ-Al2O3催化剂活性位的低温CO-FTIR方法表征及噻吩HDS活性

    Institute of Scientific and Technical Information of China (English)

    齐兴义; 徐春明; 刘植昌; 李文钊; 辛勤

    2001-01-01

    A sulfided Mo/γ-Al2O3 catalyst was characterized by low-temperature FTIR spectroscopy of adsorbed carbon monoxide, with its HDS activity being investigated with thiophene as a mold substrate. On the basis of the results here, the conclusion may be obtained that the sites for CO adsorption should be the active reaction centers of thiophene HDS.

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

    Science.gov (United States)

    Bhandari, Pushpak

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

  14. 非贵金属催化碱性硫离子-空气燃料电池%Alkaline sulfide-air fuel cell system using non-noble metal catalysts

    Institute of Scientific and Technical Information of China (English)

    黄永茂; 张志艳; 程艳坤; 李永真; 张贺

    2014-01-01

    The alkaline sulfide-air fuel cell system was assembled using alkaline sulfide solution as anode fuel and activated carbon as anodic catalyst. The electrochemical behavior of alkaline sulfide was investigated in a three-electrode system and the effects of concentration of sulfide ion,operation temperature on open circuit potential(OCP)and discharge platform were studied. The OCP of anode was rather negative and stable. Through single fuel cell test,a maximum power density of 11mW/cm2 was obtained at 0.24V with current density of 46mA/cm2,demonstrating excellent electrochemical performance for energy conversion. The alkaline sulfide-air fuel cell exhibited promising perspective due to its research potential and application value.%以碱性硫离子电解液作为阳极燃料构建了硫离子-氧气燃料电池体系,采用粉末活性炭材料制备了涂膏电极,将碱性硫化钠溶液作为阳极燃料,通过建立电化学三电极模型对电极在碱性硫离子溶液中的放电性能进行研究,主要考察了硫离子浓度、体系温度对开路电位以及放电平台的影响。电极在碱性硫离子溶液中具有较负的开路电位和稳定的放电平台;通过单体电池测试在0.24V 电压下获得11mW/cm2的最大功率密度,此时电池的电流密度为46mA/cm2,证明碱性硫离子燃料电池在阳极不使用贵金属催化剂的情况下表现出良好的放电性能,是一种具有潜在研究价值和广泛应用前景的电化学体系。

  15. Molybdatophosphoric acid as an efficient catalyst for the catalytic and chemoselective oxidation of sulfides to sulfoxides using urea hydrogen peroxide as a commercially available oxidant

    Directory of Open Access Journals (Sweden)

    ALIREZA HASANINEJAD

    2010-03-01

    Full Text Available An efficient procedure for the chemoselective oxidation of alkyl (aryl sulfides to the corresponding sulfoxides using urea hydrogen peroxide (UHP in the presence of a catalytic amount of molybdatophosphoric acid at room temperature is described. The advantages of described method are: generality, high yield and chemoselectivity, short reaction time, low cost and compliment with green chemistry protocols.

  16. Highly active sulfided CoMo catalysts supported on (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxides

    Energy Technology Data Exchange (ETDEWEB)

    Escobar, José, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Col. San Bartolo Atepehuacan, Gustavo A. Madero, México, D.F. 07730 (Mexico); De Los Reyes, José A., E-mail: jarh@xanum.uam.mx [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Ulín, Carlos A. [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Barrera, María C., E-mail: mcbdgavilan@gmail.com [Facultad de Ciencias Químicas, Universidad Veracruzana, Av. Universidad km. 7.5, Col. Santa Isabel, Coatzacoalcos, Veracruz, México, D.F. 96538 (Mexico)

    2013-12-16

    (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxide at 20 mol% Al{sub 2}O{sub 3} (80% ZrO{sub 2}–TiO{sub 2}, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl{sub 2}·8H{sub 2}O) and titanium (TiCl{sub 4}) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S{sub g} = 387 m{sup 2} g{sup −1}, V{sub p} = 0.74 ml g{sup −1}, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO{sub 2}–TiO{sub 2} deposition over alumina substrate resulted in decreased proportion of Mo{sup 6+} species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H{sub 2}S/H{sub 2} at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS{sub 2} phase (at 2.8 atoms/nm{sup 2}), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} and the corresponding Al{sub 2}O{sub 3}-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo{sup 6+} over the oxidic impregnated precursor with (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3

  17. Hydroconversion of n-alkanes on bifunctional zeolites with unusual pore architecture

    Energy Technology Data Exchange (ETDEWEB)

    Doerr, G.; Tontisirin, S.; Ernst, S. [Technische Univ. Kaiserslautern (Germany). Dept. of Chemistry, Chemical Technology

    2010-12-30

    Zeolites MCM-68 and ZSM-18, both possessing unusual pore architectures, were synthesized via hydrothermal synthesis using optimized methods. X-ray powder diffraction and scanning electron microscopy revealed that the obtained zeolites are well crystallized and do not contain visible amounts of amorphous material. The bifunctional forms of MCM- 68 and ZSM-18 (viz. the acid form loaded with small amounts of palladium) were characterized using the hydroconversion of n-decane as catalytic test reaction. In this reaction, both catalysts showed the typical behaviour known from other bifunctional large pore zeolites. (orig.)

  18. Bifunctional activation of a direct methanol fuel cell

    Science.gov (United States)

    Kulikovsky, A. A.; Schmitz, H.; Wippermann, K.; Mergel, J.; Fricke, B.; Sanders, T.; Sauer, D. U.

    We report a novel method for performance recovery of direct methanol fuel cells. Lowering of air flow rate below a critical value turns the cell into bifunctional regime, when the oxygen-rich part of the cell generates current while the rest part works in electrolysis mode (electrolytic domain). Upon restoring the normal (super-critical) air flow rate, the galvanic performance of the electrolytic domain increases. This recovery effect is presumably attributed to Pt surface cleaning on the cathode with the simultaneous increase in catalyst utilization on the anode.

  19. Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

    Science.gov (United States)

    Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

    2017-02-01

    Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

  20. 机械混合法制备酸碱双功能催化剂催化合成异佛尔酮%Synthesis of isophoroneon acid-base bifunctional catalysts by machine mixing method

    Institute of Scientific and Technical Information of China (English)

    苑丽质

    2015-01-01

    以氧化镁和氧化铝粉体为主要原料,采用机械混合法制备了不同镁铝比的酸碱双功能催化剂,选择丙酮气相合成异佛尔酮为探针反应,在固定床反应器中对其活性进行了评价,并通过XRD、XPS和TPD等表征手段对催化剂的性质和结构进行了分析。结果表明,机械混合法催化剂活性较高,镁铝比对催化剂的晶体结构、表面酸碱强度影响不大,而对催化剂的表面酸碱量有显著影响。当1∶1.8≤Mg∶Al≤1∶1时,催化剂的酸量及碱量较大,催化剂的活性较高。当镁铝比为1∶1时,丙酮的转化率和异氟尔酮的选择性分别为11.5%和62.8%。通过调节催化剂的装填量,有效地延长了反应物的停留时间,丙酮的转化率大幅提高。当反应条件为常压、反应温度300℃、空速0.67h−1时,丙酮的转化率和异佛尔酮的选择性分别为21.0%和73.0%。%The catalysts with different ratio of Mg and Al were prepared by machine mixing method with MgO and Al2O3 as raw materials,the activity of catalysts was evaluated in a fixed bed reactor with the synthesis of isophorone by gas acetone as probe reaction,and the catalysts were characterized by XRD,XPS and TPD. The results showed that the activity of catalysts prepared by machine mixing method was high,the ratio of Mg and Al had little effect on the crystalline structure and surface acid-base strength,but had significant effect on the surface acid-base amount of catalysts. When the ratio of Mg and Al was 1∶1.8 to 1∶1,the surface acid-base amount of catalysts was higher,so the activity of catalysts was higher. When the ratio of Mg and Al was 1∶1,the conversion of acetone and selectivity of isophorone were 11.5% and 62.8% respectively. By adjusting catalyst loading amount,the residence time of reactants was effectively prolong,the conversion of acetone was increased. Under the reaction conditions of atmospheric pressure,reaction temperature

  1. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; Meyer, Tricia L.; Zhang, Zhiyong; Lutterman, Daniel A.; Lee, Ho Nyung

    2016-03-02

    Strain is known to greatly influence low temperature oxygen electro catalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and Metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals' such as Pt. We attribute the improved bifunctionality to strain induced splitting of the e(g) Orbitals, which can customize orbital asymmetry at the surface. Analogous to strain induced shifts in the d-band center of noble metals relative to the Fermi level, :such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active Oxides.

  2. Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

    KAUST Repository

    Riache, Nassima

    2015-01-01

    Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

  3. Studies on Characterization of Sulfided Tertiary NiMoP/γ-Al2O3 Catalysts by TPR Technique and Their Thiophene HDS Activity%硫化态三组元NiMoP/γ-Al2O3催化剂的TPR表征及噻吩HDS活性的研究

    Institute of Scientific and Technical Information of China (English)

    齐兴义; 徐春明; 刘植昌; 李文钊; 辛勤

    2001-01-01

    A series of sulfided tertiary NiMoP/γ-Al2O3 catalysts with different contents of MoO3 were prepared by using molybdophosphoric acid of Keggin structure(H3PMo12O40) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo-0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so-called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mox+ sites on the MoS2 phase(MoS2 slab). With the introduction of nickel into the active phase of the sulfided Mo-0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/γ-Al2O3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [n(Ni)+n(Mo)]/n(Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni-Mo-S slab due to the loss of S during TPR process and vacancies or sites related to the H2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.

  4. Influence of Metal Sulfides as Anode Catalysts on Performance of H2S SOFC%金属硫化物作为阳极材料对H2S固体氧化物燃料电池性能研究

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Two anode catalysts with Pt, MoS2 and composite metal sulfides (MoS2+NiS), are investigated forelectrochemical oxidation of hydrogen sulfide in solid oxide fuel cell (SOFC) at temperatures 750-850℃. Thecatalysts comprising MoS2 and MoS2+NiS exhibited good electrical conductivity and catalytic activity. MoS2 andcomposite catalysts were found to be more active than Pt, a widely used catalyst for high temperature H2S/O2fuel cell at 750-850℃. However, MoS2 itself sublimes above 450℃. In contrast, composite catalysts containingboth Mo and transition metal (Ni) are shown to be stable and effective in promoting the oxidation of H2S in SOFCup to 850℃. However, electric contact is poor between the platinum current collecting layer and the compositemetal sulfide layer, so that the cell performance becomes worse. This problem is overcome by adding conductiveAg powder into the anode layer (forming MoS2+NiS+Ag anode material) to increase anode electrical conductanceinstead of applying a thin layer of platinum on the top of anode.

  5. Preparation of Zinc Sulfide from Waste Zinc-bearing Catalyst by Alkaline Leaching%碱法浸出含锌废催化剂制备硫化锌

    Institute of Scientific and Technical Information of China (English)

    胡慧萍; 谢丽芳; 陈启元; 王树宾

    2012-01-01

    研究了以含锌废催化剂为原料,通过碱浸、净化、沉淀制备ZnS的新工艺.重点考察浸出温度、NaOH浓度、液固比(浸出剂质量/原料质量)和浸出时间等工艺参数对Zn浸出率的影响.最佳工艺条件是:NaOH浓度5 mol/L、液固比25∶1、温度80℃、浸出时间2h,在该条件下锌浸出率可达90%;浸出液经过锌粉1次净化后采用水热法可以获得纯度较高、结晶性好的ZnS,沉锌后的滤液可以作为浸出剂循环利用.%A new process for preparing zinc sulfide from waste catalyst containing zinc by alkaline-leaching, purification, precipitation process was studied. The influences of extraction temperature, NaOH concentration, liquid-solid ratio (mass ratio) and extraction time on zinc leaching rate were emphatically investigated. The recovery of Zn was up to 90% under the optimum conditions including concentration of NaOH of 5 mol/L, liquid-solid ratio of 25 : 1 and leaching at 80 ℃ for 2 hours. Zinc sulfide with high purity and better crystallinity was synthesized successfully by hydrothermal method after leaching solution' s one-stage purification with zinc dust, and the filtrate can be recycled to be used as leaching agent.

  6. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    OpenAIRE

    F. V. Barsi; Cardoso,D.

    2009-01-01

    Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt) and bimetallic catalysts (Pt-Ni), using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on th...

  7. Core-double-shell Fe3O4@carbon@poly(In(III)-carboxylate) microspheres: cycloaddition of CO2 and epoxides on coordination polymer shells constituted by imidazolium-derived Al(III)-Salen bifunctional catalysts.

    Science.gov (United States)

    An, Qiao; Li, Zifeng; Graff, Robert; Guo, Jia; Gao, Haifeng; Wang, Changchun

    2015-03-01

    A hydrid microsphere Fe3O4@carbon@poly(In(III)-carboxylate) consisting of a cluster of Fe3O4 nanoparticles as the core, a carbon layer as the inner shell and a porous In(III)-carboxylate coordination polymer as the outer shell was prepared and applied as a recyclable catalyst for the cycloaddition reaction of CO2 and epoxides. Construction of this hybrid microsphere was achieved in the two steps, including (1) the one-pot solvothermal synthesis of Fe3O4@C particles with the abundant carboxylic groups on the carbon surface and (2) the subsequent growth of the outer shell polymers based on the precipitation coordination polymerization. Imidazolium-substituted Salen ligands were synthesized and chelated with the In(III) ions using the terminal carboxylic groups. The coordination polymer shell was formed on the Fe3O4@C particles, and the structures including shell thickness, surface area and porosity could be varied by tuning the feeding ratios of the In(III) ions and the ligands. The optimal structure of the coordination polymers showed a shell thickness of ca. 45 nm with ∼5 nm of mesopore, 174.7 m(2)/g of surface area and 0.2175 cm(3)/g of pore volume. In light of gas uptake capability, catalytic activity and magnetic susceptibility, cycloaddition of CO2 with a series of epoxides were studied by using Al-complexed Fe3O4@C@In(III)-[IL-Salen] microspheres. The results validated that the self-supporting catalytic layer with high surface area was of remarkable advantages, which were attributed from great increment of effective active sites and combination of nucleophilic/electrophilic synergistic property and CO2 uptake capability. Therefore, these hybrid microspheres provided excellent catalytic activity, prominent selectivity to cyclic carbonates and outstanding recyclability with the assistance of an applied magnetic field.

  8. In-situ Studies of the Reactions of Bifunctional and Heterocyclic Molecules over Noble Metal Single Crystal and Nanoparticle Catalysts Studied with Kinetics and Sum-Frequency Generation Vibrational Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kliewer, Christopher J. [Univ. of California, Berkeley, CA (United States)

    2009-06-30

    Sum frequency generation surface vibrational spectroscopy (SFG-VS) in combination with gas chromatography (GC) was used in-situ to monitor surface bound reaction intermediates and reaction selectivities for the hydrogenation reactions of pyrrole, furan, pyridine, acrolein, crotonaldehyde, and prenal over Pt(111), Pt(100), Rh(111), and platinum nanoparticles under Torr reactant pressures and temperatures of 300K to 450K. The focus of this work is the correlation between the SFG-VS observed surface bound reaction intermediates and adsorption modes with the reaction selectivity, and how this is affected by catalyst structure and temperature. Pyrrole hydrogenation was investigated over Pt(111) and Rh(111) single crystals at Torr pressures. It was found that pyrrole adsorbs to Pt(111) perpendicularly by cleaving the N-H bond and binding through the nitrogen. However, over Rh(111) pyrrole adsorbs in a tilted geometry binding through the {pi}-aromatic orbitals. A surface-bound pyrroline reaction intermediate was detected over both surfaces with SFG-VS. It was found that the ring-cracking product butylamine is a reaction poison over both surfaces studied. Furan hydrogenation was studied over Pt(111), Pt(100), 10 nm cubic platinum nanoparticles and 1 nm platinum nanoparticles. The product distribution was observed to be highly structure sensitive and the acquired SFG-VS spectra reflected this sensitivity. Pt(100) exhibited more ring-cracking to form butanol than Pt(111), while the nanoparticles yielded higher selectivities for the partially saturated ring dihydrofuran. Pyridine hydrogenation was investigated over Pt(111) and Pt(100). The α-pyridyl surface adsorption mode was observed with SFG-VS over both surfaces. 1,4-dihydropyridine was seen as a surface intermediate over Pt(100) but not Pt(111). Upon heating the surfaces to 350K, the adsorbed pyridine changes to a flat-lying adsorption mode. No evidence was found for the pyridinium cation. The hydrogenation of the

  9. 不同方法制备的硫化态K-Co-Mo催化剂的EXAFS研究%An EXAFS Study of Sulfided K-Co-Mo CatalystsPrepared by Different Method

    Institute of Scientific and Technical Information of China (English)

    鲍骏; 卞国柱; 伏义路; 刘涛; 谢亚宁; 胡天斗

    2001-01-01

    采用共沉淀法和溶胶-凝胶法制备了同组分的硫化态K-Co-Mo催化剂,并用EXAFS研究了体系中Mo原子和Co原子的局域配位情况.结果表明,硫化态K-Co-Mo样品中Mo原子以类似于MoS2结构的物种存在,而Co原子除了以Co9S8形式存在外,还以一种Co-Mo-S相的形式存在,Co-Mo-S的晶相结构与MoS2类似.结合活性测试结果认为Co-Mo-S的形成促进了样品催化活性的提高.此外,EXAFS结果还表明,不同制备方法对K-Co-Mo样品中Mo物种晶粒尺寸具有较大的影响,而对Co9S8粒子则影响不明显,其中,采用溶胶-凝胶方法制备,并且在氩气中处理过的样品中Mo物种具有最小的晶粒尺寸.%A kind of sulfided K-Co-Mo catalyst, prepared by sol-gel andprecipitation method respectively, was characterized by EXAFS technique. The results indicate that, in the sulfided samples, the Mo atoms exist as MoS2-like species, the Co atoms exist not only as Co9S8, but also as a kind of Co-Mo-S phase, which almost has the same structure as MoS2. Combining the activity results, it is suggested that the formation of Co-Mo-S improves the activity toward alcohol. Additionally, it is found that the sample prepared by sol-gel method and treated in argon atmosphere has the smallest size of MoS2 crystallites, while the Co9S8 shows no notable change.

  10. Overview of Support Effects in Hydrotreating Catalysts

    Institute of Scientific and Technical Information of China (English)

    Michèle Breysse

    2004-01-01

    @@ Industrial hydrotreating (HDT) catalysts are composed of a molybdenum sulfide (or tungsten sulfide) phase promoted by cobalt or nickel and usually supported on alumina. The origin of the almost exclu1sive use of alumina as support has to be ascribed to its outstanding textural and mechanical properties and its relatively low cost[1].

  11. Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate.

    Science.gov (United States)

    Sun, Peng; Long, Xiangdong; He, Hao; Xia, Chungu; Li, Fuwei

    2013-11-01

    Considerable effort has been applied to the development of new processes and catalysts for cellulose conversion to valuable platform chemicals. Isosorbide is among the most interesting products as it can be applied as a monomer and building block for the future replacement of fossil resource-based products. A sustainable method of isosorbide production from cellulose is presented in this work. The strategy relies on a bifunctional Ru catalyst supported on mesoporous niobium phosphate in a H2 atmosphere under pressure without further addition of any soluble acid. Over 50 % yield of isosorbide with almost 100 % cellulose conversion can be obtained in 1 h. The large surface area, pore size, and strong acidity of mesoporous niobium phosphate promote the hydrolysis of cellulose and dehydration of sorbitol; additionally, the appropriate size of the supported Ru nanoparticles avoids unnecessary hydrogenolysis of sorbitol. Under a cellulose/catalyst mass ratio of 43.3, the present bifunctional catalyst could be stably used up to six times, with its mesoporous structure well preserved and without detectable Ru leaching into the reaction solution.

  12. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... bifunctional requirement, which demands both adsorption and water oxidation sites. In this contribution, we explore the possibility of using Pt-Si alloys to fulfill this bifunctional requirement. Silicon, a highly oxophillic element, is alloyed into Pt as a site for water oxidation, while Pt serves as a CO...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

  13. First-Principles Study of Structure Property Relationships of Monolayer (Hydroxy)Oxide-Metal Bifunctional Electrocatalysts

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Kubal, Joseph; Greeley, Jeffrey Philip

    2015-01-01

    In the present study, on the basis of detailed density functional theory (DFT) calculations, and using Ni hydroxy(oxide) films on Pt(111) and Au(111) electrodes as model systems, we describe a detailed structural and electrocatalytic analysis of hydrogen evolution (HER) at three-phase boundaries...... of information that is inaccessible by purely experimental means, and these structures, in turn, strongly suggest that a bifunctional reaction mechanism for alkaline HER will be operative at the interface between the films, the metal substrates, and the surrounding aqueous medium. This bifunctionality produces...... important changes in the calculated barriers of key elementary reaction steps, including water activation and dissociation, as compared to traditional monofunctional Pt surfaces. The successful identification of the structures of thin metal films and three-phase boundary catalysts is not only an important...

  14. Catalytic conversion of Jerusalem artichoke tuber into hexitols using the bifunctional catalyst Ru/(AC-SO3H)%双功能催化剂Ru/(AC-SO3H)催化转化菊芋根茎制备六元醇

    Institute of Scientific and Technical Information of China (English)

    周立坤; 李振雷; 庞纪峰; 郑明远; 王爱琴; 张涛

    2015-01-01

    菊芋根茎水解反应是主要的反应路径.在H2气氛下反应,糖类产率在1 h内达到最大值,然后开始逐渐降低,同时加氢产物逐渐增加.因此, H2气氛下反应过程中生成的糖类是中间产物.以菊芋根茎为原料,1%Ru/(AC-SO3H)催化剂循环使用4次后六元醇产率由87%降至55%;而以菊粉为原料,循环4次后六元醇产率略有降低. ICP测试表明, Ru催化剂并未流失,3次循环后催化剂的CO化学吸附表明, Ru的分散度由74.2%降至17.8%.这表明催化剂失活是由菊芋根茎中的杂质毒化Ru活性位点导致的.%Jerusalem artichoke tuber (JAT) was employed as a feedstock for production of hexitols under mild conditions over a sulfonated activated carbon supported Ru catalyst (Ru/(AC-SO3H)). In compari-son with conventional Ru/AC catalyst, the sulfonation process of the carbon support was observed to create abundant surface acid groups, which in turn function as the anchoring sites for Ru nano-particles, thus increasing the dispersion of Ru. Consequently, the bifunctional Ru/(AC-SO3H) catalyst displayed significantly enhanced activity in one-pot production of hexitols from JAT; the hexitols yield achieved 92.6% over the 3%Ru/(AC-SO3H) catalyst when the reaction was conducted at 373K and 6 MPa H2 for 3 h. The stability of the catalyst was also investigated, which showed a decreasing trend in the yield of sorbitol with the run number due to poisoning of Ru surface by the impurity in the JAT feedstock. In contrast, when pure inulin was used as the feedstock, the catalyst presented excellent stability in the successive four runs.

  15. Synthesis of bifunctional antibodies for immunoassays.

    Science.gov (United States)

    DeSilva, B S; Wilson, G S

    2000-09-01

    The synthesis of bifunctional antibodies using the principle of solid-phase synthesis is described. Two Fab' fragments were chemically linked together via a bismaleimide crosslinking reagent. The F(ab')(2) fragments from intact immunoglobulin G (IgG) were prepared using an immobilized pepsin column. Goat, mouse, and human antibodies were digested completely within 4 h. The F(ab')(2) fragments thus produced did not contain any IgG impurities. Fab' fragments were produced by reducing the heavy interchain disulfide bonds using 2-mercaptoethylamine. Use of the solid-phase reactor in the preparation of the bifunctional antibodies eliminated many of the time-consuming separation steps between the fragmentation and conjugation steps. This procedure facilitates the automation of bifunctional antibody preparation and the rapid optimization of reaction conditions.

  16. Solid phase synthesis of bifunctional antibodies.

    Science.gov (United States)

    DeSilva, B S; Wilson, G S

    1995-12-15

    Bifunctional antibodies were prepared using the principle of solid-phase synthesis. The two Fab' fragments were chemically linked together via a bismaleimide crosslinking reagent. The F(ab')2 fragments from intact IgG were prepared using an immobilized pepsin column. Goat, mouse and human antibodies were digested completely within 4 h. The F(ab')2 fragments thus produced did not contain any IgG impurities. The Fab' fragments were produced by reducing the inter-heavy chain disulfide bonds using 2-mercaptoethylamine. The use of the solid-phase reactor in the preparation of the bifunctional antibodies eliminated many of the time-consuming separation steps between the fragmentation and conjugation steps. This procedure facilitates the automation of the bifunctional antibody preparation and the rapid optimization of reaction conditions.

  17. Nanopore and nanoparticle catalysts.

    Science.gov (United States)

    Thomas, J M; Raja, R

    2001-01-01

    The design, atomic characterization, performance, and relevance to clean technology of two distinct categories of new nanocatalysts are described and interpreted. Exceptional molecular selectivity and high activity are exhibited by these catalysts. The first category consists of extended, crystallographically ordered inorganic solids possessing nanopores (apertures, cages, and channels), the diameters of which fall in the range of about 0.4 to about 1.5 nm, and the second of discrete bimetallic nanoparticles of diameter 1 to 2 nm, distributed more or less uniformly along the inner walls of mesoporous (ca. 3 to 10 nm diameter) silica supports. Using the principles and practices of solid-state and organometallic chemistry and advanced physico-chemical techniques for in situ and ex situ characterization, a variety of powerful new catalysts has been evolved. Apart from those that, inter alia, simulate the behavior of enzymes in their specificity, shape selectivity, regio-selectivity, and ability to function under ambient conditions, many of these new nanocatalysts are also viable as agents for effecting commercially significant processes in a clean, benign, solvent-free, single-step fashion. In particular, a bifunctional, molecular sieve nanopore catalyst is described that converts cyclohexanone in air and ammonia to its oxime and caprolactam, and a bimetallic nanoparticle catalyst that selectively converts cyclic polyenes into desirable intermediates. Nanocatalysts in the first category are especially effective in facilitating highly selective oxidations in air, and those in the second are well suited to effecting rapid and selective hydrogenations of a range of organic compounds.

  18. Bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au: Study on luminescence and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail: junwang924@mail.ccnu.edu.cn; Fan, Shaohua; Zhao, Weiqian; Lu, Xuelian; Li, Wuke

    2013-12-02

    In this paper, the synthesis and properties of composite silica microspheres grafted with gold nanoparticles and lanthanide-polyoxometalates are described. This synthesis employs polyethyleneimine as the crosslink polymer to immobilize the Au nanoparticles and lanthanide-polyoxometalates on silica spheres, which results in the formation of bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au. The composite material was found to be catalytically active in the oxidation of styrene, and benzaldehyde and styrene oxide were the main products. Catalyzed oxidation of styrene demonstrates the size-dependent activity of catalysts and the smaller catalyst shows the higher selectivity. Moreover, the composite particles show bright red luminescence under UV light, which could be seen by naked eyes. The luminescence properties of composite material and the effect of Au nanoparticles on the luminescence of Eu ion were investigated, and energy could be more effectively transferred from ligand to lanthanide ion when Au nanoparticles were grafted on silica spheres. The integration of luminescent components and Au particles makes it possible to label catalyst and monitor the catalyzed reactions. - Highlights: • The bifunctional composite microspheres were fabricated. • Both polyoxometalates and Au nanoparticles could be grafted on silica spheres. • The composite particles exhibit the excellent luminescence and catalytic activity. • The Au nanoparticles affect the luminescence properties of Eu{sup 3+} ions.

  19. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.; Smith, Colin D.; Wang, Yong

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  20. Influences of species of metals and supports on the hydrogenation activity of carbon-supported metal sulfides catalysts; Tanso biryushi tanji shokubai no suisoka kassei ni taisuru kassei kinzoku oyobi tantaishu no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Sakanishi, K.; Hasuo, H.; Taniguchi, H.; Nagamatsu, T.; Mochida, I. [Kyushu University, Fukuoka (Japan). Institute of Advanced Material Study

    1996-10-28

    In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supported catalysts were prepared. Catalytic activities of them were investigated for the hydrogenation of 1-methylnaphthalene, to discuss the influences of metals and carbon species on the catalytic activity. Various water soluble and oil soluble Mo and Ni salts were used for NiMo supported catalysts. Among various carbon supports, Ketjen Black (KB) was effective for preparing the catalyst showing the most excellent hydrogenation activity. The KB and Black Pearl 2000 (BP2000) showing high hydrogenation activity were fine particles having high specific surface area more than 1000 m{sup 2}/g and primary particle diameter around 30 nm. This was inferred to contribute to the high dispersion support of active metals. Since such fine particles of carbon exhibited hydrophobic surface, they were suitable for preparing catalysts from the methanol-soluble metals. Although Ni and Mo added iron-based catalysts provided lower aromatic hydrogenation activity, they exhibited liquefaction activity competing with the NiMo/KB catalyst. 3 refs., 1 fig., 3 tabs.

  1. A Novel Catalytic Method for the Oxidation of Sulfides to Sulfoxides with Silica Sulfuric Acid and Sodium Nitrite in the Presence of KBr and/or NaBr as Catalyst

    Institute of Scientific and Technical Information of China (English)

    GOUDARZIAFSHAR Hamid; GHORBANI-CHOGHAMARANI Arash; NIKOORAZM Mohsen; NASERIFAR Zahra

    2009-01-01

    Highly efficient selective oxidation of sulfides to sulfoxides by NaNO2 and silica sulfuric acid catalyzed with KBr or NaBr has been reported.This oxidation was carried out in the presence of wet SiO2(50% w/w)in acetonitrile at room temperature with good to excellent yields.

  2. The role of transition metal sulfides in hydrotreatment. 3. Acidity, XPS and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    De Agudelo, M.M.; Reyes, L.G.; Do Campo, N.

    1987-05-15

    Although, recently, most of the research on catalysis has been devoted to hydrotreatment, attention has been paid to hydrodesulfurization (HDS) but very little has been done on hydrodemetallization (HDM). This article is part of a systematic study directed towards defining the role of transition metal sulfides in hydrotreatment reactions. Catalysts supported on silica or alumina have been considered. Acidity has been evaluated using pyridine as probe molecule. This property can be attributed to the sulfide phase of the catalysts. The alumina supported catalysts were more acid than the silica supported catalysts. Since the acidity might exclusively be of Lewis type, the pattern observed through the first row transition metal sulfides reflects the trend of the electron-acceptor character of these sulfides. The XPS results indicate that catalysts are partially sulfided (at 400 C). At the same time, the results corroborate a better Me-support interaction on alumina than on silica. The HDM and HDS intrinsic activities, using a desalphalted (DAO) Morichal as feed were evaluated normalizing conversion in terms of the surface metal sites per surface area. The intrinsic activity patterns obtained for the first row transition metal sulfides, were very similar to those mentioned of acidity, reaffirming the importance of the electronic structure of the sulfide phase on its catalytic activity. 21 refs.

  3. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

  4. First Application of Novel Sulfiding Agent SZ 54 in Domestic Hydrofining Unit

    Institute of Scientific and Technical Information of China (English)

    Pan Maohua

    2006-01-01

    A novel environmentally friendly sulfiding agent SZ 54 was for the first time used for presulfidation of the catalyst in the 2 Mt/a hydrofining unit at Zhenhai Refining and Chemical Company. The application results had shown that the sulfiding agent SZ54 had low smell, high flash point, and safe and environmentally friendly features. The lower decomposition temperature and stepwise chemical decomposition characteristics of this reagent can effectively avoid the reduction of metals and improve sulfur adsorption to meet the needs for sulfidizing the hydrofining catalyst,and is a good reagent worthy of extended application.

  5. Astaxanthin diferulate as a bifunctional antioxidant

    DEFF Research Database (Denmark)

    Papa, T.B.R.; Pinho, V.D.; Nascimento, E.P. do;

    2015-01-01

    Abstract Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(- 1)s(- 1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(- 1)s(- 1). The ferulate moiety in the astaxanthin diester is a better radical s....... The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability....

  6. Metal-ligand bifunctional reactivity and catalysis of protic N-heterocyclic carbene and pyrazole complexes featuring β-NH units.

    Science.gov (United States)

    Kuwata, Shigeki; Ikariya, Takao

    2014-11-28

    Metal-ligand bifunctional cooperation has attracted much attention because it offers a powerful methodology to realize a number of highly efficient and selective catalysts. In this article, recent developments in the metal-ligand cooperative reactions of protic N-heterocyclic carbene (NHC) and pyrazole complexes bearing an acidic NH group at the position β to the metal are surveyed. Protic 2-pyridylidenes as related cooperating non-innocent ligands are also described.

  7. Catalyst design for biorefining.

    Science.gov (United States)

    Wilson, Karen; Lee, Adam F

    2016-02-28

    The quest for sustainable resources to meet the demands of a rapidly rising global population while mitigating the risks of rising CO2 emissions and associated climate change, represents a grand challenge for humanity. Biomass offers the most readily implemented and low-cost solution for sustainable transportation fuels, and the only non-petroleum route to organic molecules for the manufacture of bulk, fine and speciality chemicals and polymers. To be considered truly sustainable, biomass must be derived from resources which do not compete with agricultural land use for food production, or compromise the environment (e.g. via deforestation). Potential feedstocks include waste lignocellulosic or oil-based materials derived from plant or aquatic sources, with the so-called biorefinery concept offering the co-production of biofuels, platform chemicals and energy; analogous to today's petroleum refineries which deliver both high-volume/low-value (e.g. fuels and commodity chemicals) and low-volume/high-value (e.g. fine/speciality chemicals) products, thereby maximizing biomass valorization. This article addresses the challenges to catalytic biomass processing and highlights recent successes in the rational design of heterogeneous catalysts facilitated by advances in nanotechnology and the synthesis of templated porous materials, as well as the use of tailored catalyst surfaces to generate bifunctional solid acid/base materials or tune hydrophobicity.

  8. Coupling of Alcohols over Alkali-Promoted Cobalt-Molybdenum Sulfide

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt; Jensen, Peter Arendt; Schiødt, N.C.

    2010-01-01

    Double or nothing: Higher alcohols are produced by the hydrogenation of CO with a K-promoted Co-MoS2/C catalyst. Ethanol, which is passed over the sulfide catalyst along with CO and H2, is mainly converted into 1-butanol, which indicates that alcohol condensation contributes to the build-up of hi...

  9. Catalytic activity of in situ synthesized MoWNi sulfides in hydrogenation of aromatic hydrocarbons

    Science.gov (United States)

    Topolyuk, Yu. A.; Maksimov, A. L.; Kolyagin, Yu. G.

    2017-02-01

    MoWNi-sulfide catalysts were obtained in situ by thermal decomposition of metal-polymer precursors based on the copolymers of polymaleic anhydride in a hydrocarbon raw material. The activity of the synthesized catalysts in hydrogenation of bicyclic aromatic hydrocarbons was studied, and the composition and structure of active phase nanoparticles were determined.

  10. Carbon Nanotube/Boron Nitride Nanocomposite as a Significant Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions.

    Science.gov (United States)

    Patil, Indrajit M; Lokanathan, Moorthi; Ganesan, Balakrishnan; Swami, Anita; Kakade, Bhalchandra

    2017-01-12

    It is an immense challenge to develop bifunctional electrocatalysts for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) in low temperature fuel cells and rechargeable metal-air batteries. Herein, a simple and cost-effective approach is developed to prepare novel materials based on carbon nanotubes (CNTs) and a hexagonal boron nitride (h-BN) nanocomposite (CNT/BN) through a one-step hydrothermal method. The structural analysis and morphology study confirms the formation of a homogeneous composite and merging of few exfoliated graphene layers of CNTs on the graphitic planes of h-BN, respectively. Moreover, the electrochemical study implies that CNT/BN nanocomposite shows a significantly higher ORR activity with a single step 4-electron transfer pathway and an improved onset potential of +0.86 V versus RHE and a current density of 5.78 mA cm(-2) in alkaline conditions. Interestingly, it exhibits appreciably better catalytic activity towards OER at low overpotential (η=0.38 V) under similar conditions. Moreover, this bifunctional catalyst shows substantially higher stability than a commercial Pt/C catalyst even after 5000 cycles. Additionally, this composite catalyst does not show any methanol oxidation reactions that nullify the issues due to fuel cross-over effects in direct methanol fuel cell applications.

  11. Nucleation of mercury sulfide by dealkylation

    Science.gov (United States)

    Enescu, Mironel; Nagy, Kathryn L.; Manceau, Alain

    2016-12-01

    Metal sulfide minerals are assumed to form naturally at ambient conditions via reaction of a metallic element with (poly)sulfide ions, usually produced by microbes in oxygen-depleted environments. Recently, the formation of mercury sulfide (β-HgS) directly from linear Hg(II)-thiolate complexes (Hg(SR)2) in natural organic matter and in cysteine solutions was demonstrated under aerated conditions. Here, a detailed description of this non-sulfidic reaction is provided by computations at a high level of molecular-orbital theory. The HgS stoichiometry is obtained through the cleavage of the S-C bond in one thiolate, transfer of the resulting alkyl group (R’) to another thiolate, and subsequent elimination of a sulfur atom from the second thiolate as a thioether (RSR’). Repetition of this mechanism leads to the formation of RS-(HgS)n-R chains which may self-assemble in parallel arrays to form cinnabar (α-HgS), or more commonly, quickly condense to four-coordinate metacinnabar (β-HgS). The mechanistic pathway is thermodynamically favorable and its predicted kinetics agrees with experiment. The results provide robust theoretical support for the abiotic natural formation of nanoparticulate HgS under oxic conditions and in the absence of a catalyst, and suggest a new route for the (bio)synthesis of HgS nanoparticles with improved technological properties.

  12. Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces

    DEFF Research Database (Denmark)

    Jovanov, Zarko; Hansen, Heine A.; Varela Gasque, Ana Sofia;

    2016-01-01

    "bifunctional" catalysts using Au-Cd based alloys inspired by theoretical modelling. Density functional theory calculations suggest more favourable thermodynamics for CO2 reduction to CO and methanol on mixed Au-Cd sites on Au3Cd relative to similar values on Au. We use various tools to test the bulk......Electrolysis could enable the large-scale conversion of CO2 to fuels and small molecules. This perspective discusses the state-of-the-art understanding of CO2 and CO reduction electrocatalysis and provides an overview of the most promising approaches undertaken thus far. We set to explore...

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

    Science.gov (United States)

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

    2007-08-01

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

  14. Deactivation and poisoning of fuel cell catalysts

    Science.gov (United States)

    Ross, P. N., Jr.

    1985-06-01

    The deactivation and poisoning phenomena reviewed are: the poisoning of anode (fuel electrode) catalyst by carbon monoxide and hydrogen sulfide; the deactivation of the cathode (air electrode) catalyst by sintering; and the deactivation of the cathode by corrosion of the support. The anode catalyst is Pt supported on a conductive, high area carbon black, usually at a loading of 10 w/o. This catalyst is tolerant to some level of carbon monoxide or hydrogen sulfide or both in combination, the level depending on temperature and pressure. Much less is known about hydrogen sulfide poisoning. Typical tolerance levels are 2% CO, and 10 ppM H2S. The cathode catalyst is typically Pt supported on a raphitic carbon black, usually a furnace black heat-treated to 2700 C. The Pt loading is typically 10 w/o, and the dispersion (or percent exposed) as-prepared is typically 30%. The loss of dispersion in use depends on the operational parameters, most especially the cathode potential history, i.e., higher potentials cause more rapid decrease in dispersion. The mechanism of loss of dispersion is not well known. The graphitic carbon support corrodes at a finite rate that is also potential dependent. Support corrosion causes thickening of the electrolyte film between the gas pores and the catalyst particles, which in turn causes increased diffusional resistance and performance loss.

  15. Understanding hydrodenitrogenation on novel unsupported sulfide Mo-W-Ni catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Hein, J.; Hrabar, A.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    WNi, NiMo and Mo-W-Ni unsupported catalysts were synthesized, characterized and tested with respect to their hydrodenitrogenation properties using o-propylaniline as test reactant. The bimetallic oxide precursors are crystalline metallates, whereas the trimetallic materials are amorphous. In the sulfide form, the catalysts are mixtures of agglomerated Mo(W)S{sub 2} and Ni sulfides. The performance of all catalysts is similar, suggesting the same nature of active sites regardless the composition. Due to the lack of correlation between activity and density of coordinatively unsaturated sites of the catalysts, two kinds of active sites are proposed, i.e. coordinatively unsaturated sites and electron rich sites at the edges of the sulfides. (orig.)

  16. EFFECTS OF CATALYST MORPHOLOGY ON HYDROTREATING REACTIONS

    Directory of Open Access Journals (Sweden)

    TYE CHING THIAN

    2008-08-01

    Full Text Available Due to the new environmental regulations for fuel quality, refineries need to process cleaner fuel. This requires an improvement in performance of hydrotreating catalysts. Improvements in catalyst activity require knowledge of the relationships between catalyst morphology and activity. Molybdenum sulfide, the generally agreed catalysts that give the best performance in hydrocracking and hydrotreating was investigated for its morphology effects on hydrotreating reactions. Three types of MoS2 catalysts with different morphology were studied. They are crystalline MoS2, exfoliated MoS2 and MoS2 derived from a precursor, molybdenum naphthenate. Exfoliated MoS2 with minimal long range order, with much higher rim edges has shown relative higher hydrogenation activity. Generally, results of MoS2 catalyst activities in hydrogenation, hydrodesulfurization, hydrodenitrogenation and hydrideoxy¬gena¬tion are in agreement with the rim-edge model.

  17. Effect of H{sub 2}S partial pressure on the HDS of dibenzothiophene and 4,6-dimethyldibenzothiophene over sulfided NiMoP/Al{sub 2}O{sub 3} and CoMoP/Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rabarihoela-Rakotovao, V.; Brunet, S.; Perot, G. [UMR CNRS 6503, Catalyse en Chimie Organique, Universite de Poitiers, 40 avenue du Recteur Pineau, 86022 Poitiers, Cedex (France); Diehl, F. [Institut Francais du Petrole, IFP-Lyon, Catalysis and Separation Division, Heterogeneous Catalysis Department, BP 3, 69390 Vernaison (France)

    2006-06-07

    The effect of hydrogen sulfide (H{sub 2}S) partial pressure on the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (46DMDBT) was studied over commercial NiMoP/Al{sub 2}O{sub 3} and CoMoP/Al{sub 2}O{sub 3} catalysts under conditions close to those commonly used in the hydrotreating of diesel fuels (280 or 340{sup o}C; total pressure between 2.5 and 5.5MPa). The sulfur compounds diluted in n-heptane were in proportions representative of those found in diesel fuels (0.0014MPa of DBT or 46DMDBT, 0.0058-0.1MPa of H{sub 2}S generated from dimethyldisulfide). A significant negative effect of H{sub 2}S on the HDS of the dibenzothiophenes (DBT and 46DMDBT) was observed whatever the total pressure (2.5-5.5MPa) and the catalyst used. However, the reactivity of DBT was more reduced than that of 46DMDBT. Moreover, the 'direct desulfurization pathway' (DDS) of both reactants was more inhibited by H{sub 2}S than the so-called 'hydrogenation pathway' (HYD) over the two catalysts. It was also found that the NiMoP/Al{sub 2}O{sub 3} catalyst was more sensitive to H{sub 2}S than its CoMoP/Al{sub 2}O{sub 3} counterpart whatever the experimental conditions. Several hypotheses were considered and discussed to explain these findings: specific centres for each of the two reactions (DDS and HYD) or centres being similar in nature (sulfur vacancies associated to sulfur anions) but which would differ in their acid-base properties. It was also suggested that the centres could be identical but that DDS and HYD could have different rate-limiting steps which would not involve the same part of the dual site so that their sensitivity to H{sub 2}S would be different. (author)

  18. An erbium-based bifuctional heterogeneous catalyst: a cooperative route towards C-C bond formation.

    Science.gov (United States)

    Oliverio, Manuela; Costanzo, Paola; Macario, Anastasia; De Luca, Giuseppina; Nardi, Monica; Procopio, Antonio

    2014-07-15

    Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III)-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid-base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  19. An Erbium-Based Bifuctional Heterogeneous Catalyst: A Cooperative Route Towards C-C Bond Formation

    Directory of Open Access Journals (Sweden)

    Manuela Oliverio

    2014-07-01

    Full Text Available Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid–base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  20. Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups

    OpenAIRE

    Dhakshina Moorthy, Amarajothi; Opanasenko, Maksym; Cejka, Jirí; García Gómez, Hermenegildo

    2013-01-01

    This review summarizes the use of metal organic frameworks (MOFs) as solid catalysts for condensation reactions. After an introductory section, in which condensation reactions are generally presented, a list of the MOFs employed as condensation catalyst is given. The main part of the present review is organized according to the use of MOFs as solid acids, solid bases or as bi-functional solids containing both acid and basic sites. Throughout the review, the emphasis has been made on discussin...

  1. Pt(II) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes

    OpenAIRE

    Casado-Sánchez, A.; Gómez-Ballesteros, R.; Tato, F.; Soriano, F.J.; Pascual-Coca, G.; Cabrera, S.; J. Alemán

    2016-01-01

    A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed

  2. New Tailor-Made Alkyl-Aldehyde Bifunctional Supports for Lipase Immobilization

    Directory of Open Access Journals (Sweden)

    Robson Carlos Alnoch

    2016-11-01

    Full Text Available Immobilized and stabilized lipases are important biocatalytic tools. In this paper, different tailor-made bifunctional supports were prepared for the immobilization of a new metagenomic lipase (LipC12. The new supports contained hydrophobic groups (different alkyl groups to promote interfacial adsorption of the lipase and aldehyde groups to react covalently with the amino groups of side chains of the adsorbed lipase. The best catalyst was 3.5-fold more active and 5000-fold more stable than the soluble enzyme. It was successfully used in the regioselective deacetylation of peracetylated d-glucal. The PEGylated immobilized lipase showed high regioselectivity, producing high yields of the C-3 monodeacetylated product at pH 5.0 and 4 °C.

  3. Bifunctional xylanases and their potential use in biotechnology

    Digital Repository Service at National Institute of Oceanography (India)

    Khandeparker, R.; Numan, M.Th.

    is half as sweet as sucrose, can be applicable to foods as a sweetener that is capable of improving diabetic symptoms [37]. Concluding remarks This review provides the information on most of the aspects of bifunctional enzyme with special reference... of the bifunctional xylanases it is necessary in future to utilize such hybrid protein as an alternative to expensive and polluting chemical treatments or to improve already existing enzymatic processes for utilization of veg- etal by-products in the agro...

  4. Targeting Prostate Cancer with Bifunctional Modulators of the Androgen Receptor

    Science.gov (United States)

    2013-10-01

    element of immunosuppressive regimens for organ transplantation (1). Despite these 24 Bifunctional Ligand Control of Nuclear Receptors 3 well...Gerez J, Paez-Pereda M, Rein T, Iniguez-Lluhi JA, Holsboer F, Arzt E 2013 RSUME enhances glucocorticoid receptor SUMOylation and transcriptional... transplant recipients. Transpl Immunol 27:12-18 42. Marinec PS, Lancia JK, Gestwicki JE 2008 Bifunctional molecules evade cytochrome P(450) metabolism

  5. Regeneration of Hydrotreating and FCC Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    CM Wai; JG Frye; JL Fulton; LE Bowman; LJ Silva; MA Gerber

    1999-09-30

    -earth exchanged Y zeolite in a silica-alumina matrix. X-ray fluorescence analyses showed that the rare earths used in preparing the catalysts were a mixture of lanthanum and cerium. Antimony found in the spent catalyst was added during operation of the FCC unit as a way to suppress the adverse effects of deposited nickel. The fresh HDS samples consisted of sulfided nickel and molybdenum on an alumina support. The spent catalyst showed nearly 10% vanadium on the catalyst and a modest increase in nickel and sulfur on the catalyst as a result of operations. Hydrocracking catalysts were not available for this study.

  6. Interstellar hydrogen sulfide.

    Science.gov (United States)

    Thaddeus, P.; Kutner, M. L.; Penzias, A. A.; Wilson, R. W.; Jefferts, K. B.

    1972-01-01

    Hydrogen sulfide has been detected in seven Galactic sources by observation of a single line corresponding to the rotational transition from the 1(sub 10) to the 1(sub 01) levels at 168.7 GHz. The observations show that hydrogen sulfide is only a moderately common interstellar molecule comparable in abundance to H2CO and CS, but somewhat less abundant than HCN and much less abundant than CO.

  7. Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions.

    Science.gov (United States)

    Motokura, Ken; Tomita, Mitsuru; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-01-01

    Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

  8. Synthesis of Diaryl Ethers, Diaryl Sulfides, Heteroaryl Ethers and Heteroaryl Sulfides under Microwave Heating

    Institute of Scientific and Technical Information of China (English)

    LI,Feng; ZOU,Jiong; WANG,Quan-Rui; TAO,Feng-Gang

    2004-01-01

    @@ Diaryl ether moiety is found in a pool of naturally occurring and medicinally important compounds.[1] As a consequent, considerable efforts have been devoted to the assembly of this framework.[2] Recently, we have developed a microwave heating version of the synthesis of diaryl ethers as well as aryl sulfides. Under our conditions, even the extremely electron-poor 4-nitrophenol works well and its reaction with 1-halo-4-nitrobenzenes produces 4-(nitrophenoxy)-benzonitriles in satisfactory yield. The scope of the present protocol has been expanded to hydroxylated six-membered heterocycles as well as 2-pyrimidinethiol with mildly activated aryl halides, affording heteroaryl ethers and respectively sulfides. The advantages of the present method include the wide substrate scope, no use of any metal catalysts, the ease of product isolation and high yields.

  9. Astaxanthin diferulate as a bifunctional antioxidant.

    Science.gov (United States)

    Papa, T B R; Pinho, V D; do Nascimento, E S P; Santos, W G; Burtoloso, A C B; Skibsted, L H; Cardoso, D R

    2015-01-01

    Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(-1)s(-1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(-1)s(-1). The ferulate moiety in the astaxanthin diester is a better radical scavenger than free ferulic acid as seen from the rate constant of scavenging of 1-hydroxyethyl radicals in ethanol at 25°C with a second-order rate constant of (1.68 ± 0.1) 10(8) L mol(-1)s(-1) compared with (1.60 ± 0.03) 10(7) L mol(-1)s(-1) for the astaxanthin:ferulic acid mixture, 1:2 equivalents. The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability.

  10. The role of sulfur trapped in micropores in the catalytic partial oxidation of hydrogen sulfide with oxygen

    NARCIS (Netherlands)

    Steijns, M.; Mars, P.

    1974-01-01

    The catalytic oxidation of hydrogen sulfide into sulfur with molecular oxygen has been studied in the temperature range 130–200 °C. Active carbon, molecular sieve 13X and liquid sulfur were used as catalysts. Sulfur is adsorbed in the micropores (3 < r < 40 Å) of the catalysts. Experiments with a su

  11. Exploration of cobalt phosphate as a potential catalyst for rechargeable aqueous sodium-air battery

    Science.gov (United States)

    Senthilkumar, Baskar; Khan, Ziyauddin; Park, Sangmin; Seo, Inseok; Ko, Hyunhyub; Kim, Youngsik

    2016-04-01

    Bifunctional catalysts are prominent to attain high capacity, maximum energy efficiency and long cycle-life for aqueous rechargeable Na-air batteries. In this work, we report the synthesis of bi-functional noble metal free, Co3(PO4)2 nanostructures by facile precipitation technique and evaluated its electrocatalytic activity. Co3(PO4)2 nanostructure was investigated as a potential electrocatalyst for rechargeable aqueous Na-air battery for the first time. The synthesized Co3(PO4)2 grain-like nanostructures showed better oxygen evolution activity compared to Pt/C catalyst. The fabricated Na-air battery with the Co3(PO4)2 catalyst as air-cathode delivered low overpotential and its round trip energy efficiency reached up to 83%. The Na-air battery exhibited stable cycle performance up to 50 cycles.

  12. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Dezhao, Liu; Hansen, Michael Jørgen;

    Observed hydrogen sulfide uptake rates in a biofilter treating waste air from a pig farm were too high to be explained within conventional limits of sulfide solubility, diffusion in a biofilm and bacterial metabolism. Clone libraries of 16S and 18S rRNA genes from the biofilter found no sulfide o...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  13. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Liu, Dezhao; Hansen, Michael Jørgen;

    2012-01-01

    Observed hydrogen sulfide uptake rates in a biofilter treating waste air from a pig farm were too high to be explained within conventional limits of sulfide solubility, diffusion in a biofilm and bacterial metabolism. Clone libraries of 16S and 18S rRNA genes from the biofilter found no sulfide o...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  14. Homogeneous catalysts

    CERN Document Server

    Chadwick, John C; Freixa, Zoraida; van Leeuwen, Piet W N M

    2011-01-01

    This first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste.The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.

  15. Shadow enhancers enable Hunchback bifunctionality in the Drosophila embryo.

    Science.gov (United States)

    Staller, Max V; Vincent, Ben J; Bragdon, Meghan D J; Lydiard-Martin, Tara; Wunderlich, Zeba; Estrada, Javier; DePace, Angela H

    2015-01-20

    Hunchback (Hb) is a bifunctional transcription factor that activates and represses distinct enhancers. Here, we investigate the hypothesis that Hb can activate and repress the same enhancer. Computational models predicted that Hb bifunctionally regulates the even-skipped (eve) stripe 3+7 enhancer (eve3+7) in Drosophila blastoderm embryos. We measured and modeled eve expression at cellular resolution under multiple genetic perturbations and found that the eve3+7 enhancer could not explain endogenous eve stripe 7 behavior. Instead, we found that eve stripe 7 is controlled by two enhancers: the canonical eve3+7 and a sequence encompassing the minimal eve stripe 2 enhancer (eve2+7). Hb bifunctionally regulates eve stripe 7, but it executes these two activities on different pieces of regulatory DNA--it activates the eve2+7 enhancer and represses the eve3+7 enhancer. These two "shadow enhancers" use different regulatory logic to create the same pattern.

  16. Therapeutic potential of a non-steroidal bifunctional anti-inflammatory and anti-cholinergic agent against skin injury induced by sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Yoke-Chen; Wang, James D.; Hahn, Rita A.; Gordon, Marion K.; Joseph, Laurie B. [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States); Heck, Diane E. [Department of Environmental Science, New York Medical College, Valhalla, NY (United States); Heindel, Ned D. [Department of Chemistry, Lehigh University, Bethlehem, PA (United States); Young, Sherri C. [Department of Chemistry, Muhlenberg College, Allentown, PA (United States); Sinko, Patrick J. [Department of Pharmaceutics, Rutgers University, Piscataway, NJ (United States); Casillas, Robert P. [MRIGlobal, Kansas City, MO (United States); Laskin, Jeffrey D. [Environmental and Occupational Medicine, Robert Wood Johnson Medical School, Rutgers University, Piscataway, NJ (United States); Laskin, Debra L. [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States); Gerecke, Donald R., E-mail: gerecke@eohsi.rutgers.edu [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States)

    2014-10-15

    Sulfur mustard (bis(2-chloroethyl) sulfide, SM) is a highly reactive bifunctional alkylating agent inducing edema, inflammation, and the formation of fluid-filled blisters in the skin. Medical countermeasures against SM-induced cutaneous injury have yet to be established. In the present studies, we tested a novel, bifunctional anti-inflammatory prodrug (NDH 4338) designed to target cyclooxygenase 2 (COX2), an enzyme that generates inflammatory eicosanoids, and acetylcholinesterase, an enzyme mediating activation of cholinergic inflammatory pathways in a model of SM-induced skin injury. Adult SKH-1 hairless male mice were exposed to SM using a dorsal skin vapor cup model. NDH 4338 was applied topically to the skin 24, 48, and 72 h post-SM exposure. After 96 h, SM was found to induce skin injury characterized by edema, epidermal hyperplasia, loss of the differentiation marker, keratin 10 (K10), upregulation of the skin wound marker keratin 6 (K6), disruption of the basement membrane anchoring protein laminin 322, and increased expression of epidermal COX2. NDH 4338 post-treatment reduced SM-induced dermal edema and enhanced skin re-epithelialization. This was associated with a reduction in COX2 expression, increased K10 expression in the suprabasal epidermis, and reduced expression of K6. NDH 4338 also restored basement membrane integrity, as evidenced by continuous expression of laminin 332 at the dermal–epidermal junction. Taken together, these data indicate that a bifunctional anti-inflammatory prodrug stimulates repair of SM induced skin injury and may be useful as a medical countermeasure. - Highlights: • Bifunctional anti-inflammatory prodrug (NDH4338) tested on SM exposed mouse skin • The prodrug NDH4338 was designed to target COX2 and acetylcholinesterase. • The application of NDH4338 improved cutaneous wound repair after SM induced injury. • NDH4338 treatment demonstrated a reduction in COX2 expression on SM injured skin. • Changes of skin repair

  17. Highly Active and Durable Nanocrystal-Decorated Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Lee, Dong Un; Park, Moon Gyu; Park, Hey Woong; Seo, Min Ho; Wang, Xiaolei; Chen, Zhongwei

    2015-09-21

    A highly active and durable bifunctional electrocatalyst that consists of cobalt oxide nanocrystals (Co3 O4 NC) decorated on the surface of N-doped carbon nanotubes (N-CNT) is introduced as effective electrode material for electrically rechargeable zinc-air batteries. This active hybrid catalyst is synthesized by a facile surfactant-assisted method to produce Co3 O4 NC that are then decorated on the surface of N-CNT through hydrophobic attraction. Confirmed by half-cell testing, Co3 O4 NC/N-CNT demonstrates superior oxygen reduction and oxygen evolution catalytic activities and has a superior electrochemical stability compared to Pt/C and Ir/C. Furthermore, rechargeable zinc-air battery testing of Co3 O4 NC/N-CNT reveals superior galvanodynamic charge and discharge voltages with a significantly extended cycle life of over 100 h, which suggests its potential as a replacement for precious-metal-based catalysts for electric vehicles and grid energy storage applications.

  18. The synthesis of a bifunctional copper metal organic framework and its application in the aerobic oxidation/Knoevenagel condensation sequential reaction.

    Science.gov (United States)

    Miao, Zongcheng; Luan, Yi; Qi, Chao; Ramella, Daniele

    2016-09-21

    A novel one-pot aerobic oxidation/Knoevenagel condensation reaction system was developed employing a Cu(ii)/amine bifunctional, basic metal-organic framework (MOF) as the catalyst. The sequential aerobic alcohol oxidation/Knoevenagel condensation reaction was efficiently promoted by the Cu3TATAT MOF catalyst in the absence of basic additives. The benzylidenemalononitrile product was produced in high yield and selectivity from an inexpensive benzyl alcohol starting material under an oxygen atmosphere. The role of the basic functionality was studied to demonstrate its role in the aerobic oxidation and Knoevenagel condensation reactions. The reaction progress was monitored in order to identify the reaction intermediate and follow the accumulation of the desired product. Lastly, results showed that the yield was not significantly compromised by the reuse of a batch of catalyst, even after more than five cycles.

  19. Micro-aeration for hydrogen sulfide removal from biogas

    Science.gov (United States)

    Duangmanee, Thanapong

    The presence of sulfur compounds (e.g. protein, sulfate, thiosulfate, sulfite, etc.) in the feed stream generates highly corrosive and odorous hydrogen sulfide during anaerobic digestion. The high sulfide level in the biogas stream is not only poisonous to many novel metal catalysts employed in thermo-catalytic processes but also reduces the quality of methane to produce renewable energy. This study used an innovative, low-maintenance, low-cost biological sulfide removal technology to remove sulfides simultaneously from both gas and liquid phase. ORP (Oxidation-Reduction-Potential) was used as the controlling parameter to precisely regulate air injection to the sulfide oxidizing unit (SOU). The microaeration technique provided just enough oxygen to partially oxidize sulfides to elemental sulfur without inhibiting methanogenesis. The SOU was equipped with a diffuser at the bottom for the dispersion of sulfide-laden biogas and injected air throughout the column. The SOU can be operated as a standalone unit or coupled with an anaerobic digester to simultaneously remove sulfide from the biogas and effluent. The integrated system was capable of reducing hydrogen sulfide in biogas from 2,450 to less than 2 ppmV with minimal sulfate production at the highest available sulfide loading rate of 0.24 kg/m3-day. More than 98% of sulfide removed was recovered as elemental sulfur. However, the standalone SOU was able to operate at high hydrogen sulfide loading of 1.46 kg/m 3-day at inlet sulfide concentration of 3000 ppmV and reduce the off-gas hydrogen sulfide concentrations to less than 10 ppmV. The experiment also revealed that the ORP controlled aeration was sensitive enough to prevent oxygen overdosing (dampening effect) during unexpected surges of aeration. Using generalized linear regression, a model predicting output H2S concentration based on input H2S concentrations, SOU medium heights, and biogas flow rates, was derived. With 95% confidence, output H2S concentration

  20. Nanoscal design of molybdenum sulfides for more efficient electro- and photoelectrocatalytic hydrogen evolution

    DEFF Research Database (Denmark)

    Laursen, Anders Bo

    . The electrochemical oxidation behavior of MoSx was investigated compared to that of MoS2, and MoS3. It was found that the MoSx demonstrated a unique oxidation behavior indicating that the active sites were not MoS2 or MoS3-like - further experiments are needed to clarify the relation between oxidation behavior and H2...... of active molybdenum sulfide based H2 evolution catalysts. This demonstrated the potential of molybdenum sulfides as electro- and photoelectrochemical catalysts for the H2 evolution reaction....

  1. Environmentally Benign Oxidation of Some Organic Sulfides with 34% Hydrogen Peroxide Catalyzed by Simple Heteropolyoxometalates

    Institute of Scientific and Technical Information of China (English)

    TAYEBEE,Reza; ALIZADEH,Moharnmad Hassan

    2007-01-01

    An environmentally benign oxygenation protocol was developed for selective oxidation of some types of aromatic and aliphatic sulfides in good to excellent yields utilizing 34% hydrogen peroxide catalyzed by simple heteropolyoxometalates in normal drinking water at room temperature. The catalysts could be recovered and reused for at least seven reaction cycles under the described reaction conditions without considerable loss of reactivity. This procedure introduced a new insight into the use of simple heteropolyanions as recoverable catalysts for the oxidation of organic sulfides by an environmentally acceptable protocol.

  2. Studies of Heterogeneous Catalyst Selectivity and Stability for Biorefining Applications

    Science.gov (United States)

    O'Neill, Brandon J.

    The conversion of raw resources into value-added end products has long underlain the importance of catalysts in economic and scientific development. In particular, the development of selective and stable heterogeneous catalysts is a challenge that continues to grow in importance as environmental, sociological, and economic concerns have motivated an interest in sustainability and the use of renewable raw materials. Within this context, biomass has been identified as the only realistic source of renewable carbon for the foreseeable future. The development of processes to utilize biomass feedstocks will require breakthroughs in fundamental understanding and practical solutions to the challenges related to selectivity and stability of the catalysts employed. Selectivity is addressed on multiple fronts. First, the selectivity for C-O bond scission reactions of a bifunctional, bimetallic RhRe/C catalyst is investigated. Using multiple techniques, the origin of Bronsted acidity in the catalyst and the role of pretreatment on the activity, selectivity, and stability are explored. In addition, reaction kinetics experiments and kinetic modeling are utilized to understand the role of chemical functional group (i.e. carboxylic acid versus formate ester) in determining the decarbonylation versus decarboxylation selectivity over a Pd/C catalyst. Finally, kinetic studies over Pd/C and Cu/gamma-Al2O3 were performed so that that may be paired with density functional theory calculations and microkinetic modeling to elucidate the elementary reaction mechanism, identify the active site, and provide a basis for future rational catalyst design. Next, the issue of catalyst stability, important in the high-temperature, liquid-phase conditions of biomass processing, is examined, and a method for stabilizing the base-metal nanoparticles of a Cu/gamma-Al2O 3 catalyst using atomic layer deposition (ALD) is developed. This advancement may facilitate the development of biorefining by enabling

  3. Polymer Electrolyte Membrane Electrolyzers Utilizing Non-precious Mo-based Hydrogen Evolution Catalysts.

    Science.gov (United States)

    Ng, Jia Wei Desmond; Hellstern, Thomas R; Kibsgaard, Jakob; Hinckley, Allison C; Benck, Jesse D; Jaramillo, Thomas F

    2015-10-26

    The development of low-cost hydrogen evolution reaction (HER) catalysts that can be readily integrated into electrolyzers is critical if H2 from renewable electricity-powered electrolysis is to compete cost effectively with steam reforming. Herein, we report three distinct earth-abundant Mo-based catalysts, namely those based on MoSx , [Mo3 S13 ](2-) nanoclusters, and sulfur-doped Mo phosphide (MoP|S), loaded onto carbon supports. The catalysts were synthesized through facile impregnation-sulfidization routes specifically designed for catalyst-device compatibility. Fundamental electrochemical studies demonstrate the excellent HER activity and stability of the Mo-sulfide based catalysts in an acidic environment, and the resulting polymer electrolyte membrane (PEM) electrolyzers that integrate these catalysts exhibit high efficiency and durability. This work is an important step towards the goal of replacing Pt with earth-abundant catalysts for the HER in commercial PEM electrolyzers.

  4. The mechanism of the catalytic oxidation of hydrogen sulfide *1: III. An electron spin resonance study of the sulfur catalyzed oxidation of hydrogen sulfide

    NARCIS (Netherlands)

    Steijns, M.; Koopman, P.; Nieuwenhuijse, B.; Mars, P.

    1976-01-01

    ESR experiments on the oxidation of hydrogen sulfide were performed in the temperature range 20–150 °C. Alumina, active carbon and molecular sieve zeolite 13X were investigated as catalysts. For zeolite 13X it was demonstrated that the reaction is autocatalytic and that sulfur radicals are the activ

  5. Characterization of Deactivated Bio-oil Hydrotreating Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huamin; Wang, Yong

    2015-10-06

    Deactivation of bio-oil hydrotreating catalysts remains a significant challenge because of the poor quality of pyrolysis bio-oil input for hydrotreating and understanding their deactivation mode is critical to developing improved catalysts and processes. In this research, we developed an understanding of the deactivation of two-step bio-oil hydrotreating catalysts (sulfided Ru/C and sulfided CoMo/C) through detailed characterization of the catalysts using various complimentary analytical techniques. Severe fouling of both catalysts by carbonaceous species was the major form of deactivation, which is consistent with the significant loss of surface area and pore volume of both deactivated catalysts and the significant increase of the bulk density. Further analysis of the carbonaceous species by thermogravimetric analysis and x-ray photoelectron spectroscopy indicated that the carbonaceous species was formed by condensation reaction of active species such as sugars and sugar derivatives (aldehydes and ketones) in bio-oil feedstock during bio-oil hydrotreating under the conditions and catalysts used. Microscopy results did not show metal sintering of the Ru/C catalyst. However, X-ray diffraction indicated a probable transformation of the highly-active CoMoS phase in the sulfided CoMo/C catalyst to Co8S9 and MoS2 phase with low activity. Loss of the active site by transport of inorganic elements from the bio-oil and the reactor construction material onto the catalyst surface also might be a cause of deactivation as indicated by elemental analysis of spent catalysts.

  6. RuO2 nanoparticles decorated MnOOH/C as effective bifunctional electrocatalysts for lithium-air battery cathodes with long-cycling stability

    Science.gov (United States)

    Kim, Gil-Pyo; Lim, Dongwook; Park, Inyeong; Park, Hyelee; Shim, Sang Eun; Baeck, Sung-Hyeon

    2016-08-01

    Manganite (MnOOH) is one of the most effective electrocatalysts for oxygen reduction reaction (ORR), and RuO2 nanoparticles exhibit high activity for oxygen evolution reaction (OER). We herein report a facile means of producing well dispersed RuO2/MnOOH on Ketjen black (RuO2/MnOOH/C) as a bifunctional catalyst for lithium-air (Li-air) batteries. RuO2/MnOOH/C was simply synthesized using a hydrothermal/precipitation based method, and was used as a cathode for a Li-air battery using a Swagelok-type cell. The importance of dispersing active catalysts on a carbon support was clearly demonstrated by textural, charge-discharge voltammetric, and electrochemical impedance spectroscopic (EIS) analyses, comparing results with a catalyst produced by physically mixing RuO2/MnOOH with carbon (RuO2/MnOOH + C). RuO2/MnOOH/C showed low overpotential and stable cycleability up to 170th cycles with 1000 mAh g-1 of charge-discharge capacity, which was attributed to its enhanced active surface area and low charge-transfer resistance. The results obtained suggest that this strategy can be widely applied to bifunctional electrocatalysis, such as secondary batteries and regenerative fuel cell (RFC).

  7. Experiment on Bi-functional Catalyst of Dimethyl Ether Steam Reforming for Hydrogen Production%CuMn2O4/HZSM-5催化二甲醚水蒸气重整制氢的试验研究

    Institute of Scientific and Technical Information of China (English)

    吴娇; 黄鹏; 陈晓玲; 周相满; 张武高

    2012-01-01

    搭建了二甲醚水蒸气重整制氢的小样模拟台架,并制备了二甲醚重整制氢催化剂.研究了不同水解活性组分、甲醇重整活性组分和煅烧温度下的尖晶石复合催化剂对二甲醚水蒸气催化重整制氢性能的影响.结果发现:不同水解活性组分中,HZSM-5(硅铝摩尔比r=n(SiO2)/n(Al2O3)=38)的双功能催化剂的H。产率最高;甲醇重整活性组分中,铜锰尖晶石结构催化组分(CuMn2O4)的双功能催化剂的H2产率最高;煅烧温度对CuMn2O4双功能催化剂的催化效果有明显影响,其中煅烧温度为700℃时H2产率最高.%The performance of catalysts prepared by mechanically mixing dimethyl ether (DME) hydrolysis active components and methanol reforming active components were compared in the DME steam reforming reaction. The effects of different active components and different calcination temperatures of Cu-Mn-spinel were studied. The results show that HZSM-5 (nSiO2/nAl2O3 = 38) has the highest H2 production rate among different DME hydrolysis active components. Cu-Mn-spinel has high H2 production among different methanol reforming active components. Cu-Mn-spinel that was calcined by 700 ℃ exhibits the highest activity for DME steam reforming. The result shows that DME conversion is 99.65% and H2 production is 73.15% at 350 ℃ when used the hi-functional catalyst composed of Cu-Mn-spinel(700 ℃) and HZSM-5 (38). The study is very important for fuel design of DME engine.

  8. Single flexible nanofiber to simultaneously realize electricity-magnetism bifunctionality

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ming; Sheng, Shujuan; Ma, Qianli; Lv, Nan; Yu, Wensheng; Wang, Jinxian; Dong, Xiangting; Liu, Guixia, E-mail: wenshengyu2009@sina.com, E-mail: dongxiangting888@163.com [Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, Changchun University of Science and Technology, Changchun (China)

    2016-03-15

    In order to develop new-typed multifunctional composite nanofibers, PANI/Fe{sub 3}O{sub 4}/PVP flexible bifunctional composite nanofibers with simultaneous electrical conduction and magnetism have been successfully fabricated via a facile electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of polyaniline (PANI) and Fe{sub 3}O{sub 4} nanoparticles (NPs). The bifunctional composite nanofibers simultaneously possess excellent electrical conductivity and magnetic properties. The electrical conductivity reaches up to the order of 10{sup -3} S·cm{sup -1}. The electrical conductivity and saturation magnetization of the composite nanofibers can be respectively tuned by adding various amounts of PANI and Fe{sub 3}O{sub 4} NPs. The obtained electricity-magnetism bifunctional composite nanofibers are expected to possess many potential applications in areas such as electromagnetic interference shielding, special coating, microwave absorption, molecular electronics and future nanomechanics. More importantly, the design concept and construct technique are of universal significance to fabricate other bifunctional one-dimensional nanostructures. (author)

  9. Use of Bifunctional Immunotherapeutic Agents to Target Breast Cancer

    Science.gov (United States)

    2007-07-01

    Selective Tumor Cell Targeting Using Low-Affinity, Multivalent Interactions Coby B. Carlson†,‡, Patricia Mowery‡, Robert M. Owen†, Emily C. Dykhuizen†, and...washed cells and immediately analyzed for fluorescence using a FACSCalibur flow cytometer (Becton Dickinson ). Data were ana- lyzed using CellQuest...software (Becton Dickinson ). An identical assay omitting the bifunctional conjugate assessed background fluorescence. The relative fluorescence is

  10. Sulfide detoxification in plant mitochondria.

    Science.gov (United States)

    Birke, Hannah; Hildebrandt, Tatjana M; Wirtz, Markus; Hell, Rüdiger

    2015-01-01

    In contrast to animals, which release the signal molecule sulfide in small amounts from cysteine and its derivates, phototrophic eukaryotes generate sulfide as an essential intermediate of the sulfur assimilation pathway. Additionally, iron-sulfur cluster turnover and cyanide detoxification might contribute to the release of sulfide in mitochondria. However, sulfide is a potent inhibitor of cytochrome c oxidase in mitochondria. Thus, efficient sulfide detoxification mechanisms are required in mitochondria to ensure adequate energy production and consequently survival of the plant cell. Two enzymes have been recently described to catalyze sulfide detoxification in mitochondria of Arabidopsis thaliana, O-acetylserine(thiol)lyase C (OAS-TL C), and the sulfur dioxygenase (SDO) ethylmalonic encephalopathy protein 1 (ETHE1). Biochemical characterization of sulfide producing and consuming enzymes in mitochondria of plants is fundamental to understand the regulatory network that enables mitochondrial sulfide homeostasis under nonstressed and stressed conditions. In this chapter, we provide established protocols to determine the activity of the sulfide releasing enzyme β-cyanoalanine synthase as well as sulfide-consuming enzymes OAS-TL and SDO. Additionally, we describe a reliable and efficient method to purify OAS-TL proteins from plant material.

  11. Bifunctional Imidazolium-Based Ionic Liquid Decorated UiO-67 Type MOF for Selective CO2 Adsorption and Catalytic Property for CO2 Cycloaddition with Epoxides.

    Science.gov (United States)

    Ding, Luo-Gang; Yao, Bing-Jian; Jiang, Wei-Ling; Li, Jiang-Tao; Fu, Qi-Juan; Li, Yan-An; Liu, Zhen-Hua; Ma, Jian-Ping; Dong, Yu-Bin

    2017-02-20

    A bifunctional robust and highly porous imidazolium-based ionic liquid decorated UiO-67 type MOF (UiO-67-IL, 1) was successfully constructed via solvothermal assembly of the imidazolium-based ligand and Zr(IV) ions. It exhibits a highly selective adsorption for CO2 over CH4 and N2. Furthermore, 1 herein can be used as a highly active heterogeneous catalyst for CO2 cycloaddition with epoxides under atmospheric pressure with or without cocatalyst TBAB (n-Bu4NBr).

  12. An Efficient Bifunctional Electrocatalyst for a Zinc-Air Battery Derived from Fe/N/C and Bimetallic Metal-Organic Framework Composites.

    Science.gov (United States)

    Wang, Mengfan; Qian, Tao; Zhou, Jinqiu; Yan, Chenglin

    2017-02-15

    Efficient bifunctional electrocatalysts with desirable oxygen activities are closely related to practical applications of renewable energy systems including metal-air batteries, fuel cells, and water splitting. Here a composite material derived from a combination of bimetallic zeolitic imidazolate frameworks (denoted as BMZIFs) and Fe/N/C framework was reported as an efficient bifunctional catalyst. Although BMZIF or Fe/N/C alone exhibits undesirable oxygen reaction activity, a combination of these materials shows unprecedented ORR (half-wave potential of 0.85 V as well as comparatively superior OER activities (potential@10 mA cm(-2) of 1.64 V), outperforming not only a commercial Pt/C electrocatalyst but also most reported bifunctional electrocatalysts. We then tested its practical application in Zn-air batteries. The primary batteries exhibit a high peak power density of 235 mW cm(-2), and the batteries are able to be operated smoothly for 100 cycles at a curent density of 10 mA cm(-2). The unprecedented catalytic activity can be attritued to chemical coupling effects between Fe/N/C and BMZIF and will aid the development of highly active electrocatalysts and applications for electrochemical energy devices.

  13. Catalyst mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Masel, Richard I.; Rosen, Brian A.

    2017-02-14

    Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

  14. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  15. Stability and Lifetime of K-CoMoSx Mixed Alcohol Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, J. E.; Ruddy, D.; Schaidle, J.; Ferrell, J.; Thibodeaux, J.

    2013-01-01

    Researchers have studied sulfide-type catalysts for the production of mixed alcohols from synthesis gas for several decades. Despite many advances in the art, these processes are not yet commercial, due in large part to mediocre economics and the added risk associated with uncertainty in catalyst lifetime. This talk will outline some recent studies in the lifetime and stability of K-CoMoSx-type mixed alcohol catalysts. Specifically, studies of long term operation (> 3000h), sulfiding agents, simulated methanol recycle, and morphology (probed via XRD and XPS) will be discussed, with the conclusion that these materials are likely to exhibit acceptable lifetimes in continuous operation.

  16. Influence of Si/Al Ratio on Catalytic Performance of (Co)Mo/Saponite Catalysts

    OpenAIRE

    Koningsberger, D.C.; Leliveld, R.G.; Ros, T.G.; van Dillen, A.J.; Geus, John W.

    1999-01-01

    The influence of the Si/Al ratio of the support of (Co)Mo/saponite catalysts on the performance in the hydrodesulfurisation of thiophene and hydrocracking of n-decane has been studied. The initial thiophene HDS activity of the sulfided Co catalysts increased with increasing support acidity, while with the CoMo catalysts the opposite effect was observed. The large drop in activity at lower Si/Al ratios is ascribed to the occurrence of two separate cobalt and molybdenum sulfide phases instead o...

  17. Multifunctional mesoporous silica catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

    2015-03-31

    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

  18. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

    Energy Technology Data Exchange (ETDEWEB)

    Osseo-Asare, K.; Boakye, E.; Vittal, M. [and others

    1995-04-01

    This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

  19. In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution.

    Science.gov (United States)

    Jin, Haiyan; Wang, Jing; Su, Diefeng; Wei, Zhongzhe; Pang, Zhenfeng; Wang, Yong

    2015-02-25

    Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis. Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt-cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co(0), CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method. CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER. Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nanoparticles, and the introduction of electron-rich nitrogen. In addition, when used as catalysts of OER, the CoOx@CN hybrids required 0.26 V overpotential for a current density of 10 mA cm(-2), which is comparable even superior to many other non-noble metal catalysts. More importantly, an alkaline electrolyzer that approached ∼20 mA cm(-2) at a voltage of 1.55 V was fabricated by applying CoOx@CN as cathode and anode electrocatalyst, which opened new possibilities for exploring overall water splitting catalysts.

  20. Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

    Science.gov (United States)

    Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

    2016-02-01

    Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

  1. Reactivity of non conventional supported mixed sulfides for hydro-treatment reactions; Reactivite de sulfures mixtes supportes non conventionnels pour les reactions d`hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Quartararo, J.

    1996-11-07

    The properties of non conventional NiM sulfides (M: Mn, Fe, Cu,Zn, Re, Ru) was evaluated for two hydro treating reactions: hydro desulfurization (HDS) of dibenzo thiophene and benzo thiophene and hydrogenation (HYD) of cyclohexyl. The reactions were t first studied on Ni, Mo and NiMo sulfide catalysts. The influence of the nature of the molecule on the magnitude of promoting effect was demonstrated. The non conventional mono-metallic and bimetallic catalysts studied in this work were characterized by XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy) and TEM (transmission electron microscopy). Ni exhibits a negative effect on the activity of Mn, Cu, Zn and Re sulfide catalysts. This effect could be related to the formation of two separated sulfide phases: base metal sulfide and nickel sulfide. Nevertheless, a promoting effect was found in NiRu catalyst. In this catalyst, the Ru and the Ni are in a mixed phase. The results of this study demonstrate the importance of the type of metal associated to the nickel for the promoting effect and relate this effect to the formation of a mixed phase. (author)

  2. Highly dispersed metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-08

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

  3. The aminoindanol core as a key scaffold in bifunctional organocatalysts

    Directory of Open Access Journals (Sweden)

    Isaac G. Sonsona

    2016-03-01

    Full Text Available The 1,2-aminoindanol scaffold has been found to be very efficient, enhancing the enantioselectivity when present in organocatalysts. This may be explained by its ability to induce a bifunctional activation of the substrates involved in the reaction. Thus, it is easy to find hydrogen-bonding organocatalysts ((thioureas, squaramides, quinolinium thioamide, etc. in the literature containing this favored structural core. They have been successfully employed in reactions such as Friedel–Crafts alkylation, Michael addition, Diels–Alder and aza-Henry reactions. However, the 1,2-aminoindanol core incorporated into proline derivatives has been scarcely explored. Herein, the most representative and illustrative examples are compiled and this review will be mainly focused on the cases where the aminoindanol moiety confers bifunctionality to the organocatalysts.

  4. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO2 and MnO2) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ˜1,663 m2 g-1 and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn-1 (corresponding to an energy density of 835 Wh kgZn-1), a peak power density of 55 mW cm-2, and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm-2. We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.

  5. Supported Molten Metal Catalysis. A New Class of Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ravindra Datta; Ajeet Singh; Manuela Serban; Istvan Halasz

    2006-06-02

    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.

  6. Heterogeneous Catalysts

    NARCIS (Netherlands)

    Dakka, J.; Sheldon, R.A.; Sanderson, W.A.

    1997-01-01

    Abstract of GB 2309655 (A) Heterogeneous catalysts comprising one or more metal compounds selected from the group consisting of tin, molybdenum, tungsten, zirconium and selenium compounds deposited on the surface of a silicalite are provided. Preferably Sn(IV) and/or Mo(VI) are employed. The cat

  7. Ceramic catalyst materials

    Energy Technology Data Exchange (ETDEWEB)

    Sault, A.G.; Gardner, T.J. [Sandia National Laboratories, Albuquerque, NM (United States); Hanprasopwattanna, A.; Reardon, J.; Datye, A.K. [Univ. of New Mexico, Albuquerque, NM (United States)

    1995-08-01

    Hydrous titanium oxide (HTO) ion-exchange materials show great potential as ceramic catalyst supports due to an inherently high ion-exchange capacity which allows facile loading of catalytically active transition metal ions, and an ability to be cast as thin films on virtually any substrate. By coating titania and HTO materials onto inexpensive, high surface area substrates such as silica and alumina, the economics of using these materials is greatly improved, particularly for the HTO materials, which are substantially more expensive in the bulk form than other oxide supports. In addition, the development of thin film forms of these materials allows the catalytic and mechanical properties of the final catalyst formulation to be separately engineered. In order to fully realize the potential of thin film forms of titania and HTO, improved methods for the deposition and characterization of titania and HTO films on high surface area substrates are being developed. By varying deposition procedures, titania film thickness and substrate coverage can be varied from the submonolayer range to multilayer thicknesses on both silica and alumina. HTO films can also be formed, but the quality and reproducibility of these films is not nearly as good as for pure titania films. The films are characterized using a combination of isopropanol dehydration rate measurements, point of zero charge (PZC) measurements, BET surface area, transmission electron microscopy (TEM), and elemental analysis. In order to assess the effects of changes in film morphology on catalytic activity, the films are being loaded with MoO{sub 3} using either incipient wetness impregnation or ion-exchange of heptamolybdate anions followed by calcining. The MoO{sub 3} is then sulfided to form MOS{sub 2}, and tested for catalytic activity using pyrene hydrogenation and dibenzothiophene (DBT) desulfurization, model reactions that simulate reactions occurring during coal liquefaction.

  8. Optimum bifunctionality in a 2-(2-pyridyl-2-ol)-1,10-phenanthroline based ruthenium complex for transfer hydrogenation of ketones and nitriles: impact of the number of 2-hydroxypyridine fragments.

    Science.gov (United States)

    Paul, Bhaskar; Chakrabarti, Kaushik; Kundu, Sabuj

    2016-07-05

    Considerable differences in reactivity and selectivity for 2-hydroxypyridine (2-HP) derived ruthenium complexes in transfer hydrogenation are described. Bifunctional Ru(ii)-(phenpy-OH) [phenpy-OH: 2-(2-pyridyl-2-ol)-1,10-phenanthroline] complex () exhibited excellent catalytic activity in transfer hydrogenation (TH) of ketones and nitriles. Notably, in comparison with all the reported 2-hydroxypyridine (2-HP) derived ruthenium complexes in transfer hydrogenation, complex displayed significantly higher activity. Additionally, exploiting the metal-ligand cooperativity in complex , chemoselective TH of ketones was achieved and sterically demanding ketones were readily reduced. An outer-sphere mechanism is proposed for this system as exogenous PPh3 has no significant effect on the rate of this reaction. This is a rare example of a highly active bifunctional Ru(ii) catalyst bearing only one 2-HP unit.

  9. Sulfide intrusion and detoxification in Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2014-01-01

    indicating a possible role of sulfide in the sulfur nutrition beside the detoxification function. Our results suggest different adaptations of Z. marina to reduced sediments and sulfide intrusion ranging from bacterial and chemical reoxidation of sulfide to sulfate to incorporation of sulfide into organic...

  10. Highly Dispersed Pseudo-Homogeneous and Heterogeneous Catalysts Synthesized via Inverse Micelle Solutions for the Liquefaction of Coal

    Energy Technology Data Exchange (ETDEWEB)

    Hampden-Smith, M.; Kawola, J.S.; Martino, A.; Sault, A.G.; Yamanaka, S.A.

    1999-01-05

    The mission of this project was to use inverse micelle solutions to synthesize nanometer sized metal particles and test the particles as catalysts in the liquefaction of coal and other related reactions. The initial focus of the project was the synthesis of iron based materials in pseudo-homogeneous form. The frost three chapters discuss the synthesis, characterization, and catalyst testing in coal liquefaction and model coal liquefaction reactions of iron based pseudo-homogeneous materials. Later, we became interested in highly dispersed catalysts for coprocessing of coal and plastic waste. Bifunctional catalysts . to hydrogenate the coal and depolymerize the plastic waste are ideal. We began studying, based on our previously devised synthesis strategies, the synthesis of heterogeneous catalysts with a bifunctional nature. In chapter 4, we discuss the fundamental principles in heterogeneous catalysis synthesis with inverse micelle solutions. In chapter 5, we extend the synthesis of chapter 4 to practical systems and use the materials in catalyst testing. Finally in chapter 6, we return to iron and coal liquefaction now studied with the heterogeneous catalysts.

  11. A novel method for improving cerussite sulfidization

    Institute of Scientific and Technical Information of China (English)

    Qi-cheng Feng; Shu-ming Wen; Wen-juan Zhao; Qin-bo Cao; Chao L

    2016-01-01

    Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sul-fide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

  12. Commercial Application of the ICR Series Lube Isodewaxing Catalysts

    Institute of Scientific and Technical Information of China (English)

    Wang Sijue

    2008-01-01

    This article illustrates the application of the ICR series lube oil isodewaxing catalysts in commercial scale and proposes the strategy on long cycle operation and optimization of catalysts. The results of commercial application of the catalyst have revealed that the catalyst after pretreatment including drying, sulfidation and reduction can process VGO into base oils meeting the HVI Ⅱ and HVI Ⅱ+ standards, and can manufacture base oils meeting the HVI Ⅲ standard after incorporating the filtrate oil or gatch from acetone-benzene solvent dewaxing unit. The nitrogen content of the feed oil to the IDW reactor should be controlled at 1.0-1.5 ppm, while the CO and CO2 contents in fresh hydrogen is strictly controlled to avoid poisoning of the IDW-HDF catalysts.

  13. Prevention of sulfide oxidation in sulfide-rich waste rock

    Science.gov (United States)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  14. Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, Oleh; Tsao, Leon

    1983-01-01

    Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

  15. Reaction of hydrogen sulfide with oxygen in the presence of sulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, O.; Tsao, L.

    1983-01-14

    Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

  16. Hydrogen sulfide in signaling pathways.

    Science.gov (United States)

    Olas, Beata

    2015-01-15

    For a long time hydrogen sulfide (H₂S) was considered a toxic compound, but recently H₂S (at low concentrations) has been found to play an important function in physiological processes. Hydrogen sulfide, like other well-known compounds - nitric oxide (NO) and carbon monoxide (CO) is a gaseous intracellular signal transducer. It regulates the cell cycle, apoptosis and the oxidative stress. Moreover, its functions include neuromodulation, regulation of cardiovascular system and inflammation. In this review, I focus on the metabolism of hydrogen sulfide (including enzymatic pathways of H₂S synthesis from l- and d-cysteine) and its signaling pathways in the cardiovascular system and the nervous system. I also describe how hydrogen sulfide may be used as therapeutic agent, i.e. in the cardiovascular diseases.

  17. Mechanochemical reduction of copper sulfide

    DEFF Research Database (Denmark)

    Balaz, P.; Takacs, L.; Jiang, Jianzhong

    2002-01-01

    The mechanochemical reduction of copper sulfide with iron was induced in a Fritsch P-6 planetary mill, using WC vial filled with argon and WC balls. Samples milled for specific intervals were analyzed by XRD and Mossbauer spectroscopy. Most of the reaction takes place during the first 10 min...... of milling and only FeS and Cu are found after 60 min. The main chemical process is accompanied by phase transformations of the sulfide phases as a result of milling. Djurleite partially transformed to chalcocite and a tetragonal copper sulfide phase before reduction. The cubic modification of FeS was formed...... first, transforming to hexagonal during the later stages of the process. The formation of off-stoichiometric phases and the release of some elemental sulfur by copper sulfide are also probable....

  18. XPS Characterization of Carbon Nanotube Supported CoMo Hydrodesulfurization Catalysts

    Institute of Scientific and Technical Information of China (English)

    SHANG, Hong-Yan(商红岩); LIU, Chen-Guang(刘晨光); ZHAO, Rui-Yu(赵瑞玉); WU, Ming-Bo(吴明铂); WEI, Fei(魏飞)

    2004-01-01

    In this paper, the effect of catalytic support and sulfiding method on the chemical state of supported Co-Mo catalysts is studied by XPS. After sulfidation with in-situ method, the majority of molybdenum in CNT supported CoMo catalyst is transferred to a species with a formal chemical state Mo(Ⅳ) in MoS2 phase, and the rest to Mo(Ⅴ)which consists of Mo coordinated both to O and S, such as MoO2S22- and MoO3S2-. In case of CoMo/γ-Al2O3 catalyst sulfided with in-situ method, a fraction of molybdenum is transferred to formal state Mo(Ⅳ) in the form of MoS2, but there is still a mount of unreduced Mo(Ⅵ) phase which is difficult to be sulfided. In CoMo/CNT catalytic system sulfided with ex-situ method, Mo(Ⅳ) in the form of MoS2 is detected along with a portion of unreduced Mo(Ⅵ) phase, suggesting that not all the Mo phases are reduced and sulfided by ex-situ method. As for CoMo/γ-Al2O3, a portion of molybdenum is sulfided to intermediate reduced state Mo(Ⅴ) which consists of Mo coordinated both to O and S, such as MoO2S22- and MoO3S2-, in addition, there is still a fraction of unreduced Mo(Ⅵ)phase. XPS analyses results suggest that CNT support facilitates the reduction and sulfidation of active species to a large extent, and that alumina support strongly interacts with active species, hereby producing a fraction of phase which resists complete sulfiding. Catalytic measurements of catalysts in the HDS of dibenzothiophene (DBT) show that CoMo/CNT catalysts are of higher HDS activity and selectivity than CoMo/γ-Al2O3 catalyst, which is in good relation with the sulfiding behavior of the corresponding catalyst.

  19. Assaying the catalytic potential of transition metal sulfides for abiotic carbon fixation

    Science.gov (United States)

    Cody, G. D.; Boctor, N. Z.; Brandes, J. A.; Filley, T. R.; Hazen, R. M.; Yoder, H. S.

    2004-05-01

    A suite of nickel, cobalt, iron, copper, and zinc containing sulfides are assayed for the promotion of a model carbon fixation reaction with relevance to local reducing environments of the early Earth. The assay tests the promotion of hydrocarboxylation (the Koch reaction) wherein a carboxylic acid is synthesized via carbonyl insertion at a metal-sulfide-bound alkyl group. The experimental conditions are chosen for optimal assay, i.e., high reactant concentrations and pressures (200 MPa) to enhance chemisorption, and high temperature (250°C) to enhance reaction kinetics. All of the metal sulfides studied, with the exception CuS, promote hydrocarboxylation. Two other significant reactions involve the catalytic reduction of CO to form a surface-bound methyl group, detected after nucleophilic attack by nonane thiol to form methyl nonyl sulfide, and the formation of dinonyl sulfide via a similar reaction. Estimation of the catalytic turnover frequencies for each of the metal sulfides with respect to each of the primary reactions reveals that NiS, Ni 3S 2, and CoS perform comparably to commonly employed industrial catalysts. A positive correlation between the yield of primary product to NiS and Ni 3S 2 surface areas provides strong evidence that the reactions are surface catalytic in these cases. The sulfides FeS and Fe (1-x)S are unique in that they exhibit evidence of extensive dissolution, thus, complicating interpretation regarding heterogeneous vs. homogeneous catalysis. With the exception of CuS, each of the metal sulfides promotes reactions that mimic key intermediate steps manifest in the mechanistic details of an important autotrophic enzyme, acetyl-CoA synthase. The relatively high temperatures chosen for assaying purposes, however, are incompatible with the accumulation of thioesters. The results of this study support the hypothesis that transition metal sulfides may have provided useful catalytic functionality for geochemical carbon fixation in a prebiotic

  20. One pot synthesis of cyclohexanone oxime from nitrobenzene using a bifunctional catalyst.

    Science.gov (United States)

    Rubio-Marqués, Paula; Hernández-Garrido, Juan Carlos; Leyva-Pérez, Antonio; Corma, Avelino

    2014-02-18

    Cyclohexanone oxime is formed from nitrobenzene with 97% yield in a one-pot reaction catalysed by palladium and gold nanoparticles on carbon. The reaction is carried out under hydrogen at 60 °C and the overall transformation involves a multi-step catalysed mechanism from which intermediates and catalytically active species have been identified.

  1. Bifunctional Catalysis: Direct Reductive Amination of Aliphatic Ketones with an Iridium-Phosphate Catalyst

    Directory of Open Access Journals (Sweden)

    Barbara Villa-Marcos

    2010-04-01

    Full Text Available Chiral amines are one of the ubiquitous functional groups in fine chemical, pharmaceutical and agrochemical products, and the most convenient, economical, and eco-benign synthetic pathway to these amines is direct asymmetric reductive amination (DARA of prochiral ketones. This paper shows that a wide range of aliphatic ketones can be directly aminated under hydrogenation conditions, affording chiral amines with good to excellent yields and with enantioselectivities up to 96% ee. The catalysis is effected by the cooperative action of a cationic Cp*Ir(III complex and its phosphate counteranion.

  2. Charge transfer to a semi-esterified bifunctional phenol

    Energy Technology Data Exchange (ETDEWEB)

    Brede, O.; Hermann, R.; Orthner, H. [Leipzig Univ. (Germany)

    1996-03-01

    The charge transfer from solvent radical cations of n-butyl chloride and cyclohexane to 2-butyl-6(3`-t-butyl-2`-hydroxy-5`-methylbenzyl)-4-methyl-phenylac rylate (GM) yields in the first step phenoxyl radicals as well as acrylate radical cations of this semi-acrylated bifunctional phenol. Subsequently an intramolecular charge transfer from the acrylate radical cation to the phenol group takes place. Because of the instability of phenol radical cations, under our experimental conditions (nanosecond pulse radiolysis, non-polar solvents, room temperature) phenoxyl radicals are the only observable products of phenol ionization. (author).

  3. Effect of catalyst deactivation on vacuum residue hydrocracking

    Directory of Open Access Journals (Sweden)

    Hoda S. Ahmed

    2013-12-01

    Full Text Available Accelerated deactivation tests of the pre-sulfided Mo–W/SiO2–Al2O3 commercial catalyst were performed using heavy vacuum petroleum feedstock. High reaction temperature employed in the accelerated catalyst aging resulted in large amounts of carbonaceous deposition with high aromaticity, which was found to be the principal deactivation cause. The effect of catalyst deactivation on hydrocracking of vacuum residue was studied. Experiments were carried out in a batch reactor at 60 bar, feed to catalyst ratio 10:1 and temperature 425 °C. The duration time for a cycle-run was 4 h. On increasing the interval duration times from 4 to 20 h (i.e. five cycles, the quality of the hydrocracked products was decreased. In each cycle-run, a fresh feedstock was used with the same sulfide catalyst. The quality of distillate products, such as hydrodesulfurization (HDS was decreased from 61.50% to 39.52%, while asphaltene contents of the total liquid product were increased from 2.7% to 5.2% and their boiling ranges were increased during these duration times due to the successive catalyst deactivation during the 5 cycle-runs, caused by successive adsorption of coke formation.

  4. Can Ni phosphides become viable hydroprocessing catalysts?

    Energy Technology Data Exchange (ETDEWEB)

    Soled, S.; Miseo, S.; Baumgartner, J.; Guzman, J.; Bolin, T.; Meyer, R.

    2015-05-15

    We prepared higher surface area nickel phosphides than are normally found by reducing nickel phosphate. To do this, we hydrothermally synthesized Ni hydroxy phosphite precursors with low levels of molybdenum substitution. The molybdenum substitution increases the surface area of these precursors. During pretreatment in a sulfiding atmosphere (such as H2S/H2) dispersed islands of MoS2 segregate from the precursor and provide a pathway for H2 dissociation that allows reduction of the phosphite precursor to nickel phosphide at substantially lower temperatures than in the absence of MoS2. The results reported here show that to create nickel phosphides with comparable activity to conventional supported sulfide catalysts, one would have to synthesize the phosphide with surface areas exceeding 400 m2/g (i.e. with nanoparticles less than 30 Å in lateral dimension).

  5. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    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...... meaningful for everyone. The exhibited works are designed by SANAA, Diller Scofidio + Renfro, James Corner Field Operation, JBMC Arquitetura e Urbanismo, Atelier Bow-Wow, Ateliers Jean Nouvel, COBE, Transform, BIG, Topotek1, Superflex, and by visual artist Jane Maria Petersen....

  6. X-Ray Absorption Spectroscopy of Mo and Ni K-edge of Supported Hydrotreating Catalysts

    Institute of Scientific and Technical Information of China (English)

    DuanAijun; XuChunming; ZhaoZhen; DongPeng

    2005-01-01

    X-ray absorption fine structure (XAFS) and other techniques have been used to characterize Ni-Mo/Al2O3 supported catalysts. The analysis of Mo K-edge spetrum shows that the active species over sulfide catalysts are MoS2-alike and the dispersion of Mo is high at the level of nanometer particles. There may exist some distortion of the local environment of MoS2, which has an influence on the hydrotreating activities of catalysts. Ni K-edge analysis shows that the coordination effects of Ni-Mo favor the dispersion state of active phase and imply a close relationship with catalyst activities.

  7. Design Principles for Heteroatom-Doped Carbon Nanomaterials as Highly Efficient Catalysts for Fuel Cells and Metal-Air Batteries.

    Science.gov (United States)

    Zhao, Zhenghang; Li, Mingtao; Zhang, Lipeng; Dai, Liming; Xia, Zhenhai

    2015-11-18

    Oxygen reduction reaction/oxygen evolution reaction (ORR/OER) catalytic activities of p-orbital heteroatom-doped carbon nanomaterials are demonstrated to correlate to the combination of the electron affinity and electronegativity of doping elements, which serves as an activity descriptor for the entire family of p-block element dopants. Such a descriptor has predictive power and enables effective design of new bifunctional catalysts with enhanced ORR/OER activities.

  8. Reconstructed hydrotalcite as a highly active heterogeneous base catalyst for carbon-carbon bond formations in the presence of water.

    Science.gov (United States)

    Ebitani, Kohki; Motokura, Ken; Mori, Kohsuke; Mizugaki, Tomoo; Kaneda, Kiyotomi

    2006-07-21

    The aldol reaction of carbonyl compounds is efficiently catalyzed by reconstructed hydrotalcites, obtained by treating the Mg-Al mixed oxide with water, as solid base catalysts in the presence of water. The catalysis of the reconstructed hydrotalcites is attributable to the surface base sites, created during the organization of the layered structure, with uniformly distributed strength. Furthermore, the reconstructed hydrotalcites provide a unique acid-base bifunctional surface capable of promoting the Knoevenagel and Michael reactions of nitriles with carbonyl compounds.

  9. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G

    2005-11-30

    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

  10. Rhodium-catalyzed imination of sulfoxides and sulfides: efficient preparation of N-unsubstituted sulfoximines and sulfilimines.

    Science.gov (United States)

    Okamura, Hiroaki; Bolm, Carsten

    2004-04-15

    The Rh(II)-catalyzed imination of sulfoxides and sulfides using [Rh(2)(OAc)(4)] as a catalyst and trifluoroacetamide or sulfonylamides in combination with iodobenzene diacetate and magnesium oxide affords sulfoximines and sulfilimines, respectively, in a stereospecific manner. [reaction: see text

  11. Photovoltachromic device with a micropatterned bifunctional counter electrode.

    Science.gov (United States)

    Cannavale, Alessandro; Manca, Michele; De Marco, Luisa; Grisorio, Roberto; Carallo, Sonia; Suranna, Gian Paolo; Gigli, Giuseppe

    2014-02-26

    A photovoltachromic window can potentially act as a smart glass skin which generates electric energy as a common dye-sensitized solar cell and, at the same time, control the incoming energy flux by reacting to even small modifications in the solar radiation intensity. We report here the successful implementation of a novel architecture of a photovoltachromic cell based on an engineered bifunctional counter electrode consisting of two physically separated platinum and tungsten oxide regions, which are arranged to form complementary comb-like patterns. Solar light is partially harvested by a dye-sensitized photoelectrode made on the front glass of the cell which fully overlaps a bifunctional counter electrode made on the back glass. When the cell is illuminated, the photovoltage drives electrons into the electrochromic stripes through the photoelectrochromic circuit and promotes the Li(+) diffusion towards the WO3 film, which thus turns into its colored state: a photocoloration efficiency of 17 cm(2) min(-1) W(-1) at a wavelength of 650 nm under 1.0 sun was reported along with fast response (coloration time photovoltaic functionality was also retained due to the copresence of the independently switchable micropatterned platinum electrode.

  12. Stability and kinetics of a bifunctional amylase/trypsin inhibitor.

    Science.gov (United States)

    Alagiri, S; Singh, T P

    1993-11-10

    The stability of the bifunctional amylase/trypsin inhibitor from ragi (Indian finger millet, Eleusine coracana) has been studied by methods of circular dichroism, UV absorption and intrinsic fluorescence. The inhibitor is stable in 8 M urea and 6 M guanidine-HCl. In 150 mM NaCl, thermal denaturation does not occur up to 90 degrees C. However, it is irreversibly denatured in 5 mM NaCl if heated over 73 degrees C. The acidic denaturation is reversible in both high and low salt conditions, but it shows different behavior below pH 1.65 under similar salt conditions. The helical content is about 2-4% in the pH range of 7-9 at which the inhibitor is active maximally. The NaCl concentration does not have a significant effect on the secondary structure elements. The beta-strand form does not show much variation under various conditions. Arg34-Leu35 is the reactive peptide bond in the trypsin-binding site. Trp and Tyr are involved in the binding with amylase. The bifunctional inhibitor represents the sum of individual inhibitors of trypsin and amylase.

  13. FT-IR Study of Carbon Nanotube Supported Co-Mo Catalysts

    Institute of Scientific and Technical Information of China (English)

    Hongyan Shang; Chenguang Liu1; Fei Wei

    2004-01-01

    In this paper, adsorption properties of dibenzothiophene (DBT) on carbon nanotube, carbon nanotube supported oxide state and sulfide state CoMo catalysts are studied by using thermal gravimetric analysis (TGA) technique and FT-IR spectroscopy. Activated carbon support, γ-Al2O3 support and supported CoMo catalysts are also subjected to studies for comparison. It was found that sulfide state CoMoS/MWCNT, CoMoS/AC and CoMoS/γ-Al2O3 catalysts adsorbed much more DBT molecules than their corresponding oxide state catalysts, as well as their corresponding supports. The chemically adsorbed DBT aromatic molecules did not undergo decomposition on the surface of supports, supported oxide state CoMo catalysts and sulfide state CoMo catalysts when out-gassing at 373 K. FT-IR results indicated that DBT molecules mainly stand upright on the active sites (acid sites and/or transition active phases) of CoMoS/MWCNT catalyst. However, DBT aromatic molecules mainly lie flat on MWCNT and CoMoO/MWCNT.

  14. States of carbon nanotube supported Mo-based HDS catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Hongyan; Liu, Chenguang; Xu, Yongqiang [Key Laboratory of Catalysis, CNPC, College of Chemistry and Chemical Engineering, University of Petroleum, Dongying 257061 (China); Qiu, Jieshan [Carbon Research Laboratory, Center for Nano Materials and Science, Dalian University of Technology, 158 Zhongshan Road, P. O. Box 49, Dalian 116012 (China); Wei, Fei [Department of Chemical Engineering, Tsinghua University, Being, 100084 (China)

    2007-02-15

    As HDS catalysts, the supported catalysts including oxide state Mo, Co-Mo and sulfide state Mo on carbon nanotube (CNT) were prepared, while the corresponding supported catalysts on {gamma}-Al{sub 2}O{sub 3} were prepared as comparison. Firstly, the dispersion of the active phase and loading capacity of Mo species on CNT was studied by XRD and the reducibility properties of Co-Mo catalysts in oxide state over CNTs were investigated by TPR while the sulfide Co-Mo/CNT catalysts were characterized by XRD and LRS techniques. Secondly, the activity and selectivity of hydrodesulfurization (HDS) of dibenzothiophene with Co-Mo/CNT and Co-Mo/{gamma}-Al{sub 2}O{sub 3} were studied. It has been found that the main active molybdenum species in the oxide state MoO{sub 3}/CNT catalysts were MoO{sub 2}, rather than MoO{sub 3} as generally expected. The maximum loading before formation of the bulk phase was lower than 6%m (calculated in MoO{sub 3}). The TPR studies revealed that that active species in oxide state Co-Mo/CNT catalysts were more easily reduced at relatively lower temperatures in comparison to those in Co-Mo/{gamma}-Al{sub 2}O{sub 3}, indicating that the CNT support promoted the reduction of active species. Among 0-1.0 Co/Mo atomic ratio on Co-Mo/CNT, 0.7 has the highest reducibility. It shows that the Co/Mo atomic ratio has a great effect on the reducibility of active species on CNT and their HDS activities and that the incorporation of cobalt improved the dispersion of molybdenum species on CNT and mobilization. It was also found that re-dispersion could occur during the sulfiding process, resulting in low valence state Mo{sub 3}S{sub 4} and Co-MoS{sub 2.17} active phases. The HDS of DBT showed that Co-Mo/CNT catalysts were more active than Co-Mo/{gamma}-Al{sub 2}O{sub 3} and the hydrogenolysis/hydrogenation selectivity of Co-Mo/CNT catalyst was also much higher than Co-Mo/{gamma}-Al{sub 2}O{sub 3}. For the Co-Mo/CNT catalysis system, the catalyst with Co/Mo atomic

  15. Modification of bifunctional epoxy resin using CO{sub 2} fixation process and nanoclay

    Energy Technology Data Exchange (ETDEWEB)

    Khoshkish, Morteza; Bouhendi, Hosein, E-mail: H.boohendi@ippi.ac.ir; Vafayan, Mehdi

    2014-10-15

    A bifunctional epoxy resin was modified by using a CO{sub 2} fixation solution process in the presence of tetra n-butyl ammonium bromide (TBAB) as catalyst and the modified treated resin was treated by cloisite 30B as nano additive. The Unmodified epoxy resin (UME), CO{sub 2} fixated modified epoxy resin (CFME), and CFME/clay nano composite (CFMEN), were cured by diethylenetriamine (DETA). A cycloaliphatic compound as a reactive diluent was used to control the viscosity of high viscose CFME. The exfoliation of organoclay in UME and CFME was investigated by X-ray diffraction and activation energy was computed using the advanced integral isoconversional method. The activation energy dependency demonstrated that the mechanism of UME curing did not change in the presence of nanoclay. In contrast, the CO{sub 2} fixation results showed a significant change in the activation energy dependency. The Thermal stability parameters include the initial degradation temperature (IDT), the temperature at the maximum rate of weight loss (T{sub max}), and the decomposition activation energy (E{sub d}) were determined by thermal gravimetry analysis. Dynamic mechanical thermal analysis measurements showed that the presence of organoclay in CFME increases the T{sub g} of nano composite in contrast to UME. The fracture roughness of UME, CFME and CFNE were determined by scanning electron microscope. The exfoliated UME/1%clay nanocomposite was confirmed by TEM image. - Highlights: • A new epoxy resin was synthesized using CO{sub 2} fixation reaction. • The synthesized epoxy resin was modified by an organo nano-clay. • CO{sub 2} fixation noticeably changed the curing mechanism. • CO{sub 2} fixation reaction consumes CO{sub 2} which is a harmful greenhouse gas.

  16. Synthesis and Characterization of a New Bifunctional Dye Containing Spirobenzopyran and Cinnamoyl Moiety

    Institute of Scientific and Technical Information of China (English)

    申凯华; 崔东熏

    2005-01-01

    A novel bifunctional dye containing spirobenzopyran and cinnaznoyl moiety has been prepared and its photochromic behavior following irradiation at different wavelengths of monochrome UV light was investigated.The colourless bifunctional dye in film or solution exhibits unusual photochromism through structural and geometrical transformation from spirobenzopyran to merocyanine accompanying with photocrosslinking reaction in cinnamoyl moieties. Two kinds of photochemical reaction were achieved by irradiation at the different wavelengths of monochrome UV light (275 nm, 365 nm) selectively. The photochromic process of the bifunctional dye was discussed and the dynamic behaviors of the decolorization process were investigated.

  17. Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2009-12-01

    Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.

  18. Synthesis of furan from allenic sulfide derivatives

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In this paper, we report the synthesis of furan derivatives from allenic sulfides. By the reaction with NaH, β-Hydroxyl allenic sulfides were found to generate furan products in excellent yields with the removal of phenylthio group. β-Aldehyde allenic sulfides were found to give similar furan products with one more substituent when treated with additional nucleophilic reagents. β-ketone allenic sulfides can also cyclize to give furan derivatives with the promotion of P2O5.

  19. Synthesis of furan from allenic sulfide derivatives

    Institute of Scientific and Technical Information of China (English)

    PENG LingLing; ZHANG Xiu; MA Jie; ZHONG ZhenZhen; ZHANG Zhe; ZHANG Yan; WANG JianBo

    2009-01-01

    In this paper, we report the synthesis of furan derivatives from allenic sulfides. By the reaction with NaH.,β-Hydroxyl allenic sulfides were found to generate furan products in excellent yields with the removal of phenylthio group.β-Aldehyde allenic sulfides were found to give similar furan products with one more substituent when treated with additional nucleophilic reagents. β-ketone allenic sulfides can also cyclize to give furan derivatives with the promotion of P2O5.

  20. NiFe layered double hydroxide/reduced graphene oxide nanohybrid as an efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions

    Science.gov (United States)

    Zhan, Tianrong; Zhang, Yumei; Liu, Xiaolin; Lu, SiSi; Hou, Wanguo

    2016-11-01

    Highly active and low-cost bifunctional electrocatalysts for oxygen evolution and reduction reactions (OER and ORR) hold a heart position for the renewable energy technologies such as metal-air batteries and fuel cells. Here, we reported the synthesis of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanohybrid via the facile solvothermal method followed by chemical reduction. The template role of surfactant and the hybridization of rGO supplied the NiFe-LDH/rGO catalyst with a porous nanostructure and an enhanced conductivity, favoring both mass transport and charge communication of electrocatalytic reactions. The NiFe-LDH/rGO composite not only displayed highly efficient OER activity in alkaline solution with a low onset overpotential of 240 mV, but also only needed an overpotential of 250 mV to reach the 10 mA cm-2 current density. The NiFe-LDH/rGO nanohybrid also offered excellent ORR catalytic activity with onset potential at 0.796 V in alkaline media. The rotating-disk and rotating-ring-disk electrodes both revealed that the ORR on NiFe-LDH/rGO mainly involved a direct four-electron reaction pathways accompanying part of the two-electron process. The excellent bifunctional activity of the NiFe-LDH/rGO nanohybrid could be attributed to the synergistic effects of rGO and NiFe-LDH components due to the strongly coupled interactions.

  1. Monolayer-precision synthesis of molybdenum sulfide nanoparticles and their nanoscale size effects in the hydrogen evolution reaction.

    Science.gov (United States)

    Seo, Bora; Jung, Gwan Yeong; Sa, Young Jin; Jeong, Hu Young; Cheon, Jae Yeong; Lee, Jeong Hyeon; Kim, Ho Young; Kim, Jin Chul; Shin, Hyeon Suk; Kwak, Sang Kyu; Joo, Sang Hoon

    2015-04-28

    Metal sulfide-based nanostructured materials have emerged as promising catalysts for hydrogen evolution reaction (HER), and significant progress has been achieved in enhancing their activity and durability for the HER. The understanding of nanoscale size-dependent catalytic activities can suggest critical information regarding catalytic reactivity, providing the scientific basis for the design of advanced catalysts. However, nanoscale size effects in metal sulfide-based HER catalysts have not yet been established fully, due to the synthetic difficulty in precisely size-controlled metal sulfide nanoparticles. Here we report the preparation of molybdenum sulfide (MoS2) nanoparticles with monolayer precision from one to four layers with the nearly constant basal plane size of 5 nm, and their size-dependent catalytic activity in the HER. Using density functional theory (DFT) calculations, we identified the most favorable single-, double-, and triple-layer MoS2 model structures for the HER, and calculated elementary step energetics of the HER over these three model structures. Combining HER activity measurements and the DFT calculation results, we establish that the turnover frequency of MoS2 nanoparticles in the HER increases in a quasi-linear manner with decreased layer numbers. Cobalt-promoted MoS2 nanoparticles also exhibited similar HER activity trend. We attribute the higher HER activity of smaller metal sulfide nanoparticles to the higher degree of oxidation, higher Mo-S coordination number, formation of the 1T phase, and lower activation energy required to overcome transition state. This insight into the nanoscale size-dependent HER activity trend will facilitate the design of advanced HER catalysts as well as other hydrotreating catalysts.

  2. The Effect of K and Acidity of NiW-Loaded HY Zeolite Catalyst for Selective Ring Opening of 1-Methylnaphthalene.

    Science.gov (United States)

    Lee, You-Jin; Kim, Eun-Sang; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

    2016-05-01

    Bi-functional catalysts were prepared using HY zeolites with various SiO2/Al2O3 ratios for acidic function, NiW for metallic function, and K for acidity control. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction was investigated using the prepared bi-functional catalysts with different levels of acidity in a fixed bed reactor system. In NiW/HY catalysts without K addition, the acidity decreased with the SiO2/Al2O3 mole ratio of the HY zeolite. Ni1.1W1.1/HY(12) catalyst showed the highest acidity but slightly lower yields for the selective ring opening than Ni1.1W1.1/HY(30) catalyst. The acidity of the catalyst seemed to play an important role as the active site for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. Catalyst acidity could be controlled between Ni1.1W1.1/HY(12) and Ni1.1W1.1/HY(30) by adding a moderate amount of K to Ni1.1W1.1/HY(12) catalyst. K0.3Ni1.1W1.1/HY(12) catalyst should have the optimum acidity for the selective ring opening. The addition of a moderate amount of K to the NiW/HY catalyst must improve the catalytic performance due to the optimization of catalyst acidity.

  3. Nanostructured metal sulfides for energy storage.

    Science.gov (United States)

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-07

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  4. 30 CFR 250.604 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  5. 30 CFR 250.504 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  6. 30 CFR 250.808 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of...

  7. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    Directory of Open Access Journals (Sweden)

    F. V. Barsi

    2009-06-01

    Full Text Available Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt and bimetallic catalysts (Pt-Ni, using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on the catalytic properties for n-hexane isomerization. The method used for metal dispersion in the zeolite was competitive ion exchange using ammine complexes [Ni(NH36]Cl2 and [Pt(NH34]Cl2 as precursors. Four series of catalysts with constant atomic metal content had total metal amounts between 130 and 280 µmol M/g cat. Catalysts were characterized by temperature programmed reduction (TPR and subjected to catalytic evaluation for n-hexane isomerization at 250 ºC and 1 atm using H2/C6 = 9 molar ratio. TPR results show an easier reducibility of Ni+2 cations in the presence of Pt, which was evidenced by the displacement of the reduction peak of those cations towards lower temperatures in bimetallic catalysts. The bimetallic catalysts presented a higher activity in the isomerization of n-hexane when compared to the monometallic ones, as well better stability as the Pt content in the solid increases. The results of the activity as a function of the Pt content in the bimetallic catalysts show a maximum value around 50% of Pt. An addition of Pt above this critical value leads to a small decrease of the catalytic activity.

  8. Commercial Application of Technique for Removing Sulfates from Reforming Catalyst

    Institute of Scientific and Technical Information of China (English)

    JiChangqing

    2002-01-01

    In the course of reduction of reforming catalyst by not hydrogen a certain amount of chlorine containing compounds is added to the recycle hydrogen to facilitate the reduction of sulfates.The outcome of commercial application of this technique has revealed that the procedure of "regeneration by chlorination→reduction→sulfate removal→sulfiding and oil feed-in"aimed at sulate removal is very simple and can recover the reaction activity of reforming catalyst after having been poisoned by sulfates.This procedure can be disseminated for application in refineries.

  9. Bifunctional chelates of RH-105 and AU199 as potential radiotherapeutic agents

    Energy Technology Data Exchange (ETDEWEB)

    Droege, P.

    1997-03-01

    Research is presented on new bifunctional chelating ligand systems with stability on the macroscopic and radiochemical levels. The synthesis of the following complexes are described: rhodium 105, palladium 109, and gold 198.

  10. Bifunctional chelating agent for the design and development of site specific radiopharmaceuticals and biomolecule conjugation strategy

    Science.gov (United States)

    Katti, Kattesh V.; Prabhu, Kandikere R.; Gali, Hariprasad; Pillarsetty, Nagavara Kishore; Volkert, Wynn A.

    2003-10-21

    There is provided a method of labeling a biomolecule with a transition metal or radiometal in a site specific manner to produce a diagnostic or therapeutic pharmaceutical compound by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radio metal or a transition metal, and covalently linking the resulting metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. Also provided is a method of synthesizing the --PR.sub.2 containing biomolecules by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radiometal or a transition metal, and covalently linking the resulting radio metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. There is provided a therapeutic or diagnostic agent comprising a --PR.sub.2 containing biomolecule.

  11. Effects of Feed Composition and Feed Impurities in the Catalytic Conversion of Syngas to Higher Alcohols over Alkali-Promoted Cobalt–Molybdenum Sulfide

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt; Jensen, Peter Arendt; Jensen, Anker Degn

    2011-01-01

    Alkali-promoted cobalt–molybdenum sulfide is a potential catalyst for the conversion of syngas into higher alcohols. This work is an investigation of how the feed composition influences the behavior of the sulfide catalyst. In a sulfur-free syngas the production of higher alcohols is observed...... to be optimal with an equimolar mixture of CO and H2 in the feed, while the methanol production benefits from an increasing hydrogen content in the feed. The influence of NH3 and H2O in the syngas feed has also been investigated. Ammonia (741 ppmv) in the feed is observed to cause a general and largely...

  12. The bi-functional organization of human basement membranes.

    Science.gov (United States)

    Halfter, Willi; Monnier, Christophe; Müller, David; Oertle, Philipp; Uechi, Guy; Balasubramani, Manimalha; Safi, Farhad; Lim, Roderick; Loparic, Marko; Henrich, Paul Bernhard

    2013-01-01

    The current basement membrane (BM) model proposes a single-layered extracellular matrix (ECM) sheet that is predominantly composed of laminins, collagen IVs and proteoglycans. The present data show that BM proteins and their domains are asymmetrically organized providing human BMs with side-specific properties: A) isolated human BMs roll up in a side-specific pattern, with the epithelial side facing outward and the stromal side inward. The rolling is independent of the curvature of the tissue from which the BMs were isolated. B) The epithelial side of BMs is twice as stiff as the stromal side, and C) epithelial cells adhere to the epithelial side of BMs only. Side-selective cell adhesion was also confirmed for BMs from mice and from chick embryos. We propose that the bi-functional organization of BMs is an inherent property of BMs and helps build the basic tissue architecture of metazoans with alternating epithelial and connective tissue layers.

  13. The bi-functional organization of human basement membranes.

    Directory of Open Access Journals (Sweden)

    Willi Halfter

    Full Text Available The current basement membrane (BM model proposes a single-layered extracellular matrix (ECM sheet that is predominantly composed of laminins, collagen IVs and proteoglycans. The present data show that BM proteins and their domains are asymmetrically organized providing human BMs with side-specific properties: A isolated human BMs roll up in a side-specific pattern, with the epithelial side facing outward and the stromal side inward. The rolling is independent of the curvature of the tissue from which the BMs were isolated. B The epithelial side of BMs is twice as stiff as the stromal side, and C epithelial cells adhere to the epithelial side of BMs only. Side-selective cell adhesion was also confirmed for BMs from mice and from chick embryos. We propose that the bi-functional organization of BMs is an inherent property of BMs and helps build the basic tissue architecture of metazoans with alternating epithelial and connective tissue layers.

  14. Chemoselective Reactivity of Bifunctional Cyclooctynes on Si(001)

    CERN Document Server

    Reutzel, Marcel; Lipponer, Marcus A; Länger, Christian; Höfer, Ulrich; Koert, Ulrich; Dürr, Michael

    2016-01-01

    Controlled organic functionalization of silicon surfaces as integral part of semiconductor technology offers new perspectives for a wide range of applications. The high reactivity of the silicon dangling bonds, however, presents a major hindrance for the first basic reaction step of such a functionalization, i.e., the chemoselective attachment of bifunctional organic molecules on the pristine silicon surface. We overcome this problem by employing cyclooctyne as the major building block of our strategy. Functionalized cyclooctynes are shown to react on Si(001) selectively via the strained cyclooctyne triple bond while leaving the side groups intact. The achieved selectivity originates from the distinctly different adsorption dynamics of the separate functionalities: A direct adsorption pathway is demonstrated for cyclooctyne as opposed to the vast majority of other organic functional groups. The latter ones react on Si(001) via a metastable intermediate which makes them effectively unreactive in competition wi...

  15. GSK-3: A Bifunctional Role in Cell Death Pathways

    Directory of Open Access Journals (Sweden)

    Keith M. Jacobs

    2012-01-01

    Full Text Available Although glycogen synthase kinase-3 beta (GSK-3β was originally named for its ability to phosphorylate glycogen synthase and regulate glucose metabolism, this multifunctional kinase is presently known to be a key regulator of a wide range of cellular functions. GSK-3β is involved in modulating a variety of functions including cell signaling, growth metabolism, and various transcription factors that determine the survival or death of the organism. Secondary to the role of GSK-3β in various diseases including Alzheimer’s disease, inflammation, diabetes, and cancer, small molecule inhibitors of GSK-3β are gaining significant attention. This paper is primarily focused on addressing the bifunctional or conflicting roles of GSK-3β in both the promotion of cell survival and of apoptosis. GSK-3β has emerged as an important molecular target for drug development.

  16. GSK-3β: A Bifunctional Role in Cell Death Pathways

    Science.gov (United States)

    Jacobs, Keith M.; Bhave, Sandeep R.; Ferraro, Daniel J.; Jaboin, Jerry J.; Hallahan, Dennis E.; Thotala, Dinesh

    2012-01-01

    Although glycogen synthase kinase-3 beta (GSK-3β) was originally named for its ability to phosphorylate glycogen synthase and regulate glucose metabolism, this multifunctional kinase is presently known to be a key regulator of a wide range of cellular functions. GSK-3β is involved in modulating a variety of functions including cell signaling, growth metabolism, and various transcription factors that determine the survival or death of the organism. Secondary to the role of GSK-3β in various diseases including Alzheimer's disease, inflammation, diabetes, and cancer, small molecule inhibitors of GSK-3β are gaining significant attention. This paper is primarily focused on addressing the bifunctional or conflicting roles of GSK-3β in both the promotion of cell survival and of apoptosis. GSK-3β has emerged as an important molecular target for drug development. PMID:22675363

  17. [Bifunctional inhibitor of alpha-amylase/trypsin from wheat grain].

    Science.gov (United States)

    Islamov, R A; Furusov, O V

    2007-01-01

    A trypsin inhibitor, isolated from whole-wheat grain (Triticum aestivum L.) by the method of bio-specific chromatography on trypsin-Sepharose, was potent in inhibiting human salivary alpha-amylase. The bi-functional alpha-amylase/trypsin inhibitor was characterized by a narrow specificity for other alpha-amylases and proteinases. The high thermostability of the inhibitor was lost in the presence of SH group-reducing agents. The inhibitor-trypsin complex retained its activity against alpha-amylase. The inhibitor-alpha-amylase complex was active against trypsin. Studies of the enzyme kinetics demonstrated that the inhibition of alpha-amylase and trypsin was noncompetitive. Our results suggest the existence of two independent active sites responsible for the interaction with the enzymes.

  18. Organusulfur Catalysis With Reduced Molybdenum Sulfides Containing the Mo6S8 Cluster

    Energy Technology Data Exchange (ETDEWEB)

    Thomas Jay Paskach

    2002-08-27

    Industrial synthesis of sulfur-containing organic chemicals basically focuses on the broad categories of mercaptans (thiols), alkylsulfides (thioethers), polysulfides, and thiophenes. Of the organo-sulfur compounds produced, by far the most important in terms of quantities produced is methyl mercaptan (methanethiol or MeSH), which is produced mainly for the downstream production of methionine and methanesulfonyl chloride. Higher thiols are also used in the manufacture of rubber and plastics as polymerization regulators, chain transfer agents, or initiators. Other important organosulfur chemicals are dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), both of which are used extensively for presulfiding of industrial hydroprocessing catalysts, and substituted thiophenes which are used as intermediates for production of agrochemicals, dyes, and pharmaceuticals. Thiols are produced commercially at the rate of about 10{sup 4} ton/yr from hydrogen sulfide (H{sub 2}S) and alcohols or olefins, using homogeneous free-radical synthesis, or heterogeneous catalysts based on solid acids or supported metal oxides and/or sulfides. Despite this large production rate, and the industrial importance of the organosulfur compounds, only limited research has been devoted to the development of new catalytic materials for their synthesis. Additionally, for most organosulfur catalytic reactions, only limited information exists about reaction mechanisms, active sites, adsorbed surface species, and especially the nature of the catalysts under reaction conditions.

  19. Mechanochemical activation of iron ore-based catalysts for the hydrogenation of brown coal

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, P.N.; Kuznetsova, L.I.; Chumakov, V.G.; Moiseeva, G.A. [Rossijskaya Akademiya Nauk, Krasnoyarsk (Russian Federation). Inst. of Chemistry and Chemical Technology

    2000-10-01

    Genesis of pyrrhotite catalysts from different iron ore concentrates and pure iron oxides was investigated using the method of mechanochemical treatment in a planetary mill. The dispersion and fine crystalline structure of oxide and pyrrhotite particles were studied as the function of mechanical load, sulfiding temperature and mode of preparation. Methods for the preparation of high performance iron ore-based catalysts for brown coal hydrogenation have been developed. (orig.)

  20. Bi-functional modified-phosphate catalyzed the synthesis of α-α′-(EE)-bis(benzylidene)-cycloalkanones: Microwave versus conventional-heating

    KAUST Repository

    Solhy, Abderrahim

    2011-02-01

    The impregnation of hydroxyapatite (HAP) by NaNO3 leads to a modified-hydroxyapatite which has a bi-functional acid-base property. Sodium-modified-hydroxyapatite (Na-HAP) efficiently catalyzed the cross-aldol condensation of arylaldehydes and cycloketones to afford α-α′- (EE)-bis(benzylidene)-cycloalkanones in good yields under microwave irradiation. Moreover, the methodology described in this paper provides a very easy and efficient synthesis carried out in water as the greenest available solvent under conventional heating. A comparison study between these two different modes of heating was investigated. The catalyst was easily recovered and efficiently re-used. © 2010 Elsevier B.V.

  1. SYNTHESIS OF NOVEL BI-FUNCTIONAL COPOLYMER BEA RING STERICALLY HINDERED PHENOL AND HINDERED AMINE GROUPS VIA RING-OPENING METATHESIS POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Bo-yong Xue; Kenichi Ogata; Akinori Toyota

    2008-01-01

    Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl2(=CHPh)(PCy3)2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol (SHP) and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),'H-NMR and differential scanning calorimetry (DSC).The number average molecular weight(Mn)and functional unit content of the resulting copolymer could be regulated by varying the concentration of catalyst and monomer feed.

  2. TiN@nitrogen-doped carbon supported Pt nanoparticles as high-performance anode catalyst for methanol electrooxidation

    Science.gov (United States)

    Zhang, Jun; Ma, Li; Gan, Mengyu; Fu, Shenna; Zhao, Yi

    2016-08-01

    In this paper, TiN@nitrogen-doped carbons (NDC) composed of a core-shell structure are successfully prepared through self-assembly and pyrolysis treatment using γ-aminopropyltriethoxysilane as coupling agent, polyaniline as carbon and nitrogen source, respectively. Subsequently, TiN@NDC supporting Pt nanoparticles (Pt/TiN@NDC) are obtained by a microwave-assisted polyol process. The nitrogen-containing functional groups and TiN nanoparticles play a critical role in decreasing the average particle size of Pt and improving the electrocatalytic activity of Pt/TiN@NDC. Transmission electron microscope results reveal that Pt nanoparticles are uniformly dispersed in the TiN@NDC surface with a narrow particle size ranging from 1 to 3 nm in diameter. Moreover, the Pt/TiN@NDC catalyst shows significantly improved catalytic activity and high durability for methanol electrooxidation in comparison with Pt/NDC and commercial Pt/C catalysts, revealed by cyclic voltammetry and chronoamperometry. Strikingly, this novel Pt/TiN@NDC catalyst reveals a better CO tolerance related to Pt/NDC and commercial Pt/C catalysts, which due to the bifunctional mechanism and strong metal-support interaction between Pt and TiN@NDC. In addition, the probable reaction steps for the electrooxidation of CO adspecies on Pt NPs on the basis of the bifunctional mechanism are also proposed. These results indicate that the TiN@NDC is a promising catalyst support for methanol electrooxidation.

  3. Opioid bifunctional ligands from morphine and the opioid pharmacophore Dmt-Tic.

    Science.gov (United States)

    Balboni, Gianfranco; Salvadori, Severo; Marczak, Ewa D; Knapp, Brian I; Bidlack, Jean M; Lazarus, Lawrence H; Peng, Xuemei; Si, Yu Gui; Neumeyer, John L

    2011-02-01

    Bifunctional ligands containing an ester linkage between morphine and the δ-selective pharmacophore Dmt-Tic were synthesized, and their binding affinity and functional bioactivity at the μ, δ and κ opioid receptors determined. Bifunctional ligands containing or not a spacer of β-alanine between the two pharmacophores lose the μ agonism deriving from morphine becoming partial μ agonists 4 or μ antagonists 5. Partial κ agonism is evidenced only for compound 4. Finally, both compounds showed potent δ antagonism.

  4. Biomass Conversion over Heteropoly Acid Catalysts

    KAUST Repository

    Zhang, Jizhe

    2015-04-01

    Biomass is a natural resource that is both abundant and sustainable. Its efficient utilization has long been the focus of research and development efforts with the aim to substitute it for fossil-based feedstock. In addition to the production of biofuels (e.g., ethanol) from biomass, which has been to some degree successful, its conversion to high value-added chemicals is equally important. Among various biomass conversion pathways, catalytic conversion is usually preferred, as it provides a cost-effective and eco-benign route to the desired products with high selectivities. The research of this thesis is focused on the conversion of biomass to various chemicals of commercial interest by selective catalytic oxidation. Molecular oxygen is chosen as the oxidant considering its low cost and environment friendly features in comparison with commonly used hydrogen peroxide. However, the activation of molecular oxygen usually requires high reaction temperatures, leading to over oxidation and thus lower selectivities. Therefore, it is highly desirable to develop effective catalysts for such conversion systems. We use kegging-type heteropoly acids (HPAs) as a platform for catalysts design because of their high catalytic activities and ease of medication. Using HPA catalysts allows the conversion taking place at relatively low temperature, which is beneficial to saving production cost as well as to improving the reaction selectivity. The strong acidity of HPA promotes the hydrolysis of biomass of giant molecules (e.g. cellulose), which is the first as well as the most difficult step in the conversion process. Under certain circumstances, a HPA combines the merits of homogeneous and heterogeneous catalysts, acting as an efficient homogeneous catalyst during the reaction while being easily separated as a heterogeneous catalyst after the reaction. We have successfully applied HPAs in several biomass conversion systems. Specially, we prepared a HPA-based bi-functional catalyst

  5. Bifunctional quaternary ammonium compounds to inhibit biofilm growth and enhance performance for activated carbon air-cathode in microbial fuel cells

    Science.gov (United States)

    Li, Nan; Liu, Yinan; An, Jingkun; Feng, Cuijuan; Wang, Xin

    2014-12-01

    The slow diffusion of hydroxyl out of the catalyst layer as well as the biofouling on the surface of cathode are two problems affecting power for membrane-less air-cathode microbial fuel cells (MFCs). In order to solve both of them simultaneously, here we simply modify activated carbon air-cathode using a bifunctional quaternary ammonium compound (QAC) by forced evaporation. The maximum power density reaches 1041 ± 12 mW m-2 in an unbuffered medium (0.5 g L-1 NaCl), which is 17% higher than the control, probably due to the accelerated anion transport in the catalyst layer. After 2 months, the protein content reduced by a factor of 26 and the power density increases by 33%, indicating that the QAC modification can effectively inhibit the growth of cathodic biofilm and improve the stability of performance. The addition of NaOH and QAC epoxy have a negative effect on power production due to the clogging of pores in catalyst layer.

  6. Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

    Science.gov (United States)

    Hilsenbeck, Shane J.; McCarley, Robert E.; Schrader, Glenn L.; Xie, Xiaobing

    1999-02-16

    New amorphous molybdenum/tungsten sulfides with the general formula M.sup.n+.sub.2x/n (L.sub.6 S.sub.8)S.sub.x, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M.sub.6 S.sub.8).sup.0 cluster units are present. Vacuum thermolysis of the amorphous Na.sub.2x (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH first produces poorly crystalline NaMo.sub.6 S.sub.8 by disproportionation at 800.degree. C. and well-crystallized NaMo.sub.6 S.sub.8 at .gtoreq. 900.degree. C. Ion-exchange of the sodium material in methanol with soluble M.sup.2+ and M.sup.3+ salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M.sup.n+.sub.2x/n (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M.sup.n+.sub.2x/n Mo.sub.6 S.sub.8+x (MeOH).sub.y ›MMOS! (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as "Chevrel phase-like" in that both contain Mo.sub.6 S.sub.8 cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst showed to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS.sub.2 catalysts.

  7. Production of propene from 1-butene metathesis reaction on tungsten based heterogeneous catalysts

    Institute of Scientific and Technical Information of China (English)

    Huijuan Liu; Ling Zhang; Xiujie Li; Shengjun Huang; Shenglin Liu; Wenjie Xin; Sujuan Xie; Longya Xu

    2009-01-01

    A new propene production route from 1-butene metathesis has been developed on heterogeneous 10WO_3/Al_2O_3-HY catalysts with different HY contents. It is found that the catalysts play bi-functionally first for the isomerization of 1-butene to 2-butene and then for the cross-metathesis between 1-butene and 2-butene to propene and 2-pentene. The combination of HY zeolite and Al_2O_3 is prerequisite for the production of propene. The propene yield keeps increasing with the HY content in the range of 10-70 wt%,where 10WO_3/Al_2O_3-70HY exhibits the highest propene yield. The MS-H_2-TPR and MS-O_2-TPO characterizations indicate that the increase of HY content in the catalysts weakens the interaction between W species and supports,whereas enhance the probability of coking on the metal species and acid sites.

  8. Dihydrogen Activation by Titanium Sulfide Complexes

    Science.gov (United States)

    Sweeney, Zachary K.; Polse, Jennifer L.; Bergman*, Robert G.; Andersen*, Richard A.

    2005-01-01

    activation by metal-sulfide hydrodesulfurization catalysts. PMID:16633550

  9. Morphology tuning of CoMo catalysts: Effect of La and Fe as an additive

    Directory of Open Access Journals (Sweden)

    Yu Pei

    2016-01-01

    Full Text Available Three catalysts CoMo/γ-Al2O3, CoMo-La/γ-Al2O3, CoMo-Fe/γ-Al2O3 with different morphologies were prepared for study the effect of introduction of La and Fe on morphology properties and hydrodesulfurization (HDS activity. The morphology properties of catalysts were characterized by BET, XPS and HRTEM. In addition, the catalytic performances of catalysts were investigated. The results indicated that the introduction of La and Fe promoted the sulfidation of Mo species and made the average length and stacking layer numbers of MoS2 slabs longer and higher. These effects could improve the activity of catalysts for HDS. The present results indicated that the catalyst modified by Fe had the best HDS activity with the optimal morphology among three catalysts

  10. Hydrodeoxygenation of Phenolic Compounds by Sulfided (CoMo/Al2O3 Catalysts, a Combined Experimental and Theoretical Study Hydrodésoxygénation de composés phénoliques en présence de catalyseurs sulfurés (CoMo/Al2O3 : une étude expérimentale et théorique

    Directory of Open Access Journals (Sweden)

    Badawi M.

    2013-04-01

    Full Text Available The hydrodeoxygenation of model phenol compounds (phenol and 2-ethylphenol was carried over unpromoted Mo/Al2O3 and promoted CoMo/Al2O3 catalysts. Hydrodeoxygenation proceeds by two pathways: – hydrogenation of the aromatic ring followed by Csp3-O bond cleavage (HYD pathway, (hydrogenation of the aromatic ring followed by Csp3-O bond cleavage; – direct cleavage of the Csp2-O bond (DDO pathway. Both routes were favored by the presence of Co on the catalyst, while the presence of the alkyl substituent on the phenolic ring favors the DDO route but inhibits the HYD pathway. IR (InfraRed spectroscopy shows that while phenol mostly dissociates on these catalysts, a significant fraction of 2-ethylphenol remains non dissociated. The adsorption energies of both reactants and possible reaction intermediates on promoted and non-promoted sulfide phases as computed by DFT (Density-Functional Theory confirm these findings and allow rationalizing the catalytic activity trends observed experimentally. L’hydrodésoxygénation de deux composés phénoliques modèles (phénol et 2-éthylphénol a été étudiée sur deux catalyseurs Mo/Al2O3 et CoMo/Al2O3 sulfurés. La désoxygénation de ces molécules fait intervenir deux voies parallèles et indépendantes, à savoir : – l’hydrogénation du noyau aromatique suivie par la rupture de la liaison Csp3-O (voie HYD, (hydrogenation of the aromatic ring followed by Csp3-O bond cleavage; – la rupture directe de la liaison Csp2-O (voie de DésOxygénation Directe – DOD. Ces deux voies sont favorisées en présence du catalyseur promu par le cobalt (CoMo/Al2O3. La présence du groupe éthyle permet d’améliorer la voie DOD mais conduit à une diminution de la voie HYD. Les études menées par spectroscopie IR (InfraRouge montrent que le phénol est majoritairement dissocié sur ces catalyseurs alors que le 2-éthylphénol semble plutôt adsorbé de façon non-dissociative. Les énergies d’adsorption de

  11. Evaluation of nanostructured Pt-Ru catalyst for application in DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Ocampo, A.L.; Gamboa, S.A. [Centro de Investigacion en Energia-UNAM, Morelos (Mexico); Sebastien, P.J. [Centro de Investigacion en Energia-UNAM, Morelos (Mexico)]|[Chiapas Politecnica Univ., Chiapas (Mexico); Morgado, J.; Montoya, J.A. [IMP, Eje Central Lazaro Cardenas, (Mexico); Savadogo, O. [Ecole Polytechnique, Montreal, PQ (Canada). Laboratoire d' electrochimie et de materiaux energetiques

    2006-07-01

    Slow methanol oxidation kinetics and the poisoning of the anode catalyst are the major factors that limit the performance of the direct methanol fuel cell (DMFC). Catalysts with higher catalytic activity are needed in order to overcome these challenges. Although platinum (Pt) is a good catalyst for methanol oxidation, it can be highly affected by carbon monoxide (CO) reaction intermediates. Superior catalytic activity occurs in Pt based alloys, such as platinum ruthenium (Pt-Ru), platinum molybdenum (Pt-Mo), platinum tin (Pt-Sn), and platinum osmium (Pt-Os). This is due to the bifunctional mechanism and/or by the electronic effect, which indicates a promotional effect of the alloyed metal on Pt. The most studied binary system is the Pt-Ru (ruthenium), which has shown the best catalytic activity. There are many factors that influence the physical properties and the electrochemical performance of the Pt-Ru catalyst. These include the preparation method; the atomic ratio between platinum and ruthenium; the nature of the catalyst support; and, an optional heat treatment. Other important factors such as the particle size, the morphology, the electrochemically active area, and the crystalline phase influence the physical properties. In this study, nanostructured Pt-Ru catalysts were fabricated and evaluated physicochemically and electrochemically for its use in direct methanol fuel cell (DMFC). The catalysts were synthesized from the carbonyl compounds of Pt and Ru via a pyrolysis-condensation reaction. The high resolution results showed a homogenous distribution of the nanostructured catalysts on Vulcan support. The catalyst was evaluated by XRD, HRTEM, electrochemical impedance spectroscopy and the methanol oxidation on the catalyst was studied using volt-amperometry. The performance of the catalyst was found to be similar or better than the commercial one. It was concluded that it is possible to synthesize Pt-Ru/C with good morphological characteristics and improve it

  12. Foundation Flash Catalyst

    CERN Document Server

    Goralski, Greg

    2010-01-01

    This book offers an introduction to Flash Catalyst for designers with intermediate to advanced skills. It discusses where Catalyst sits within the production process and how it communicates with other programs. It covers all of the features of the Flash Catalyst workspace, teaching you how to create designs from scratch, how to build application designs and add functionality, and how to master the Catalyst/Flex workflow. * Introduces Flash Catalyst * Focuses on production process * Covers the interrelation between Flash Catalyst and Photoshop/Illustrator/Flex/Flash What you'll learn Starting f

  13. Simultaneous H2 Generation and Biomass Upgrading in Water by an Efficient Noble-Metal-Free Bifunctional Electrocatalyst.

    Science.gov (United States)

    You, Bo; Jiang, Nan; Liu, Xuan; Sun, Yujie

    2016-08-16

    As an environmentally friendly approach to generate H2 , electrocatalytic water splitting has attracted worldwide interest. However, its broad employment has been inhibited by costly catalysts and low energy conversion efficiency, mainly due to the sluggish anodic half reaction, the O2 evolution reaction (OER), whose product O2 is not of significant value. Herein, we report an efficient strategy to replace OER with a thermodynamically more favorable reaction, the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), catalyzed by 3D Ni2 P nanoparticle arrays on nickel foam (Ni2 P NPA/NF). HMF is one of the primary dehydration intermediates of raw biomass and FDCA is of many industrial applications. As a bifunctional electrocatalyst, Ni2 P NPA/NF is not only active for HMF oxidation but also competent for H2 evolution. In fact, a two-electrode electrolyzer employing Ni2 P NPA/NF for simultaneous H2 and FDCA production required a voltage at least 200 mV smaller compared with pure water splitting to achieve the same current density, as well as exhibiting robust stability and nearly unity Faradaic efficiencies.

  14. Characterization and Hydrodesulfurization Properties of Catalysts Derived from Amorphous Metal-boron Materials

    Energy Technology Data Exchange (ETDEWEB)

    Parks, Greg; Pease, Melissa; Layman, Kathryn A.; Burns, Autumn W.; Bussell, Mark E.; Wang, Xianqin; Hanson, Jonathan; Rodriguez, Jose A.

    2007-01-22

    Unsupported and silica-supported amorphous metal-boron materials (Ni-B, Mo-O-B, and Ni-Mo-O-B) were prepared by NaBH4 reduction of aqueous or impregnated metal salts. The resulting materials were characterized by a range of techniques, including conventional and time-resolved X-ray diffraction. The latter technique was used to determine the onset of crystallization of the amorphous materials during annealing in He flow and to identify the phases formed. Annealing of unsupported Ni-B resulted in the crystallization of predominantly Ni3B, followed by Ni metal, whereas Ni-B/SiO2 formed Ni and then NiO. There was no evidence for crystallization of B-containing phases for Mo-O-B or Mo-O-B/SiO2 on annealing; instead, the predominant phase formed was MoO2. In general, the phases formed for Ni-Mo-O-B and Ni-Mo-O-B/SiO2 were consistent with those formed in the monometallic materials, but at higher annealing temperatures. Catalysts prepared by sulfiding Ni-B/SiO2 and Ni-Mo-O-B/SiO2 materials had significantly higher thiophene HDS activities than conventionally prepared sulfided Ni/SiO2 and Ni-Mo/SiO2 catalysts, whereas a sulfided Mo-O-B/SiO2 catalyst had a dramatically lower HDS activity than a sulfided Mo/SiO2 catalyst.

  15. Hydrogenation of fructose to 2,5-dimethyltetrahydrofuran using a sulfur poisoned Pt/C catalyst

    Science.gov (United States)

    In order to expand the number of biobased chemicals available, fructose has been hydrogenated to 2,5-dimethyltetrahydrofuran using a sulfided Pt/C catalyst. The reaction was carried out in a stirred reactor at 10.3 MPa H2 and 175°C which allowed a 10% fructose solution to be converted in about 2 h. ...

  16. Insights into the dual activation mechanism involving bifunctional cinchona alkaloid thiourea organocatalysts: an NMR and DFT study.

    Science.gov (United States)

    Zhu, Jun-Ling; Zhang, Yong; Liu, Chong; Zheng, An-Min; Wang, Wei

    2012-11-02

    In-depth understanding of the activation mechanism in asymmetric organocatalysis is of great importance for rational development of highly efficient catalytic systems. In this Article, the mechanism for the direct vinylogous Michael reaction of α,β-unsaturated γ-butyrolactam (Nu) and chalcone (EI) catalyzed by the bifunctional cinchona alkaloid thiourea organocatalyst (Cat) was studied with a combination of experimental (NMR) and theoretical (DFT) approaches, through which a new dual activation pathway was found. The key feature of this new dual activation mechanism (Pathway C) is that one N-H(A) of the thiourea moiety and the N-H of the protonated amine in Cat simultaneously activate Nu, while the other N-H(B) of the thiourea moiety activates EI. Both the NMR measurement and the DFT calculation identified that the interaction of Cat with Nu is stronger than that with EI in the catalyst-substrate complexes. Kinetic studies via variable-temperature NMR measurements indicated that, with the experimental activation energy E(a) of 10.2 kcal/mol, the reaction is all first-order in Nu, EI, and Cat. The DFT calculation further revealed that the C-C bond formation is both the rate-determining and the stereoselectivity-controlling steps. In agreement with the experimental data, the energy barrier for the rate-determining step along Pathway C was calculated as 8.8 kcal/mol. The validity of Pathway C was further evidenced by the calculated enantioselectivity (100% ee) and diastereoselectivity (60:1 dr), which are in excellent match with the experimental data (98% ee and >30:1 dr, respectively). Mechanistic study on the Michael addition of nitromethane to chalcone catalyzed by the Catalyst I further identified the generality of this new dual activation mechanism in cinchona alkaloid thiourea organocatalysis.

  17. Hydrogen sulfide and translational medicine

    OpenAIRE

    Guo, Wei; Cheng, Ze-yu; Zhu, Yi-Zhun

    2013-01-01

    Hydrogen sulfide (H2S) along with carbon monoxide and nitric oxide is an important signaling molecule that has undergone large numbers of fundamental investigations. H2S is involved in various physiological activities associated with the regulation of homeostasis, vascular contractility, pro- and anti-inflammatory activities, as well as pro- and anti-apoptotic activities etc. However, the actions of H2S are influenced by its concentration, reaction time, and cell/disease types. Therefore, H2S...

  18. Redox Biochemistry of Hydrogen Sulfide*

    OpenAIRE

    Kabil, Omer; Banerjee, Ruma

    2010-01-01

    H2S, the most recently discovered gasotransmitter, might in fact be the evolutionary matriarch of this family, being both ancient and highly reduced. Disruption of γ-cystathionase in mice leads to cardiovascular dysfunction and marked hypertension, suggesting a key role for this enzyme in H2S production in the vasculature. However, patients with inherited deficiency in γ-cystathionase apparently do not present vascular pathology. A mitochondrial pathway disposes sulfide and couples it to oxid...

  19. Highly Efficient Biomimetic Oxidation of Sulfide to Sulfone by Hydrogen Peroxide in the Presence of Manganese meso-Tetraphenylporphyrin

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Xian-Tai; JI,Hong-Bing; YUAN,Qiu-Lan; XU,Jian-Chang; PEI,Li-Xia; WANG,Le-Fu

    2008-01-01

    Low amount of manganese meso-tetraphenyl porphyrin [Mn(TPP)] was used for highly efficient selective oxidation of sulfide to sulfone by hydrogen peroxide at room temperature.Sulfones were produced directly with yields generally around 90% while the catalyst concentration was only 4 ×10-5 mol·L-1.In a large-scale experiment of thioanisole oxidation,the isolated yield of sulfone (87%) was obtained and the turnover number (TON) reached up to 8×106,which is the highest TON for the oxidation systems of sulfide to sulfone catalyzed by metalloporphyrins.

  20. NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil.

    Science.gov (United States)

    Liu, Jing; He, Jing; Wang, Luying; Li, Rong; Chen, Pan; Rao, Xin; Deng, Lihong; Rong, Long; Lei, Jiandu

    2016-03-29

    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.

  1. Sulfide intrusion and detoxification in seagrasses ecosystems

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    Sulfide intrusion in seagrasses represents a global threat to seagrasses and thereby an important parameter in resilience of seagrass ecosystems. In contrast seegrasses colonize and grow in hostile sediments, where they are constantly exposed to invasion of toxic gaseous sulfide. Remarkably little...... strategies of seagrasses to sustain sulfide intrusion. Using stable isotope tracing, scanning electron microscopy with x-ray analysis, tracing sulfur compounds combined with ecosystem parameters we found different spatial, intraspecific and interspecific strategies to cope with sulfidic sediments. 1...... not present in terrestrial plants at that level. Sulfide is not necessarily toxic but used as sulfur nutrition, presupposing healthy seagrass ecosystems that can support detoxification mechanisms. Presence or absence of those mechanisms determines susceptibility of seagrass ecosystems to sediment sulfide...

  2. Pd Close Coupled Catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhong Hua SHI; Mao Chu GONG; Yao Qiang CHEN

    2006-01-01

    A catalyst comprised novel high surface area alumina support was prepared to control emission of automobiles. The results showed that prepared catalyst could satisfy the requirements of a high performance close coupled catalyst for its good catalytic activity at low temperature and good stability at high temperature.

  3. Effect of Ni on the characteristics and hydrogenation activity of sulfide Mo/{gamma}-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Schachtl, E.; Wuttke, E.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center

    2012-07-01

    The hydrogenation of phenanthrene was explored on sulfide Mo/{gamma}-Al{sub 2}O{sub 3} catalysts promoted with increasing concentrations of Ni. The characterization of the materials was done by N{sub 2}-physisorption, X-ray diffraction, transmission electron microscopy, temperature programmed sulfidation and NO adsorption experiments. Increasing loading of Ni improves the dispersion of MoS{sub 2} species; however, at Ni/(Mo+Ni) molar ratio higher than 0.5, segregation of Ni-sulfides is observed. The presence of Ni also facilitates the sulfidation of oxidic catalyst precursors by lowering the reduction temperature of Mo species. In the sulfide catalysts, Ni changes the structure of MoS{sub 2} leading to shorter slabs with higher stacking degree than on Mo/{gamma}-Al{sub 2}O{sub 3}, and increases the concentration of coordinatively unsaturated sites. The kinetic results (increased hydrogenation rate and changed reaction network in the presence of Ni) suggest that a highly active kind of active site is created by Ni promotion. (orig.)

  4. Hydrogen sulfide is a novel potential virulence factor of Mycoplasma pneumoniae: characterization of the unusual cysteine desulfurase/desulfhydrase HapE.

    Science.gov (United States)

    Großhennig, Stephanie; Ischebeck, Till; Gibhardt, Johannes; Busse, Julia; Feussner, Ivo; Stülke, Jörg

    2016-04-01

    Mycoplasma pneumoniae is a human pathogen causing atypical pneumonia with a minimalized and highly streamlined genome. So far, hydrogen peroxide production, cytadherence, and the ADP-ribosylating CARDS toxin have been identified as pathogenicity determinants. We have studied haemolysis caused by M. pneumoniae, and discovered that hydrogen peroxide is responsible for the oxidation of heme, but not for lysis of erythrocytes. This feature could be attributed to hydrogen sulfide, a compound that has previously not been identified as virulence factor in lung pathogens. Indeed, we observed hydrogen sulfide production by M. pneumoniae. The search for a hydrogen sulfide-producing enzyme identified HapE, a protein with similarity to cysteine desulfurases. In contrast to typical cysteine desulfurases, HapE is a bifunctional enzyme: it has both the cysteine desulfurase activity to produce alanine and the cysteine desulfhydrase activity to produce pyruvate and hydrogen sulfide. Experiments with purified HapE showed that the enzymatic activity of the protein is responsible for haemolysis, demonstrating that HapE is a novel potential virulence factor of M. pneumoniae.

  5. Bifunctional avidin with covalently modifiable ligand binding site.

    Directory of Open Access Journals (Sweden)

    Jenni Leppiniemi

    Full Text Available The extensive use of avidin and streptavidin in life sciences originates from the extraordinary tight biotin-binding affinity of these tetrameric proteins. Numerous studies have been performed to modify the biotin-binding affinity of (streptavidin to improve the existing applications. Even so, (streptavidin greatly favours its natural ligand, biotin. Here we engineered the biotin-binding pocket of avidin with a single point mutation S16C and thus introduced a chemically active thiol group, which could be covalently coupled with thiol-reactive molecules. This approach was applied to the previously reported bivalent dual chain avidin by modifying one binding site while preserving the other one intact. Maleimide was then coupled to the modified binding site resulting in a decrease in biotin affinity. Furthermore, we showed that this thiol could be covalently coupled to other maleimide derivatives, for instance fluorescent labels, allowing intratetrameric FRET. The bifunctional avidins described here provide improved and novel tools for applications such as the biofunctionalization of surfaces.

  6. A novel bifunctional transcriptional regulator of riboflavin metabolism in Archaea.

    Science.gov (United States)

    Rodionova, Irina A; Vetting, Matthew W; Li, Xiaoqing; Almo, Steven C; Osterman, Andrei L; Rodionov, Dmitry A

    2017-01-09

    Riboflavin (vitamin B2) is the precursor of flavin mononucleotide (FMN) and flavin adenine dinucleotide, which are essential coenzymes in all free-living organisms. Riboflavin biosynthesis in many Bacteria but not in Archaea is controlled by FMN-responsive riboswitches. We identified a novel bifunctional riboflavin kinase/regulator (RbkR), which controls riboflavin biosynthesis and transport genes in major lineages of Crenarchaeota, Euryarchaeota and Thaumarchaeota. RbkR proteins are composed of the riboflavin kinase domain and a DNA-binding winged helix-turn-helix-like domain. Using comparative genomics, we predicted RbkR operator sites and reconstructed RbkR regulons in 94 archaeal genomes. While the identified RbkR operators showed significant variability between archaeal lineages, the conserved core of RbkR regulons includes riboflavin biosynthesis genes, known/predicted vitamin uptake transporters and the rbkR gene. The DNA motifs and CTP-dependent riboflavin kinase activity of two RbkR proteins were experimentally validated in vitro The DNA binding activity of RbkR was stimulated by CTP and suppressed by FMN, a product of riboflavin kinase. The crystallographic structure of RbkR from Thermoplasma acidophilum was determined in complex with CTP and its DNA operator revealing key residues for operator and ligand recognition. Overall, this study contributes to our understanding of metabolic and regulatory networks for vitamin homeostasis in Archaea.

  7. Bifunctional alkyl nitrates - trace constituents of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Kastler, J. [Department of Analytical and Environmental Chemistry, University of Ulm (Germany); Ballschmiter, K. [Center of Technology Assessment in Baden-Wuerttemberg, Stuttgart (Germany)

    1998-04-01

    Mono- and multifunctional esters of nitric acid (alkyl nitrates or organonitrates) form very complex mixtures of organic trace constituents in air. An analytical method was developed which combines selectivity in separation and detection in order to simplify this complexity in analytical terms. Mononitrates, dinitrates, keto nitrates, hydroxy nitrates of alkanes and alkenes, respecitvely, and bifunctional terpene nitrates were synthesized as reference substances. A specially developed new HPLC stationary phase (organonitrate phase) allows a group separation of mono-, di-, and hydroxy nitrates. After the HPLC preseparation the single components were finally separated by capillary HRGC-ECD and HRGC-MSD on polar and non-polar stationary phases. Mass spectrometric detection in the selected-ion-mode using the highly selective NO{sub 2}{sup +} fragment (m/z = 46 amu) led to very good selectivities for the nitric acid ester moiety. The analysis of a 100 m{sup 3} ambient air sample using this new analytical protocol allowed the identification of seven hydroxy nitrates and 24 dinitrates ranging from C2 to C7, 22 of them for the first time ever. (orig.) With 3 figs., 3 tabs., 20 refs.

  8. Bioinspired Bifunctional Membrane for Efficient Clean Water Generation.

    Science.gov (United States)

    Liu, Yang; Lou, Jinwei; Ni, Mengtian; Song, Chengyi; Wu, Jianbo; Dasgupta, Neil P; Tao, Peng; Shang, Wen; Deng, Tao

    2016-01-13

    Solving the problems of water pollution and water shortage is an urgent need for the sustainable development of modern society. Different approaches, including distillation, filtration, and photocatalytic degradation, have been developed for the purification of contaminated water and the generation of clean water. In this study, we explored a new approach that uses solar light for both water purification and clean water generation. A bifunctional membrane consisting of a top layer of TiO2 nanoparticles (NPs), a middle layer of Au NPs, and a bottom layer of anodized aluminum oxide (AAO) was designed and fabricated through multiple filtration processes. Such a design enables both TiO2 NP-based photocatalytic function and Au NP-based solar-driven plasmonic evaporation. With the integration of these two functions into a single membrane, both the purification of contaminated water through photocatalytic degradation and the generation of clean water through evaporation were demonstrated using simulated solar illumination. Such a demonstration should also help open up a new strategy for maximizing solar energy conversion and utilization.

  9. Bifunctional drugs for the treatment of asthma and chronic obstructive pulmonary disease.

    Science.gov (United States)

    Page, Clive; Cazzola, Mario

    2014-08-01

    Over the last decade, there has been a steady increase in the use of fixed-dose combinations of drugs for the treatment of a range of diseases, including hypertension, cancer, AIDS, tuberculosis and other infectious diseases. It is now evident that patients with asthma or chronic obstructive pulmonary disease (COPD) can also benefit from the use of fixed-dose combinations, including combinations of a long-acting β2-agonist and an inhaled corticosteroid, and combinations of long-acting β2-agonists and long-acting muscarinic receptor antagonists. In fact, there are now a number of "triple-inhaler" fixed-dose combinations under development, with the first such triple combination having been approved in India. This use of combinations containing drugs with complementary pharmacological actions in the treatment of patients with asthma or COPD has also led to the discovery and development of drugs having two different primary pharmacological actions in the same molecule, which we have called "bifunctional drugs". In this review, we discuss the state of the art of these new bifunctional drugs as novel treatments for asthma and COPD that can be categorised as bifunctional bronchodilators, bifunctional bronchodilator/anti-inflammatory drugs and bifunctional anti-inflammatory drugs.

  10. Single flexible nanofiber to achieve simultaneous photoluminescence-electrical conductivity bifunctionality.

    Science.gov (United States)

    Sheng, Shujuan; Ma, Qianli; Dong, Xiangting; Lv, Nan; Wang, Jinxian; Yu, Wensheng; Liu, Guixia

    2015-02-01

    In order to develop new-type multifunctional composite nanofibers, Eu(BA)3 phen/PANI/PVP bifunctional composite nanofibers with simultaneous photoluminescence and electrical conductivity have been successfully fabricated via electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of Eu(BA)3 phen and polyaniline (PANI). X-Ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), fluorescence spectroscopy and a Hall effect measurement system are used to characterize the morphology and properties of the composite nanofibers. The results indicate that the bifunctional composite nanofibers simultaneously possess excellent photoluminescence and electrical conductivity. Fluorescence emission peaks of Eu(3+) ions are observed in the Eu(BA)3 phen/PANI/PVP photoluminescence-electrical conductivity bifunctional composite nanofibers. The electrical conductivity reaches up to the order of 10(-3)  S/cm. The luminescent intensity and electrical conductivity of the composite nanofibers can be tuned by adjusting the amounts of Eu(BA)3 phen and PANI. The obtained photoluminescence-electrical conductivity bifunctional composite nanofibers are expected to possess many potential applications in areas such as microwave absorption, molecular electronics, biomedicine and future nanomechanics. More importantly, the design concept and construction technique are of universal significance to fabricate other bifunctional one-dimensional naonomaterials.

  11. Hydrogen sulfide and vascular relaxation

    Institute of Scientific and Technical Information of China (English)

    SUN Yan; TANG Chao-shu; DU Jun-bao; JIN Hong-fang

    2011-01-01

    Objective To review the vasorelaxant effects of hydrogen sulfide (H2S) in arterial rings in the cardiovascular system under both physiological and pathophysiological conditions and the possible mechanisms involved.Data sources The data in this review were obtained from Medline and Pubmed sources from 1997 to 2011 using the search terms "hydrogen sulfide" and ""vascular relaxation".Study selection Articles describing the role of hydrogen sulfide in the regulation of vascular activity and its vasorelaxant effects were selected.Results H2S plays an important role in the regulation of cardiovascular tone.The vasomodulatory effects of H2S depend on factors including concentration,species and tissue type.The H2S donor,sodium hydrosulfide (NarS),causes vasorelaxation of rat isolated aortic rings in a dose-dependent manner.This effect was more pronounced than that observed in pulmonary arterial rings.The expression of KATP channel proteins and mRNA in the aortic rings was increased compared with pulmonary artery rings.H2S is involved in the pathogenesis of a variety of cardiovascular diseases.Downregulation of the endogenous H2S pathway is an important factor in the pathogenesis of cardiovascular diseases.The vasorelaxant effects of H2S have been shown to be mediated by activation of KATP channels in vascular smooth muscle cells and via the induction of acidification due to activation of the CI/HCO3 exchanger.It is speculated that the mechanisms underlying the vasoconstrictive function of H2S in the aortic rings involves decreased NO production and inhibition of cAMP accumulation.Conclusion H2S is an important endogenous gasotransmitter in the cardiovascular system and acts as a modulator of vascular tone in the homeostatic regulation of blood pressure.

  12. Electrochemical Investigation of Interaction between a Bifunctional Probe and GG Mismatch Duplex.

    Science.gov (United States)

    Li, Jiao; He, Hanping; Peng, Xiaoqian; Huang, Min; Zhang, Xiuhua; Wang, Shengfu

    2015-01-01

    A bifunctional probe (FecNC), containing a recognition part and an electrochemical active center, was applied to electrochemical detection of GG mismatch duplexes. The preparation of gold electrodes modified by mismatch and complementatry duplexes was characterized by electrochemical impedance spectroscopy (EIS) and optimized for better detection in terms of self-assembly time, hybridization time, and incubation time. The interaction between FecNC and DNA duplexes modified on the surface of a gold electrode was explored by square wave voltammetry (SWV) and EIS. The results showed that the DNA duplexes with GG mismatch on the surface of a gold electrode was easily detected by the largest electrochemical signal of the bifunctional probe because of its selective binding to GG mismatches. The bifunctional probe could offer a simple, effective electrochemical detection of GG mismatches, and theoretical bases for development of electrochemical biosensors. Further, the method would be favorable for diagnosis of genetic diseases.

  13. Laccase-mediated oxidation of small organics: bifunctional roles for versatile applications.

    Science.gov (United States)

    Jeon, Jong-Rok; Chang, Yoon-Seok

    2013-06-01

    Laccases have been widely used in several biotechnological areas, including organic synthesis, bioremediation, and pulp/textile bleaching. In most applications, the enzymatic actions start with single-electron oxidation of small organics followed by formation of the corresponding radicals. These radicals are subsequently involved in either oxidative coupling (i.e., bond formation) or bond cleavage of target organics. These bifunctional actions--catabolic versus anabolic--are readily identifiable in in vivo metabolic processes involving laccases. Here, we characterize the bifunctionality of laccase-mediated oxidation of small organics and present the view that knowledge of the biological functions of these metabolic processes in vivo can illuminate potential biotechnological applications of this bifunctionality.

  14. Medical Functions of Hydrogen Sulfide.

    Science.gov (United States)

    Olas, Beata

    2016-01-01

    Hydrogen sulfide (H(2)S) is a gasomediator synthesized from L- and D-cysteine in various tissues. It is involved in a number of physiological and pathological processes. H(2)S exhibits antiatherosclerotic, vasodilator, and proangiogenic properties, and protects the kidney and heart from damage following ischemia/reperfusion injury. H(2)S donors may be natural or synthetic, and may be used for the safe treatment of a wide range of diseases. This review article summarizes the current state of knowledge of the therapeutic function of H(2)S.

  15. Nano-structured noble metal catalysts based on hexametallate architecture for the reforming of hydrocarbon fuels

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, Todd H.

    2015-09-15

    Nano-structured noble metal catalysts based on hexametallate lattices, of a spinel block type, and which are resistant to carbon deposition and metal sulfide formation are provided. The catalysts are designed for the reforming of hydrocarbon fuels to synthesis gas. The hexametallate lattices are doped with noble metals (Au, Pt, Rh, Ru) which are atomically dispersed as isolated sites throughout the lattice and take the place of hexametallate metal ions such as Cr, Ga, In, and/or Nb. Mirror cations in the crystal lattice are selected from alkali metals, alkaline earth metals, and the lanthanide metals, so as to reduce the acidity of the catalyst crystal lattice and enhance the desorption of carbon deposit forming moieties such as aromatics. The catalysts can be used at temperatures as high as 1000.degree. C. and pressures up to 30 atmospheres. A method for producing these catalysts and applications of their use also is provided.

  16. Highly efficient redox isomerisation of allylic alcohols catalysed by pyrazole-based ruthenium(IV) complexes in water: mechanisms of bifunctional catalysis in water.

    Science.gov (United States)

    Bellarosa, Luca; Díez, Josefina; Gimeno, José; Lledós, Agustí; Suárez, Francisco J; Ujaque, Gregori; Vicent, Cristian

    2012-06-18

    The catalytic activity of ruthenium(IV) ([Ru(η(3):η(3)-C(10)H(16))Cl(2)L]; C(10)H(16) = 2,7-dimethylocta-2,6-diene-1,8-diyl, L = pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, 2-(1H-pyrazol-3-yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η(6)-arene)Cl(2)(3,5-dimethylpyrazole)]; arene = C(6)H(6), p-cymene or C(6)Me(6)) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10-60 min, turn-over frequency = 750-3000 h(-1)) and, in some cases, at 35 °C in 60 min. The nature of the aqueous species formed in water by this complex has been analysed by ESI-MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)]. Different competitive pathways based on outer-sphere mechanisms, which imply hydrogen-transfer processes, have been analysed. The overall isomerisation implies two hydrogen-transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer-sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The

  17. Ammonia and hydrogen sulfide removal using biochar

    Science.gov (United States)

    Reducing ammonia and hydrogen sulfide emissions from livestock facilities is an important issue for many communities and livestock producers. Ammonia has been regarded as odorous, precursor for particulate matter (PM), and contributed to livestock mortality. Hydrogen sulfide is highly toxic at elev...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-04

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

  19. Energy Storage in Bifunctional TiO2 Composite Materials under UV and Visible Light

    Directory of Open Access Journals (Sweden)

    Jialin Li

    2009-11-01

    Full Text Available This paper provides an overview of recent studies on energy storage in bifunctional TiO2 composite materials under UV and visible light. The working mechanism, property improvements and applications of these bifunctional TiO2 composite systems are introduced, respectively. The latest results obtained in our laboratory, especially a new process for photoelectric conversion and energy storage in TiO2/Cu2O bilayer films under visible light, are also presented. Hopefully this review will stimulate more fundamental and applied research on this subject in the future.

  20. Sulfide toxicity kinetics of a uasb reactor

    Directory of Open Access Journals (Sweden)

    D. R. Paula Jr.

    2009-12-01

    Full Text Available The effect of sulfide toxicity on kinetic parameters of anaerobic organic matter removal in a UASB (up-flow anaerobic sludge blanket reactor is presented. Two lab-scale UASB reactors (10.5 L were operated continuously during 12 months. The reactors were fed with synthetic wastes prepared daily using glucose, ammonium acetate, methanol and nutrient solution. One of the reactors also received increasing concentrations of sodium sulfide. For both reactors, the flow rate of 16 L.d-1 was held constant throughout the experiment, corresponding to a hydraulic retention time of 15.6 hours. The classic model for non-competitive sulfide inhibition was applied to the experimental data for determining the overall kinetic parameter of specific substrate utilization (q and the sulfide inhibition coefficient (Ki. The application of the kinetic parameters determined allows prediction of methanogenesis inhibition and thus the adoption of operating parameters to minimize sulfide toxicity in UASB reactors.

  1. Increased photocatalytic activity of Zn(II)/Cu(II) oxides and sulfides by coupling and supporting them onto clinoptilolite nanoparticles in the degradation of benzophenone aqueous solution.

    Science.gov (United States)

    Esmaili-Hafshejani, Javad; Nezamzadeh-Ejhieh, Alireza

    2016-10-05

    Photocatalytic activity of the coupled ZnO-CuO and ZnS-CuS semiconductors supported onto clinoptilolite nanoparticles (CNP) and micronized one (CMP) was studied in photodegradation of benzophenone (BP) aqueous solution. The ZnO-CuO/CNP (or MCP) and ZnS-CuS/CNP (or MCP) catalysts were prepared via calcination and sulfiding of their Zn(II)-Cu(II) ion-exchanged samples, respectively. XRD patterns confirmed loading of the mentioned semiconductors onto the zeolite, and nano dimension of the catalysts was confirmed by XRD and TEM results. Typical Tauc plots obtained from UV-vis DRS spectra showed red shifts for the band gap energies of the supported coupled semiconductors with respect to the supported monocomponent ones especially for ZnO/NCP and ZnS/NCP catalysts. Also, in both indirect and direct transitions, these red shifts were more considerable in the oxidic systems with respect to the sulfidic systems. Accordingly, the supported oxidic systems showed better photocatalytic activity than the sulfidic one. In the oxidic systems changing the dose of CuO played important role while in the sulfidic systems ZnS played considerable role in the degradation of BP. In the used systems, CuO and ZnS played the main e/h generators in the oxidic and sulfidic systems, respectively, while ZnO and CuS played the preventer e/h recombination. Based on the results, production of e/h is the rate limiting step in the used systems. The maximum degradation activity of the catalysts was obtained at: 0.12gL(-1) of ZnO0.80-CuO3.18/NCP and 0.10gL(-1) of ZnS1.39-CuS2.88/NCP catalysts, initial BP concentration of 30mgL(-1) at pH 7.5.

  2. The sulfide ore looping oxidation process: An alternative to current roasting and smelting practice

    Science.gov (United States)

    McHugh, Larry F.; Balliett, Robert; Mozolic, Jean A.

    2008-07-01

    This novel method utilizes the reactions of metal sulfides and metal oxides. It is applicable to single-metal systems such as Mo, Cu, Co, Ni, Fe, and Zn individual sulfides and to mixed sulfides such as chalcopyrite and Mo/Fe. In addition to primary ores, waste stream products such as spent catalysts can be effectively processed. The benchmark work done on MoS2/MoO3 resulted in an MoO2 product with less than 0.095 wt.% sulfur. Other sulfide concentrate materials showed similar results. In the first stage of the looping process, a highly concentrated SO2 off-gas stream is produced that could be directed to an acid plant or converted to liquid. The products from the first process step can be directed down line for further processing or can be used as is. In the second step of looping oxidation, the product is oxidized back to its fully oxidized state and is mainly looped back to drive the oxidation process in the first reaction. There are also several opportunities for energy recovery and conversion, making looping oxidation an energy-efficient process.

  3. Effect of temperature in hydrocracking of light cycle oil on a noble metal-supported catalyst for fuel production

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, A.; Arandes, J.M.; Castano, P.; Olazar, M.; Bilbao, J. [Universidad del Pais Vasco (UPV-EHU), Departamento de Ingenieria Quimica, Bilbao (Spain); Barona, A. [Universidad del Pais Vasco (UPV-EHU), Escuela de Ingenieria, Departamento de Ingenieria Quimica y Medio Ambiente, Alda, Urkijo s/n, Bilbao (Spain)

    2012-04-15

    The effect of temperature has been studied in hydrocracking of light cycle oil (LCO), byproduct of fluidized catalytic cracking (FCC) units on a bifunctional catalyst (Pt-Pd/HY zeolite). The increase in both temperature and H{sub 2} partial pressure have an important attenuating effect on catalyst deactivation, given that they decrease sulfur equilibrium adsorption and enhance hydrocracking of coke precursors. Therefore, the catalyst maintains significant hydrodesulfurization and hydrocracking activity. As the temperature is increased, hydrocracking conversion and naphtha selectivity increase, although there is no significant dearomatization of the medium distillate fraction in the range of the studied experimental conditions. 400 C is the more suitable temperature for obtaining a high yield of naphtha with a high content of i-paraffins. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Catalyst Alloys Processing

    Science.gov (United States)

    Tan, Xincai

    2014-10-01

    Catalysts are one of the key materials used for diamond formation at high pressures. Several such catalyst products have been developed and applied in China and around the world. The catalyst alloy most widely used in China is Ni70Mn25Co5 developed at Changsha Research Institute of Mining and Metallurgy. In this article, detailed techniques for manufacturing such a typical catalyst alloy will be reviewed. The characteristics of the alloy will be described. Detailed processing of the alloy will be presented, including remelting and casting, hot rolling, annealing, surface treatment, cold rolling, blanking, finishing, packaging, and waste treatment. An example use of the catalyst alloy will also be given. Industrial experience shows that for the catalyst alloy products, a vacuum induction remelt furnace can be used for remelting, a metal mold can be used for casting, hot and cold rolling can be used for forming, and acid pickling can be used for metal surface cleaning.

  5. Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis.

    Science.gov (United States)

    Kumar, Manoj; Francisco, Joseph S

    2016-03-18

    The role of metal free dual catalysis in the hydrogen sulfide (H2S)-induced activation of carbon dioxide (CO2) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus.

  6. The hydrogen sulfide emissions abatement program at the Geysers Geothermal Power Plant

    Science.gov (United States)

    Allen, G. W.; Mccluer, H. K.

    1974-01-01

    The scope of the hydrogen sulfide (H2S) abatement program at The Geysers Geothermal Power Plant and the measures currently under way to reduce these emissions are discussed. The Geysers steam averages 223 ppm H2S by weight and after passing through the turbines leaves the plant both through the gas ejector system and by air-stripping in the cooling towers. The sulfide dissolved in the cooling water is controlled by the use of an oxidation catalyst such as an iron salt. The H2S in the low Btu ejector off gases may be burned to sulfur dioxide and scrubbed directly into the circulating water and reinjected into the steam field with the excess condensate. Details are included concerning the disposal of the impure sulfur, design requirements for retrofitting existing plants and modified plant operating procedures. Discussion of future research aimed at improving the H2S abatement system is also included.

  7. Pt-Re-Sn/Al{sub 2}O{sub 3} trimetallic catalysts for naphtha reforming processes without presulfiding step

    Energy Technology Data Exchange (ETDEWEB)

    Mazzieri, V.A.; Grau, J.M.; Vera, C.R.; Yori, J.C.; Parera, J.M.; Pieck, C.L. [Instituto de Investigaciones en Catalisis y Petroquimica, INCAPE, FIQ-UNL, CONICET, Santiago del Estero 2654, 3000 Santa Fe (Argentina)

    2005-12-12

    The n-heptane reforming and the cyclopentane hydrogenolysis reactions over noble metal monometallic catalysts (0.3% Pt), bimetallic catalysts (0.3% Pt, x% Re, x=0.1, 0.3, 0.9 and 2.0, sulfided) and trimetallic catalysts (0.3% Pt, 0.3% Re, y% Sn, y=0.1, 0.3, 0.6 and 0.9, unsulfided) were studied. The metal function was supported over a chlorided {gamma}-alumina that provided the acid function. The reforming of n-heptane was performed at 450{sup o}C, molar ratio H{sub 2}/n-C{sub 7}=4 and WHSV=7.3 while the hydrogenolysis of cyclopentane was performed at 350{sup o}C, H{sub 2}/CP=20 and WHSV=2.4. The sulfided 0.3Pt-0.3Re catalyst (with 0.06% S) was found to be the best performing bimetallic one. It had a great stability, typical of this kind of catalysts, and also produced a reformate with a high iso-heptanes/toluene ratio. This is advantageous for fulfilling the current environmental regulations that limit the amount of aromatic hydrocarbons in reformulated gasolines. The best trimetallic catalyst was 0.3Pt-0.3Re-0.6Sn which had a similar activity and selectivity as sulfided 0.3Pt-0.3Re, though it displayed a higher stability and a lower hydrogenolysis activity, without the need of presulfidation. Tin affected the metal and acid functions of the catalyst simultaneously and inhibited them to such different degrees that a very convenient metal/acid activity ratio was obtained, resulting in an improvement of the activity, selectivity and stability of the catalysts. It can be concluded that it is possible to prepare trimetallic naphtha reforming catalysts of the Pt-Re-Sn kind with a better performance than conventional sulfided Pt-Re catalysts and with the additional advantage that they do not need complicated sulfiding pretreatments. This simplifies the commercial operation of the reformer unit and enables the application of this catalyst to continuously operated processes.

  8. The functionalities of Pt/{gamma}-Al{sub 2}O{sub 3} catalysts in simultaneous HDS and HDA reactions

    Energy Technology Data Exchange (ETDEWEB)

    V.G. Baldovino-Medrano; Sonia A. Giraldo; Aristobulo Centeno [Universidad Industrial de Santander (UIS), Bucaramanga (Colombia). Centro de Investigaciones en Catalisis (CICAT)

    2008-08-15

    A Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was tested in simultaneous hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of naphthalene reactions. Samples of it were subjected to different pretreatments: reduction, reduction-sulfidation, sulfidation with pure H{sub 2}S and non-activation. The reduced catalyst presented the best performance, even comparable to that of Co(Ni)Mo catalysts. All catalyst samples were selective to the HDS reaction over HDA, and to the direct desulfurization pathway of dibenzothiophene HDS over the hydrogenation reaction pathway of HDS. The effect of H{sub 2}S partial pressure on the functionalities of the reduced Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied. The results showed that an increase in H{sub 2}S partial pressure does not cause poisoning, but an inhibition effect, without changing the catalyst selectivity. Accordingly, the activity trends were ascribed to adsorption differences between the different reactive molecules over the same catalytic active site. TPR characterization along with a thermodynamics analysis showed that the active phase of reduced Pt/{gamma}-Al{sub 2}O{sub 3} is constituted by Pt{sup 0} particles. However, presulfidation of the catalyst leads to a mixture of PtS and Pt{sup 0}which has a negative effect on the catalytic performance without changing catalyst functionalities. 61 refs., 4 figs., 1 tab.

  9. Resin Catalyst Hybrids

    Institute of Scientific and Technical Information of China (English)

    S. Asaoka

    2005-01-01

    @@ 1Introduction: What are resin catalyst hybrids? There are typically two types of resin catalyst. One is acidic resin which representative is polystyrene sulfonic acid. The other is basic resin which is availed as metal complex support. The objective items of this study on resin catalyst are consisting of pellet hybrid, equilibrium hybrid and function hybrid of acid and base,as shown in Fig. 1[1-5].

  10. Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides

    Science.gov (United States)

    Wohlgemuth-Ueberwasser, Cora C.; Fonseca, Raúl O. C.; Ballhaus, Chris; Berndt, Jasper

    2013-01-01

    Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic-ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO1.5, and the resistance of Cu2S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ + 1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.

  11. Organusulfur Catalysis With Reduced Molybdenum Sulfides Containing the Mo6S8 Cluster

    Energy Technology Data Exchange (ETDEWEB)

    Paskach, Thomas Jay [Iowa State Univ., Ames, IA (United States)

    2002-08-27

    Industrial synthesis of sulfur-containing organic chemicals basically focuses on the broad categories of mercaptans (thiols), alkylsulfides (thioethers), polysulfides, and thiophenes. Of the organo-sulfur compounds produced, by far the most important in terms of quantities produced is methyl mercaptan (methanethiol or MeSH), which is produced mainly for the downstream production of methionine and methanesulfonyl chloride. Higher thiols are also used in the manufacture of rubber and plastics as polymerization regulators, chain transfer agents, or initiators. Other important organosulfur chemicals are dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), both of which are used extensively for presulfiding of industrial hydroprocessing catalysts, and substituted thiophenes which are used as intermediates for production of agrochemicals, dyes, and pharmaceuticals. Thiols are produced commercially at the rate of about 104 ton/yr from hydrogen sulfide (H2S) and alcohols or olefins, using homogeneous free-radical synthesis, or heterogeneous catalysts based on solid acids or supported metal oxides and/or sulfides. Despite this large production rate, and the industrial importance of the organosulfur compounds, only limited research has been devoted to the development of new catalytic materials for their synthesis. Additionally, for most organosulfur catalytic reactions, only limited information exists about reaction mechanisms, active sites, adsorbed surface species, and especially the nature of the catalysts under reaction conditions.

  12. Characterization and evaluation of Pt-Ru catalyst supported on multi-walled carbon nanotubes by electrochemical impedance

    Energy Technology Data Exchange (ETDEWEB)

    Ocampo, A.L.; Miranda-Hernandez, M.; Sebastian, P.J. [Centro de Investigacion en Energia-UNAM, Temixco, 62580 Morelos (Mexico); Morgado, J.; Montoya, J.A. [IMP, Eje Central Lazaro Cardenas 152, 07730 D.F. Mexico (Mexico)

    2006-10-06

    In this work the authors present the results of a systematic characterization and evaluation of the carbon nanotube supported Pt-Ru (Pt-Ru/CNT) for its use as methanol oxidation catalyst. Its activity was compared with that of Pt and Pt-Ru catalysts supported on Vulcan and synthesized from carbonyl precursors, and another commercial Pt-Ru catalyst. The cyclic voltammetry, CO stripping and electrochemical impedance techniques were employed to determine the electrocatalytic activity of the catalysts. The electrochemical studies were performed in 0.5M H{sub 2}SO{sub 4} containing different concentrations of methanol (0.05-1M). The results showed a noticeable influence of the catalyst support (CNT) on the performance of the catalyst for CO oxidation. The electrochemical impedance studies allowed us to separate the different steps in the methanol oxidation reaction and to control these steps or reactions by varying the applied potential and the methanol concentration. At low methanol concentration and potentials the de-hydrogenation of methanol predominated. But, at high potential and methanol concentrations, the CO oxidation predominated. These results allowed us to clearly describe at what potential and concentration ranges the bi-functional effect of Ru becomes evident. Our results indicated that the CO oxidation occurs both on Pt and Ru. Compared to other catalysts, Pt-Ru supported on carbon nanotubes showed superior catalytic activity for CO and methanol oxidation. (author)

  13. 21 CFR 177.2490 - Polyphenylene sulfide resins.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyphenylene sulfide resins. 177.2490 Section 177... Components of Articles Intended for Repeated Use § 177.2490 Polyphenylene sulfide resins. Polyphenylene sulfide resins (poly(1,4-phenylene sulfide) resins) may be safely used as coatings or components...

  14. States of Carbon Nanotube Supported Mo-Based HDS Catalysts

    Institute of Scientific and Technical Information of China (English)

    Hongyan Shang; Chenguang Liu; Yongqiang Xu; Jieshan Qiu; Fei Wei

    2006-01-01

    The dispersion of the active phase and loading capacity of the Mo species on carbon nanotube (CNT) was studied by the XRD technique. The reducibility properties of Co-Mo catalysts in the oxide state over CNTs were investigated by TPR, while the sulfided Co-Mo/CNT catalysts were characterized by means of the XRD and LRS techniques. The activity and selectivity with respect to the hydrodesulfurization (HDS) performances on carbon nanotube supported Co-Mo catalysts were evaluated. It was found that the main active molybdenum species in the oxide state MoO3/CNT catalysts were MoO2, but not MoO3, as generally expected. The maximum loading before the formation of the bulk phase was lower than 6% (percent by mass, based on MoO3). TPR studies revealed that the active species in the oxide state Co-Mo/CNT catalysts were reduced more easily at relatively lower temperatures in comparison to those of the Co-Mo/γ-Al2O3 catalysts, indicating that the CNT support promoted or favored the reduction of the active species. The active species of a Co-Mo-0.7/CNT catalyst were more easily reduced than those of the Co-Mo/CNT catalysts with Co/Mo atomic ratios of 0.2, 0.35, and 0.5, respectively, suggesting that the Co/Mo atomic ratio has a great effect on the reducibility of the active species. It was found that the incorporation of cobalt improved the dispersion of the molybdenum species on the support, and a phenomenon of mobilization and re-dispersion had occurred during the sulfurization process, resulting in low valence state Mo3S4 and Co-MoS2.17 active phases. HDS measurements showed that the Co-Mo/CNT catalysts were more active than the Co-Mo/γ-Al2O3 ones for the desulfurization of DBT, and the hydrogenolysis/hydrogenation selectivity of the Co-Mo/CNT catalysts was also much higher than those of the Co-Mo/γ-Al2O3. The Co-Mo/CNT catalyst with a Co/Mo atomic ratio of 0.7 showed the highest activity, whereas the catalyst with a Co/Mo atomic ratio of 0.35 had the highest selectivity.

  15. Adequate hydrogen sulfide, healthy circulation

    Institute of Scientific and Technical Information of China (English)

    DU Jun-bao; CHEN Stella; JIN Hong-fang; TANG Chao-shu

    2011-01-01

    Previously,hydrogen sulfide (H2S) was considered to be a toxic gas.However,recently it was discovered that it could be produced in mammals and even in plants,throughtheproductionandmetabolismof sulfur-containing amino acids.In mammals,H2S is mainly catalyzed by cystathionine-γ-lyase (CSE),cystathionin-β-lyase (CBS) and 3-mercaptopyruvate sulfurtransferase (MPST) with the substrate of L-cysteine.Endogenous H2S exerts many important physiological and pathophysiological functions,including hypotensive action,vasorelaxation,myocardial dilation,inhibition of smooth muscle cell proliferation,and antioxidatve actions.Importantly,it plays a very important role in the pathogenesis of systemic hypertension,pulmonary hypertension,atherosclerosis,myocardialinjury,angiogenesis,hyperhomocysteinemi aandshock.Therefore,H2S is now being considered to be a novel gasotransmitter after nitric oxide and carbon monoxide in the regulation of circulatory system.

  16. Redox biochemistry of hydrogen sulfide.

    Science.gov (United States)

    Kabil, Omer; Banerjee, Ruma

    2010-07-16

    H(2)S, the most recently discovered gasotransmitter, might in fact be the evolutionary matriarch of this family, being both ancient and highly reduced. Disruption of gamma-cystathionase in mice leads to cardiovascular dysfunction and marked hypertension, suggesting a key role for this enzyme in H(2)S production in the vasculature. However, patients with inherited deficiency in gamma-cystathionase apparently do not present vascular pathology. A mitochondrial pathway disposes sulfide and couples it to oxidative phosphorylation while also exposing cytochrome c oxidase to this metabolic poison. This report focuses on the biochemistry of H(2)S biogenesis and clearance, on the molecular mechanisms of its action, and on its varied biological effects.

  17. Purification, characterization, and cloning of a bifunctional molybdoenzyme with hydratase and alcohol dehydrogenase activity

    NARCIS (Netherlands)

    Jin, J.; Straathof, A.J.J.; Pinkse, M.W.H.; Hanefeld, U.

    2010-01-01

    A bifunctional hydratase/alcohol dehydrogenase was isolated from the cyclohexanol degrading bacterium Alicycliphilus denitrificans DSMZ 14773. The enzyme catalyzes the addition of water to α,β-unsaturated carbonyl compounds and the subsequent alcohol oxidation. The purified enzyme showed three subun

  18. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    DEFF Research Database (Denmark)

    Li, Hu; Khokarale, Santosh Govind; Kotni, Ramakrishna;

    2014-01-01

    carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl...

  19. Design and Synthesis of Bifunctional Oxime Reactivators of OP- inhibited Cholinesterase

    Science.gov (United States)

    2013-08-01

    military and civilian personnel. Reactivators of OP inhibited cholinesterases can serve as OP agent antidotes but can be limited by their poor...assisted bifunctional catalytic mechanism 46 O N O N OH 11 REPORTABLE OUTCOMES: None CONCLUSION: We have successfully evaluated the synthetic

  20. High surface area carbon for bifunctional air electrodes applied in zinc-air batteries

    Energy Technology Data Exchange (ETDEWEB)

    Arai, H. [on leave from NTT Laboratories (Japan); Mueller, S.; Haas, O. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Bifunctional air electrodes with high surface area carbon substrates showed low reduction overpotential, thus are promising for enhancing the energy efficiency and power capability of zinc-air batteries. The improved performance is attributed to lower overpotential due to diffusion of the reaction intermediate, namely the peroxide ion. (author) 1 fig., 2 refs.

  1. Solvent free depolymerization of Kraft lignin to alkyl-phenolics using supported NiMo and CoMo catalysts

    NARCIS (Netherlands)

    Kumar, Chowdari Ramesh; Anand, Narani; Kloekhorst, Arjan; Cannilla, Catia; Bonura, Giuseppe; Frusteri, Francesco; Barta, Katalin; Heeres, Hero Jan

    2015-01-01

    The catalytic hydrotreatment of Kraft lignin using sulfided NiMo and CoMo catalysts on different acidic and basic supports (Al2O3, ZSM-5, activated carbon (AC) and MgO-La2O3) was studied in the absence of a solvent. Experiments were carried out in a batch set-up at a reaction temperature of 350 degr

  2. Highly dispersed CoMoS phase on titania nanotubes as efficient HDS catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cortes-Jacome, M.A.; Escobar, J.; Angeles Chavez, C.; Lopez-Salinas, E.; Romero, E.; Ferrat, G.; Toledo-Antonio, J.A. [Molecular Engineering Program, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, G.A. Madero, 07730 Mexico, D.F. (Mexico)

    2008-01-15

    Nanotubular titania (NT) to be used as support for CoMo-based hydrodesulfurization (HDS) catalyst was synthesized and characterized by various techniques. NT annealed at 400 C (under nitrogen) was constituted by nanotubes of {proportional_to}5.5 nm (internal diameter) and retained 236 m{sup 2}/g of surface area. Mo at 3 atoms/nm{sup 2} (nominal loading) and cobalt at Co/(Co + Mo) = 0.3 were impregnated under nearly neutral, acidic or basic media. By XPS analyses of NT-supported sulfided catalysts, highly dispersed MoS{sub 2} particles of low stacking degree (1-2 slabs) aligned along the nanotubes were observed by HR-TEM in all sulfided materials. The CoMo catalysts supported on nanostructured titania had dibenzothiophene (DBT) HDS activity (in pseudo first order kinetic constant basis) values {proportional_to}1.35 and {proportional_to}1.7 times (Mo impregnated under near neutral and basic media, respectively) higher to that of a commercial reference with alumina carrier. According to shifts to higher binding energy of the Co 2p peak corresponding to sulfided cobalt (as determined by XPS), MoS{sub 2} dispersed on NT support could be efficiently promoted by Co (''CoMoS'' phase formation), opening the possibility of developing new highly active HDS catalysts. (author)

  3. Bifunctional heterogeneous catalysis of silica-alumina-supported tertiary amines with controlled acid-base interactions for efficient 1,4-addition reactions.

    Science.gov (United States)

    Motokura, Ken; Tanaka, Satoka; Tada, Mizuki; Iwasawa, Yasuhiro

    2009-10-19

    We report the first tunable bifunctional surface of silica-alumina-supported tertiary amines (SA-NEt(2)) active for catalytic 1,4-addition reactions of nitroalkanes and thiols to electron-deficient alkenes. The 1,4-addition reaction of nitroalkanes to electron-deficient alkenes is one of the most useful carbon-carbon bond-forming reactions and applicable toward a wide range of organic syntheses. The reaction between nitroethane and methyl vinyl ketone scarcely proceeded with either SA or homogeneous amines, and a mixture of SA and amines showed very low catalytic activity. In addition, undesirable side reactions occurred in the case of a strong base like sodium ethoxide employed as a catalytic reagent. Only the present SA-supported amine (SA-NEt(2)) catalyst enabled selective formation of a double-alkylated product without promotions of side reactions such as an intramolecular cyclization reaction. The heterogeneous SA-NEt(2) catalyst was easily recovered from the reaction mixture by simple filtration and reusable with retention of its catalytic activity and selectivity. Furthermore, the SA-NEt(2) catalyst system was applicable to the addition reaction of other nitroalkanes and thiols to various electron-deficient alkenes. The solid-state magic-angle spinning (MAS) NMR spectroscopic analyses, including variable-contact-time (13)C cross-polarization (CP)/MAS NMR spectroscopy, revealed that acid-base interactions between surface acid sites and immobilized amines can be controlled by pretreatment of SA at different temperatures. The catalytic activities for these addition reactions were strongly affected by the surface acid-base interactions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-05-01

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

  5. Microbial control of hydrogen sulfide production

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J. [Univ. of Oklahoma, Tulsa, OK (United States)] [and others

    1995-12-31

    A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.

  6. Comparison of homogeneous and heterogeneous catalysts for glucose-to-fructose isomerization in aqueous media.

    Science.gov (United States)

    Choudhary, Vinit; Pinar, Ana B; Lobo, Raul F; Vlachos, Dionisios G; Sandler, Stanley I

    2013-12-01

    Herein, the first comparison of the mechanisms of glucose-to-fructose isomerization in aqueous media enabled by homogeneous (CrCl3 and AlCl3 ) and heterogeneous catalysts (Sn-beta) by using isotopic-labeling studies is reported. A pronounced kinetic isotope effect (KIE) was observed if the deuterium label was at the C2 position, thus suggesting that a hydrogen shift from the C2 to C1 positions was the rate-limiting step with the three catalysts. (13) C and (1) H NMR spectroscopic investigations confirmed that an intra-hydride-transfer reaction pathway was the predominant reaction channel for all three catalysts in aqueous media. Furthermore, the deuterium atom in the labeled glucose could be mapped onto hydroxymethylfurfural and formic acid through reactions that followed the isomerization step in the presence of Brønsted acids. In all three catalysts, the active site appeared to be a bifunctional Lewis-acidic/Brønsted-basic site, based on a speciation model and first-principles calculations. For the first time, a mechanistic similarities between the homogeneous and heterogeneous catalysis of aldose-to-ketose isomerization is established and it is suggested that learning from homogeneous catalysis could assist in the development of improved heterogeneous catalysts.

  7. Comparison of bifunctional chelates for {sup 64}Cu antibody imaging

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Cara L.; Crisp, Sarah; Bensimon, Corinne [MDS Nordion, Vancouver, BC (Canada); Yapp, Donald T.T.; Ng, Sylvia S.W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); University of British Columba, The Faculty of Pharmaceutical Sciences, Vancouver, BC (Canada); Sutherland, Brent W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); Gleave, Martin [Prostate Centre at Vancouver General Hospital, Vancouver, BC (Canada); Jurek, Paul; Kiefer, Garry E. [Macrocyclics Inc., Dallas, TX (United States)

    2010-11-15

    Improved bifunctional chelates (BFCs) are needed to facilitate efficient {sup 64}Cu radiolabeling of monoclonal antibodies (mAbs) under mild conditions and to yield stable, target-specific agents. The utility of two novel BFCs, 1-Oxa-4,7,10-triazacyclododecane-5-S-(4-isothiocyanatobenzyl)-4,7,10-triacetic acid (p-SCN-Bn-Oxo-DO3A) and 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-4-S-(4-isothiocyanatobenzyl)-3,6,9-triacetic acid (p-SCN-Bn-PCTA), for mAb imaging with {sup 64}Cu were compared to the commonly used S-2-(4-isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane-tetraacetic acid (p-SCN-Bn-DOTA). The BFCs were conjugated to trastuzumab, which targets the HER2/neu receptor. {sup 64}Cu radiolabeling of the conjugates was optimized. Receptor binding was analyzed using flow cytometry and radioassays. Finally, PET imaging and biodistribution studies were done in mice bearing either HER2/neu-positive or HER2/neu-negative tumors. {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab were prepared at room temperature in >95% radiochemical yield (RCY) in <30 min, compared to only 88% RCY after 2 h for the preparation of {sup 64}Cu-DOTA-trastuzumab under the same conditions. Cell studies confirmed that the immunoreactivity of the mAb was retained for each of the bioconjugates. In vivo studies showed that {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab had higher uptake than the {sup 64}Cu-DOTA-trastuzumab at 24 h in HER2/neu-positive tumors, resulting in higher tumor to background ratios and better tumor images. By 40 h all three of the {sup 64}Cu-BFC-trastuzumab conjugates allowed for clear visualization of the HER2/neu-positive tumors but not the negative control tumor. The antibody conjugates of PCTA and Oxo-DO3A were shown to have superior {sup 64}Cu radiolabeling efficiency and stability compared to the analogous DOTA conjugate. In addition, {sup 64}Cu-PCTA and Oxo-DO3A antibody conjugates may facilitate earlier imaging with greater target to background ratios than

  8. Effect of rhodium modification on structures of sulfiede Rh-Mo-K/Al2O3 catalysts studied by XAFS

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Local structures of the molybdenum sulfide species in the sultided Rh-Mo-K/Al2O3 catalysts with various rhodium loadings have been investigated by XAFS.From the fitting results.the Mo-Mo coordination number for the sample free of rhodium(ca.3.7) is similar to that for the crystalline MoS2,indicating that the supported sulfided molybdenum species mainly present as large pateches of MoS2-like slabs.For the rhodium-modified samples,however,the amplitudes of the Mo-S and Mo-Mo coordination shells are sharply reduced,revealing a high dispersion of the MoS2-like species in the catalysts,The scheme of the microstructures of the sulfided molybdenum species stabilized on the alumina support is discussed based upon the analysis of the EXAFS data.

  9. Removal of methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide from contaminated air by Thiobacillus thioparus TK-m.

    OpenAIRE

    Kanagawa, T; Mikami, E.

    1989-01-01

    Methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide were efficiently removed from contaminated air by Thiobacillus thioparus TK-m and oxidized to sulfate stoichiometrically. More than 99.99% of dimethyl sulfide was removed when the load was less than 4.0 g of dimethyl sulfide per g (dry cell weight) per day.

  10. Hydrogen Sulfide Induces Oxidative Damage to RNA and DNA in a Sulfide-Tolerant Marine Invertebrate

    OpenAIRE

    Joyner-Matos, Joanna; Predmore, Benjamin L.; Stein, Jenny R.; Leeuwenburgh, Christiaan; Julian, David

    2010-01-01

    Hydrogen sulfide acts as an environmental toxin across a range of concentrations and as a cellular signaling molecule at very low concentrations. Despite its toxicity, many animals, including the mudflat polychaete Glycera dibranchiata, are periodically or continuously exposed to sulfide in their environment. We tested the hypothesis that a broad range of ecologically relevant sulfide concentrations induces oxidative stress and oxidative damage to RNA and DNA in G. dibranchiata. Coelomocytes ...

  11. Alloy catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...

  12. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  13. Reducible oxide based catalysts

    Science.gov (United States)

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  14. Magnetic catalyst bodies

    NARCIS (Netherlands)

    Teunissen, Wendy; Bol, A.A.; Geus, John W.

    2001-01-01

    After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the particles.

  15. Nitrate-reducing, sulfide-oxidizing bacteria as microbial oxidants for rapid biological sulfide removal.

    Science.gov (United States)

    De Gusseme, Bart; De Schryver, Peter; De Cooman, Michaël; Verbeken, Kim; Boeckx, Pascal; Verstraete, Willy; Boon, Nico

    2009-01-01

    The emission of hydrogen sulfide into the atmosphere of sewer systems induces the biological production of sulfuric acid, causing severe concrete corrosion. As a possible preventive solution, a microbial consortium of nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB) was enriched in a continuously stirred tank reactor in order to develop a biological technique for the removal of dissolved sulfide. The consortium, dominated by Arcobacter sp., was capable of removing 99% of sulfide. Stable isotope fractioning of the sulfide indicated that the oxidation was a biological process. The capacity of the NR-SOB consortium for rapid removal of sulfide was demonstrated by using it as an inoculum in synthetic and real sewage. Removal rates up to 52 mg sulfide-S g VSS(-1) h(-1) were achieved, to our knowledge the highest removal rate reported so far for freshwater species in the absence of molecular oxygen. Further long-term incubation experiments revealed the capacity of the bacteria to oxidize sulfide without the presence of nitrate, suggesting that an oxidized redox reserve is present in the culture.

  16. The use of mixed pyrrhotite/pyrite catalysts for co-liquefaction of coal and waste rubber tires

    Energy Technology Data Exchange (ETDEWEB)

    Dadyburjor, D.B.; Zondlo, J.W.; Sharma, R.K. [West Virginia Univ., Morgantown, WV (United States)] [and others

    1995-12-31

    The overall objective of this research program is to determine the optimum processing conditions for tire/coal co-liquefaction. The catalysts used will be a ferric-sulfide-based materials, as well as promising catalysts from other consortium laboratories. The intent here is to achieve the maximum coal+tire conversion at the mildest conditions of temperature and pressure. Specific objectives include an investigation of the effects of time, temperature, pressure, catalyst and co-solvent on the conversion and product slate of the co-liquefaction. Accomplishments and conclusions are discussed.

  17. Hydrogen sulfide in hemostasis: friend or foe?

    Science.gov (United States)

    Olas, Beata

    2014-06-25

    Hydrogen sulfide (H2S) is a well known toxic gas that is synthesized from the amino acids: cysteine (Cys) and homocysteine (Hcy) by three enzymes: cystathionine-β-synthase (CBS), cystathionine-γ-lyase (CSE) and mercaptopyruvate sulfurtransferase (3-MST). Hydrogen sulfide, like carbon monoxide (CO) or nitric oxide (NO) is a signaling molecule in different biological systems, including the cardiovascular system. Moreover, hydrogen sulfide plays a role in the pathogenesis of various cardiovascular diseases. It modulates different elements of hemostasis (activation of blood platelet, and coagulation process) as well as proliferation and apoptosis of vascular smooth muscle cells. However, the biological role and the therapeutic potential of H2S is not clear. This review summarizes the different functions of hydrogen sulfide in hemostasis.

  18. [Fatal outcome of an hydrogen sulfide poisoning].

    Science.gov (United States)

    Querellou, E; Jaffrelot, M; Savary, D; Savry, C; Perfus, J-P

    2005-10-01

    We report a case of fatal outcome poisoning by massive exposure to hydrogen sulfide of a sewer worker. This rare event was associated with a moderate intoxication of two members of the rescue team. The death was due to asystole and massive lung oedema. Autopsy analysis showed diffuse necrotic lesions in lungs. Hydrogen sulfide is a direct and systemic poison, produced by organic matter decomposition. The direct toxicity mechanism is still unclear. The systemic toxicity is due to an acute toxicity by oxygen depletion at cellular level. It is highly diffusable and potentially very dangerous. At low concentration, rotten egg smell must trigger hydrogen sulfide suspicion since at higher concentration it is undetectable, making intoxication possible. In case of acute intoxication, there is an almost instantaneous cardiovascular failure and a rapid death. Hydrogen sulfide exposure requires prevention measures and more specifically the use of respiratory equipment for members of the rescue team.

  19. Mechanism of mechanical activation for sulfide ores

    Institute of Scientific and Technical Information of China (English)

    HU Hui-ping; CHEN Qi-yuan; YIN Zhou-lan; HE Yue-hui; HUANG Bai-yun

    2007-01-01

    Structural changes for mechanically activated pyrite, sphalerite, galena and molybdenite with or without the exposure to ambient air, were systematically investigated using X-ray diffraction analysis(XRD), particle size analysis, gravimetrical method, X-ray photo-electron spectroscopy(XPS) and scanning electron microscopy(SEM), respectively. Based on the above structural changes for mechanically activated sulfide ores and related reports by other researchers, several qualitative rules of the mechanisms and the effects of mechanical activation for sulfide ores are obtained. For brittle sulfide ores with thermal instability, and incomplete cleavage plane or extremely incomplete cleavage plane, the mechanism of mechanical activation is that a great amount of surface reactive sites are formed during their mechanical activation. The effects of mechanical activation are apparent. For brittle sulfide ores with thermal instability, and complete cleavage plane, the mechanism of mechanical activation is that a great amount of surface reactive sites are formed, and lattice deformation happens during their mechanical activation. The effects of mechanical activation are apparent. For brittle sulfide ores with excellent thermal stability, and complete cleavage plane, the mechanism of mechanical activation is that lattice deformation happens during their mechanical activation. The effects of mechanical activation are apparent. For sulfide ores with high toughness, good thermal stability and very excellent complete cleavage plane, the mechanism of mechanical activation is that lattice deformation happens during their mechanical activation, but the lattice deformation ratio is very small. The effects of mechanical activation are worst.

  20. Catalysts, methods of making catalysts, and methods of use

    KAUST Repository

    Renard, Laetitia

    2014-03-06

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  1. Flame spray synthesis of CoMo/Al2O3 hydrotreating catalysts

    DEFF Research Database (Denmark)

    Høj, Martin; Linde, Kasper; Hansen, Thomas Klint

    2011-01-01

    The first alumina supported and unsupported cobalt molybdenum hydrotreating catalysts have been prepared by one-step flame spray pyrolysis (FSP) by spraying and combusting tris(acetylacetonato)aluminum, cobalt 2-ethylhexanoate and molybdenum 2-ethylhexaoate dissolved in toluene. The oxide particles.......After activation by sulfidation the activity of the catalysts were measured for the three hydrotreating reactions hydrodesulfurization, hydrodenitrogenation and hydrogenation using a model oil containing dibenzothiophene, indole and naphthalene in n-heptane solution. The best catalyst was the FSP-produced material...... containing 16wt.% Mo (atomic ratio Co/Mo=1/3), which did not contain crystalline MoO3 and only small amounts of CoAl2O4. The hydrotreating activity was approximately 75% of that of commercial cobalt molybdenum catalysts prepared by wet impregnation of pre-shaped alumina extrudates. Since the commercial...

  2. Energetic methods to study bifunctional biotin operon repressor.

    Science.gov (United States)

    Beckett, D

    1998-01-01

    measurements. The results of quantitative studies of the biotin regulatory system can be interpreted in the context of the biological function of the system. The biotin holoenzyme ligases are a class of enzymes found across the evolutionary spectrum. Only a subset of these enzymes, including BirA, also function as transcriptional repressors. The tight binding of the allosteric effector may be understood in light of the bifunctional nature of the BirA-bio-5'-AMP complex. It is possible that the unusually high thermodynamic and kinetic stability of the complex ensures that the most probable state of the protein in vivo is the adenylate-bound form. This complex, not the unliganded protein, is active in both enzymatic transfer of biotin and site-specific DNA binding. This ensures that on depletion of the intracellular pool of apoBCCP, BirA-bio-5'-AMP accumulates and binds to bioO to repress transcription of the biotin biosynthesis operon. The intracellular demand for and synthesis of biotin are, consequently, tightly coupled in the system. The dimerization that accompanies adenylate binding to BirA appears to be significant for site-specific binding of the protein to bioO. Functionally, the simultaneous binding of the two monomers to the two operator half-sites, regardless of the kinetic mechanism by which it occurs, ensures coordinate regulation of transcription initiation from both biotin operon promoters. The multifaceted approach utilized in studies of the biotin regulatory system can serve as a model for studies of any complex transcriptional regulatory system. It is critical in elucidating the functional energetics of any of these systems that the assembly first be dissected into the constituent interactions and that each of these interactions be studied in isolation. This is not only critical for understanding the physicochemical properties of each individual contributing interaction, but is also a necessary precursor to studies of thermodynamic linkage in the system. (AB

  3. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty

    2007-10-01

    Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

  4. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... 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...

  5. Hydrogen sulfide can inhibit and enhance oxygenic photosynthesis in a cyanobacterium from sulfidic springs

    NARCIS (Netherlands)

    Klatt, Judith M.; Haas, Sebastian; Yilmaz, Pelin; de Beer, Dirk; Polerecky, Lubos

    2015-01-01

    We used microsensors to investigate the combinatory effect of hydrogen sulfide (H2S) and light on oxygenic photosynthesis in biofilms formed by a cyanobacterium from sulfidic springs. We found that photosynthesis was both positively and negatively affected by H2S: (i) H2S accelerated the recovery of

  6. Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors

    NARCIS (Netherlands)

    Villa Gomez, D.K.; Cassidy, J.; Keesman, K.J.; Sampaio, R.M.; Lens, P.N.L.

    2014-01-01

    Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4 2- ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing

  7. NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

    Science.gov (United States)

    An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

  8. Hydrogen sulfide induces oxidative damage to RNA and DNA in a sulfide-tolerant marine invertebrate.

    Science.gov (United States)

    Joyner-Matos, Joanna; Predmore, Benjamin L; Stein, Jenny R; Leeuwenburgh, Christiaan; Julian, David

    2010-01-01

    Hydrogen sulfide acts as an environmental toxin across a range of concentrations and as a cellular signaling molecule at very low concentrations. Despite its toxicity, many animals, including the mudflat polychaete Glycera dibranchiata, are periodically or continuously exposed to sulfide in their environment. We tested the hypothesis that a broad range of ecologically relevant sulfide concentrations induces oxidative stress and oxidative damage to RNA and DNA in G. dibranchiata. Coelomocytes exposed in vitro to sulfide (0-3 mmol L(-1) for 1 h) showed dose-dependent increases in oxidative stress (as 2',7'-dichlorofluorescein fluorescence) and superoxide production (as dihydroethidine fluorescence). Coelomocytes exposed in vitro to sulfide (up to 0.73 mmol L(-1) for 2 h) also acquired increased oxidative damage to RNA (detected as 8-oxo-7,8-dihydroguanosine) and DNA (detected as 8-oxo-7,8-dihydro-2'-deoxyguanosine). Worms exposed in vivo to sulfide (0-10 mmol L(-1) for 24 h) acquired elevated oxidative damage to RNA and DNA in both coelomocytes and body wall tissue. While the consequences of RNA and DNA oxidative damage are poorly understood, oxidatively damaged deoxyguanosine bases preferentially bind thymine, causing G-T transversions and potentially causing heritable point mutations. This suggests that sulfide can be an environmental mutagen in sulfide-tolerant invertebrates.

  9. Indium sulfide buffer/CIGSSe interface engineering: Improved cell performance by the addition of zinc sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Allsop, N.A. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany)]. E-mail: allsop@hmi.de; Camus, C. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany); Haensel, A. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany); Gledhill, S.E. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany); Lauermann, I. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany); Lux-Steiner, M.C. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany); Fischer, Ch.-H. [Hahn-Meitner-Institut Berlin, Department SE2, Glienicker Str. 100, D-14109 Berlin (Germany)

    2007-05-31

    Indium sulfide buffer layers deposited by the spray-ion layer gas reaction (Spray-ILGAR) technique are a viable alternative to the traditional cadmium sulfide buffer layer in thin film solar cells. In the present work we report on the results of manipulating the absorber/buffer interface between the chalcopyrite Cu(In,Ga)(S,Se){sub 2} absorber (CIGSSe) and the indium sulfide buffer. It is shown that the deposition of a small amount of zinc sulfide at the absorber/buffer interface can be used to increase the open circuit voltage. A small but significant increase of 20 mV (up to 580 mV), as compared to the pure indium sulfide buffered cells is possible leading to an increase in the overall efficiency.

  10. Upgrading of LCO by partial hydrogenation of aromatics and ring opening of naphthenes over bi-functional catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Calemma, Vincenzo; Giardino, Roberto; Ferrari, Marco [Eni R and M, Via Maritano 26, 20097 San Donato M.se (Italy)

    2010-07-15

    Available options to upgrade LCO to diesel fuel are: i) aromatic saturation (ASAT) ii) mild hydrocracking and iii) aromatic saturation followed by selective ring opening (SRO) of naphthenic structures. Although the above mentioned routes lead to significant product quality enhancement, they suffer from several disadvantages. Hydrocracking leads to significant yields in gasoline-range products, ASAT is characterized by a relatively high consumption of hydrogen with only limited improvement of product quality in terms of density and cetane properties, ASAT + SRO route leads to higher improvements of product quality but it requires a very high hydrogen consumption which strongly affects the economics of the process. An alternative upgrading route consists in partial polyaromatic compound saturation and selective opening of both naphthenic and benzo-naphthenic structures to produce less condensed naphthenic structures and alkyl-benzenes respectively. In this case the hydrogen needed to improve product quality at the same level, of cetane properties and density, is lower in comparison with ASAT. This paper reports the results obtained during a research program aimed at upgrading LCO via selective ring opening. The hydroconversion of a low sulfur hydrotreated LCO has been studied over iridium and platinum loaded on different supports. The results of this study indicate that the properties of products heavily depend on the characteristics of the support and the metal used. The data obtained with the Ir/amorphous silica-alumina (MSA) show the possibility to get a clear increase of CN and decrease of density in comparison with the mere aromatic saturation. The practical consequence of this result is the possibility of producing products with CN and density similar to products obtained by complete dearomatization but still containing a significant percentage of aromatic structures so allowing a consistent saving of hydrogen. (author)

  11. Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.

    Science.gov (United States)

    Liu, Siyang; Zhu, Qingqing; Guan, Qingxin; He, Liangnian; Li, Wei

    2015-05-01

    Bio-aviation fuel was firstly synthesized by hydroprocessing castor oil in a continuous-flow fixed-bed microreactor with the main objective to obtain the high yield of aviation fuel and determine the elemental compositions of the product phases as well as the reaction mechanism. Highest aviation range alkane yields (91.6 wt%) were achieved with high isomer/n-alkane ratio (i/n) 4.4-7.2 over Ni supported on acidic zeolites. In addition, different fuel range alkanes can be obtained by adjusting the degree of hydrodeoxygenation (HDO) and hydrocracking. And the observations are rationalized by a set of reaction pathways for the various product phases.

  12. Catalyst for microelectromechanical systems microreactors

    Science.gov (United States)

    Morse, Jeffrey D.; Sopchak, David A.; Upadhye, Ravindra S.; Reynolds, John G.; Satcher, Joseph H.; Gash, Alex E.

    2010-06-29

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  13. Epoxidation catalyst and process

    Science.gov (United States)

    Linic, Suljo; Christopher, Phillip

    2010-10-26

    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.

  14. Light Absorbers and Catalysts for Solar to Fuel Conversion

    Science.gov (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

  15. New Catalysts for ROMP

    Institute of Scientific and Technical Information of China (English)

    H. Berke; C. Frech; A. Lhamazares; O. Blacque; H.W. Schmalle; C. Adlhart; P. Chen

    2005-01-01

    @@ 1Introduction Ring Opening Metathesis Polymerization (ROMP) is based on the olefin metathesis reaction, which requires transition metal catalysts. Mainly molybdenum, tungsten and ruthenium based catalysts have up to now been used. The "in-between" metal rhenium was only rarely applied in olefin metathesis reactions, and not at all in ROMP processes.We have found that cationic phosphine substituted dinitrosyl rhenium complexes[1]1a and 1b effectively catalyze ROMP of norbonene, dicyclopentadiene and of cyclooctene. See Fig. 1.

  16. Characterization and Hydrodesulfurization Properties of Catalysts Derived from Amorphous Metal-Boron Materials

    Energy Technology Data Exchange (ETDEWEB)

    Parks,G.; Pease, M.; Burns, A.; Layman, K.; Bussell, M.; Wang, X.; Hanson, J.; Rodriquez, J.

    2007-01-01

    Unsupported and silica-supported amorphous metal-boron materials (Ni-B, Mo-O-B, and Ni-Mo-O-B) were prepared by NaBH{sub 4} reduction of aqueous or impregnated metal salts. The resulting materials were characterized by a range of techniques, including conventional and time-resolved X-ray diffraction. The latter technique was used to determine the onset of crystallization of the amorphous materials during annealing in He flow and to identify the phases formed. Annealing of unsupported Ni-B resulted in the crystallization of predominantly Ni{sub 3}B, followed by Ni metal, whereas Ni-B/SiO{sub 2} formed Ni and then NiO. There was no evidence for crystallization of B-containing phases for Mo-O-B or Mo-O-B/SiO{sub 2} on annealing; instead, the predominant phase formed was MoO{sub 2}. In general, the phases formed for Ni-Mo-O-B and Ni-Mo-O-B/SiO2 were consistent with those formed in the monometallic materials, but at higher annealing temperatures. Catalysts prepared by sulfiding Ni-B/SiO{sub 2} and Ni-Mo-O-B/SiO{sub 2} materials had significantly higher thiophene HDS activities than conventionally prepared sulfided Ni/SiO2 and Ni-Mo/SiO{sub 2} catalysts, whereas a sulfided Mo-O-B/SiO{sub 2} catalyst had a dramatically lower HDS activity than a sulfided Mo/SiO{sub 2} catalyst.

  17. A study of the stability of cadmium sulfide/copper sulfide and cadmium sulfide copper-indium-diselenide solar cells

    Science.gov (United States)

    Noel, G.; Richard, N.; Gaines, G.

    1984-08-01

    Groups of high efficiency cadmium sulfide/copper sulfide solar cells were exposed to combinations of stresses designed to isolate and accelerate intrinsic degradation mechanisms. Stresses included elevated temperature, illumination intensity, and cell loading conditions. All stress exposures and tests were conducted in a benign (high purity argon) atmosphere. Two primary intrinsic modes of degradation were identified: degradation of the open circuit voltage under continuous illumination and nonzero loading was found to be self recovering upon interruption of illumination or upon shorting or reverse biasing the cells. It was attributed to traps in the depletion region. Recovery from decay of light generated current was not spontaneous but could be partially accomplished by annealing in a reducing (hydrogen) environment. It was attributed to changes in the stoichiometry of the copper sulfide under the influence of electric fields and currents.

  18. Bifunctional metamaterials with simultaneous and independent manipulation of thermal and electric fields.

    Science.gov (United States)

    Lan, Chuwen; Bi, Ke; Fu, Xiaojian; Li, Bo; Zhou, Ji

    2016-10-03

    Metamaterials offer a powerful way to manipulate a variety of physical fields ranging from wave fields (electromagnetic field, acoustic field, elastic wave, etc.), static fields (static magnetic field, static electric field) to diffusive fields (thermal field, diffusive mass). However, the relevant reports and studies are usually limited to a single physical field or functionality. In this study, we proposed and experimentally demonstrated a bifunctional metamaterial which could manipulate thermal and electric fields simultaneously and independently. Specifically, a composite with independently controllable thermal and electric conductivity was introduced, on the basis of which a bifunctional device capable of shielding thermal flux and concentrating electric current simultaneously was designed, fabricated and characterized. This work provides an encouraging example of metamaterials transcending their natural limitations, which offers a promising future in building a broad platform for the manipulation of multi-physics fields.

  19. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili

    2014-08-19

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Bifunctional metamaterials with simultaneous and independent manipulation of thermal and electric fields

    Science.gov (United States)

    Lan, Chuwen; Bi, Ke; Fu, Xiaojian; Li, Bo; Zhou, Ji

    2016-10-01

    Metamaterials offer a powerful way to manipulate a variety of physical fields ranging from wave fields (electromagnetic field, acoustic field, elastic wave, etc.), static fields (static magnetic field, static electric field) to diffusive fields (thermal field, diffusive mass). However, the relevant reports and studies are usually conducted on a single physical field or functionality. In this study, we proposed and experimentally demonstrated a bifunctional metamaterial which can manipulate thermal and electric fields simultaneously and independently. Specifically, a composite with independently controllable thermal and electric conductivity was introduced, on the basis of which a bifunctional device capable of shielding thermal flux and concentrating electric current simultaneously was designed, fabricated and characterized. This work provides an encouraging example of metamaterials transcending their natural limitations, which offers a promising future in building a broad platform for manipulation of multi-physics field.

  1. Improving stability and biocompatibility of alginate/chitosan microcapsule by fabricating bi-functional membrane.

    Science.gov (United States)

    Zheng, Guoshuang; Liu, Xiudong; Wang, Xiuli; Chen, Li; Xie, Hongguo; Wang, Feng; Zheng, Huizhen; Yu, Weiting; Ma, Xiaojun

    2014-05-01

    Cell encapsulation technology holds promise for the cell-based therapy. But poor mechanical strength and biocompatibility of microcapsule membrane are still obstacles for the clinical applications. A novel strategy is presented to prepare AC₁ C₂ A microcapsules with bi-functional membrane (that is, both desirable biocompatibility and membrane stability) by sequentially complexing chitosans with higher deacetylation degree (C₁) and lower deacetylation degree (C₂) on alginate (A) gel beads. Both in vitro and in vivo evaluation of AC₁C₂ A microcapsules demonstrate higher membrane stability and less cell adhesion, because the introduction of C₂ increases membrane strength and decreases surface roughness. Moreover, diffusion test of AC₁C₂ A microcapsules displays no inward permeation of IgG protein suggesting good immunoisolation function. The results demonstrate that AC₁C₂ A microcapsules with bi-functional membrane could be a promising candidate for microencapsulated cell implantation with cost effective usage of naturally biocompatible polysaccharides.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-15

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

  3. Sulfide capacities of fayalite-base slags

    Science.gov (United States)

    Simeonov, S. R.; Sridhar, R.; Toguri, J. M.

    1995-04-01

    The sulfide capacities of fayalite-base slags were measured by a gas-slag equilibration technique under controlled oxygen and sulfur potentials similar to those encountered in the pyrometallurgical processing of nonferrous metals. The oxygen pressure range was from 10-9.5 to 10-11 MPa and the sulfur pressure range from 10-3 to 10-4.5 MPa, over a temperature range of 1473 to 1623 K. The slags studied were FeO-SiO2 at silica saturation and those with addition of CaO, MgO, and Al2O3 to determine their effect on sulfide capacities. For these slags, the sulfide capacities were found to vary from 10-3.3 to 10-5. The sulfide capacities increased with increasing temperature from 1473 to 1623 K. A comparison of the reported plant data on sulfur content of industrial slags shows good agreement with the present experimental results. The present data will be useful in estimating metal losses in slag due to metal sulfide entrainment in nonferrous smelters.

  4. Radiation Induced Crosslinking of Polyethylene in the Presence of Bifunctional Vinyl Monomers

    DEFF Research Database (Denmark)

    Joshi, M. S.; Singer, Klaus Albert Julius; Silverman, J.

    1977-01-01

    Several reports have been published showing that the radiation induced grafting of bifunctional vinyl monomers to low density polyethylene results in a product with an unusually high density of crosslinks. The same grafting reactions are shown to reduce the incipient gel dose by more than a factor...... of fifty. This paper is concerned with the apparent crosslinking produced by the radiation grafting of two monomers to polyethylene: acrylic acid and acrylonitrile....

  5. Preliminary X-ray investigation of a bifunctional inhibitor from Indian finger millet (ragi).

    Science.gov (United States)

    Srinivasan, A; Raman, A; Singh, T P

    1991-11-05

    A bifunctional alpha-amylase/trypsin inhibitor that has two binding sites has been purified from ragi. The inhibitor has been crystallized from its ammonium sulphate solution by the vapour diffusion method. The crystals belong to the orthogonal space group P2(1)2(1)2(1) with unit cell dimensions a = 30.49 A, b = 56.30 A, c = 73.65 A and Z = 4.

  6. Catalytic activity of nanostructured Au: Scale effects versus bimetallic/bifunctional effects in low-temperature CO oxidation on nanoporous Au

    Directory of Open Access Journals (Sweden)

    Lu-Cun Wang

    2013-02-01

    Full Text Available The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure–activity correlations and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG samples prepared from different Au alloys (AuAg, AuCu by selective leaching of a less noble metal (Ag, Cu were employed, whose structure (surface area, ligament size as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS. The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed.

  7. The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways

    KAUST Repository

    Tang, Xiaoyan

    2016-10-04

    α-Methylene-γ-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C═C bond and a highly stable five-membered γ-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL)VAP. Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester P(MBL)ROP with Mn up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes, thus affording cross-linked polymer P(MBL)CLP. The formation of the three types of polymers, P(MBL)VAP, P(MBL)CLP, and P(MBL)ROP, can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La–X (X = OR, NR2, R) group. The resulting P(MBL)ROP is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.

  8. Co(II)1-xCo(0)x/3Mn(III)2x/3S Nanoparticles Supported on B/N-Codoped Mesoporous Nanocarbon as a Bifunctional Electrocatalyst of Oxygen Reduction/Evolution for High-Performance Zinc-Air Batteries.

    Science.gov (United States)

    Wang, Zilong; Xiao, Shuang; An, Yiming; Long, Xia; Zheng, Xiaoli; Lu, Xihong; Tong, Yexiang; Yang, Shihe

    2016-06-01

    Rechargeable Zn-air battery is an ideal type of energy storage device due to its high energy and power density, high safety, and economic viability. Its large-scale application rests upon the availability of active, durable, low-cost electrocatalysts for the oxygen reduction reaction (ORR) in the discharge process and oxygen evolution reaction (OER) in the charge process. Herein we developed a novel ORR/OER bifunctional electrocatalyst for rechargeable Zn-air batteries based on the codoping and hybridization strategies. The B/N-codoped mesoporous nanocarbon supported Co(II)1-xCo(0)x/3Mn(III)2x/3S nanoparticles exhibit a superior OER performance compared to that of IrO2 catalyst and comparable Zn-air battery performance to that of the Pt-based battery. The rechargeable Zn-air battery shows high discharge peak power density (over 250 mW cm(-2)) and current density (180 mA cm(-2) at 1 V), specific capacity (∼550 mAh g(-1)), small charge-discharge voltage gap of ∼0.72 V at 20 mA cm(-2) and even higher stability than the Pt-based battery. The advanced performance of the bifunctional catalysts highlights the beneficial role of the simultaneous formation of Mn(III) and Co(0) as well as the dispersed hybridization with the codoped nanocarbon support.

  9. Collagen/chitosan based two-compartment and bi-functional dermal scaffolds for skin regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Feng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Wang, Mingbo [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); She, Zhending [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China); Fan, Kunwu; Xu, Cheng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Chu, Bin; Chen, Changsheng [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shi, Shengjun, E-mail: shengjunshi@yahoo.com [The Burns Department of Zhujiang Hospital, Southern Medical University, Guangzhou 510280 (China); Tan, Rongwei, E-mail: tanrw@landobiom.com [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China)

    2015-07-01

    Inspired from the sophisticated bilayer structures of natural dermis, here, we reported collagen/chitosan based two-compartment and bi-functional dermal scaffolds. Two functions refer to mediating rapid angiogenesis based on recombinant human vascular endothelial growth factor (rhVEGF) and antibacterial from gentamicin, which were encapsulated in PLGA microspheres. The gentamicin and rhVEGF encapsulated PLGA microspheres were further combined with collagen/chitosan mixtures in low (lower layer) and high (upper layer) concentrations, and molded to generate the two-compartment and bi-functional scaffolds. Based on morphology and pore structure analyses, it was found that the scaffold has a distinct double layered porous and connective structure with PLGA microspheres encapsulated. Statistical analysis indicated that the pores in the upper layer and in the lower layer have great variations in diameter, indicative of a two-compartment structure. The release profiles of gentamicin and rhVEGF exceeded 28 and 49 days, respectively. In vitro culture of mouse fibroblasts showed that the scaffold can facilitate cell adhesion and proliferation. Moreover, the scaffold can obviously inhibit proliferation of Staphylococcus aureus and Serratia marcescens, exhibiting its unique antibacterial effect. The two-compartment and bi-functional dermal scaffolds can be a promising candidate for skin regeneration. - Highlights: • The dermal scaffold is inspired from the bilayer structures of natural dermis. • The dermal scaffold has two-compartment structures. • The dermal scaffold containing VEGF and gentamicin encapsulated PLGA microspheres • The dermal scaffold can facilitate cell adhesion and proliferation.

  10. A New Synthesis of TE2A-a Potential Bifunctional Chelator for {sup 64}Cu

    Energy Technology Data Exchange (ETDEWEB)

    Pandya, Darpan N.; Kwak, Won Jung; Park, Jeong Chan; Gawande, Manoj B.; Yoo, Jeong Soo [Kyungpook National University, Daegu (Korea, Republic of); Kim, Jung Young; An, Gwang Il [Molecular Imaging Research Center, Seoul (Korea, Republic of); Ryu, Eun Kyoung [Korea Basic Science Institute, Chungbuk (Korea, Republic of)

    2010-09-15

    The development of a new bifunctional chelator, which holds radio metals strongly in living systems, is a prerequisite for the successful application of disease-specific biomolecules to medical diagnosis and therapy. Recently, TE2A was reported to make kinetically more stable Cu({Pi}) complexes than TETA. Herein, we report a new synthetic route to TE2A and explore its potential as a bifunctional chelator. TE2A was synthesized using the regioselective alkylation of benzyl bromoacetate and successive de protection of the methylene bridge and benzyl group. Salt-free TE2A was radiolabeled with {sup 64}Cu and micro PET imaging was performed to follow the clearance pattern of the {sup 64}Cu-TE2A complex. TE2A was conjugated with cyclic RGD peptide and the TE2A-c(RGDyK) conjugate was radiolabeled with {sup 64}Cu. TE2A was prepared in salt-free form cyclam in an overall yield of 74%. The micro PET images showed that {sup 64}Cu-TE2A is excreted rapidly from the body by the kidney and liver. TE2A was successfully conjugated with c(RGDyK) peptide through on carboxylate group and the TE2A-c(RGDyK) conjugate was radiolabeled with {sup 64}Cu in 94% yield within 30 min. TE2A can be used by itself as a bifunctional chelator without any further structural modification.

  11. Characterization of a bifunctional xylanase/endoglucanase from yak rumen microorganisms.

    Science.gov (United States)

    Chang, Lei; Ding, Mozhu; Bao, Lei; Chen, Yingzhi; Zhou, Jungang; Lu, Hong

    2011-06-01

    A new gene, RuCelA, encoding a bifunctional xylanase/endoglucanase, was cloned from a metagenomic library of yak rumen microorganisms. RuCelA showed activity against xylan and carboxymethylcellulose (CMC), suggesting bifunctional xylanase/endoglucanase activity. The optimal conditions for xylanase and endoglucanase activities were 65°C, pH 7.0 and 50°C, pH 5.0, respectively. In addition, the presence of Co(+) and Co(2+) can greatly improve RuCelA's endoglucanase activity, while inhibits its xylanase activity. Further examination of substrate preference showed a higher activity against barley glucan and lichenin than against xylan and CMC. Using xylan and barley glucan as substrates, RuCelA displayed obvious synergistic effects with β-1,4-xylosidase and β-1,4-glucosidase. Generation of soluble oligosaccharides from lignocellulose is the key step in bioethanol production, and it is greatly notable that RuCelA can produce xylo-oligosaccharides and cello-oligosaccharides in the continuous saccharification of pretreated rice straw, which can be further degraded into fermentable sugars. Therefore, the bifunctional RuCelA distinguishes itself as an ideal candidate for industrial applications.

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

    Energy Technology Data Exchange (ETDEWEB)

    MAVRIKAKIS, MANOS

    2007-05-03

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

  13. Bi-functional Au/FeS (Au/Co{sub 3}O{sub 4}) composite for in situ SERS monitoring and degradation of organic pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Shuzhen; Cai, Qian; Lu, Kailing; Liao, Fan, E-mail: fliao@suda.edu.cn; Shao, Mingwang, E-mail: mwshao@suda.edu.cn [Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University (China)

    2016-01-15

    The bi-functional Au/FeS (Au/Co{sub 3}O{sub 4}) composite was fabricated by in situ reducing Au nanoparticles onto the surface of FeS (Co{sub 3}O{sub 4}). The as-prepared FeS possessed a multi-structure composed of plenty of nanoplates, which were coated by Au nanoparticles with an average size of ∼47.5 nm. While the Co{sub 3}O{sub 4} showed a thin hexagonal sheet containing Au nanoparticles on its surface with an average size of ∼79.0 nm. Both the as-prepared Au/FeS and Au/Co{sub 3}O{sub 4} composites exhibited excellent SERS performance, capable of enhancing the Raman signals of R6G molecules with the enhancement factor up to 1.81 × 10{sup 6} and 7.60 × 10{sup 4}, respectively. Moreover, Au/FeS (Au/Co{sub 3}O{sub 4}) composite also has been verified to have intrinsic peroxidase-like activity, which could decompose H{sub 2}O{sub 2} into hydroxyl radicals and then degrade organic pollutants into small molecules. Therefore, SERS can be used to real-time and in situ monitoring the degradation process of R6G molecules, employing the Au/FeS (Au/Co{sub 3}O{sub 4}) composite both as SERS substrate and catalyst. Graphical abstract: SERS was used to real-time and in situ monitoring the degradation of R6G, employing the Au/FeS and Au/Co{sub 3}O{sub 4} composites both as SERS substrates and catalysts.

  14. Solar thermal extraction of copper from sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Winkel, L.; Guesdon, C.; Sturzenegger, M.

    2003-03-01

    With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates re-search on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (Cu{sub 2}S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS{sub 2}) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO{sub 2}, and is beneficial to the removal of volatile impurities. Chemical equilibrium calculations for CuFeS{sub 2} contaminated with enargite (Cu{sub 3}AsS{sub 4}) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation. (author)

  15. Sulfide and methane production in sewer sediments.

    Science.gov (United States)

    Liu, Yiwen; Ni, Bing-Jie; Ganigué, Ramon; Werner, Ursula; Sharma, Keshab R; Yuan, Zhiguo

    2015-03-01

    Recent studies have demonstrated significant sulfide and methane production by sewer biofilms, particularly in rising mains. Sewer sediments in gravity sewers are also biologically active; however, their contribution to biological transformations in sewers is poorly understood at present. In this study, sediments collected from a gravity sewer were cultivated in a laboratory reactor fed with real wastewater for more than one year to obtain intact sediments. Batch test results show significant sulfide production with an average rate of 9.20 ± 0.39 g S/m(2)·d from the sediments, which is significantly higher than the areal rate of sewer biofilms. In contrast, the average methane production rate is 1.56 ± 0.14 g CH4/m(2)·d at 20 °C, which is comparable to the areal rate of sewer biofilms. These results clearly show that the contributions of sewer sediments to sulfide and methane production cannot be ignored when evaluating sewer emissions. Microsensor and pore water measurements of sulfide, sulfate and methane in the sediments, microbial profiling along the depth of the sediments and mathematical modelling reveal that sulfide production takes place near the sediment surface due to the limited penetration of sulfate. In comparison, methane production occurs in a much deeper zone below the surface likely due to the better penetration of soluble organic carbon. Modelling results illustrate the dependency of sulfide and methane productions on the bulk sulfate and soluble organic carbon concentrations can be well described with half-order kinetics.

  16. Membrane for hydrogen recovery from streams containing hydrogen sulfide

    Science.gov (United States)

    Agarwal, Pradeep K.

    2007-01-16

    A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

  17. Design and synthesis of chiral Ti-1,1'-bi-2-naphthol coordination polymers for heterogeneous catalytic asymmetric oxidation of sulfides

    Institute of Scientific and Technical Information of China (English)

    YUAN Xiao-ya; WANG Xiao-tian

    2008-01-01

    Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1'-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti(OiPr)4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity (over 99%ee) in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioselectivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.

  18. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  19. Modeling of Sulfide Microenvironments on Mars

    Science.gov (United States)

    Schwenzer, S. P.; Bridges, J. C.; McAdam, A.; Steer, E. D.; Conrad, P. G.; Kelley, S. P.; Wiens, R. C.; Mangold, N.; Grotzinger, J.; Eigenbrode, J. L.; Franz, H. B.; Sutter, B.

    2016-01-01

    Yellowknife Bay (YKB; sol 124-198) is the second site that the Mars Science Laboratory Rover Curiosity investigated in detail on its mission in Gale Crater. YKB represents lake bed sediments from an overall neutral pH, low salinity environment, with a mineralogical composition which includes Ca-sulfates, Fe oxide/hydroxides, Fe-sulfides, amorphous material, and trioctahedral phyllosilicates. We investigate whether sulfide alteration could be associated with ancient habitable microenvironments in the Gale mudstones. Some textural evidence for such alteration may be pre-sent in the nodules present in the mudstone.

  20. Iron-sulfide crystals in probe deposits

    DEFF Research Database (Denmark)

    Laursen, Karin; Frandsen, Flemming

    1998-01-01

    Iron-sulfides were observed in deposits collected on a probe inserted at the top of the furnace of a coal-fired power station in Denmark. The chemical composition of the iron-sulfides is equivalent to pyrrhotite (FeS). The pyrrhotites are present as crystals and, based on the shape of the crystals......, it was deduced that they were not deposited but instead grew within the deposit. The presence of unburned char particles within the deposits supports the concept that a reducing environment existed in the deposits. Two processes are proposed for explaining the existence of pyrrhotite crystals within a deposit...

  1. New insides in the characterization of HDS industrial catalysts by HAADF-STEM

    Science.gov (United States)

    Del Angel, Paz; Ponce, Arturo; Arellano, Josefina; Yacaman, Miguel J.; Hernandez-Pichardo, Martha; Montoya, J. Ascencion; Escobar, Jose

    2015-03-01

    Hydrodesulfurization (HDS) catalysts are of great importance in the petroleum industry. Transition metal sulphides catalysts of Ni(Co)Mo(W)/Al2O3 are widely used for hydrotreating reactions, like hydrodenitrogenation and HDS. One of the main issue in these catalysts is to understand the mechanism of the reaction, where MoS2 plays the most important role in the catalytic activity. We studied an industrial NiMo/Alumina sulfide catalyst highly active by using aberration-corrected HAADF-STEM techniques. The used catalysts was a state-of- the art commercial nickel-molybdenum alumina-supported formulation, including organic agent modifier. This type of material belongs to a novel family of catalysts specially designed for ultra-low sulfur production from straight-run gas oil (SRGO), cycle oil, coker gas oil, or their combinations at operating conditions of commercial interest in hydrotreating units at industrial scale. Aberration corrected HAADF-STEM allowed to observe the nanostructure and location of MoS2 and his interaction with the alumina. The results indicate that the MoS2 is highly dispersed on the alumina, however the location of Ni is one of the task of this kind of catalyst.

  2. Use of biogenic sulfide for ZnS precipitation

    NARCIS (Netherlands)

    Esposito, G.; Veeken, A.; Weijma, J.; Lens, P.N.L.

    2006-01-01

    A 600 ml continuously stirred tank reactor was used to assess the performance of a zinc sulfide precipitation process using a biogenic sulfide solution (the effluent of a sulfate-reducing bioreactor) as sulfide source. In all experiments, a proportional-integral (PI) control algorithm was used to co

  3. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.; Graaff, M. de; Bosch, P.L. van den; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.W.M.

    2013-01-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concl

  4. Understanding of catalyst deactivation caused by sulfur poisoning and carbon deposition in steam reforming of liquid hydrocarbon fuels

    Science.gov (United States)

    Xie, Chao

    2011-12-01

    The present work was conducted to develop a better understanding on the catalyst deactivation in steam reforming of sulfur-containing liquid hydrocarbon fuels for hydrogen production. Steam reforming of Norpar13 (a liquid hydrocarbon fuel from Exxon Mobile) without and with sulfur was performed on various metal catalysts (Rh, Ru, Pt, Pd, and Ni) supported on different materials (Al2O3, CeO2, SiO2, MgO, and CeO2- Al2O3). A number of characterization techniques were applied to study the physicochemical properties of these catalysts before and after the reactions. Especially, X-ray absorption near edge structure (XANES) spectroscopy was intensively used to investigate the nature of sulfur and carbon species in the used catalysts to reveal the catalyst deactivation mechanism. Among the tested noble metal catalysts (Rh, Ru, Pt, and Pd), Rh catalyst is the most sulfur tolerant. Al2O3 and CeO2 are much better than SiO2 and MgO as the supports for the Rh catalyst to reform sulfur-containing hydrocarbons. The good sulfur tolerance of Rh/Al2O3 can be attributed to the acidic nature of the Al2O3 support and its small Rh crystallites (1-3 nm) as these characteristics facilitate the formation of electron-deficient Rh particles with high sulfur tolerance. The good catalytic performance of Rh/CeO2 in the presence of sulfur can be ascribed to the promotion effect of CeO2 on carbon gasification, which significantly reduced the carbon deposition on the Rh/CeO2catalyst. Steam reforming of Norpar13 in the absence and presence of sulfur was further carried out over CeO2-Al2O3 supported monometallic Ni and Rh and bimetallic Rh-Ni catalysts at 550 and 800 °C. Both monometallic catalysts rapidly deactivated at 550 °C, iv and showed poor sulfur tolerance. Although ineffective for the Ni catalyst, increasing the temperature to 800 °C dramatically improved the sulfur tolerance of the Rh catalyst. Sulfur K-edge XANES revealed that metal sulfide and organic sulfide are the dominant sulfur

  5. Mechanism of pyrrhotite formation from ferric oxyhydroxide catalyst; Kokoritsu sekitan ekika shokubai no kaihatsu (Okishi suisankatetsu shokubai karano pyrrhotite seisei kyodo)

    Energy Technology Data Exchange (ETDEWEB)

    Tazawa, K.; Koyama, T.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    It is thought that iron-based catalysts for coal liquefaction exercise their catalytic activity by forming pyrrhotite (Fe(1-x)S). However, there are still a lot of unknown problems remained concerning the formation and agglomeration behaviors of pyrrhotite. These make a difficulty for improving the activity of iron-based catalysts. In this study, sulfiding behaviors of {alpha}-iron oxyhydroxide ({alpha}-FeOOH) and {gamma}-iron oxyhydroxide ({gamma}-FeOOH) were investigated to reveal the formation and agglomeration behaviors of pyrrhotite. It was found that pyrrhotite was easily converted from ferric oxyhydroxide catalysts having large specific surface areas at the sulfiding temperature below 250{degree}C, and fine crystallites of pyrrhotite were formed at the initial stage of sulfiding. Crystal growth of pyrrhotite at the sulfiding temperature over 350{degree}C depended on the catalyst forms. It was also found that smaller crystallites of pyrrhotite were formed from {gamma}-FeOOH than from {alpha}-FeOOH and amorphous iron oxyhydroxide. 5 refs., 7 figs., 1 tab.

  6. Unraveling the redox behavior of a CoMoS hydrodesulfurization catalyst : A scanning transmission X-ray microscopy study in the tender X-ray range

    NARCIS (Netherlands)

    Al Samarai, Mustafa; Meirer, Florian; Karunakaran, Chithra; Wang, Jian; Vogt, Eelco T C; Zandbergen, Henny W.; Weber, Thomas; Weckhuysen, Bert M.; De Groot, Frank M F

    2015-01-01

    We visualize the elemental zoning in an alumina-supported cobalt molybdenum sulfide (CoMoS) catalyst with scanning transmission X-ray microscopy (STXM). We use the Canadian Light Source beamline 10-ID's (SM) unique combination of soft X-ray and tender X-ray STXM to determine the spatial variation of

  7. NETWORK CROWN ETHER POLYMERS WITH CENTRIC FUNCTIONAL GROUPS.Ⅱ.SYNTHESIS OF NETROWK CROWN ETHER POLYMER WITH PENDANT SULFIDE SIDE CHAIN AND ITS PLATINUM COMPLEX

    Institute of Scientific and Technical Information of China (English)

    CHENYuanyin; MENGLingzhi; 等

    1995-01-01

    Network crown ether polymer with pendant sulfide side chain in the network structure units has been synthesized via ring-opening copolymerization of β-ethylthioethyl glycidyl ether and diethylene glycol bisglycidyl ether.A kind of active catalyst suitable for this reaction was suggested.The title polymer was found to be a good ligand for platinous chloride,and the platinous complex could catalyze the hydrosilylation of ole fins with triethoxysilane efficiently.

  8. Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

    Science.gov (United States)

    Wang, Zhuang; Li, Mian; Fan, Liquan; Han, Jianan; Xiong, Yueping

    2017-04-01

    The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-Nx and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

  9. Sn-MCM-41 as Efficient Catalyst for the Conversion of Glucose into 5-Hydroxymethylfurfural in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Qing Xu

    2013-11-01

    Full Text Available Recently, much attention has been paid to the development of technologies that facilitate the conversion of biomass into platform chemicals such as 5-hydroxymethylfurfural (5-HMF. In this paper, a tin-containing silica molecular sieve (Sn-MCM-41 was found to act as a bifunctional heterogeneous catalyst for the efficient conversion of glucose into 5-HMF in ionic liquid. In the presence of [EMIM]Br, the yield of 5-HMF converted from glucose reached 70% at 110 °C after 4 h. During the reaction, the active center of the catalyst first catalyzed the isomerization of glucose into fructose and then the dehydration of fructose into 5-HMF. After the reaction, the heterogeneous catalyst Sn-MCM-41 could be easily recovered and reused without a significant loss in activity. The catalyst Sn-MCM-41 was also able to catalyze the conversion of fructose into 5-HMF at an 80% yield. Moreover, the low toxicity of the Sn-based catalyst makes the method a greener approach for the conversion of saccharides into 5-HMF.

  10. X-Ray Absorption Spectroscopy of Mo and Ni K-edge of Supported Hydrotreating Catalysts%硫化态加氢精制催化剂的Mo和NiK边XAFS研究

    Institute of Scientific and Technical Information of China (English)

    段爱军; 徐春明; 赵震; 董鹏

    2005-01-01

    X-ray absorption fine structure (XAFS) and other techniques have been used to characterize Ni-Mo/Al2O3supported catalysts. The analysis of Mo K-edge spetrum shows that the active species over sulfide catalysts are MoS2-alike and the dispersion of Mo is high at the level of nanometer particles. There may exist some distortion of the local environment of MoS2, which has an influence on the hydrotreating activities of catalysts. Ni K-edge analysis shows that the coordination effects of Ni-Mo favor the dispersion state of active phase and imply a close relationship with catalyst activities.

  11. Supported organoiridium catalysts for alkane dehydrogenation

    Science.gov (United States)

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  12. Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices.

    NARCIS (Netherlands)

    Tangerman, A.

    2009-01-01

    This review deals with the measurement of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices of rats and humans (blood, serum, tissues, urine, breath, feces and flatus). Hydrogen sulfide and methanethiol both contain the active thiol (-SH

  13. Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices

    NARCIS (Netherlands)

    Tangerman, Albert

    2009-01-01

    This review deals with the measurement of the volatile Sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices of rats and humans (blood, serum, tissues, urine, breath, feces and flatus). Hydrogen sulfide and methanethiol both contain the active thiol (-SH

  14. Modeling Sulfides, pH and Hydrogen Sulfide Gas in the Sewers of San Francisco

    DEFF Research Database (Denmark)

    Vollertsen, Jes; Revilla, Nohemy; Hvitved-Jacobsen, Thorkild;

    2015-01-01

    An extensive measuring campaign targeted on sewer odor problems was undertaken in San Francisco. It was assessed whether a conceptual sewer process model could reproduce the measured concentrations of total sulfide in the wastewater and H2S gas in the sewer atmosphere, and to which degree...... such simulations have potential for further improving odor and sulfide management. The campaign covered measurement of wastewater sulfide by grab sampling and diurnal sampling, and H2S gas in the sewer atmosphere was logged. The tested model was based on the Wastewater Aerobic/Anaerobic Transformations in Sewers...... (WATS) sewer process concept, which never had been calibrated to such an extensive dataset. The study showed that the model was capable of reproducing the general levels of wastewater sulfide, wastewater pH, and sewer H2S gas. It could also reproduce the general variability of these parameters, albeit...

  15. Comparison of Hydrogen Sulfide Analysis Techniques

    Science.gov (United States)

    Bethea, Robert M.

    1973-01-01

    A summary and critique of common methods of hydrogen sulfide analysis is presented. Procedures described are: reflectance from silver plates and lead acetate-coated tiles, lead acetate and mercuric chloride paper tapes, sodium nitroprusside and methylene blue wet chemical methods, infrared spectrophotometry, and gas chromatography. (BL)

  16. Microbial Fuel Cells for Sulfide Removal

    NARCIS (Netherlands)

    Rabaey, K.; Sompel, van de S.; Maignien, L.; Boon, N.; Aelterman, P.; Clauwaert, P.; Schamphelaire, de L.; The Pham, H.; Vermeulen, J.; Verhaege, M.; Lens, P.N.L.; Verstraete, W.

    2006-01-01

    Thus far, microbial fuel cells (MFCs) have been used to convert carbon-based substrates to electricity. However, sulfur compounds are ubiquitously present in organic waste and wastewater. In this study, a MFC with a hexacyanoferrate cathodic electrolyte was used to convert dissolved sulfide to eleme

  17. 30 CFR 250.490 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... been confirmed. Well-control fluid means drilling mud and completion or workover fluid as appropriate... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Drilling Operations Hydrogen Sulfide § 250.490 Hydrogen... section when conducting drilling, well-completion/well-workover, and production operations in zones...

  18. Hydrogen Sulfide in Preeclampsia : Potential Therapeutic Implications

    NARCIS (Netherlands)

    Holwerda, Kim

    2015-01-01

    The thesis provide insights into the production and possible therapeutic effect of the gaseous molecule hydrogen sulfide (H2S) in preeclampsia (PE). H2S is an important molecule in the (human) body. It is among others involved in blood pressure regulation, stimulation of vascular growth and modulati

  19. Platinum metals in magmatic sulfide ores

    Science.gov (United States)

    Naldrett, A.J.; Duke, J.M.

    1980-01-01

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. Copyright ?? 1980 AAAS.

  20. Monitoring sulfide and sulfate-reducing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, R.S.

    1995-12-31

    Simple yet precise and accurate methods for monitoring sulfate-reducing bacteria (SRB) and sulfide remain useful for the study of bacterial souring and corrosion. Test kits are available to measure sulfide in field samples. A more precise methylene blue sulfide assay for both field and laboratory studies is described here. Improved media, compared to that in API RP-38, for enumeration of SRB have been formulated. One of these, API-RST, contained cysteine (1.1 mM) as a reducing agent, which may be a confounding source of sulfide. While cysteine was required for rapid enumeration of SRB from environmental samples, the concentration of cysteine in medium could be reduced to 0.4 mM. It was also determined that elevated levels of yeast extract (>1 g/liter) could interfere with enumeration of SRB from environmental samples. The API-RST medium was modified to a RST-11 medium. Other changes in medium composition, in addition to reduction of cysteine, included reduction of the concentration of phosphate from 3.4 mM to 2.2 mM, reduction of the concentration of ferrous iron from 0.8 mM to 0.5 mM and preparation of a stock mineral solution to ease medium preparation. SRB from environmental samples could be enumerated in a week in this medium.

  1. Fuel cell catalyst degradation

    DEFF Research Database (Denmark)

    Arenz, Matthias; Zana, Alessandro

    2016-01-01

    Fuel cells are an important piece in our quest for a sustainable energy supply. Although there are several different types of fuel cells, the by far most popular is the proton exchange membrane fuel cell (PEMFC). Among its many favorable properties are a short start up time and a high power density...... increasing focus. Activity of the catalyst is important, but stability is essential. In the presented perspective paper, we review recent efforts to investigate fuel cell catalysts ex-situ in electrochemical half-cell measurements. Due to the amount of different studies, this review has no intention to give...

  2. Aerogel derived catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, J. G., LLNL

    1996-12-11

    Aerogels area class of colloidal materials which have high surface areas and abundant mesoporous structure. SiO{sub 2} aerogels show unique physical, optical and structural properties. When catalytic metals are incorporated in the aerogel framework, the potential exists for new and very effective catalysts for industrial processes. Three applications of these metal-containing SiO{sub 2} aerogels as catalysts are briefly reviewed in this paper--NO{sub x} reduction, volatile organic compound destruction, and partial oxidation of methane.

  3. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S.G.; Banks, R.L.

    1986-05-20

    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.

  4. Mesoporous molecular sieve catalysts

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane

    be used as solid acid catalysts but can also be used as a size-selective matrix. It was shown that it is possible to encapsulate 1-2 nm sized gold nanoparticles by silicalite-1 or ZSM-5 zeolite crystals thereby forming a sintering-stable and substrate size-selective oxidation catalyst. After carrying out...... calcination experiments, both in situ and ex situ indicated that the gold nanoparticles embedded in the crystals were highly stable towards sintering. The catalytic tests proved that the embedded gold nanoparticles were active in selective aldehyde oxidation and were only accessible through the micropores...

  5. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...... and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...

  6. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2015-01-01

    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with sca......Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field...... with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most...

  7. Sulfide removal by moderate oxygenation of anaerobic sludge environments

    Energy Technology Data Exchange (ETDEWEB)

    Van der Zee, F.P.; Villaverde, S.; Polanco, F. [Valladolid Univ., Valladolid (Spain). Dept. of Chemical Engineering; Garcia, P.A.

    2004-07-01

    Treating wastewater through anaerobic bioreactors results in the formation of hydrogen sulfide. The sulfide can be removed from the biogas by introducing air directly into the anaerobic bioreactor system. This study presents the results of batch experiments that provided a better insight into the fate of sulfur compounds and oxygen during microaerobic sulfide oxidation in granular sludge. It was shown that sulfide could be removed rapidly upon introduction of low amounts of oxygen to the sulfide-amended batch vials with granular sludge treating vinasse. Initially, the sulfide was oxidized to elemental sulfur, thiosulfate and polysulfide. Significant production of sulfate did not occur. The introduction of oxygen, however, could result in the growth of aerobic organic-chemical oxygen demand-oxidizing bacteria that compete with sulfide oxidation for oxygen. 6 refs., 1 tab., 1 fig.

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

    DEFF Research Database (Denmark)

    2011-01-01

    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. Heterogeneous chromium catalysts

    NARCIS (Netherlands)

    2005-01-01

    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based silica-c

  10. Deactivation of Oxidation Catalysts

    Science.gov (United States)

    1991-05-01

    Levenspiel (Reference 10) have proposed an equivalent general expression of the form dS _KST (4) dtk to account for deactivation due to catalyst pore...Voorhies, A., IEC, 1954, vol. 37, p. 318. 10. Szepe, S., and 0. Levenspiel , Proc. 4th Europ. Symp. Chem. React. Eng., Pergamon Press, p. 265. 11. U.S

  11. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-05-14

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory oxide support containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one methylating agent under conditions suitable for the methylating agent compounds to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

  12. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard

    2013-01-01

    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...

  13. Bioleaching of spent hydrotreating catalyst by acidophilic thermophile Acidianus brierleyi: Leaching mechanism and effect of decoking.

    Science.gov (United States)

    Bharadwaj, Abhilasha; Ting, Yen-Peng

    2013-02-01

    Bioleaching of spent hydrotreating catalyst by thermophillic archae Acidianus brierleyi was investigated. The spent catalyst (containing Al, Fe, Ni and Mo as major elements) was characterized, and the effect of pretreatment (decoking) on two-step and spent medium leaching was examined at 1% w/v pulp density. Decoking resulted in removal of carbonaceous deposits and volatile impurities, and affected the solubility of metal compounds through oxidization of the metal sulfides. Nearly 100% extraction was achieved using spent medium leaching for Fe, Ni and Mo, and 67% for Al. Bioleaching reduced nickel concentration in the leachate below the regulated levels for safe waste disposal. Chemical (i.e. abiotic) leaching using equimolar concentration of sulfuric acid produced by the bacteria during two-step process achieved a lower leaching efficiency (by up to 30%). Results indicated that A. brierleyi successfully leached heavy metals from spent catalyst.

  14. Attrition Resistant Iron-Based Catalysts For F-T SBCRs

    Energy Technology Data Exchange (ETDEWEB)

    Adeyinka A. Adeyiga

    2006-01-31

    {alpha} of 0.9. Research is proposed to enable further development and optimization of these catalysts by (1) better understanding the role and interrelationship of various catalyst composition and preparation parameters on attrition resistance, activity, and selectivity of these catalysts, (2) the presence of sulfide ions on a precipitated iron catalyst, and (3) the effect of water on sulfided iron F-T catalysts for its activity, selectivity, and attrition. Catalyst preparations will be based on spray drying. The research employed, among other measurements, attrition testing and F-T synthesis at high pressure. Catalyst activity and selectivity is evaluated using a small fixed-bed reactor and a continuous stirred tank reactor (CSTR). The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1-m-diameter, 2-m-tall spray dryer. The binder silica content was varied from 0 to 20 wt%. The results show that the use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO2 wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than the type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). The two catalysts were also tested at The Center for Applied Energy Research in Lexington, Kentucky of the University

  15. Hydrogen sulfide conversion with nanophase titania

    Science.gov (United States)

    Beck, D.D.; Siegel, R.W.

    1996-08-20

    A process is described for disassociating H{sub 2}S in a gaseous feed using an improved catalytic material in which the feed is contacted at a temperature of at least about 275 C with a catalyst of rutile nanocrystalline titania having grain sizes in the range of from about 1 to about 100 nanometers. Other transition metal catalysts are disclosed, each of nanocrystalline material with grain sizes in the 1-100 nm range. 5 figs.

  16. Thermal desorption study of catalytic systems. Communication 20. Adsorption of water vapors on the calcium aluminate components of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nissenbaum, V.D.; Danyushevskii, V.Y.; Golosman, E.Z.; Rubinstein, A.M.; Yakerson, V.I.

    1985-05-01

    Ca aluminates are used as a component of catalysts of gas-phase processes, some of which take place with the participation of water. Nickel calcium aluminate catalysts are thus used for hydrogenation of CO and CO/sub 2/ to CH/sub 4/ and water; zinc calcium aluminate catalysts are used for sulfur purification of process gases, where water is liberated during sulfiding of ZnO; and copper zinc calcium aluminate catalysts are used in low-temperature conversion of CO with water vapor. It is also known that Ca aluminates undergo various transformations in aqueous media with the formation of Ca hydroaluminates. This paper discusses the adsorption of water from the gas phase on calcium aluminate systems, which was investigated by the thermal desorption method. Samples of varying phase composition, different CaO/Al/sub 2/O/sub 3/ ratios, and specific surface areas were also studied and are reported on here.

  17. Preparation, characterization of Mo catalysts supported on Ni- containing calcium deficient hydroxyapatite and reactivity for the thiophene HDS reaction

    Directory of Open Access Journals (Sweden)

    Cherif A.

    2013-09-01

    Full Text Available Ni-containing Calcium Hydroxyapatite (NiCaHAp; 3.31 wt.% Ni was synthesized by coprecipitation and used as catalyst support. Molybdenum was supported on NiCaHAp by impregnation using ammonium heptamolybdate. The prepared catalysts Mo(x/NiCaHAp (x: 2 to 8 wt % in Mo were characterized by elemental analysis, XRD, FT-IR, N2 adsorption-desorption and TEM-EDX. The catalysts were sulfided in-situ at 673 K under flowing H2S/H2 (15 Vol.% H2S and tested in hydrodesulfurization (HDS of thiophene at 673 K. The main XRD peaks of hydroxyapatite CaHAp phase were observed in all samples and a peak due probably to crystalline MoO3 phase was also identified from the results. However, no crystalline phase of NiO was found for the catalysts, which showed its Ni species were highly dispersed. The sulfided catalysts Mo(x/NiCaHAp presented are active in HDS of thiophene, despite the presence of some large MoO3 crystallites and incomplete sulfidation. This activity may be due to interaction of NiO and MoO3 on CaHAp resulting in the formation of Ni-Mo-S phase under flowing H2S/H2. When the molybdenum content increased the HDS activity increasead slightly, which was caused by the agglomeration of MoO3. The Mo(8/NiCaHAp catalyst is about two times less active for thiophene HDS than the commercial NiMoP/Al2O3.

  18. Rapid reduction of N-nitrosamine disinfection byproducts in water with hydrogen and porous nickel catalysts.

    Science.gov (United States)

    Frierdich, Andrew J; Shapley, John R; Strathmann, Timothy J

    2008-01-01

    There is a need for new technologies to rapidly and economically treatwater contaminated with N-nitrosodimethylamine (NDMA) and related compounds because of their high toxicity and recent detection in drinking water sources as a consequence of industrial releases and chlorine disinfection of wastewater effluent Treatment of N-nitrosamines with H2 in conjunction with a high surface area porous nickel material, a model nonprecious metal catalyst, has been evaluated. Experiments show that NDMA is reduced rapidly and catalytically to dimethylamine and N2 (e.g., t1/2 = 1.5 min for 500 mg/L catalyst and PH2 = 1 atm), and kinetic trends are consistent with a surface-mediated mechanism involving scission of the N-nitrosamine N-N bond and subsequent reactions with adsorbed atomic hydrogen. The metal-loading-normalized pseudo-first-order rate constant (77.9 +/- 13.1 L g(Ni)(-1) h(-1)) exceeds values reported for Pd-based catalysts. Several related N-nitrosamines react at rates similar to those of NDMA, indicating a weak dependence on structure. The reaction rates for NDMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO4(2-), HCO(3-), and NOM) exerts only a small effect on reaction rates. Nitrate is also reduced by the Ni catalyst, and high nitrate concentrations competitively inhibit the reduction of NDMA. (Bi)sulfide poisons the catalyst by strong chemisorption to the Ni surface. Cost-normalized rate constants for the Ni catalyst are highly favorable compared to Pd-based catalysts, indicating that, with further development, Ni-based catalysts may become attractive alternatives to precious metal catalysts.

  19. Kinetic analysis on photocatalytic degradation of gaseous acetaldehyde, ammonia and hydrogen sulfide on nanosized porous TiO2 films

    Directory of Open Access Journals (Sweden)

    Iis Sopyan

    2007-01-01

    Full Text Available The characteristics of the UV illumination-assisted degradation of gaseous acetaldehyde, hydrogen sulfide, and ammonia on highly active nanostructured-anatase and rutile films were investigated. It was found that the anatase film showed a higher photocatalytic activity than the counterpart did, however, the magnitude of difference in the photocatalytic activity of both films decreased in the order ammonia>acetaldehyde>hydrogen sulfide. To elucidate the reasons for the observation, the adsorption characteristics and the kinetics of photocatalytic degradation of the three reactants on both films were analyzed. The adsorption analysis examined using a simple Langmuir isotherm, showed that adsorbability on both films decreased in the order ammonia>acetaldehyde>hydrogen sulfide, which can be explained in terms of the decreasing electron-donor capacity. Acetaldehyde and ammonia adsorbed more strongly and with higher coverage on anatase film (1.2 and 5.6 molecules/nm2, respectively than on rutile (0.6 and 4.7 molecules/nm2, respectively. Conversely, hydrogen sulfide molecules adsorbed more strongly on rutile film (0.7 molecules/nm2 than on anatase (0.4 molecules/nm2. Exposure to UV light illumination brought about the photocatalytic oxidation of the three gases in contact with both TiO2 films, and the decrease in concentration were measured, and their kinetics are analyzed in terms of the Langmuir–Hinshelwood kinetic model. From the kinetic analysis, it was found that the anatase film showed the photocatalytic activities that were factors of ~8 and ~5 higher than the rutile film for the degradation of gaseous ammonia and acetaldehyde, respectively. However, the activity was only a factor of ~1.5 higher for the photodegradation of hydrogen sulfide. These observations are systematically explained by the charge separation efficiency and the adsorption characteristics of each catalyst as well as by the physical and electrochemical properties of each

  20. Polymer nanocomposite membranes with hierarchically structured catalysts for high throughput dehalogenation

    Science.gov (United States)

    Crock, Christopher A.

    Halogenated organics are categorized as primary pollutants by the Environmental Protection Agency. Trichloroethylene (TCE), which had broad industrial use in the past, shows persistence in the environment because of its chemical stability. The large scale use and poor control of TCE resulted in its prolonged release into the environment before the carcinogenic risk associated with TCE was fully understood. TCE pollution stemmed from industrial effluents and improper disposal of solvent waste. Membrane reactors are promising technology for treating TCE polluted groundwater because of the high throughput, relatively low cost of membrane fabrication and facile retrofitting of existing membrane based water treatment facilities with catalytic membrane reactors. Compared to catalytic fluidized or fixed bed reactors, catalytic membrane reactors feature minimal diffusional limitation. Additionally, embedding catalyst within the membrane avoids the need for catalyst recovery and can prevent aggregation of catalytic nanoparticles. In this work, Pd/xGnP, Pd-Au/xGnP, and commercial Pd/Al2O3 nanoparticles were employed in batch and flow-through membrane reactors to catalyze the dehalogenation of TCE in the presence of dissolved H2. Bimetallic Pd-Au/xGnP catalysts were shown to be more active than monometallic Pd/xGnP or commercial Pd/Al 2O3 catalysts. In addition to synthesizing nanocomposite membranes for high-throughput TCE dehalogenation, the membrane based dehalogenation process was designed to minimize the detrimental impact of common catalyst poisons (S2-, HS-, and H2S -) by concurrent oxidation of sulfide species to gypsum in the presence of Ca2+ and removal of gypsum through membrane filtration. The engineered membrane dehalogenation process demonstrated that bimetallic Pd-Au/xGnP catalysts resisted deactivation by residual sulfide species after oxidation, and showed complete removal of gypsum during membrane filtration.

  1. Controlled Covalent Functionalization of Thermally Reduced Graphene Oxide To Generate Defined Bifunctional 2D Nanomaterials

    Science.gov (United States)

    Faghani, Abbas; Donskyi, Ievgen S.; Fardin Gholami, Mohammad; Ziem, Benjamin; Lippitz, Andreas; Unger, Wolfgang E. S.; Böttcher, Christoph; Rabe, Jürgen P.

    2017-01-01

    Abstract A controlled, reproducible, gram‐scale method is reported for the covalent functionalization of graphene sheets by a one‐pot nitrene [2+1] cycloaddition reaction under mild conditions. The reaction between commercially available 2,4,6‐trichloro‐1,3,5‐triazine and sodium azide with thermally reduced graphene oxide (TRGO) results in defined dichlorotriazine‐functionalized sheets. The different reactivities of the chlorine substituents on the functionalized graphene allow stepwise post‐modification by manipulating the temperature. This new method provides unique access to defined bifunctional 2D nanomaterials, as exemplified by chiral surfaces and multifunctional hybrid architectures. PMID:28165179

  2. An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide

    Science.gov (United States)

    Yang, Libin; Qi, Honglan; Zhang, Chengxiao; Sun, Xuping

    2016-06-01

    The development of highly efficient electrocatalysts for water splitting is critical for various renewable-energy technologies. In this letter, we demonstrate a cobalt phosphide nanowire array grown on a Ti mesh (CoP/TM) behaving as a bifunctional electrocatalyst for water splitting. The CoP/TM electrode delivers 10 mA cm-2 at an overpotential of 72 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) in 1.0 M KOH. Furthermore, its corresponding two-electrode alkaline electrolyzer displays 10 mA cm-2 at 1.64 V.

  3. MoO3 nanoparticle anchored graphene as bifunctional agent for water purification

    Science.gov (United States)

    Lahan, Homen; Roy, Raju; Namsa, Nima D.; Das, Shyamal K.

    2016-10-01

    We report here a facile one step hydrothermal method to anchor MoO3 nanoparticles in graphene. The bifunctionality of graphene-MoO3 nanoparticles is demonstrated via dye adsorption and antibacterial activities. The nanocomposite showed excellent adsorption of methylene blue, a cationic dye, from water compared to pristine MoO3 and graphene. However, it showed negligible adsorption of methyl orange, an anionic dye. Again, the graphene-MoO3 nanoparticles exhibited bacteriostatic property against both Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria.

  4. Mutability of bifunctional thigh muscle activity in pedaling due to contralateral leg force generation.

    Science.gov (United States)

    Kautz, S A; Brown, D A; Van der Loos, H F M; Zajac, F E

    2002-09-01

    Locomotion requires uninterrupted transitions between limb extension and flexion. The role of contralateral sensorimotor signals in executing smooth transitions is little understood even though their participation is crucial to bipedal walking. However, elucidating neural interlimb coordinating mechanisms in human walking is difficult because changes to contralateral sensorimotor activity also affect the ipsilateral mechanics. Pedaling, conversely, is ideal for studying bilateral coordination because ipsilateral mechanics can be independently controlled. In pedaling, the anterior and posterior bifunctional thigh muscles develop needed anterior and posterior crank forces, respectively, to dominate the flexion-to-extension and extension-to-flexion transitions. We hypothesized that contralateral sensorimotor activity substantially contributes to the appropriate activation of these bifunctional muscles during the limb transitions. Bilateral pedal forces and surface electromyograms (EMGs) from four thigh muscles were collected from 15 subjects who pedaled with their right leg against a right-crank servomotor, which emulated the mechanical load experienced in conventional two-legged coupled-crank pedaling. In one pedaling session, the contralateral (left) leg pseudo-pedaled (i.e., EMG activity and pedal forces were pedaling-like, but pedal force was not allowed to affect crank rotation). In other sessions, the mechanically decoupled contralateral leg was first relaxed and then produced rhythmic isometric force trajectories during either leg flexion or one of the two limb transitions of the pedaling leg. With contralateral force production in the extension-to-flexion transition (predominantly by the hamstrings), rectus femoris activity and work output increased in the pedaling leg during its flexion-to-extension transition, which occurs simultaneously with contralateral extension-to-flexion in conventional pedaling. Similarly, with contralateral force production in the

  5. Studies of supported metal catalysts. Final report, September 1, 1979-April 30, 1984

    Energy Technology Data Exchange (ETDEWEB)

    Hercules, D.M.

    1984-04-01

    A variety of surface spectroscopic techniques, coupled with chemical activity measurements, has been used to study supported heterogeneous catalysts. The catalytic systems investigated are: Ni on Al/sub 2/O/sub 3/ and SiO/sub 2/, Co on Al/sub 2/O/sub 3/, Co and Zn on Al/sub 2/O/sub 3/, Mo on Al/sub 2/O/sub 3/, Mo in TiO/sub 2/, W on Al/sub 2/O/sub 3/, Co and Mo on Al/sub 2/O/sub 3/ and Ni and W on Al/sub 2/O/sub 3/. Emphasis has been on defining the nature of the surface species on the oxidic catalysts, prior to treatment or activation. Reaction of catalysts with H/sub 2/ and H/sub 2/S/H/sub 2/ have been used for diagnosing different species. Treatment with Ha2S/H/sub 2/ also has been used to elucidate the species on sulfided hydrotreating catalysts. Other aspects of the research involved evaluation of photoacoustic spectroscopy for studying catalysts and use of curve resolving techniques to maximize use of ESCA spectra for studying catalysts. In general, the species on catalysts with loadings below monolayer coverage are determined by the nature of the support. For example, on ..gamma..-Al/sub 2/O/sub 3/ distributions of the metal between tetrahedral (Td) and octahedral (Oh) sites occurs. Reactivity of metals in Oh and Td support sites differ; in Mo-Al/sub 2/O/sub 3/ catalysts, the metal in Td sites is reduced only to Mo(+5) by H/sub 2/ (500/sup 0/C) but Oh Mo is reduced to Mo(+4). Sulfiding Mo/Al/sub 2/O/sub 3/ catalysts produces MoS/sub 2/ but leaves some metal unsulfided (Mo+5). Clear evidence for interaction species was found for ternary catalyst systems, viz. Co-Mo-Al/sub 2/O/sub 3/.

  6. TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

    Science.gov (United States)

    Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.

    2013-01-01

    High surface area TiO2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid - Ni3/2PW12O40 was applied as oxide precursor of the active components. The catalyst was characterized by SBET, XRD, UV-vis DRS, Raman spectroscopy, XPS, TPR and HRTEM. The results obtained were compared with those for the NiW catalysts prepared over high surface area titania and alumina supports. A polytungstate phase evidenced by Raman spectroscopy was observed indicating the destruction of the initial heteropolyanion. The catalytic experiments revealed two times higher thiophene conversion on NiW catalyst supported on Ti-NT than those of catalysts supported on alumina and titania. Increased HDS activity of the NiW catalyst supported on Ti-NT could be related to a higher amount of W oxysulfide entities interacting with Ni sulfide particles as consequence of the electronic effects of the Ti-NT observed with XPS analysis.

  7. Sulfide, the first inorganic substrate for human cells.

    Science.gov (United States)

    Goubern, Marc; Andriamihaja, Mireille; Nübel, Tobias; Blachier, François; Bouillaud, Frédéric

    2007-06-01

    Hydrogen sulfide (H2S) is produced inside the intestine and is known as a poison that inhibits cellular respiration at the level of cytochrome oxidase. However, sulfide is used as an energetic substrate by many photo- and chemoautotrophic bacteria and by animals such as the lugworm Arenicola marina. The concentrations of sulfide present in their habitats are comparable with those present in the human colon. Using permeabilized colonic cells to which sulfide was added by an infusion pump we show that the maximal respiratory rate of colonocyte mitochondria in presence of sulfide compares with that obtained with succinate or L-alpha-glycerophosphate. This oxidation is accompanied by mitochondrial energization. In contrast, other cell types not naturally exposed to high concentration of sulfide showed much lower oxidation rates. Mitochondria showed a very high affinity for sulfide that permits its use as an energetic substrate at low micromolar concentrations, hence, below the toxic level. However, if the supply of sulfide exceeds the oxidation rate, poisoning renders mitochondria inefficient and our data suggest that an anaerobic mechanism involving partial reversion of Krebs cycle already known in invertebrates takes place. In conclusion, this work provides additional and compelling evidence that sulfide is not only a toxic compound. According to our study, sulfide appears to be the first inorganic substrate for mammalian cells characterized thus far.

  8. The Evolution of Sulfide Tolerance in the Cyanobacteria

    Science.gov (United States)

    Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

  9. Harvesting Nanocatalytic Heat Localized in Nanoalloy Catalyst as a Heat Source in a Nanocomposite Thin Film Thermoelectric Device.

    Science.gov (United States)

    Zhao, Wei; Shan, Shiyao; Luo, Jin; Mott, Derrick M; Maenosono, Shinya; Zhong, Chuan-Jian

    2015-10-20

    This report describes findings of an investigation of harvesting nanocatalytic heat localized in a nanoalloy catalyst layer as a heat source in a nanocomposite thin film thermoelectric device for thermoelectric energy conversion. This device couples a heterostructured copper-zinc sulfide nanocomposite for thermoelectrics and low-temperature combustion of methanol fuels over a platinum-cobalt nanoalloy catalyst for producing heat localized in the nanocatalyst layer. The possibility of tuning nanocatalytic heat in the nanocatalyst and thin film thermoelectric properties by compositions points to a promising pathway in thermoelectric energy conversion.

  10. Metallic Iron-Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media.

    Science.gov (United States)

    Long, Xia; Li, Guixia; Wang, Zilong; Zhu, HouYu; Zhang, Teng; Xiao, Shuang; Guo, Wenyue; Yang, Shihe

    2015-09-23

    We report on the synthesis of iron-nickel sulfide (INS) ultrathin nanosheets by topotactic conversion from a hydroxide precursor. The INS nanosheets exhibit excellent activity and stability in strong acidic solutions as a hydrogen evolution reaction (HER) catalyst, lending an attractive alternative to the Pt catalyst. The metallic α-INS nanosheets show an even lower overpotential of 105 mV at 10 mA/cm(2) and a smaller Tafel slope of 40 mV/dec. With the help of DFT calculations, the high specific surface area, facile ion transport and charge transfer, abundant electrochemical active sites, suitable H(+) adsorption, and H2 formation kinetics and energetics are proposed to contribute to the high activity of the INS ultrathin nanosheets toward HER.

  11. Speciation of arsenic in sulfidic waters

    Directory of Open Access Journals (Sweden)

    Ford Robert G

    2003-03-01

    Full Text Available Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH2S from 10-7.5 to 10-3.0 M, ΣAs from 10-5.6 to 10-4.8 M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH30, and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10-4.3 M at neutral pH. Conversion from neutral As(OH30 to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions.

  12. Iron-sulfide redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2016-06-14

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  13. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... by the competition between chain‐branching and ‐propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO2 + S....

  14. Iron-sulfide redox flow batteries

    Science.gov (United States)

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2013-12-17

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  15. Subsurface heaters with low sulfidation rates

    Energy Technology Data Exchange (ETDEWEB)

    John, Randy Carl; Vinegar, Harold J

    2013-12-10

    A system for heating a hydrocarbon containing formation includes a heater having an elongated ferromagnetic metal heater section. The heater is located in an opening in a formation. The heater section is configured to heat the hydrocarbon containing formation. The exposed ferromagnetic metal has a sulfidation rate that goes down with increasing temperature of the heater, when the heater is in a selected temperature range.

  16. Hydrogen sulfide prodrugs—a review

    Directory of Open Access Journals (Sweden)

    Yueqin Zheng

    2015-09-01

    Full Text Available Hydrogen sulfide (H2S is recognized as one of three gasotransmitters together with nitric oxide (NO and carbon monoxide (CO. As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications.

  17. Hydrogen sulfide prodrugs—a review

    Science.gov (United States)

    Zheng, Yueqin; Ji, Xingyue; Ji, Kaili; Wang, Binghe

    2015-01-01

    Hydrogen sulfide (H2S) is recognized as one of three gasotransmitters together with nitric oxide (NO) and carbon monoxide (CO). As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications. PMID:26579468

  18. Redetermination of piperidinium hydrogen sulfide structure

    Science.gov (United States)

    Andras, Maria T.; Hepp, Aloysius F.; Fanwick, Phillip E.; Duraj, Stan A.; Gordon, Edward M.

    1994-01-01

    The presence of adventitious water in a reaction between dicyclopentamethylene thiuram-disulfide (C5H10NCS2)(sub 2) and a picoline solution of tricyclopentadienyl indium(III) (C5H5)(sub 3). It resulted in the formation of piperidinium hydrogen sulfide (C5H13NS). The piperidinium hydrogen sulfide produced in this way was unambiguously characterized by X-ray crystallography. The structure determination showed that the piperidinium hydrogen sulfide crystal (MW = 119.23 g/mol) has an orthorhombic (Pbcm) unit cell whose parameters are: a = 9.818(2), b = 7.3720(1), c = 9.754(1) A, V = 706.0(3) A(exp 3), Z=4. D(sub chi) = 1.122 g cm(exp -3), Mo K(alpha) (lamda = 0.71073), mu= 3.36 cm(exp -1), F(000) = 264.0, T =293 K, R = 0.036 for 343 reflections with F(sub O)(sup 2) greater than 3 sigma (F(sub O)(sup 2)) and 65 variables. The compound consists of (C5H10NH2)(+) cations and (SH)(-) anions with both species residing on crystallographic mirror planes. N-H -- S hydrogen bonding contributes to the interconnection of neighboring piperidinium components of the compound.

  19. Air-water transfer of hydrogen sulfide

    DEFF Research Database (Denmark)

    Yongsiri, C.; Vollertsen, J.; Rasmussen, M. R.;

    2004-01-01

    experiments. By means of the overall mass–transfer coefficient (KLa), the transfer coefficient of hydrogen sulfide (KLaH2S), referring to total sulfide, was correlated to that of oxygen (KLaO2) (i.e., the reaeration coefficient). Results demonstrate that both turbulence and pH in the water phase play...... a significant role for KLaH2S. An exponential expression is a suitable representation for the relationship between KLaH2S and the Froude number at all pH values studied (4.5 to 8.0). Because of the dissociation of hydrogen sulfide, KLaH2S increased with decreasing pH at a constant turbulence level. Relative...... differences in KLaH2S at pH values between 4.5 and 8.0 became larger as the turbulence level increased, whereas those at pH between 4.5 and 7.0 did not statistically show any change. At constant pH, KLaH2S/KLaO2 was observed not to be dependent on the turbulence range studied. KLaH2S/KLaO2 ratio was 0...

  20. Fluorination process using catalysts

    Science.gov (United States)

    Hochel, R.C.; Saturday, K.A.

    1983-08-25

    A process is given for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/, AgF/sub 2/ and NiF/sub 2/, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/ and AgF/sub 2/, whereby the fluorination is significantly enhanced.

  1. Fluorination process using catalyst

    Science.gov (United States)

    Hochel, Robert C.; Saturday, Kathy A.

    1985-01-01

    A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

  2. Photo catalyst; Ko shokubai

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-07-01

    While titanium oxide is excited by the light, electrons of titanium oxide are taken away by the light energy to form positive holes. Water will be decomposed into hydrogen ion and hydroxy radical (OH) by these positive holes. This hydroxy radical is a strong reactive substance called active oxygen, it decomposes organisms. Besides this photo- catalyst function, the titanium oxide can also make surface of a substance superhydrophilic. The super hydrophilicity results in not forming water drops on the glass surface but spreading all over the surface to prevent a covering of fog on the glass surface. The published patents concerning the photo catalysts were 593 from Jan. 1998 to Jan. 1999. The applicant order is the first TOTO 143, the second Daikin Industry 19, the third Toshiba Raitech, Nitto Denko, Hitachi 17 respectively. (NEDO)

  3. High-Activity Dealloyed Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

    2014-09-30

    Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

  4. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-03-12

    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.

  5. SulfrZol(R)54硫化剂在2Mt/a加氢装置应用%Application of SulfrZol(R) 54 pre-sulfiding agent in a 2.0 MM TPY hydrogenation unit

    Institute of Scientific and Technical Information of China (English)

    王以科

    2012-01-01

    he SulfrZol? 54 pre-sulfiding agent was first tried in a 2.0 MM TPY hydrogenation unit of a petrochemical company. The commercial application results indicate that the SulfrZol? Pre-sulfiding agent can meet the pre-sulfiding requirements of hydrogenation catalysts. The decomposition temperature of SulfrZol 54 pre-sulfiding agent is lower than that of conventional pre-sulfiding agents, and the pre-sulfiding time for oxidized catalysts can be greatly shortened. In addition, the SulfrZol? 54 pre-sulfiding agent, which is low in odor, toxicity and decomposition temperature and high in flash point, offers good safety and operability. It can replace conventional pre-sulfiding agents like carbon disulfide, dimethyl disulfide, etc in pre-sulfiding of hydrogenation catalysts.%主要阐述SulfrZol(R) 54硫化剂在某炼油化工股份公司2 Mt/a加氢精制装置的首次应用.从使用效果来看,SulfrZol(R) 54硫化剂完全能满足加氢催化剂的硫化需要,并且从SulfrZol(R) 54硫化剂分解温度来看低于一般硫化剂,可以大大缩短加氢装置氧化态催化剂预硫化时间.另外,从SulfrZol(R) 54硫化剂与其它硫化剂物性分析来看,具有气味低、毒性小、分解温度低、闪点高等特点,有更好的安全性和操作性.因此,SulfrZol(R) 54硫化剂完全可以替代二硫化碳、二甲基二硫等传统硫化剂作为加氢催化剂硫化需要.

  6. A bifunctional spin label reports the structural topology of phospholamban in magnetically-aligned bicelles.

    Science.gov (United States)

    McCaffrey, Jesse E; James, Zachary M; Svensson, Bengt; Binder, Benjamin P; Thomas, David D

    2016-01-01

    We have applied a bifunctional spin label and EPR spectroscopy to determine membrane protein structural topology in magnetically-aligned bicelles, using monomeric phospholamban (PLB) as a model system. Bicelles are a powerful tool for studying membrane proteins by NMR and EPR spectroscopies, where magnetic alignment yields topological constraints by resolving the anisotropic spectral properties of nuclear and electron spins. However, EPR bicelle studies are often hindered by the rotational mobility of monofunctional Cys-linked spin labels, which obscures their orientation relative to the protein backbone. The rigid and stereospecific TOAC label provides high orientational sensitivity but must be introduced via solid-phase peptide synthesis, precluding its use in large proteins. Here we show that a bifunctional methanethiosulfonate spin label attaches rigidly and stereospecifically to Cys residues at i and i+4 positions along PLB's transmembrane helix, thus providing orientational resolution similar to that of TOAC, while being applicable to larger membrane proteins for which synthesis is impractical. Computational modeling and comparison with NMR data shows that these EPR experiments provide accurate information about helix tilt relative to the membrane normal, thus establishing a robust method for determining structural topology in large membrane proteins with a substantial advantage in sensitivity over NMR.

  7. Bifunctional Ag/C3N4.5 composite nanobelts for photocatalysis and antibacterium

    Science.gov (United States)

    Lei, Renbo; Jian, Jikang; Zhang, Zhihua; Song, Bo; Wu, Rong

    2016-09-01

    Multiple functions can be achieved in carbon nitride-based composite nanomaterials by tuning their components and structures. Here, we report on a large-scale synthesis of novel bifunctional Ag/C3N4.5 composite nanobelts (CNBs) with efficient photocatalytic and antibacterial activity. The Ag/C3N4.5 CNBs were synthesized in high yield by a two-step route including a homogeneous precipitation process and a subsequent calcination treatment. The structural, morphological, compositional, and spectroscopic characterizations revealed that the Ag/C3N4.5 CNBs are composed of N-deficient melem ultrathin nanobelts and crystalline Ag nanoparticles attached to the surface of the nanobelts with good contact. The band gap of the Ag/C3N4.5 CNBs is determined to be about 3.04 eV. The efficient photocatalytic and antibacterial activities of the composite nanomaterials are verified by testing the degradation of Rhodamine B (RhB) and the inhibition zone to bacterium E. coli. The work provides a facile route to bifunctional carbon nitride-based composites with potential applications in the fields of the environment and biology.

  8. Cell Growth on ("Janus") Density Gradients of Bifunctional Zeolite L Crystals.

    Science.gov (United States)

    Kehr, Nermin Seda; Motealleh, Andisheh; Schäfer, Andreas H

    2016-12-28

    Nanoparticle density gradients on surfaces have attracted interest as two-dimensional material surfaces that can mimic the complex nano-/microstructure of the native extracellular matrix, including its chemical and physical gradients, and can therefore be used to systematically study cell-material interactions. In this respect, we report the preparation of density gradients made of bifunctional zeolite L crystals on glass surfaces and the effects of the density gradient and biopolymer functionalization of zeolite L crystals on cell adhesion. We also describe how we created "Janus" density gradient surfaces by gradually depositing two different types of zeolite L crystals that were functionalized and loaded with different chemical groups and guest molecules onto the two distinct sides of the same glass substrate. Our results show that more cells adhered on the density gradient of biopolymer-coated zeolites than on uncoated ones. The number of adhered cells increased up to a certain surface coverage of the glass by the zeolite L crystals, but then it decreased beyond the zeolite density at which a higher surface coverage decreased fibroblast cell adhesion and spreading. Additionally, cell experiments showed that cells gradually internalized the guest-molecule-loaded zeolite L crystals from the underlying density gradient containing bifunctional zeolite L crystals.

  9. Cyclic isoDGR and RGD peptidomimetics containing bifunctional diketopiperazine scaffolds are integrin antagonists.

    Science.gov (United States)

    Panzeri, Silvia; Zanella, Simone; Arosio, Daniela; Vahdati, Leila; Dal Corso, Alberto; Pignataro, Luca; Paolillo, Mayra; Schinelli, Sergio; Belvisi, Laura; Gennari, Cesare; Piarulli, Umberto

    2015-04-13

    The cyclo[DKP-isoDGR] peptidomimetics 2-5, containing bifunctional diketopiperazine (DKP) scaffolds that differ in the configuration of the two DKP stereocenters and in the substitution at the DKP nitrogen atoms, were prepared and examined in vitro in competitive binding assays with purified αv β3 and αv β5 integrin receptors. IC50 values ranged from low nanomolar (ligand 3) to submicromolar with αv β3 integrin. The biological activities of ligands cyclo[DKP3-RGD] 1 and cyclo[DKP3-isoDGR] 3, bearing the same bifunctional DKP scaffold and showing similar αV β3 integrin binding values, were compared in terms of their cellular effects in human U373 glioblastoma cells. Compounds 1 and 3 displayed overlapping inhibitory effects on the FAK/Akt integrin activated transduction pathway and on integrin-mediated cell infiltration processes, and qualify therefore, despite the different RGD and isoDGR sequences, as integrin antagonists. Both compounds induced apoptosis in glioma cells after 72 hour treatment.

  10. Characterization of a bifunctional enzyme with (p)ppGpp-hydrolase/synthase activity in Leptospira interrogans.

    Science.gov (United States)

    He, Ping; Deng, Cong; Liu, Boyu; Zeng, LingBing; Zhao, Wei; Zhang, Yan; Jiang, XuCheng; Guo, XiaoKui; Qin, JinHong

    2013-11-01

    Alarmone Guanosine 5'-diphosphate (or 5'-triphosphate) 3'-diphosphate [(p)ppGpp] is the key component that globally regulates stringent control in bacteria. There are two homologous enzymes, RelA and SpoT in Escherichia coli, which are responsible for fluctuations in (p)ppGpp concentration inside the cell, whereas there exists only a single RelA/SpoT enzyme in Gram-positive bacteria. We have identified a bifunctional enzyme with (p)ppGpp-hydrolase/synthase activity in Leptospira interrogans. We show that the relLin gene (LA_3085) encodes a protein that fully complements the relA/spoT double mutants in E. coli. The protein functions as a (p)ppGpp degradase as well as a (p)ppGpp synthase when the cells encounter amino acid stress and deprivation of carbon sources. N-terminus HD and RSD domains of relLin (relLinN ) were observed to restore growth of double mutants of E. coli. Finally, We demonstrate that purified RelLin and RelLinN show high (p)ppGpp synthesis activity in vitro. Taken together, our results suggest that L. interrogans contain a single Rel-like bifunctional protein, RelLin , which plays an important role in maintaining the basal level of (p)ppGpp in the cell potentially contributing to the regulation of bacterial stress response.

  11. Sulfide scaling in low enthalpy geothermal environments; A survey

    Energy Technology Data Exchange (ETDEWEB)

    Criaud, A.; Fouillac, C. (Bureau de Recherches Geologiques et Minieres (BRGM), 45 - Orleans (France))

    1989-01-01

    A review of the sulfide scaling phenomena in low-temperature environments is presented. While high-temperature fluids tend to deposit metal sulfides because of their high concentrations of dissolved metals and variations of temperature, pressure and fluid chemistry, low temperature media are characterized by very low metal content but much higher dissolved sulfide. In the case of the goethermal wells of the Paris Basin, detailed studies demonstrate that the relatively large concentrations of chloride and dissolved sulfide are responsible for corrosion and consequent formation of iron sulfide scale composed of mackinawite, pyrite and pyrrhotite. The effects of the exploitation schemes are far less important than the corrosion of the casings. The low-enthalpy fluids that do not originate from sedimentary aquifers (such as in Iceland and Bulgaria), have a limited corrosion potential, and the thin sulfide film that appears may prevent the progress of corrosion.

  12. Oxidation and Precipitation of Sulfide in Sewer Networks

    DEFF Research Database (Denmark)

    Nielsen, A. H.

    calibrated and validated against field data. In the extension to the WATS model, sulfur transformations were described by six processes: 1. Sulfide production taking place in the biofilm and sediments covering the permanently wetted sewer walls; 2. Biological sulfide oxidation in the permanently wetted...... on oxidation and precipitation of sulfide, which are considered important processes in the sulfur cycle in wastewater and biofilms of sewer networks. Based on experimental studies, it was the objective to establish kinetics and stoichiometry of oxidation and precipitation of sulfide and to integrate...... the processes in an already existing sewer process model, thereby improving its capabilities for prediction of sulfide buildup in wastewater and atmosphere of sewer networks. Accordingly, efforts were made to develop experimental procedures for estimation of model parameters. Sulfide oxidation in both...

  13. Organization of the human mitochondrial hydrogen sulfide oxidation pathway.

    Science.gov (United States)

    Libiad, Marouane; Yadav, Pramod Kumar; Vitvitsky, Victor; Martinov, Michael; Banerjee, Ruma

    2014-11-07

    Sulfide oxidation is expected to play an important role in cellular switching between low steady-state intracellular hydrogen sulfide levels and the higher concentrations where the physiological effects are elicited. Yet despite its significance, fundamental questions regarding how the sulfide oxidation pathway is wired remain unanswered, and competing proposals exist that diverge at the very first step catalyzed by sulfide quinone oxidoreductase (SQR). We demonstrate that, in addition to sulfite, glutathione functions as a persulfide acceptor for human SQR and that rhodanese preferentially synthesizes rather than utilizes thiosulfate. The kinetic behavior of these enzymes provides compelling evidence for the flow of sulfide via SQR to glutathione persulfide, which is then partitioned to thiosulfate or sulfite. Kinetic simulations at physiologically relevant metabolite concentrations provide additional support for the organizational logic of the sulfide oxidation pathway in which glutathione persulfide is the first intermediate formed.

  14. Adsorption of 2 Chloroethyl Ethyl Sulfide on Silica: Binding Mechanism and Energy of a Bifunctional Hydrogen-Bond Acceptor at the Gas Surface Interface

    Science.gov (United States)

    2014-11-19

    in 1997 mandated the destruction of mustard stockpiles worldwide, HD can be readily synthesized by terrorists or militaries who choose to ignore the...Babaeva, M. A. Infrared Spectrum of Ammonia Adsorbed by Si−OH Groups on a Silica Surface. Opt. Spectrosc. 1983, 54, 665−666. (21) Civalleri, B

  15. Effect of Particle Size on the HDS Activity of Molybdenum Sulfide

    Directory of Open Access Journals (Sweden)

    Carola Contreras

    2016-01-01

    Full Text Available More than half of the total world oil reserves are heavy oil, extra heavy oil, and bitumen; however their catalytic conversion to more valuable products is challenging. The use of submicronic particles or nanoparticles of catalysts suspended in the feedstock may be a viable alternative to the conversion of heavy oils at refinery level or downhole (in situ upgrading. In the present work, molybdenum sulfide (MoS2 particles with varying diameters (10000–10 nm were prepared using polyvinylpyrrolidone as capping agent. The prepared particles were characterized by DLS, TEM, XRD, and XPS and tested in the hydrodesulfurization (HDS of a vacuum gas oil (VGO. A correlation between particle size and activity is presented. It was found that particles with diameters around 13 nm show double the HDS activity compared with the material with micrometric particle sizes (diameter ≈ 10,000 nm.

  16. Influences of silver sulfide on the bioleaching of chalcopyrite, pyrite and chalcopyrite-containing ore

    Institute of Scientific and Technical Information of China (English)

    胡岳华; 王军; 邱冠周; 王淀佐

    2002-01-01

    The effects of silver sulfide (Ag2S) on the bioleaching of chalcopyrite and pyrite were investigated in this paper. It has been shown that Ag2S enhanced the yields of bioleaching of chalcopyrite but inhibited the bio-oxidation of pyrite. The addition of Ag2S selectively increased the copper dissolution from the chalcopyrite-containing ores in shake flasks with a recovery of 85.3% compared with 24.3% without Ag2S, while slightly decreased the iron yields from 51% to 41.8%. The copper extraction of the chalcoopyrite-containing waste rock in column leaching charged with 18 kg mass increased up to 21.7% in the presence of Ag2S, while only 3.4% in the absence of the catalyst. The mechanism of Ag2S catalysis could be explained well by the "Mixed potential model".

  17. Measurement of plasma hydrogen sulfide in vivo and in vitro

    OpenAIRE

    Shen, Xinggui; Pattillo, Christopher B.; Pardue, Sibile; Bir, Shyamal C.; Wang, Rui; Kevil, Christopher G.

    2011-01-01

    The gasotransmitter hydrogen sulfide is known to regulate multiple cellular functions during normal and pathophysiological states. However, a paucity of concise information exists regarding quantitative amounts of hydrogen sulfide involved in physiological and pathological responses. This is primarily due to disagreement among various methods employed to measure free hydrogen sulfide. In this article, we describe a very sensitive method of measuring the presence of H2S in plasma down to nanom...

  18. Steam Reforming of Dimethyl Ether over Coupled Catalysts of CuO-ZnO-Al2O3-ZrO2 and Solid-acid Catalyst%二甲醚水蒸气重整制氢CuO-ZnO-Al2O3-ZrO2/固体酸复合催化剂

    Institute of Scientific and Technical Information of China (English)

    冯冬梅; 左宜赞; 王德峥; 王金福

    2009-01-01

    Steam reforming (SR) of dimethyl ether (DME) was investigated for the production of hydrogen for fuel cells. The activity of a series of solid acids for DME hydrolysis was investigated. The solid acid catalysts were ZSM-5[Si/Al= 25, 38 and 50: denoted Z(Si/Al)] and acidic alumina (γ-Al2O3) with an acid strength order that was Z(25)>Z(38)>Z(50)>γ-Al2O3. Stronger acidity gave higher DME hydrolysis conversion. Physical mixtures containing a CuO-ZnO-Zl2O3-ZrO2 catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR. DME SR activity strongly depended on the activity for DME hydrolysis. Z(25) was the best solid acid catalyst for DME SR and gave a DME conversion>90% [T= 240℃,n(H2O)/n(DME) = 3.5, space velocity = 1179 ml·(g cat) -1·h-1, and P= 0.1MPa]. The influences of the reaction temperature, space velocity and feed molar ratio were studied. Hydrogen production significantly depended on temperature and space velocity. A bifunctional catalyst of CuO-ZnO-Al2O3-ZrO2 catalyst and ZSM-5 gave a high H2 production rate and CO2 selectivity.

  19. Mechanish of dTTP Inhibition of the Bifunctional dCTP Deaminase:dUTPase Encoded by Mycobacterium tuberculosis

    DEFF Research Database (Denmark)

    Helt, Signe Smedegaard; Thymark, Majbritt; Harris, Pernille;

    2008-01-01

    to be characterised and provides evidence for bifunctionality of dCTP deaminase occurring outside the Archaea kingdom. A steady-state kinetic analysis revealed that the affinity for dCTP and deoxyuridine triphosphate as substrates for the synthesis of deoxyuridine monophosphate were very similar, a result...

  20. Pyrrolidinyl-sulfamide derivatives as a new class of bifunctional organocatalysts for direct asymmetric Michael addition of cyclohexanone to nitroalkenes.

    Science.gov (United States)

    Chen, Jia-Rong; Fu, Liang; Zou, You-Quan; Chang, Ning-Jie; Rong, Jian; Xiao, Wen-Jing

    2011-07-21

    A series of chiral pyrrolidinyl-sulfamide derivatives have been identified as efficient bifunctional organocatalysts for the direct Michael addition of cyclohexanone to a wide range of nitroalkenes. The desired Michael adducts were obtained in high chemical yields and excellent stereoselectivities (up to 99/1 dr and 95% ee).

  1. INVESTIGATION OF THIN FILM CADMIUM SULFIDE SOLAR CELLS.

    Science.gov (United States)

    SOLAR CELLS , *CADMIUM COMPOUNDS, FILMS, SULFIDES, VAPOR PLATING, VACUUM APPARATUS, SINGLE CRYSTALS, TITANIUM, COPPER COMPOUNDS, CHLORIDES, INDIUM, MOLYBDENUM, SILICON COMPOUNDS, MONOXIDES, SURFACE PROPERTIES, ENERGY CONVERSION.

  2. Hydrogen sulfide inhibits the renal fibrosis of obstructive nephropathy.

    Science.gov (United States)

    Song, Kai; Wang, Fen; Li, Qian; Shi, Yong-Bing; Zheng, Hui-Fen; Peng, Hanjing; Shen, Hua-Ying; Liu, Chun-Feng; Hu, Li-Fang

    2014-06-01

    Hydrogen sulfide has recently been found decreased in chronic kidney disease. Here we determined the effect and underlying mechanisms of hydrogen sulfide on a rat model of unilateral ureteral obstruction. Compared with normal rats, obstructive injury decreased the plasma hydrogen sulfide level. Cystathionine-β-synthase, a hydrogen sulfide-producing enzyme, was dramatically reduced in the ureteral obstructed kidney, but another enzyme cystathionine-γ-lyase was increased. A hydrogen sulfide donor (sodium hydrogen sulfide) inhibited renal fibrosis by attenuating the production of collagen, extracellular matrix, and the expression of α-smooth muscle actin. Meanwhile, the infiltration of macrophages and the expression of inflammatory cytokines including interleukin-1β, tumor necrosis factor-α, and monocyte chemoattractant protein-1 in the kidney were also decreased. In cultured kidney fibroblasts, a hydrogen sulfide donor inhibited the cell proliferation by reducing DNA synthesis and downregulating the expressions of proliferation-related proteins including proliferating cell nuclear antigen and c-Myc. Further, the hydrogen sulfide donor blocked the differentiation of quiescent renal fibroblasts to myofibroblasts by inhibiting the transforming growth factor-β1-Smad and mitogen-activated protein kinase signaling pathways. Thus, low doses of hydrogen sulfide or its releasing compounds may have therapeutic potentials in treating chronic kidney disease.

  3. Limitation of Sulfide Capacity Concept for Molten Slags

    Science.gov (United States)

    Jung, In-Ho; Moosavi-Khoonsari, Elmira

    2016-04-01

    The sulfide capacity concept has been widely used in pyrometallurgy to define sulfur removal capacities of slags. Typically, the sulfide capacity is considered to be a unique slag property depending only on temperature regardless of partial pressures of oxygen and sulfur. In the present study, it is demonstrated that sulfide capacities of slags in particular those of Na2O-containing slags can vary with partial pressures of oxygen and sulfur due to large solubility of sulfide in Na2O-containing slag systems.

  4. Influence of iron on sulfide inhibition in dark biohydrogen fermentation.

    Science.gov (United States)

    Dhar, Bipro Ranjan; Elbeshbishy, Elsayed; Nakhla, George

    2012-12-01

    Sulfide impact on biohydrogen production using dark fermentation of glucose at 37 °C was investigated. Dissolved sulfide (S(2-)) at a low concentration (25mg/L) increased biohydrogen production by 54% relative to the control (without iron addition). Whereas on initial dissolved S(2-) concentration of 500 mg/L significantly inhibited the biohydrogen production with total cumulative biohydrogen decreasing by 90% compared to the control (without iron addition). At sulfide concentrations of 500 mg S(2-)/L, addition of Fe(2+) at 3-4 times the theoretical requirement to precipitate 100% of the dissolved S(2-) entirely eliminated the inhibitory effect of sulfide.

  5. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States); Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-09-01

    In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al2O3, and Pt/ γ-Al2O3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

  6. Privileged chiral ligands and catalysts

    CERN Document Server

    Zhou, Qi-Lin

    2011-01-01

    This ultimate ""must have"" and long awaited reference for every chemist working in the field of asymmetric catalysis starts with the core structure of the catalysts, explaining why a certain ligand or catalyst is so successful. It describes in detail the history, the basic structural characteristics, and the applications of these ""privileged catalysts"". A novel concept that gives readers a much deeper insight into the topic.

  7. Oxygen-reducing catalyst layer

    Energy Technology Data Exchange (ETDEWEB)

    O' Brien, Dennis P. (Maplewood, MN); Schmoeckel, Alison K. (Stillwater, MN); Vernstrom, George D. (Cottage Grove, MN); Atanasoski, Radoslav (Edina, MN); Wood, Thomas E. (Stillwater, MN); Yang, Ruizhi (Halifax, CA); Easton, E. Bradley (Halifax, CA); Dahn, Jeffrey R. (Hubley, CA); O' Neill, David G. (Lake Elmo, MN)

    2011-03-22

    An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  8. Catalyst systems and uses thereof

    Science.gov (United States)

    Ozkan, Umit S.; Holmgreen, Erik M.; Yung, Matthew M.

    2012-07-24

    A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

  9. MEASURING METAL SULFIDE COMPLEXES IN OXIC RIVER WATERS WITH SQUARE WAVE VOLTAMMETRY. (R825395)

    Science.gov (United States)

    A sulfide identification protocol was developed to quantify specific metal sulfides that could exist in river water. Using a series of acid additions, nitrogen purges, and voltammetric analyses, metal sulfides were identified and semiquantified in three specific gr...

  10. Reciprocal regulation as a source of ultrasensitivity in two-component systems with a bifunctional sensor kinase.

    Directory of Open Access Journals (Sweden)

    Ronny Straube

    2014-05-01

    Full Text Available Two-component signal transduction systems, where the phosphorylation state of a regulator protein is modulated by a sensor kinase, are common in bacteria and other microbes. In many of these systems, the sensor kinase is bifunctional catalyzing both, the phosphorylation and the dephosphorylation of the regulator protein in response to input signals. Previous studies have shown that systems with a bifunctional enzyme can adjust the phosphorylation level of the regulator protein independently of the total protein concentrations--a property known as concentration robustness. Here, I argue that two-component systems with a bifunctional enzyme may also exhibit ultrasensitivity if the input signal reciprocally affects multiple activities of the sensor kinase. To this end, I consider the case where an allosteric effector inhibits autophosphorylation and, concomitantly, activates the enzyme's phosphatase activity, as observed experimentally in the PhoQ/PhoP and NRII/NRI systems. A theoretical analysis reveals two operating regimes under steady state conditions depending on the effector affinity: If the affinity is low the system produces a graded response with respect to input signals and exhibits stimulus-dependent concentration robustness--consistent with previous experiments. In contrast, a high-affinity effector may generate ultrasensitivity by a similar mechanism as phosphorylation-dephosphorylation cycles with distinct converter enzymes. The occurrence of ultrasensitivity requires saturation of the sensor kinase's phosphatase activity, but is restricted to low effector concentrations, which suggests that this mode of operation might be employed for the detection and amplification of low abundant input signals. Interestingly, the same mechanism also applies to covalent modification cycles with a bifunctional converter enzyme, which suggests that reciprocal regulation, as a mechanism to generate ultrasensitivity, is not restricted to two

  11. Toxicological analysis of 17 autopsy cases of hydrogen sulfide poisoning resulting from the inhalation of intentionally generated hydrogen sulfide gas.

    Science.gov (United States)

    Maebashi, Kyoko; Iwadate, Kimiharu; Sakai, Kentaro; Takatsu, Akihiro; Fukui, Kenji; Aoyagi, Miwako; Ochiai, Eriko; Nagai, Tomonori

    2011-04-15

    Although many cases of fatal hydrogen sulfide poisoning have been reported, in most of these cases, it resulted from the accidental inhalation of hydrogen sulfide gas. In recent years, we experienced 17 autopsy cases of fatal hydrogen sulfide poisoning due to the inhalation of intentionally generated hydrogen sulfide gas. In this study, the concentrations of sulfide and thiosulfate in blood, urine, cerebrospinal fluid and pleural effusion were examined using GC/MS. The sulfide concentrations were blood: 0.11-31.84, urine: 0.01-1.28, cerebrospinal fluid: 0.02-1.59 and pleural effusion: 2.00-8.59 (μg/ml), while the thiosulfate concentrations were blood: 0-0.648, urine: 0-2.669, cerebrospinal fluid: 0.004-0.314 and pleural effusion: 0.019-0.140 (μmol/ml). In previous reports, the blood concentration of thiosulfate was said to be higher than that of sulfide in hydrogen sulfide poisoning cases, although the latter was higher than the former in 8 of the 14 cases examined in this study. These results are believed to be strongly influenced by the atmospheric concentration of hydrogen sulfide the victims were exposed to and the time interval between exposure and death.

  12. Study of catalytic reduction and photodegradation of methylene blue by heterogeneous catalyst.

    Science.gov (United States)

    Sohrabnezhad, Sh

    2011-10-15

    The photocatalytic degradation of methylene blue is investigated in aqueous solution containing CoS/nanoAl-MCM-41 photocatalyst under visible light. The catalyst is characterized by X-ray diffraction (XRD), UV-vis diffused reflectance spectra (UV-vis DRS) and transmission electron microscopy (TEM) techniques. The effect of CoS, nanoAl-MCM-41 support and different wt% of CoS over the support on the photocatalytic degradation and influence of parameters such as CoS loading, catalyst amount, pH and initial concentration of methylene blue on degradation are evaluated. Hypsochromic effects (i.e. blue shifts of spectral bands) resulting from N-demethylation of the dimethylamino group in methylene blue occurs in presence of CoS/nanoAl-MCM-41 under ambient condition. Meanwhile, the bleaching of methylene blue MB, by sulfide ion, in an aqueous solution is studied in the presence nanoAl-MCM-41 catalyst. In the presence of sulfide ions, MB is bleached to its colorless leuco (LMB) and MBH(2)(+) forms. In an acidified solution (pHdye to MBH(2)(+) form is observed. Using nanoAl-MCM-41 with encapsulated CoS nanoparticles only causes demethylation of MB in aqueous solution.

  13. Growth of epitaxial silicon nanowires on a Si substrate by a metal-catalyst-free process.

    Science.gov (United States)

    Ishiyama, Takeshi; Nakagawa, Shuhei; Wakamatsu, Toshiki

    2016-07-28

    The growth of epitaxial Si nanowires by a metal-catalyst-free process has been investigated as an alternative to the more common metal-catalyzed vapor-liquid-solid process. The well-aligned Si nanowires are successfully grown on a (111)-oriented Si substrate without any metal catalysts by a thermal treatment using silicon sulfide as a Si source at approximately 1200 °C. The needle-shaped Si nanowires, which have a core-shell structure that consists of a single-crystalline Si core along the direction consistent with the substrate direction and a surface coating of silicon oxide, are grown by a metal-catalyst-free process. In this process, the silicon sulfide in the liquid phase facilitates the nucleation and nanowire growth. In contrast, oxygen-rich nanowires that consist of crystalline Si at the tip and lumpy silicon oxide on the body are observed in a sample grown at 1300 °C, which disturbs the epitaxial growth of Si nanowires.

  14. A water soluble heteropolyoxotungstate as a selective, efficient and environment friendly oxidation catalyst

    Indian Academy of Sciences (India)

    Prasenjit Maity; Double Mukesh; Sumit Bhaduri; Goutam Kumar Lahiri

    2009-07-01

    A series of water soluble Keggin type heteropolyoxotungstates have been tested as oxidation catalysts in aqueous-biphasic media with dilute H2O2 (30%) as the oxygen atom donor, without using any phase transfer agent. The Zn substituted polyoxoanion {(NH4)7Zn0.5[-ZnO4W11O30ZnO5(OH2)].H2O} has been found to be the most efficient catalyst, which oxidizes a wide range of organic functionalities with good turnovers and high selectivities. The functionalities that undergo oxidations are: organic sulfides, pyridines, anilines, benzyl alcohols and benzyl halides. The oxidations of sulfides to sulfoxides and/or sulfones have been studied in detail, and a simple kinetic model consisting of two consecutive reactions, is shown to give good fit with the experimental data. In the catalytic system described here product isolation is easy, and the aqueous catalyst solution can be re-used several times with little loss in its efficiency.

  15. High-pressure sulfidation of hydrotreating catalysts: Genesis and properties of the active phase

    NARCIS (Netherlands)

    Dugulan, A.I.

    2008-01-01

    The global petroleum demand is projected to increase in the next decennia as oil is expected to remain the primary source of energy around the globe contributing to approximately 40% of the total consumption. The production of high-quality fuels from crude oil involves physical separation steps but

  16. REACTOR FILLED WITH CATALYST MATERIAL, AND CATALYST THEREFOR

    NARCIS (Netherlands)

    Sie, S.T.

    1995-01-01

    Abstract of WO 9521691 (A1) Described is a reactor (1) at least partially filled with catalyst granules (11), which is intended for catalytically reacting at least one gas and at least one liquid with each other. According to the invention the catalyst granules (11) are collected in agglomerates

  17. Modeling Sulfides, pH and Hydrogen Sulfide Gas in the Sewers of San Francisco.

    Science.gov (United States)

    Vollertsen, Jes; Revilla, Nohemy; Hvitved-Jacobsen, Thorkild; Nielsen, Asbjørn Haaning

    2015-11-01

    An extensive measuring campaign targeted on sewer odor problems was undertaken in San Francisco. It was assessed whether a conceptual sewer process model could reproduce the measured concentrations of total sulfide in the wastewater and H2S gas in the sewer atmosphere, and to which degree such simulations have potential for further improving odor and sulfide management. The campaign covered measurement of wastewater sulfide by grab sampling and diurnal sampling, and H2S gas in the sewer atmosphere was logged. The tested model was based on the Wastewater Aerobic/Anaerobic Transformations in Sewers (WATS) sewer process concept, which never had been calibrated to such an extensive dataset. The study showed that the model was capable of reproducing the general levels of wastewater sulfide, wastewater pH, and sewer H2S gas. It could also reproduce the general variability of these parameters, albeit with some uncertainty. It was concluded that the model could be applied for the purpose in mind.

  18. Mechanochemistry, catalysis, and catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Butyagin, P.Yu.

    1987-07-01

    The physical basis of mechanochemistry and the reasons for the initiation and acceleration of chemical reactions upon the mechanical treatment of solids have been considered. The phenomenon of mechanical catalysis has been described in the example case of the oxidation of CO on oxide surfaces, and the nature of the active sites and the laws governing the mechanically activated chemisorption of gases on cleavage and friction surfaces of solids have been examined. The possibilities of the use of the methods of mechanochemistry in processes used to prepare catalysts have been analyzed in examples of decomposition reactions of inorganic compounds and solid-phase synthesis.

  19. Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

    Science.gov (United States)

    Fielder, William L.; Singer, Joseph

    1988-01-01

    A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

  20. Oxygen electrode bifunctional electrocatalyst NiCo/sub 2/O/sub 4/ spinel

    Energy Technology Data Exchange (ETDEWEB)

    Fielder, W.L.; Singer, J.

    1988-09-01

    A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.