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Sample records for high cobalt catalyst

  1. Bifunctional cobalt F-T catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.G.; Coughlin, P.K.; Yang, C.L.; Rabo, J.A.

    1986-03-01

    Results on the catalytic screening of Fischer-Tropsch catalysts containing shape selective components are reported. Catalysts consist of promoted cobalt intimately contacted with Union Carbide molecular sieves and were tested using a Berty type internally recycled reactor. Methods of preparation, promoters and shape selective components were varied and aimed at improving catalyst performance. Catalysts were developed demonstrating high C/sub 5/ + yields with high olefin content and low methane production while maintaining stability under both low and high H/sub 2/:CO ratio conditions.

  2. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    Science.gov (United States)

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  3. The Application of Moessbauer Emission Spectroscopy to Industrial Cobalt Based Fischer-Tropsch Catalysts

    International Nuclear Information System (INIS)

    Loosdrecht, J. van de; Berge, P. J. van; Craje, M. W. J.; Kraan, A. M. van der

    2002-01-01

    The application of Moessbauer emission spectroscopy to study cobalt based Fischer-Tropsch catalysts for the gas-to-liquids process was investigated. It was shown that Moessbauer emission spectroscopy could be used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer-Tropsch catalysts. Oxidation was observed under conditions that are in contradiction with the bulk cobalt phase thermodynamics. This can be explained by oxidation of small cobalt crystallites or by surface oxidation. The formation of re-reducible Co 3+ species was observed as well as the formation of irreducible Co 3+ and Co 2+ species that interact strongly with the alumina support. The formation of the different cobalt species depends on the oxidation conditions. Iron was used as a probe nuclide to investigate the cobalt catalyst preparation procedure. A high-pressure Moessbauer emission spectroscopy cell was designed and constructed, which creates the opportunity to study cobalt based Fischer-Tropsch catalysts under realistic synthesis conditions.

  4. Graphene sheets/cobalt nanocomposites as low-cost/high-performance catalysts for hydrogen generation

    International Nuclear Information System (INIS)

    Zhang, Fei; Hou, Chengyi; Zhang, Qinghong; Wang, Hongzhi; Li, Yaogang

    2012-01-01

    The production of clean and renewable hydrogen through the hydrolysis of sodium borohydride has received much attention owing to increasing global energy demands. Graphene sheets/cobalt (GRs/Co) nanocomposites, which are highly efficient catalysts, have been prepared using a one-step solvothermal method in ethylene glycol. Co 2+ salts were converted to Co nanoparticles, which were simultaneously inserted into the graphene layers with the reduction of graphite oxide sheets to GRs. The as-synthesized samples were characterized by X-ray diffraction, Fourier transform infrared spectra, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and vibrating sample magnetometer. The maximum saturation magnetization value reached 80.8 emu g −1 , meaning they are more suitable for magnet-controlled generation of H 2 than noble metal catalysts. The catalytic activity of the composite was investigated by the hydrolysis of sodium borohydride in aqueous solution both with and without a GRs support. It was found that the high electronic conductive GRs support increased the hydrogen generation rate (about two times) compared with pure cobalt. The improved hydrogen generation rate, low cost and uncomplicated recycling makes the GRs/Co nanocomposites promising candidates as catalysts for hydrogen generation. Highlights: ► Graphene sheets/cobalt nanocomposites were prepared by a one-step solvothermal method. ► The maximum saturation magnetization value of the composites reached 80.8 emu g −1 . ► The graphene support greatly increased the catalytic activity of cobalt. ► An easily removed, recycled and controlled functional filter was obtained.

  5. Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

    Science.gov (United States)

    Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

    2018-05-01

    Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

  6. Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Dongyan; Liu, Xinmin; Cao, Changqing; Guo, Qingjie [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Dai, Ping [College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao 266061 (China)

    2008-08-01

    Low cost transition metal catalysts with high performance are attractive for the development of on-board hydrogen generation systems by catalytic hydrolysis of sodium borohydride (NaBH{sub 4}) in fuel cell fields. In this study, hydrogen production from alkaline NaBH{sub 4} via hydrolysis process over carbon-supported cobalt catalysts was studied. The catalytic activity of the supported cobalt catalyst was found to be highly dependent on the calcination temperatures. The hydrogen generation rate increases with calcination temperatures in the range of 200-400 C, but a high calcination temperature above 500 C led to markedly decreased activity. X-ray diffraction patterns reveal that the catalysts experience phase transition from amorphous Co-B to crystalline cobalt hydroxide with increase in calcination temperatures. The reaction performance is also dependent on the concentration of NaBH{sub 4}, and the hydrogen generation rate increases for lower NaBH{sub 4} concentrations and decreases after reaching a maximum at 10 wt.% of NaBH{sub 4}. (author)

  7. Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

    Science.gov (United States)

    Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

    2016-08-24

    A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

  8. New efficient catalyst for ammonia synthesis: barium-promoted cobalt on carbon

    DEFF Research Database (Denmark)

    Hagen, Stefan; Barfod, Rasmus; Fehrmann, Rasmus

    2002-01-01

    Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia......Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia...

  9. Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

    Science.gov (United States)

    Klettlinger, Jennifer L. S.; Yen, Chia H.; Nakley, Leah M.; Surgenor, Angela D.

    2016-01-01

    Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 ?C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  10. Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

    KAUST Repository

    Sun, Xiaohui

    2017-11-16

    The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size, distribution, and accessibility has proven challenging because of the clear interdependence between these crucial performance parameters. Here we present a stepwise methodology that, making use of a cobalt-containing metal organic framework as hard template (ZIF-67), allows addressing this long-standing challenge. Condensation of silica in the Co-metal organic framework pore space followed by pyrolysis and subsequent calcination of these composites renders highly loaded cobalt nanocomposites (~ 50 wt.% Co), with cobalt oxide reducibility in the order of 80% and a good particle dispersion, that exhibit high activity, C5 + selectivity and stability in Fischer-Tropsch synthesis.

  11. Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Mondal, Arijit; Mukherjee, Debkumar, E-mail: debkumarmukherjee@rediffmail.com [Ramsaday College, Department of Chemistry (India); Adhikary, Bibhutosh, E-mail: adhikarybibhu@yahoo.com [Indian Institute of Engineering, Sciences and Technology, Shibpur, Department of Chemistry (India); Ahmed, Md Azharuddin [University of Calcutta, Department of Physics (India)

    2016-05-15

    Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4–6 nm) can also be prepared from PdCl{sub 2} and K{sub 2}PtCl{sub 4}, respectively, using the same surfactant but require high temperature (~120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90–95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.Graphical Abstract.

  12. Nitrogen oxides storage catalysts containing cobalt

    Science.gov (United States)

    Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

    2010-10-12

    Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

  13. Cobalt Fischer-Tropsch catalysts: influence of cobalt dispersion and titanium oxides promotion

    Energy Technology Data Exchange (ETDEWEB)

    Azib, H

    1996-04-10

    The aim of this work is to study the effect of Sol-Gel preparation parameters which occur in silica supported cobalt catalysts synthesis. These catalysts are particularly used for the waxes production in natural gas processing. The solids have been characterized by several techniques: transmission electron microscopy (TEM), X-ray absorption near edge spectroscopy (XANES), programmed temperature reduction (TPR), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), Magnetism, thermodesorption of H{sub 2} (TPD). The results indicate that the control of the cobalt dispersion and oxide phases nature is possible by modifying Sol-Gel parameters. The catalytic tests in Fischer-Tropsch synthesis were conducted on a pilot unit under pressure (20 atm) and suggested that turnover rates were independent of Co crystallite size, Co phases in the solids (Co deg., cobalt silicate) and titanium oxide promotion. On the other methane, the C{sub 3}{sup +} hydrocarbon selectivity is increased with increasing crystallite size. Inversely, the methane production is favoured by very small crystallites, cobalt silicate increase and titanium addition. However, the latter, used as a cobalt promoter, has a benefic effect on the active phase stability during the synthesis. (author). 149 refs., 102 figs., 71 tabs.

  14. Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

    KAUST Repository

    Xia, Wei

    2015-02-05

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

  15. Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

    KAUST Repository

    Xia, Wei; Salmeia, Khalifah A.; Vagin, Sergei I.; Rieger, Bernhard

    2015-01-01

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

  16. Effect of Cobalt Source on the Catalyst Reducibility and Activity of ...

    African Journals Online (AJOL)

    The effect of cobalt precursor (nitrate, acetate and chloride salts) on the catalyst reducibility and dispersion, ... balt catalysts (>5.0 wt%) prepared using ammonium cobalt ... heated from 323 K to 1073 K using a heating ramp of 10 K min–1.

  17. Characterization and Catalytic Activity of Montmorillonite K10-Supported Cobalt Catalysts

    International Nuclear Information System (INIS)

    Gobara, H.M.; Ghattas, M.S.; Henien, S.A.

    2010-01-01

    Montmorillonite K10-supported cobalt catalysts were prepared by wet impregnation method. The samples were analyzed by XRD, TPR, FTTR and BET characterization techniques. [Three phases of cobalt species were identified namely, cobalt oxide (Co 3 O 4 ), cobalt silicate (Co 2 S 1 O 4 ) and cobalt aluminate (CoAl 2 O 4 ). These species were most probably existing within the inter lamellar spaces of the meso porous montmorillonite K10 support]. The two bands observed at 1385 and 760 cm 1 were characteristic of metal species rather than the support, being mostly of Co - O bond vibration. The hysteresis loop, pore size distribution, pore volume and BET surface area were greatly affected by cobalt loading. The catalyst containing 18 wt% cobalt was the most selective sample for ethylene production from ethanol dehydration.

  18. Development of Hydrotalcite Based Cobalt Catalyst by Hydrothermal and Co-precipitation Method for Fischer-Tropsch Synthesis

    Directory of Open Access Journals (Sweden)

    Muhammad Faizan Shareef

    2017-10-01

    Full Text Available This paper presents the effect of a synthesis method for cobalt catalyst supported on hydrotalcite material for Fischer-Tropsch synthesis. The hydrotalcite supported cobalt (HT-Co catalysts were synthesized by co-precipitation and hydrothermal method. The prepared catalysts were characterized by using various techniques like BET (Brunauer–Emmett–Teller, SEM (Scanning Electron Microscopy, TGA (Thermal Gravimetric Analysis, XRD (X-ray diffraction spectroscopy, and FTIR (Fourier Transform Infrared Spectroscopy. Fixed bed micro reactor was used to test the catalytic activity of prepared catalysts. The catalytic testing results demonstrated the performance of hydrotalcite based cobalt catalyst in Fischer-Tropsch synthesis with high selectivity for liquid products. The effect of synthesis method on the activity and selectivity of catalyst was also discussed. Copyright © 2017 BCREC Group. All rights reserved Received: 3rd November 2016; Revised: 26th February 2017; Accepted: 9th March 2017; Available online: 27th October 2017; Published regularly: December 2017 How to Cite: Sharif, M.S., Arslan, M., Iqbal, N., Ahmad, N., Noor, T. (2017. Development of Hydrotalcite Based Cobalt Catalyst by Hydrothermal and Co-precipitation Method for Fischer-Tropsch Synthesis. Bulletin of Chemical Reaction Engineering & Catalysis, 12(3: 357-363 (doi:10.9767/bcrec.12.3.762.357-363

  19. Cobalt supported on carbon nanofibers as catalysts for the Fischer-Tropsch synthesis

    NARCIS (Netherlands)

    Bezemer, G.L.

    2006-01-01

    The Fischer-Tropsch (FT) process converts synthesis gas (H2/CO) over a heterogeneous catalyst into hydrocarbons. Generally, cobalt catalysts supported on oxidic carriers are used for the FT process, however it appears to be difficult to obtain and maintain fully reduced cobalt particles. To overcome

  20. Control of carbon nanotube growth using cobalt nanoparticles as catalyst

    International Nuclear Information System (INIS)

    Huh, Yoon; Green, Malcolm L.H.; Kim, Young Heon; Lee, Jeong Yong; Lee, Cheol Jin

    2005-01-01

    We have controllably grown carbon nanotubes using uniformly distributed cobalt nanoparticles as catalyst. Cobalt nanoparticles with a uniform size were synthesized by chemical reaction and colloidal solutions including the cobalt nanoparticles were prepared. The cobalt nanoparticles were uniformly distributed on silicon substrates by a spin-coating method. Carbon nanotubes with a uniform diameter were synthesized on the cobalt nanoparticles by thermal chemical vapor deposition of acetylene gas. The density and vertical alignment of carbon nanotubes could be controlled by adjusting the density of cobalt (Co) nanoparticles

  1. The effect of zirconium on cobalt catalyst in fischer-tropsch synthesis

    International Nuclear Information System (INIS)

    Moradi, GH.R.; Mahbob Basir, M.; Taeb, A.

    2003-01-01

    A series of 10 wt % Co/SiO 2 catalysts with different loading ratios of zirconia (0, 5, 10, 15, 20) has been prepared through an original pseudo sol-gel method. All catalysts were characterized by BET, XRD, SEM, and TPR experiments. The catalytic performance of the catalysts for the so-called fischer- tropsch synthesis was examined under H 2 /CO=2 at 230 d ig C and 8 bar in a fixed bed microreactor. By increasing zirconia, the Co-SiO 2 interaction decreases and is replaced by Co-Zr interaction which favours reduction of the catalyst at lower temperatures. While it leads to a higher degree of reduction and as increase in the metallic cobalt atoms on the surface. The activity of the promoted catalysts increases with the addition of zirconia (max. by a factor 2.5). The C 1 0 + selectivity increased with the addition of zirconia (from 42.3% in unpromoted catalyst to 68.8 % in the 20 % ZrO 2 promoted. This can be attributed to the higher amount of the surface Cobalt metal present and to the larger Cobalt particle size

  2. Influence of Cobalt Precursor on Efficient Production of Commercial Fuels over FTS Co/SiC Catalyst

    Directory of Open Access Journals (Sweden)

    Ana Raquel de la Osa

    2016-07-01

    Full Text Available β-SiC-supported cobalt catalysts have been prepared from nitrate, acetate, chloride and citrate salts to study the dependence of Fischer–Tropsch synthesis (FTS on the type of precursor. Com/SiC catalysts were synthetized by vacuum-assisted impregnation while N2 adsorption/desorption, XRD, TEM, TPR, O2 pulses and acid/base titrations were used as characterization techniques. FTS catalytic performance was carried out at 220 °C and 250 °C while keeping constant the pressure (20 bar, space velocity (6000 Ncm3/g·h and syngas composition (H2/CO:2. The nature of cobalt precursor was found to influence basic behavior, extent of reduction and metallic particle size. For β-SiC-supported catalysts, the use of cobalt nitrate resulted in big Co crystallites, an enhanced degree of reduction and higher basicity compared to acetate, chloride and citrate-based catalysts. Consequently, cobalt nitrate provided a better activity and selectivity to C5+ (less than 10% methane was formed, which was centered in kerosene-diesel fraction (α = 0.90. On the contrary, catalyst from cobalt citrate, characterized by the highest viscosity and acidity values, presented a highly dispersed distribution of Co nanoparticles leading to a lower reducibility. Therefore, a lower FTS activity was obtained and chain growth probability was shortened as observed from methane and gasoline-kerosene (α = 0.76 production when using cobalt citrate.

  3. Model studies of secondary hydrogenation in Fischer-Tropsch synthesis studied by cobalt catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Aaserud, Christian

    2003-07-01

    Mass transfer effects are very important in Fischer-Tropsch (FT) synthesis. In order to study the FT synthesis without the influence of any transport limitations, cobalt foils have been used as model catalysts. The effect of pretreatment (number of calcinations and different reduction times) for cobalt foil catalysts at 220 {sup o}C, 1 bar and H{sub 2}/CO = 3 has been studied in a microreactor. The foils were examined by Scanning electron microscopy (SEM). It was found that the catalytic activity of the cobalt foil increases with the number of pretreatments possibly due to an increase in the surface area of the cobalt foil. The SEM results support the assumption that the surface area of the cobalt foil increases with the number of pretreatments. The reduction time was also found to influence the catalytic activity of the cobalt foil. Highest activity was obtained using a reduction time of only five min (compared to one and thirty min). The decrease in activity after reduction for thirty min compared to five min was suggested to be due to restructuring of the surface of the cobalt foil and a reduction time of only 1 min was not enough to reduce the cobalt foil sufficiently. Time of reduction did also influence the product distribution. Increased reduction time resulted in a lower selectivity to light products and increased selectivity to heavier components. The paraffin/olefin ratio increased with increasing CO-conversion also for cobalt foils. The paraffin/olefin ratio also increased when the reduction period of the cobalt foil was increased at a given CO-conversion. Hydrogenation of propene to propane has been studied as a model reaction for secondary hydrogenation of olefins in the FT synthesis. The study has involved promoted and unpromoted cobalt FT catalysts supported on different types of supports and also unsupported cobalt. Hydrogenation of propene was carried out at 120 {sup o}C, 1.8 bar and H{sub 2}/C{sub 3}H{sub 6} 6 in a fixed bed microreactor. The rate

  4. Catalytic activity of cobalt and cerium catalysts supported on calcium hydroxyapatite in ethanol steam reforming

    Directory of Open Access Journals (Sweden)

    Dobosz Justyna

    2016-09-01

    Full Text Available In this paper, Co,Ce/Ca10(PO46(OH2 catalysts with various cobalt loadings for steam reforming of ethanol (SRE were prepared by microwave-assisted hydrothermal and sol-gel methods, and characterized by XRD, TEM, TPR-H2, N2 adsorption-desorption measurements and cyclohexanol (CHOL decomposition tests. High ethanol conversion (close to 100% was obtained for the catalysts prepared by both methods but these ones prepared under hydrothermal conditions (HAp-H ensured higher hydrogen yield (3.49 mol H2/mol C2H5OH as well as higher amount of hydrogen formed (up to 70% under reaction conditions. The superior performance of 5Co,10Ce/HAp-H catalyst is thought to be due to a combination of factors, including increased reducibility and oxygen mobility, higher density of basic sites on its surface, and improved textural properties. The results also show a significant effect of cobalt loading on catalysts efficiency in hydrogen production: the higher H2 yield exhibit catalysts with lower cobalt content, regardless of the used synthesis method.

  5. Polyacrylonitrile Fibers Anchored Cobalt/Graphene Sheet Nanocomposite: A Low-Cost, High-Performance and Reusable Catalyst for Hydrogen Generation.

    Science.gov (United States)

    Zhang, Fei; Huang, Guoji; Hou, Chengyi; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang

    2016-06-01

    Cobalt and its composites are known to be active and inexpensive catalysts in sodium borohydride (NaBH4) hydrolysis to generate clean and renewable hydrogen energy. A novel fiber catalyst, cobalt/graphene sheet nanocomposite anchored on polyacrylonitrile fibers (Co/GRs-PANFs), which can be easily recycled and used in any reactor with different shapes, were synthesized by anchoring cobalt/graphene (Co/GRs) on polyacrylonitrile fibers coated with graphene (GRs-PANFs) at low temperature. The unique structure design effectively prevents the inter-sheet restacking of Co/GRs and fully exploits the large surface area of novel hybrid material for generate hydrogen. And the extra electron transfer path supplied by GRs on the surface of GRs-PANFs can also enhance their catalysis performances. The catalytic activity of the catalyst was investigated by the hydrolysis of NaBH4 in aqueous solution with GRs-PANFs. GRs powders and Co powders were used as control groups. It was found that both GRs and fiber contributed to the hydrogen generation rate of Co/GRs-PANFs (3222 mL x min(-1) x g(-1)), which is much higher than that of cobalt powders (915 mL x min(-1) x g(-1)) and Co/GRs (995 mL x min(-1) x g(-1)). The improved hydrogen generation rate, low cost and uncomplicated recycling make the Co/GRs-PANFs promising candidate as catalysts for hydrogen generation.

  6. Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

    Directory of Open Access Journals (Sweden)

    Gary Jacobs

    2014-03-01

    Full Text Available This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co0 site densities (e.g., in research catalysts, ultra-small crystallites (e.g., <2–4.4 nm formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co0 (e.g., Cu, or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at high loading. Computational studies indicate that certain promoters may inhibit polymeric C formation by hindering C-C coupling.

  7. Preparation of Fischer-Tropsch catalysts from cobalt/iron hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Howard, B.H.; Boff, J.J.; Zarochak, M.F. [Pittsburgh Energy Technology Center, PA (United States)] [and others

    1995-12-31

    Compounds with the (hydrotalcites) have properties that make them attractive as precursors for Fischer-Tropsch catalysts. A series of single-phase hydrotalcites with cobalt/iron atom ratios ranging from 75/25 to 25/75 has been synthesized. Mixed cobalt/iron oxides have been prepared from these hydrotalcites by controlled thermal decomposition. Thermal decomposition at temperatures below 600 {degrees}C typically produced a single-phase mixed metal oxide with a spinel structure. The BET surface areas of the spinal samples have been found to be as high as about 150 m{sup 2}/g. Appropriate reducing pretreatments have been developed for several of these spinels and their activity, selectivity, and activity and selectivity maintenance have been examined at 13 MPa in a fixed-bed microreactor.

  8. EXAFS Determination of the Structure of Cobalt in Carbon-Supported Cobalt and Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Bouwens, S.M.A.M.; Veen, J.A.R. van; Beer, V.H.J. de; Prins, R.

    1991-01-01

    The structure of the cobalt present in carbon-supported Co and Co-Mo sulfide catalysts was studied by means of X-ray absorption spectroscopy at the Co K-edge and by X-ray photoelectron spectroscopy (XPS). Thiophene hydrodesulfurization activities were used to measure the catalytic properties of

  9. Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

    2015-01-15

    Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was more beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.

  10. Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C═O Bonds.

    Science.gov (United States)

    Chen, Feng; Topf, Christoph; Radnik, Jörg; Kreyenschulte, Carsten; Lund, Henrik; Schneider, Matthias; Surkus, Annette-Enrica; He, Lin; Junge, Kathrin; Beller, Matthias

    2016-07-20

    Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phen@α-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.

  11. Effect of cobalt sources on properties of co-b catalysts synthesized by sol-gel method

    Energy Technology Data Exchange (ETDEWEB)

    Figen, Aysel Kantürk; Co ú kuner, Bilge; Özdemir, Özgül Dere [Department of Chemical Engineering, Yildiz Technical University Istanbul (Turkey); Burçin Pi ú kin, Mehmet [Department of Bioengineering, Y Õ ld Õ z Technical University, Istanbul (Turkey)

    2013-07-01

    In this studying, Co-B catalysts were prepared by sol-gel method via kinds of cobalt source for clarifying the effect of these for characteristic properties of Co-B catalysts. Co sources, cobalt(II)chloride (CoCl{sub 2} .6H{sub 2}O), cobalt(II)sulfate (CoSO{sub 4} .7H{sub 2}O) and cobalt(II)nitrate (Co(NO{sub 3}){sub 2} .6H{sub 2}O), were used as a metal source with boron oxide (B{sub 2}O{sub 3} ) while citric acid (C{sub 6}H{sub 8}O{sub 7} ) used as organic ligand to forming sol-gel structure. The crystalline structures of Co-B catalysts were determined by X-ray diffraction. The N{sub 2} sorption technique was used for analyzing catalysts surface area. The variety of Co-B catalysts morphological properties were investigated via scanning electron microscope. By the effect of cobalt sources the Co-B catalyst’s properties were altered that clarified from analysis results. The amorphous Co-B catalyst produced from CoCl{sub 2}.6H{sub 2} O as metal source had the largest porous surface area with 122.7 m 2 .g -1 . Investigation of hydrolysis were performed under variety of temperatures (22, 40 and 60 o C), NaOH concentrations (1-15 wt. %) and NaBH 4 /Co-B catalyst ratio (2-40 wt./wt.) ratios in order to investigate the activation of Co-B catalyst. The maximum hydrogen generation rate 0.84L H 2 .min -1 .g -1 was obtained under 40 °C, 10 wt. % NaOH and 9.52wt./wt. NaBH{sub 4}/Co-B catalyst ratio. Yet the kinetic investigations, the reaction order was found that zero order with 0.9954 coefficient of correlation and 51.83 kJ/mol activation energy. Key words: Sol-gel, Co-B Catalyst, Boron.

  12. The formation and influence of carbon on cobalt-based Fischer-Tropsch synthesis catalysts : an integrated review

    NARCIS (Netherlands)

    Moodley, D.J.; Loosdrecht, van de J.; Saib, A.M.; Niemantsverdriet, J.W.; Davis, B.H.; Occelli, M.L.; Speight, J.G.

    2010-01-01

    Cobalt-based Fischer-Tropsch synthesis (FTS) catalysts are the systems of choice for use in gas-to-liquid (GTL) processes. As with most catalysts, cobalt systems gradually lose their activity with increasing time on stream. There are various mechanisms that have been proposed for the deactivation of

  13. Cobalt-embedded carbon nanofiber derived from a coordination polymer as a highly efficient heterogeneous catalyst for activating oxone in water.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Tong, Wai-Chi; Du, Yunchen

    2018-03-01

    Carbon fiber (CF) supported cobalt nanoparticles (NPs) are promising catalysts for activating Oxone because carbon is non-metal and earth-abundant, and CF-based catalysts exhibit a high aspect ratio, which affords more accessible and dense catalytic sites. Nevertheless, most of CF-supported catalysts are fabricated by post-synthetic methods, which involve complicated preparations. More importantly, metallic NPs are attached to the outer surface of CF rather than embedded within CF. However, there is still a great demand for developing Co-bearing carbon fibers for Oxone activation via simple and effective methods. Thus, this study proposes to develop a cobalt NP-embedded carbon nanofiber (CCNF) by a simple hydrothermal reaction of Co and nitrilotriacetic acid (NA), followed by one-step carbonization. Owing to the coordinative structure of CoNA, the derivative CCNF exhibits a fibrous carbon matrix embedded with evenly distributed and densely packed Co 3 O 4 and magnetic Co 0 nanoparticles. The fibrous structure, magnetism and embedded Co NPs enable CCNF to be a promising catalyst for Oxone activation. As degradation of Rhodamine B (RhB) is selected as a model reaction, CCNF not only rapidly activates Oxone to fully degrade RhB but also shows a much higher catalytic activity than the most common Oxone activator, Co 3 O 4 . CCNF also exhibits the lowest activation energy than any reported catalysts for Oxone activation to degrade RhB. In addition, CCNF could be re-used to activate Oxone for RhB degradation. These results indicate that CCNF is a conveniently prepared and highly effective fibrous Co/C hybrid material for activating Oxone to oxidize contaminants in water. Copyright © 2017. Published by Elsevier Ltd.

  14. Characterization and performances of cobalt-tungsten and molybdenum-tungsten carbides as anode catalyst for PEFC

    International Nuclear Information System (INIS)

    Izhar, Shamsul; Yoshida, Michiko; Nagai, Masatoshi

    2009-01-01

    The preparation of carbon-supported cobalt-tungsten and molybdenum-tungsten carbides and their activity as an anode catalyst for a polymer electrolyte fuel cell were investigated. The electrocatalytic activity for the hydrogen oxidation reaction over the catalysts was evaluated using a single-stack fuel cell and a rotating disk electrode. The characterization of the catalysts was performed by XRD, temperature-programmed carburization, temperature-programmed reduction and X-ray photoelectron spectroscopy. The maximum power densities of the 30 wt% 873 K-carburized cobalt-tungsten and molybdenum-tungsten mixed with Ketjen carbon (cobalt-tungsten carbide (CoWC)/Ketjen black (KB) and molybdenum-tungsten carbide (MoWC)/KB) were 15.7 and 12.0 mW cm -2 , respectively, which were 14 and 11%, compared to the in-house membrane electrode assembly (MEA) prepared from a 20 wt% Pt/C catalyst. The CoWC/KB catalyst exhibited the highest maximum power density compared to the MoWC/KB and WC/KB catalysts. The 873 K-carburized CoW/KB catalyst formed the oxycarbided and/or carbided CoW that are responsible for the excellent hydrogen oxygen reaction

  15. Recovery of Cobalt from leach solution of spent oil Hydrodesulphurization catalyst using a synergistic system consisting of VersaticTM10 and Cyanex®272

    Science.gov (United States)

    Yuliusman; Ramadhan, I. T.; Huda, M.

    2018-03-01

    Catalyst are often used in the petroleum refinery industry, especially cobalt-based catalyst such as CoMoX. Every year, Indonesia’s oil industry produces around 1350 tons of spent hydrodesulphurization catalyst in which cobalt makes up for 7%wt. of them. Cobalt is a non-renewable and highly valuable resource. Taking into account the aforementioned reasons, this research was made to recover cobalt from spent hydrodesulphurization catalyst so that it can be reused by industries needing them. The methods used in the recovery of cobalt from the waste catalyst leach solution are liquid-liquid extraction using a synergistic system of VersaticTM 10 and Cyanex®272. Based on the experiments done using the aforementioned methods and materials, the optimum condition for the extraction process: concentration of VersaticTM 10 of 0.35 M, Cyanex®272 of 0.25 M, temperature of 23-25°C (room temperature), and pH of 6 with an extraction percentage of 98.80% and co-extraction of Ni at 93.51%.

  16. Nickel and cobalt bimetallic hydroxide catalysts for urea electro-oxidation

    International Nuclear Information System (INIS)

    Yan Wei; Wang Dan; Botte, Gerardine G.

    2012-01-01

    Nickel–Cobalt bimetallic hydroxide electrocatalysts, synthesized through a one-step electrodeposition method, were evaluated for the oxidation of urea in alkaline conditions with the intention of reducing the oxidation overpotential for this reaction. The Nickel–Cobalt bimetallic hydroxide catalysts were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Raman spectroscopy, cyclic voltammetry (CV), and polarization techniques. A significant reduction in the overpotential (150 mV) of the reaction was observed with the Nickel–Cobalt bimetallic hydroxide electrode (ca. 43% Co content) when compared to a nickel hydroxide electrode. The decrease of the urea oxidation potential on the Nickel–Cobalt bimetallic hydroxide electrodes reveals great potential for future applications of urea electro-oxidation, including wastewater remediation, hydrogen production, sensors, and fuel cells.

  17. On the Deactivation of Cobalt-based Fischer-Tropsch Catalysts

    NARCIS (Netherlands)

    Cats, K.H.

    2016-01-01

    The Fischer-Tropsch Synthesis (FTS) process is an attractive way to obtain synthetic liquid fuel from alternative energy sources such as natural gas, coal or biomass. However, the deactivation of the catalyst, consisting of cobalt nanoparticles supported on TiO2, currently hampers the industrial

  18. Recovery of molybdenum and cobalt powders from spent hydrogenation catalyst

    International Nuclear Information System (INIS)

    Rabah, M.A.; Hewaidy, I.F.; Farghaly, F.E.

    1996-01-01

    Free powders as well as compact shapes of molybdenum and cobalt have been successfully recovered from spent hydrogenation and desulphurization catalysts. A process flow sheet was followed involving crushing, milling, particle sizing, hydrometallurgical acid leaching roasting of the obtained salts in an atmospheric oxygen to obtain the respective oxides. These were reduced by hydrogen gas at 110 degree C and 900 degree C respectively. Parameters affecting the properties of the products and the recovery efficiency value such as acid concentration, particle diameter of the solid catalyst, temperature time under a constant mass flow rate the hydrogen gas, have been investigated. A mixture of concentration.sulphuric and nitric acids (3:1 by volume) achieved adequate recovery of both metals. The latter increased with the increase in acid concentration, time up 10 3 hours and temperature: 100 degree C and with the decrease in particle diameter of the spent catalyst. The PH of the obtained filtrate was adjusted to 2 with ammonia to precipitate insoluble ammonium molybdate and a solution of cobalt sulphate. Cobalt hydroxide can be precipitate from the latter solution at a PH = 7.6 using excess ammonium hydroxide solution. The obtained results showed that the metallic products are technically pure meeting the standard specifications. Compact shapes of molybdenum acquire density values increasing with the increase of the pressing load whereby a maximum density value of 2280 kg/m 3 is attained at 0.75 MPa. Maximum recovery efficiency amounts to 96%. 10 figs., 3 tabs

  19. Catalysts for synthetic liquid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Bruce, L.A.; Turney, T.W.

    1987-12-01

    Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

  20. Electrically conductive aluminum oxide thin film used as cobalt catalyst-support layer in vertically aligned carbon nanotube growth

    International Nuclear Information System (INIS)

    Azam, Mohd Asyadi; Ismail, Syahriza; Mohamad, Noraiham; Isomura, Kazuki; Shimoda, Tatsuya

    2015-01-01

    This paper will present the unique characteristics of aluminum oxide (Al–O) and cobalt catalyst included in aligned carbon nanotube (CNT) electrode system of energy storage device, namely electrochemical capacitor. Electrical conductivity and nanostructure of the thermally oxidized Al–O used as catalyst-support layer in vertically grown single-walled CNTs were studied. Al–O films were characterized by means of current–voltage measurement and high resolution transmission electron microscopy analysis. The Al–O support layer was found to be conductive, with a relatively low resistance and, approximately 20 nm film thickness of Al–O is suggested to be too thin to form insulating barrier. The scanning TEM—annular dark field analysis confirmed that the nanosized cobalt catalyst particles distributed on Al–O surfaces and also embedded inside the Al–O film structure. (paper)

  1. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.

    2010-11-24

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  2. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.; Widger, Peter C. B.; Ahmed, Syud M.; Jeske, Ryan C.; Hirahata, Wataru; Lobkovsky, Emil B.; Coates, Geoffrey W.

    2010-01-01

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  3. An Efficient and Recyclable Nanoparticle-Supported Cobalt Catalyst for Quinoxaline Synthesis

    Directory of Open Access Journals (Sweden)

    Fatemeh Rajabi

    2015-11-01

    Full Text Available The syntheses of quinoxalines derived from 1,2-diamine and 1,2-dicarbonyl compounds under mild reaction conditions was carried out using a nanoparticle-supported cobalt catalyst. The supported nanocatalyst exhibited excellent activity and stability and it could be reused for at least ten times without any loss of activity. No cobalt contamination could be detected in the products by AAS measurements, pointing to the excellent activity and stability of the Co nanomaterial.

  4. Cobalt catalysts for the conversion of methanol and for Fischer-tropsch synthesis to produce hydrocarbons

    International Nuclear Information System (INIS)

    Mauldin, C.H.; Davis, S.M.; Arcuri, K.B.

    1987-01-01

    A regeneration stable catalyst is described for the conversion at reaction conditions of methanol or synthesis gas to liquid hydrocarbons which consists essentially of from about 2 percent to about 25 percent cobalt, based on the weight of the catalyst composition, composited with titania, or a titania-containing support, to which is added sufficient of a zirconium, hafnium, cerium, or uranium promoter to provide a weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt greater than about 0.101:1

  5. Hydroformylation and kinetics of 1-hexene over ruthenium, cobalt and rhodium zerolite catalysts

    International Nuclear Information System (INIS)

    Wang, C.; Wei, W.

    1989-01-01

    In this paper, six kinds of catalysts were prepared by cation exchange with rhodium, ruthenium and cobalt chloropentaamino dichoride and zeolites. Effects such as support materials, PPH 3 to metal ratio, reaction temperature, total pressure, H 2 /CO ratio, reaction time and solvents have been investigated in an autoclave. The most favorable results of 1-hexene hydroformylation were obtained in the temperature range 100-150 degrees C at a pressure of 5.0MPa (H 2 /CO=1:1) and the addition of free PPh 3 . The bimetallic catalysts showed high catalytic activing for hydroformylation because of the synergistic effect of bimetallic systems. This paper reports the results of experiments and catalysts characterization by means of IR and XRD spectroscopy

  6. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Burtron H. Davis

    1999-01-30

    The effects of copper on Fischer-Tropsch activity, selectivity and water-gas shift activity were studied over a wide range of syngas conversion. Three catalyst compositions were prepared for this study: (a) 100Fe/4.6Si/1.4K, (b) 100Fe/4.6Si/0.10Cu/1.4K and (c) 100Fe/4.6Si/2.0Cu/1.4K. The results are reported in Task 2. The literature review for cobalt catalysts is approximately 90% complete. Due to the size of the document, it has been submitted as a separate report labeled Task 6.

  7. Coatings of active and heat-resistant cobalt-aluminium xerogel catalysts.

    Science.gov (United States)

    Schubert, Miriam; Schubert, Lennart; Thomé, Andreas; Kiewidt, Lars; Rosebrock, Christopher; Thöming, Jorg; Roessner, Frank; Bäumer, Marcus

    2016-09-01

    The application of catalytically coated metallic foams in catalytic processes has a high potential for exothermic catalytic reactions such as CO2 methanation or Fischer-Tropsch synthesis due to good heat conductivity, improved turbulent flow properties and high catalyst efficiencies. But the preparation of homogenous catalyst coats without pore blocking is challenging with conventional wash coating techniques. Here, we report on a stable and additive free colloidal CoAlOOH suspension (sol) for the preparation of catalytically active Co/Al2O3 xerogel catalysts and coatings. Powders with 18wt% Co3O4 prepared from this additive free synthesis route show a catalytic activity in Fischer-Tropsch synthesis and CO2 methanation which is similar to a catalyst prepared by incipient wetness impregnation (IWI) after activating the material under flowing hydrogen at 430°C. Yet, the xerogel catalyst exhibits a much higher thermal stability as compared to the IWI catalyst, as demonstrated in catalytic tests after different heat agings between 430°C and 580°C. It was also found that the addition of polyethylene glycol (PEG) to the sol influences the catalytic properties of the formed xerogels negatively. Only non-reducible cobalt spinels were formed from a CoAlOOH sol with 20wt% PEG. Metallic foams with pores sizes between 450 and 1200μm were coated with the additive free CoAlOOH sol, which resulted in homogenous xerogel layers. First catalytic tests of the coated metal foams (1200μm) showed good performance in CO2 methanation. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Nitrogen-Doped Carbon Encapsulated Nickel/Cobalt Nanoparticle Catalysts for Olefin Migration of Allylarenes

    DEFF Research Database (Denmark)

    Kramer, Søren; Mielby, Jerrik Jørgen; Buss, Kasper Spanggård

    2017-01-01

    Olefin migration of allylarenes is typically performed with precious metal-based homogeneous catalysts. In contrast, very limited progress has been made using cheap, earth-abundant base metals as heterogeneous catalysts for these transformations - in spite of the obvious economic and environmental...... advantages. Herein, we report on the use of an easily prepared heterogeneous catalyst material for the migration of olefins, in particular allylarenes. The catalyst material consists of nickel/cobalt alloy nanoparticles encapsulated in nitrogen-doped carbon shells. The encapsulated nanoparticles are stable...

  9. Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

    Science.gov (United States)

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

    2018-05-01

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

  10. Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

    OpenAIRE

    Gary Jacobs; Wenping Ma; Burtron H. Davis

    2014-01-01

    This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing...

  11. Lump Kinetic Analysis of Syngas Composition Effect on Fischer-Tropsch Synthesis over Cobalt and Cobalt-Rhenium Alumina Supported Catalyst

    Directory of Open Access Journals (Sweden)

    Dewi Tristantini

    2016-03-01

    Received: 10th November 2015; Revised: 10th February 2016; Accepted: 16th February 2016 How to Cite: Tristantini, D., Suwignjo, R.K. (2016. Lump Kinetic Analysis of Syngas Composition Effect on Fischer-Tropsch Synthesis over Cobalt and Cobalt-Rhenium Alumina Supported Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 84-92. (doi:10.9767/bcrec.11.1.424.84-92 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.424.84-92

  12. Preparation, surface characterization and performance of a Fischer-Tropsch catalyst of cobalt supported on silica nanosprings

    International Nuclear Information System (INIS)

    Kengne, Blaise-Alexis Fouetio; Alayat, Abdulbaset M.; Luo, Guanqun; McDonald, Armando G.; Brown, Justin; Smotherman, Hayden; McIlroy, David N.

    2015-01-01

    Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: The reduction of cobalt (Co) catalyst supported on silica nanosprings for Fischer-Tropsch synthesis (FTS) has been monitored by X-ray photoelectron spectroscopy (XPS) and compared to FT catalytic activity. The cobalt is present in the starting catalyst as a Co 3 O 4 spinel phase. A two-step reduction of Co 3 O 4 to CoO and then to Co 0 is observed, which is consistent with the results of H 2 -temperature programmed reduction. During the reduction the two steps occur concurrently. The deconvolution of the Co 2p core level state for the catalyst reduced at 385 °C and 1.0 × 10 −6 Torr of H 2 revealed signatures of Co 0 , CoO, and Co 3 O 4 . The reduction saturates at a Co o concentration of approximately 41% after 20 h, which correlates with the activity and lifetime of the catalyst during FTS testing. Conversely, at 680 °C and 10 Torr of H 2 , the catalyst is completely reduced after 10 h. The evolution of the Co d-band at the Fermi level in the valence band XPS spectrum definitively verifies the metallic phase of Co. FTS evaluation of the Co/NS catalyst reduced at 609 °C showed higher production rate (3-fold) of C 6 -C 17 hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

  13. Thermal degradation of Shredded Oil Palm Empty Fruit Bunches (SOPEFB) embedded with Cobalt catalyst by Thermogravimetric Analysis (TGA)

    Science.gov (United States)

    Alias, R.; Hamid, N. H.; Jaapar, J.; Musa, M.; Alwi, H.; Halim, K. H. Ku

    2018-03-01

    Thermal behavior and decomposition kinetics of shredded oil palm empty fruit bunches (SOPEFB) were investigated in this study by using thermogravimetric analysis (TGA). The SOPEFB were analyzed under conditions of temperature 30 °C to 900 °C with nitrogen gas flow at 50 ml/min. The SOPEFB were embedded with cobalt (II) nitrate solution with concentration 5%, 10%, 15% and 20%. The TG/DTG curves shows the degradation behavior of SOPEFB following with char production for each heating rate and each concentration of cobalt catalyst. Thermal degradation occurred in three phases, water drying phase, decomposition of hemicellulose and cellulose phase, and lignin decomposition phase. The kinetic equation with relevant parameters described the activation energy required for thermal degradation at the temperature regions of 200 °C to 350 °C. Activation energy (E) for different heating rate with SOPEFB embedded with different concentration of cobalt catalyst showing that the lowest E required was at SOPEFB with 20% concentration of cobalt catalyst..

  14. Cobalt oxide-based catalysts deposited by cold plasma for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Kazimierski, P.; Jozwiak, L.; Sielski, J.; Tyczkowski, J., E-mail: jacek.tyczkowski@p.lodz.pl

    2015-11-02

    In proton exchange membrane fuel cells (PEMFC), both the anodic hydrogen oxidation reaction and the cathodic oxygen reduction reaction (ORR) require appropriate catalysts. So far, platinum-based catalysts are still the best option for this purpose. However, because these catalysts are too expensive for making commercially viable fuel cells, extensive research over the past decade has focused on developing noble metal-free alternative catalysts. In this paper, an approach based on cobalt oxide films fabricated by plasma-enhanced metal-organic chemical vapor deposition is presented. Such a material can be used to prepare catalysts for ORR in PEMFC. The films containing CoO{sub X} were deposited on a carbon paper thereby forming the electrode. Morphology and atomic composition of the films were investigated by scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively. The possibility of their application as the electro-catalyst for ORR in PEMFC was investigated and the electro-catalytic activities were evaluated by the electrochemical measurements and single cell tests. It was found that the fuel cell with Pt as the anode catalyst and CoO{sub X} deposit as the cathode catalyst was characterized by the open circuit voltage of 635 mV, Tafel slope of approx. 130 mV/dec and the maximum power density of 5.3 W/m{sup 2}. - Highlights: • Cobalt oxide catalyst for proton exchange membrane fuel cells was plasma deposited. • The catalyst exhibits activity for the oxygen reduction reaction. • Morphology and atomic composition of the catalyst were determined.

  15. Enhanced activity and durability of platinum anode catalyst by the modification of cobalt phosphide for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Li, Xiang; Wang, Hongjuan; Yu, Hao; Liu, Ziwu; Wang, Haihui; Peng, Feng

    2015-01-01

    Graphical abstract: A novel Pt/CoP/CNTs electrocatalyst with has been designed and prepared, which exhibits high activity and stability for methanol oxidation reaction. - Highlights: • Pt-cobalt phosphide catalyst supported on carbon nanotubes (Pt/CoP/CNTs) is designed. • Pt/CoP/CNTs exhibit high activity and stability for methanol oxidation reaction(MOR). • The effect of CoP content on electrocatalytic performances for MOR is studied. • CoP decreases the Pt particle size and increases the electrochemical surface areas. • The interaction between Pt and CoP is evidenced by X-ray photoelectron spectroscopy. - Abstract: In this study, carbon nanotubes (CNTs) supported Pt-cobalt phosphide (CoP) electrocatalyst (Pt/CoP/CNTs) is designed and prepared for methanol oxidation (MOR) for the first time. The modification of CoP decreases the Pt particle size significantly and increases the electrochemical surface areas due to the interaction between Pt and CoP, which is evidenced by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Among all these catalysts, Pt/4%CoP/CNTs catalyst exhibits the best MOR activity of 1600 mA mg −1 Pt , which is six times that of Pt/CNTs. Moreover, this catalyst also exhibits the higher onset current density and steady current density than the other Pt-based catalysts. The work provides a promising method to develop the highly active and stable Pt-based catalyst for direct methanol fuel cells.

  16. Reduction of Nitrogen Oxides using zeolite catalysts exchanged with cobalt

    International Nuclear Information System (INIS)

    Garcia M, E.A.; Bustamante L, F.; Montes de C, C.

    1999-01-01

    The Selective Catalytic Reduction (SCR) of NOx by methane in excess oxygen was studied over several zeolite catalysts; namely cobalt loaded mordenite, ferrierite, SM-5 and the corresponding acid forms. When NO2 predominated n the NOx mixture the acid forms showed the highest N2 formation rates under dry conditions. Mordenite supported catalysts were the most active ones followed by ferrierite and ZSM-5. The most active Co-Mordenite catalyst was tested using a NOx mixture, containing mostly NO, under dry conditions and in the presence of water and SO2. The addition of 8 % water to the reaction mixture lead to a reversible deactivation, mainly at low temperatures. When the reaction mixture contained 60 ppm SO2, the N2 formation rate decreased about a half likely due to SO2 poisoning

  17. Structural Modification of Cobalt Catalysts: Effect of Wetting Studied by X-Ray and Infrared Techniques

    Directory of Open Access Journals (Sweden)

    Khodakov A.

    1999-07-01

    Full Text Available The effect of wetting on the structure and localisation of cobalt species on various supports (Al2O3, SiO2, TiO2, HZSM-5 zeolite was studied using X-ray diffraction, Fourier transform infrared spectroscopy with CO as a molecular probe, X-ray photoelectron spectroscopy and extended X-ray absorption fine structure analysis. Aqueous impregnation to incipient wetness of reduced and passivated cobalt catalysts results, even in the absence of any promoter, in a considerable decrease in the concentration of Co crystalline phases and modifies the surface sites. The decrease in the concentration of Co3O4 crystallites was especially pronounced on silica supported catalysts prepared via impregnation of cobalt and on a mixture of Co3O4 and HZSM-5 zeolite. Saturation with water of the passivated Co/SiO2 sample results in an amorphous solid with a local structure close to that of Co2SiO4. For Co/Al2O3 and Co/TiO2 catalysts, the effect of wetting on the concentration of Co3O4 crystalline phase was considerably smaller.

  18. Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis.

    Science.gov (United States)

    Wan, Gang; Yu, Pengfei; Chen, Hangrong; Wen, Jianguo; Sun, Cheng-Jun; Zhou, Hua; Zhang, Nian; Li, Qianru; Zhao, Wanpeng; Xie, Bing; Li, Tao; Shi, Jianlin

    2018-04-01

    The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Preparation, surface characterization and performance of a Fischer-Tropsch catalyst of cobalt supported on silica nanosprings

    Energy Technology Data Exchange (ETDEWEB)

    Kengne, Blaise-Alexis Fouetio [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States); Alayat, Abdulbaset M. [Environmental Science Program, University of Idaho, Moscow, ID 83844-3006 (United States); Luo, Guanqun [Department of Forest, Rangeland & Fire Sciences, University of Idaho, Moscow, ID 83844-1132 (United States); McDonald, Armando G. [Environmental Science Program, University of Idaho, Moscow, ID 83844-3006 (United States); Department of Forest, Rangeland & Fire Sciences, University of Idaho, Moscow, ID 83844-1132 (United States); Brown, Justin; Smotherman, Hayden [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States); McIlroy, David N., E-mail: dmcilroy@uidaho.edu [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States)

    2015-12-30

    Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: The reduction of cobalt (Co) catalyst supported on silica nanosprings for Fischer-Tropsch synthesis (FTS) has been monitored by X-ray photoelectron spectroscopy (XPS) and compared to FT catalytic activity. The cobalt is present in the starting catalyst as a Co{sub 3}O{sub 4} spinel phase. A two-step reduction of Co{sub 3}O{sub 4} to CoO and then to Co{sup 0} is observed, which is consistent with the results of H{sub 2}-temperature programmed reduction. During the reduction the two steps occur concurrently. The deconvolution of the Co 2p core level state for the catalyst reduced at 385 °C and 1.0 × 10{sup −6} Torr of H{sub 2} revealed signatures of Co{sup 0}, CoO, and Co{sub 3}O{sub 4}. The reduction saturates at a Co{sup o} concentration of approximately 41% after 20 h, which correlates with the activity and lifetime of the catalyst during FTS testing. Conversely, at 680 °C and 10 Torr of H{sub 2}, the catalyst is completely reduced after 10 h. The evolution of the Co d-band at the Fermi level in the valence band XPS spectrum definitively verifies the metallic phase of Co. FTS evaluation of the Co/NS catalyst reduced at 609 °C showed higher production rate (3-fold) of C{sub 6}-C{sub 17} hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

  20. Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube

    International Nuclear Information System (INIS)

    Arthur, Ernest Evans; Li, Fang; Momade, Francis W.Y.; Kim, Hern

    2014-01-01

    Hydrogen was generated from ammonia borane complex by hydrolysis using cobalt nanocluster catalyst supported on polydopamine functionalized MWCNTs (multi-walled carbon nanotubes). The impregnation-chemical reduction method was used for the preparation of the supported catalyst. The nanocluster catalyst support was formed by in-situ oxidative polymerization of dopamine on the MWCNTs in alkaline solution at room temperature. The structural and physical–chemical properties of the nanocluster catalyst were characterized by FT-IR (Fourier transform infrared spectroscopy), EDX (energy-dispersive X-ray spectroscopy), SEM (scanning electron microscope), XRD (X-ray diffraction) and TEM (transmission electron microscopy). The nanocluster catalyst showed good catalytic activity for the hydrogen generation from aqueous ammonia borane complex. A reusability test to determine the practical usage of the catalyst was also investigated. The result revealed that the catalyst maintained an appreciable catalytic performance and stability in terms of its reusability after three cycle of reuse for the hydrolysis reaction. Also, the activation energy for the hydrolysis of ammonia borane complex was estimated to be 50.41 kJmol −1 , which is lower than the values of some of the reported catalyst. The catalyst can be considered as a promising candidate in developing highly efficient portable hydrogen generation systems such as PEMFC (proton exchange membrane fuel cells). - Highlights: • Co/Pdop-o-MWCNT (Pdop functionalized MWCNT supported cobalt nanocluster) catalyst was synthesized for hydrogen generation. • It is an active catalyst for hydrogen generation via hydrolysis of ammonia borane. • It showed good stability in terms of reusability for the hydrogen generation

  1. New cobalt-mediated radical polymerization (CMRP of methyl methacrylate initiated by two single-component dinuclear β-diketone cobalt (II catalysts.

    Directory of Open Access Journals (Sweden)

    Feng Bao

    Full Text Available Two dinuclear cobalt complexes based on bis-diketonate ligands (ligand 1: 3,3'-(1,3-phenylenebis(1-phenylpropane-1,3-dione; ligand 2: 3,3'-(1,4-phenylenebis(1-phenylpropane-1,3-dione were successfully synthesized. The two neutral catalysts all showed satisfactory activities in the cobalt-mediated radical polymerization (CMRP of methyl methacrylate (MMA with the common initiator of azodiisobutyronitrile (AIBN. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities. Mono- or dicomponent low polydispersity polymers could be obtained by using the two dinuclear catalysts under proper reaction conditions. All these improvements facilitate the implementation of the acrylate CMRP and open the door to the scale-up of the syntheses and applications of the multicomponent low polydispersity polymers.

  2. Catalytic performance and characterization of cobalt-nickel nano catalysts for CO hydrogenation

    International Nuclear Information System (INIS)

    Feyzi, Mostafa; Gholivand, Mohammad Bagher; Babakhanian, Arash

    2014-01-01

    A series of Co-Ni nano catalysts were prepared by co-precipitation method. We investigated the effect of Co/Ni molar ratios precipitate and calcination conditions on the catalytic performance of cobalt nickel catalysts for Fisher-Tropsch synthesis (FTS). The catalyst containing 90%Co/10%Ni was found to be optimal for the conversion of synthesis gas to light olefins. The activity and selectivity of the optimal catalyst were studied in different operational conditions. The results show that the best operational conditions are the H 2 /CO=2/1 molar feed ratio at 310 .deg. C and GHSV=1,200 h - 1 under 5 bar of pressure. The prepared catalysts were characterized by powder X-ray diffraction (XRD), N 2 adsorption-desorption measurements such as BET and BJH methods, transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA)

  3. Direct Synthesis of Methanol by Partial Oxidation of Methane with Oxygen over Cobalt Modified Mesoporous H-ZSM-5 Catalyst

    Directory of Open Access Journals (Sweden)

    Yuni Krisyuningsih Krisnandi

    2015-11-01

    Full Text Available Partial oxidation of methane over mesoporous catalyst cobalt modified H-ZSM-5 has been carried out. Mesoporous Na-ZSM-5 (Si/Al = 35.4 was successfully synthesized using double template method which has high surface area (450 m2/g and average pore diameter distribution of 1.9 nm. The as-synthesized Na-ZSM-5 was converted to H-ZSM-5 through multi-exchange treatment with ammonium ion solution, causing decreased crystallinity and surface area, but increased porous diameter, due to dealumination during treatment process. Moreover, H-ZSM-5 was loaded with cobalt (Co = 2.5% w by the incipient impregnation method and calcined at 550 °C. Partial oxidation of methane was performed in the batch reactor with 0.75 bar methane and 2 bar of nitrogen (with impurities of 0.5% oxygen as the input at various reaction time (30, 60 and 120 min. The reaction results show that cobalt species in catalyst has an important role, because H-ZSM-5 cannot produce methanol in partial oxidation of methane. The presence of molecular oxygen increased the percentage of methanol yield. The reaction is time-dependent with the highest methanol yield (79% was acquired using Co/H-ZSM-5 catalyst for 60 min.

  4. Effect of pretreatment temperature on catalytic performance of the catalysts derived from cobalt carbonyl cluster in Fischer-Tropsch Synthesis

    Directory of Open Access Journals (Sweden)

    Byambasuren O

    2017-02-01

    Full Text Available The monometallic cobalt-based catalysts were prepared by pretreating the catalysts derived from carbonyl cluster precursor (CO6Co2CC(COOH2 supported on γ-Al2O3 with hydrogen at 180, 220, and 260°C respectively. The temperature effect of the pretreatments on the structure evolution of cluster precursors and the catalytic performance of the Fischer-Tropsch (F-T synthesis was investigated. The pretreated catalyst at 220°C with unique phase structure exhibited best catalytic activity and selectivity among three pretreated catalysts. Moreover, the catalysts exhibited high dispersion due to the formation of hydrogen bonds between the cluster precursor and γ-Al2O3 support.

  5. Structural modifications under reactive atmosphere of cobalt catalysts; Modifications structurales sous atmospheres reactionnelles de catalyseurs a base de cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Ducreux, O.

    1999-11-23

    The purpose of this work was to develop in situ methods under reactive dynamic conditions (XRD and Fourier transform infrared spectroscopy) to describe the active phase structure in order to understand Fischer-Tropsch catalyst behaviour and improve the natural gas conversion process performance. Experiments were designed to correlate structural modifications with catalytic results. The effect of ruthenium used as a promoter has also been studied. The impregnation process increases cobalt-support interaction. The presence of ruthenium promoter reduces this effect. Interactions between Co{sub 3}O{sub 4} oxide and support play an important role in the reducibility of cobalt and in the resulting metal structure. This in turn strongly influences the catalytic behaviour. Our results show a close correlation between structure modification and reactivity in the systems studied. Cobalt metal and CO can react to form a carbide Co{sub 2}C under conditions close to those of the Fischer-Tropsch synthesis. This carbide formation seems to be related to a deactivation process. The presence of interstitial carbon formed by dissociation of CO is proposed as a key to understanding the mechanism of the Fischer-Tropsch reaction. A specific catalyst activation treatment was developed to increase the catalytic activity. This work permits correlation of materials structure with their chemical properties and demonstrates the contribution of in situ physico-chemical characterisation methods to describe solids under reactive atmosphere. (author)

  6. Improved hydrogen generation from alkaline NaBH{sub 4} solution using cobalt catalysts supported on modified activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Dongyan; Guo, Qingjie; Yue, Xuehai [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Dai, Ping [College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao 266061 (China)

    2008-12-15

    Hydrogen production from alkaline sodium borohydride (NaBH{sub 4}) solution via hydrolysis process over activated carbon supported cobalt catalysts is studied. Activated carbons are used in their original form and after liquid phase oxidation with HNO{sub 3}. The changes in surface functional groups of the activated carbon are detected by FTIR spectroscopy. The effects of HNO{sub 3} oxidation on the properties of the activated carbon and the resulting catalyst performance are investigated. FTIR analysis reveals that the oxidative treatment leads to the formation of various functional groups on the surface of the activated carbon. Cobalt catalysts supported on the modified activated carbon are found to exhibit higher activity and stability. (author)

  7. Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water

    Energy Technology Data Exchange (ETDEWEB)

    Moonshiram, Dooshaye; Gimbert-Suriñach, Carolina [Institute; Guda, Alexander [International; Picon, Antonio; Lehmann, C. Stefan; Zhang, Xiaoyi; Doumy, Gilles; March, Anne Marie; Benet-Buchholz, Jordi [Institute; Soldatov, Alexander [International; Llobet, Antoni [Institute; Departament; Southworth, Stephen H.

    2016-08-09

    Time resolved X-ray absorption spectroscopy (X-TAS) has been used to study the light induced hydrogen evolution reaction catalyzed by a highly stable cobalt complex, [Ru(bpy)3]2+ photosensitizer and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. XANES and EXAFS analysis of a binary mixture of the octahedral Co(III) pre-catalyst and [Ru(bpy)3]2+ after illumination, revealed in-situ formation of a square pyramidal Co(II) intermediate, with electron transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds followed by its decay in the microsecond timescales. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and Finite Difference Method (FDM). These findings allowed us to unequivocally assign the full mechanistic pathway followed by the catalyst as well as to determine the rate limiting step of the process, which consists in the protonation of the Co(I). This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

  8. Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

    Science.gov (United States)

    Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

    2018-01-01

    Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.; Ahmed, Syud M.; Coates, Geoffrey W.

    2011-01-01

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  10. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.

    2011-07-26

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  11. Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

    Science.gov (United States)

    Klettlinger, Jennifer Lindsey Suder

    2012-01-01

    The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the

  12. Morphology-Tuned Synthesis of Nickel Cobalt Selenides as Highly Efficient Pt-Free Counter Electrode Catalysts for Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Qian, Xing; Li, Hongmei; Shao, Li; Jiang, Xiancai; Hou, Linxi

    2016-11-02

    In this work, morphology-tuned ternary nickel cobalt selenides based on different Ni/Co molar ratios have been synthesized via a simple precursor conversion method and used as counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). The experimental facts and mechanism analysis clarified the possible growth process of product. It can be found that the electrochemical performance and structures of ternary nickel cobalt selenides can be optimized by tuning the Ni/Co molar ratio. Benefiting from the unique morphology and tunable composition, among the as-prepared metal selenides, the electrochemical measurements showed that the ternary nickel cobalt selenides exhibited a more superior electrocatalytic activity in comparison with binary Ni and Co selenides. In particular, the three-dimensional dandelion-like Ni 0.33 Co 0.67 Se microspheres delivered much higher power conversion efficiency (9.01%) than that of Pt catalyst (8.30%) under AM 1.5G irradiation.

  13. Removal of carbonaceous deposits from the surface of cobalt-molybdate catalyst via oxidative regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Yoshimura, Y.; Furimsky, E.

    1986-10-01

    The oxidative regeneration of cobalt-molybdate catalyst used during the hydrodeoxygenation of a phenol solution and for hydrotreatment of Athabasca bitumen was carried out in a fixed-bed reactor. SO/sub 2/, CO and CO/sub 2/ were analysed as the major products. The surface area of the spent catalysts was the main factor influencing the initial rate of regeneration, i.e. the greater the surface area the higher the initial rate. A mechanism proposed includes 12 reactions which may play an important role in the overall burn-off of hydrotreatment catalysts. 10 refs., 4 figs., 3 tabs.

  14. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    OpenAIRE

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanof...

  15. Non-carbon titanium cobalt nitride nanotubes supported platinum catalyst with high activity and durability for methanol oxidation reaction

    Science.gov (United States)

    Chen, Xiaoxiang; Li, Wuyi; Pan, Zhanchang; Xu, Yanbin; Liu, Gen; Hu, Guanghui; Wu, Shoukun; Li, Jinghong; Chen, Chun; Lin, Yingsheng

    2018-05-01

    Titanium cobalt nitride nanotubes (Ti0.95Co0.05N NTs) hybrid support, a novel robust non-carbon support material prepared by solvothermal and post-nitriding processes, is further decorated with Pt nanoparticles for the electrooxidation of methanol. The catalyst is characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The morphology, structure and composition of the synthesized Ti0.95Co0.05N NTs suggest that the nanotube wall is porous and consists of homogeneous cohesively attached nitrides nanocube particles. Notable, Ti0.95Co0.05N NTs supported Pt catalyst exhibits significantly improved catalytic activity and durability for methanol electrooxidation compared with the conventional JM Pt/C catalyst. The experimental data indicate that enhanced catalytic activity and stability of Pt/Ti0.95Co0.05N NTs towards methanol electrooxidation might be mainly attributed to the tubular nanostructures and synergistic effect introduced by the Co doping. Both of them are playing an important role in improving the activity and durability of the Ti0.95Co0.05N NTs catalyst.

  16. Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas.

    Science.gov (United States)

    Yang, Jianping; Zhao, Yongchun; Zhang, Junying; Zheng, Chuguang

    2014-12-16

    To remove Hg(0) in coal combustion flue gas and eliminate secondary mercury pollution of the spent catalyst, a new regenerable magnetic catalyst based on cobalt oxide loaded magnetospheres from fly ash (Co-MF) was developed. The catalyst, with an optimal loading of 5.8% cobalt species, attained approximately 95% Hg(0) removal efficiency at 150 °C under simulated flue gas atmosphere. O2 could enhance the Hg(0) removal activity of magnetospheres catalyst via the Mars-Maessen mechanism. SO2 displayed an inhibitive effect on Hg(0) removal capacity. NO with lower concentration could promote the Hg(0) removal efficiency. However, when increasing the NO concentration to 300 ppm, a slightly inhibitive effect of NO was observed. In the presence of 10 ppm of HCl, greater than 95.5% Hg(0) removal efficiency was attained, which was attributed to the formation of active chlorine species on the surface. H2O presented a seriously inhibitive effect on Hg(0) removal efficiency. Repeated oxidation-regeneration cycles demonstrated that the spent Co-MF catalyst could be regenerated effectively via thermally treated at 400 °C for 2 h.

  17. Modeling of cobalt-based catalyst use during CSS for low-temperature heavy oil upgrading

    Science.gov (United States)

    Kadyrov, R.; Sitnov, S.; Gareev, B.; Batalin, G.

    2018-05-01

    One of the methods, which is actively used on deposits of heavy oils of the Upper Kungurian (Ufimian) sandstones of the Republic of Tatarstan, is cyclic steam simulation (CSS). This method consists of 3 stages: injection, soaking, and production. Steam is injected into a well at a temperature of 300 to 340° C for a period of weeks to months. Then, the well is allowed to sit for days to weeks to allow heat to soak into the formation. Finally, the hot oil is pumped out of the well for a period of weeks or months. Once the production rate falls off, the well is put through another cycle. The injection of the catalyst solution before the injection of steam opens the possibility for upgrading the heavy oil in the process of aquathermolysis directly in the reservoir. In this paper, the possibility of using a catalyst precursor based on cobalt for upgrading the hydrocarbons of this field in the process of their extraction is represented. SARA analysis on oil saturated sandstones shows an increase in the proportion of saturated hydrocarbons by 11.1% due to the hydrogenation of aromatic hydrocarbons and their derivatives, the content of resins and asphaltenes are remained practically unchanged. A new method for estimating the adsorption of a catalyst based on taking into account the change in the concentration of the base metal before and after simulation of catalyst injection in the thermobaric conditions of the reservoir is proposed. During the study of catalyst adsorption in the rock, when simulating the CSS process, it is found that almost 28% of the cobalt, which is the main element of the catalyst precursor, is retained in the rock.

  18. Cobalt Oxide Catalysts on Commercial Supports for N2O Decomposition.

    Czech Academy of Sciences Publication Activity Database

    Klegová, A.; Pacultová, K.; Fridrichová, D.; Volodarskaja, A.; Kovanda, J.; Jirátová, Květa

    2017-01-01

    Roč. 40, č. 5 (2017), s. 981-990 ISSN 0930-7516. [International Congress of Chemical and Process Engineering CHISA 2016 /22./ and the 19th Conference PRES 2016. Prague, 27.08.2016-31.08.2016] R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : N2O decomposition * cobalt oxide * shaped catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 2.051, year: 2016

  19. Catalytic oxidation of volatile organic compounds (n-hexane, benzene, toluene, o-xylene promoted by cobalt catalysts supported on γ-Al2O3-CeO2

    Directory of Open Access Journals (Sweden)

    R. Balzer

    2014-09-01

    Full Text Available Cobalt catalysts supported on γ-alumina, ceria and γ-alumina-ceria, with 10 or 20%wt of cobalt load, prepared by the wet impregnation method and characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, field emission transmission electron microscopy (FETEM, N2 adsorption-desorption isotherms (BET/BJH methods, energy-dispersive X-ray spectroscopy (EDX, X-ray photoemission spectroscopy (XPS, O2-chemisorption and temperature programmed reduction (TPR were used to promote the oxidation of volatile organic compounds (n-hexane, benzene, toluene and o-xylene. For a range of low temperatures (50-350 °C, the activity of the catalysts with a higher cobalt load (20% wt was greater than that of the catalysts with a lower cobalt load (10% wt. The Co/γ-Al2O3-CeO2 catalytic systems presented the best performances. The results obtained in the characterization suggest that the higher catalytic activity of the Co20/γ-Al2O3-CeO2 catalyst may be attributed to the higher metal content and amount of oxygen vacancies, as well as the effects of the interaction between the cobalt and the alumina and cerium oxides.

  20. Dipyridine cobalt chloride as an efficient and chemoselective catalyst for the synthesis of 1,1-diacetates under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Sobhan Rezayati

    2014-02-01

    Full Text Available 1,1-Diacetates(acylals were prepared by direct condensation of various aldehydes with acetic anhydride using dipyridine cobalt chloride (CoPy2Cl2 as an efficient and green catalyst under solvent-free conditions at room temperature. The important features of this catalyst method are that the catalyst is solid, stable at high temperatures, soluble in water, stable in air, immiscible in common organic solvents, and low toxic and, above all, it is reusable. CoPy2Cl2 can be recycled after a simple work-up and reused at least five runs without appreciable loss of its catalytic activity. High chemo-selectivity toward aldehyde in the presence of ketones is another advantage of the present method which provides selective protection of aldehydes in their mixtures with ketones.

  1. Cobalt hydroxide nanoflakes and their application as supercapacitors and oxygen evolution catalysts

    Science.gov (United States)

    Rovetta, A. A. S.; Browne, M. P.; Harvey, A.; Godwin, I. J.; Coleman, J. N.; Lyons, M. E. G.

    2017-09-01

    Finding alternative routes to access and store energy has become a major issue recently. Transition metal oxides have shown promising behaviour as catalysts and supercapacitors. Recently, liquid exfoliation of bulk metal oxides appears to be an effective route which provides access to two-dimensional (2D) nano-flakes, the size of which can be easily selected. These 2D materials exhibit excellent electrochemical charge storage and catalytic activity for the oxygen evolution reaction. In this study, various sized selected cobalt hydroxide nano-flake materials are fabricated by this time efficient and highly reproducible process. Subsquently, the electrochemical properties of the standard size Co(OH)2 nanoflakes were investigated. The oxide modified electrodes were prepared by spraying the metal oxide flake suspension onto a porous conductive support electrode foam, either glassy carbon or nickel. The cobalt hydroxide/nickel foam system was found to have an overpotential value at 10 mA cm-2 in 1 M NaOH as low as 280 mV and an associated redox capacitance exhibiting numerical values up to 1500 F g-1, thereby making it a viable dual use electrode.

  2. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

    Directory of Open Access Journals (Sweden)

    Subbarao Duvvuri

    2011-11-01

    Full Text Available Abstract This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR, temperature-programmed oxidation (TPO, CO-chemisorption, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM-EDX and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low, 650°C (medium and 731°C (high. The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1% while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%.

  3. Study of heterogeneous catalytic processes over cobalt, molybdenum and cobalt-molybdenum catalysts supported on alumina by temperature-programmed desorption and temperature-programmed reaction. 1. Adsorption of hydrozen

    International Nuclear Information System (INIS)

    Rozanov, V.V.; Tsao Yamin; Krylov, O.V.

    1996-01-01

    Hydrogen adsorption on reduced, sulphidized and reoxidized specimens of molybdenum-and cobalt-molybdenum-containing catalysts applied on aluminium oxide has been studied by the method of thermal desorption (TD). Comparison of TD spectra of hydrogen and data of X-ray phase analysis of the specimens and mass-spectrometric analysis of the products desorbed from the surface of catalysts after their successive reduction sulphidizing, carbonizing and reoxidation permitted a correlation between various forms of hydrogen adsorption and certain centres on the surface of the catalysts. 12 refs., 2 figs

  4. Cobalt catalysts, and use thereof for the conversion of methanol and for fischer-tropsch synthesis, to produce hydrocarbons

    International Nuclear Information System (INIS)

    Mauldin, C.H.; Davis, S.M.; Arcuri, K.B.

    1988-01-01

    This patent describes a process useful for the conversion of methanol to hydrocarbons which comprises contacting the methanol at reaction conditions with a catalyst which comprises from about 2 percent to about 25 percent cobalt, based on the weight of the catalyst composition, composited with titania, or a titania-containing support, to which is added a zirconium, hafnium, cerium, or uranium promoter, the weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt being greater than about 0.010:1; the reaction conditions being defined within ranges as follows: Methanol:H/sub 2/ ratio: greater than about 4:1, Space Velocities, Hr/sup -1/:about 0.1 to 10, Temperatures, 0 C.:about 150 to 350, Methanol Partial Pressure, psia: about 100 to 1000

  5. One-step prepared cobalt-based nanosheet as an efficient heterogeneous catalyst for activating peroxymonosulfate to degrade caffeine in water.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Lai, Hong-Kai; Tong, Shaoping

    2018-03-15

    Two-dimensional (2D) planar cobalt-containing materials are promising catalysts for activating peroxymonosulfate (PMS) to degrade contaminants because 2D sheet-like morphology provides large reactive surfaces. However, preparation of these sheet-supported cobaltic materials typically involves multiple steps and complex reagents, making them less practical for PMS activation. In this study, a cobalt-based nanosheet (CoNS) is particularly developed using a one-step hydrothermal process with a single reagent in water. The resulting CoNS can exhibit a thickness as thin as a few nanometers and 2-D morphology. CoNS is also primarily comprised of cobalt species in a coordinated form of Prussian Blue analogue, which consists of both Co 3+ and Co 2+ . These features make CoNS promising for activating PMS in aqueous systems. As degradation of an emerging contaminant, caffeine, is selected as a representative reaction, CoNS not only successfully activates PMS to fully degrade caffeine in 20 min but also exhibits a much higher catalytic activity than the most common PMS activator, Co 3 O 4 . Via studying inhibitive effects of radical scavengers, caffeine degradation by CoNS-activated PMS is primarily attributed to sulfate radicals and hydroxyl radicals to a lesser extent. The degradation products of caffeine by CoNS-activated PMS are also identified and a potential degradation pathway is proposed. Moreover, CoNS could be also re-used to activate PMS for caffeine degradation without activity loss. These results indicate that CoNS is a conveniently prepared and highly effective and stable 2-D catalyst for aqueous chemical oxidation reactions. Copyright © 2017. Published by Elsevier Inc.

  6. Methanol Reforming over Cobalt Catalysts Prepared from Fumarate Precursors: TPD Investigation

    Directory of Open Access Journals (Sweden)

    Eftichia Papadopoulou

    2016-02-01

    Full Text Available Temperature-programmed desorption (TPD was employed to investigate adsorption characteristics of CH3OH, H2O, H2, CO2 and CO on cobalt-manganese oxide catalysts prepared through mixed Co-Mn fumarate precursors either by pyrolysis or oxidation and oxidation/reduction pretreatment. Pyrolysis temperature and Co/Mn ratio were the variable synthesis parameters. Adsorption of methanol, water and CO2 was carried out at room temperature. Adsorption of H2 and H2O was carried out at 25 and 300 °C. Adsorption of CO was carried out at 25 and 150 °C. The goal of the work was to gain insight on the observed differences in the performance of the aforementioned catalysts in methanol steam reforming. TPD results indicated that activity differences are mostly related to variation in the number density of active sites, which are able to adsorb and decompose methanol.

  7. Bioinspired catalytic generation of high-valent cobalt-oxo species by the axially coordinated CoPc on pyridine-functionalized MWCNTs for the elimination of organic contaminants

    Science.gov (United States)

    Li, Nan; Wang, Ying; Wu, Chenren; Lu, Wangyang; Pei, Kemei; Chen, Wenxing

    2018-03-01

    Enzymes have always been a source of inspiration for the design and improvement of catalysts. Many examples are occurring in heme/non-heme metalloenzymes with the generation of active high-valent metal-oxo intermediates that are controlled by the surrounding amino acids/protein and axial residue ligands, facilitating the efficient oxidation of substrates in biochemical processes. Here, the high-valent cobalt-oxo species have been formed during the heterolysis of H2O2 activated by the bioinspired catalyst, axially coordinated cobalt phthalocyanine (CoPc) on pyridine-functionalized multi-walled carbon nanotubes (MWCNTs-Py), characterized by ultraviolet-visible and X-ray photoelectron spectroscopy. Formation process of the active cobalt-oxo species has been further confirmed by electrospray ionization mass spectrometry analysis and the results from the density functional theory (B3LYP/6-311G) calculations. Such high-valent cobalt-oxo species exhibit high reactivity and enough persistence for the oxidation of the target substrate, C.I. Acid Red 1. The oxidation products are nearly biodegradable small molecules identified by ultra-performance liquid chromatography/high-definition mass spectrometry. This strategy provides a foundation on developing efficient and persistent catalytic system, in particular oxidation processes based on the complex catalysts with N4 macrocycle structures.

  8. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  9. Boron-containing catalysts for dry reforming of methane to synthesis gas

    KAUST Repository

    Takanabe, Kazuhiro

    2018-01-04

    The present invention uses a cobalt catalyst for carbon dioxide reforming of lower alkanes to synthesis gas having a cobalt catalyst on an oxide support where the supported cobalt catalyst has been modified with a boron precursor. The boron-treated cobalt catalyst systems as described herein show significant increases in the conversion of CH4 and CO2 during the dry reforming of methane (DRM) reaction as compared to traditional catalysts. Described herein are supported catalysts and methods of using the catalysts for the dry reforming of methane to synthesis gas, with the supported catalysts in the present invention include a boron-treated cobalt catalyst disposed on an oxide support. Also described herein are processes for preparing the supported catalysts.

  10. Competitive Adsorption-Assisted Formation of One-Dimensional Cobalt Nanochains with High CO Hydrogenation Activity

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Xin [State; Ren, Zhibo [State; Institute; Zhu, Xiaolin [State; Zhang, Qinwei [State; Mei, Donghai [Institute; Chen, Biaohua [State

    2017-10-31

    In the present work, cobalt nanochains have been successfully synthesized by a novel co assisted self-assembling formation strategy. A dramatic morphology transformation from cobalt nanoparticles to nanochains are observed when co molecules were introduced into the synthetic system. DFT calculations further confirm that competitive co-adsorbed co and oleylamine over the cobalt nanoparticles facilitates the formation of cobalt nanochains, which show higher co hydrogenation performance. The present work provides a new strategic and promising method for controllable synthesis of catalyst nanomaterials with the preferred surface structure and morphology.

  11. Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

    International Nuclear Information System (INIS)

    Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

    2014-01-01

    This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H 2 -temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H 2 /CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C 5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum

  12. Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

    Energy Technology Data Exchange (ETDEWEB)

    Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Ali, Sardar, E-mail: alikhan-635@yahoo.com [Centralized Analytical Laboratory, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my [Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

    2014-10-24

    This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

  13. Fischer-Tropsch synthesis in slurry-phase reactors using Co/SBA-15 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, J.J.; Lima, L.A.; Lima, W.S.; Rodrigues, M.G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], e-mail: meiry@deq.ufcg.edu.br; Fernandes, F.A.N. [Universidade Federal do Ceara (UFCE), CE (Brazil). Dept. de Engenharia Quimica

    2011-07-15

    The objective of this work is to describe the production of bifunctional catalysts using the incipient humidity method, producing catalysts with 15 wt.% cobalt supported in SBA-15 molecular sieve, to be applied in the Fischer-Tropsch (FT) reaction. The originality of this work is its focus on the use of a 15 wt.% Co/SBA-15 catalyst in FT synthesis in slurry reactors. The deposition of cobalt over SBA-15 support was accomplished by impregnation with a 0.1-M aqueous solution of cobalt nitrate. The Fischer-Tropsch synthesis was carried out with the catalyst at 240 deg C and 20 atm, under a COH{sub 2} atmosphere (molar ratio= 1), in a slurry reactor for 8 hours. X-ray diffraction measurements showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present under the form of Co{sub 3}O{sub 4} in the catalyst. The addition of cobalt in the SBA-15 decreased the specific superficial area of the molecular sieve. The 15 wt.% Co/SBA-15 catalyst had a 40% CO conversion rate and a high selectivity towards the production of C{sub 5}{sup +} (53.9% after 8 hours). (author)

  14. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  15. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.; Poater, Albert; Childers, M. Ian; Widger, Peter C B; Lapointe, Anne M.; Lobkovsky, Emil B.; Coates, Geoffrey W.; Cavallo, Luigi

    2013-01-01

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  16. Quasi-zero-dimensional cobalt-doped CeO2 dots on Pd catalysts for alcohol electro-oxidation with enhanced poisoning-tolerance.

    Science.gov (United States)

    Tan, Qiang; Zhu, Haiyan; Guo, Shengwu; Chen, Yuanzhen; Jiang, Tao; Shu, Chengyong; Chong, Shaokun; Hultman, Benjamin; Liu, Yongning; Wu, Gang

    2017-08-31

    Deactivation of an anode catalyst resulting from the poisoning of CO ad -like intermediates is one of the major problems for methanol and ethanol electro-oxidation reactions (MOR & EOR), and remains a grand challenge towards achieving high performance for direct alcohol fuel cells (DAFCs). Herein, we report a new approach for the preparation of ultrafine cobalt-doped CeO 2 dots (Co-CeO 2 , d = 3.6 nm), which can be an effective anti-poisoning promoter for Pd catalysts towards MOR and EOR in alkaline media. Compared to Pd/CeO 2 and pure Pd, the hybrid Pd/Co-CeO 2 nanocomposite catalyst exhibited a much enhanced activity and remarkable anti-poisoning ability for both MOR and EOR. The nanocomposite catalyst showed much higher mass activity (4×) than a state-of-the-art PtRu catalyst. The promotional mechanism was elucidated using extensive characterization and density-functional theory (DFT). A bifunctional effect of the Co-CeO 2 dots was discovered to be due to (i) an enhanced electronic interaction between Co-CeO 2 and Pd dots and (ii) the increased oxygen storage capacity of Co-CeO 2 dots to facilitate the oxidation of CO ad . Therefore, the Pd/Co-CeO 2 nanocomposite appears to be a promising catalyst for advanced DAFCs with low cost and high performance.

  17. Cobalt doped antimony oxide nano-particles based chemical sensor and photo-catalyst for environmental pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Jamal, Aslam [Centre for Advanced Materials and Nano-Engineering (CAMNE) and Department of Chemistry, Faculty of Sciences and Arts, Najran University, P. O. Box 1988, Najran 11001 (Saudi Arabia); Rahman, Mohammed M. [Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Khan, Sher Bahadar, E-mail: drkhanmarwat@gmail.com [Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Faisal, Mohd. [Centre for Advanced Materials and Nano-Engineering (CAMNE) and Department of Chemistry, Faculty of Sciences and Arts, Najran University, P. O. Box 1988, Najran 11001 (Saudi Arabia); Akhtar, Kalsoom [Division of Nano Sciences and Department of Chemistry, Ewha Womans University, Seoul 120-750 (Korea, Republic of); Rub, Malik Abdul; Asiri, Abdullah M.; Al-Youbi, Abdulrahman O. [Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia)

    2012-11-15

    Graphical abstract: A dichloromethane chemical sensor using cobalt antimony oxides has been fabricated. This sensor showed high sensitivity and will be a useful candidate for environmental and health monitoring. Also it showed high photo-catalytic activity and can be a good candidate as a photo-catalyst for organic hazardous materials. Highlights: Black-Right-Pointing-Pointer Reusable chemical sensor. Black-Right-Pointing-Pointer Green environmental and eco-friendly chemi-sensor. Black-Right-Pointing-Pointer High sensitivity. Black-Right-Pointing-Pointer Good candidate for environmental and health monitoring. - Abstract: Cobalt doped antimony oxide nano-particles (NPs) have been synthesized by hydrothermal process and structurally characterized by utilizing X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier transforms infrared spectrophotometer (FT-IR) which revealed that the synthesized cobalt antimony oxides (CoSb{sub 2}O{sub 6}) are well crystalline nano-particles with an average particles size of 26 {+-} 10 nm. UV-visible absorption spectra ({approx}286 nm) were used to investigate the optical properties of CoSb{sub 2}O{sub 6}. The chemical sensing of CoSb{sub 2}O{sub 6} NPs have been primarily investigated by I-V technique, where dichloromethane is used as a model compound. The analytical performance of dichloromethane chemical sensor exhibits high sensitivity (1.2432 {mu}A cm{sup -2} mM{sup -1}) and a large linear dynamic range (1.0 {mu}M-0.01 M) in short response time (10 s). The photo catalytic activity of the synthesized CoSb{sub 2}O{sub 6} nano-particles was evaluated by degradation of acridine orange (AO), which degraded 58.37% in 200 min. These results indicate that CoSb{sub 2}O{sub 6} nano-particles can play an excellent research impact in the environmental field.

  18. Boron-containing catalysts for dry reforming of methane to synthesis gas

    KAUST Repository

    Takanabe, Kazuhiro; Basset, Jean-Marie; Park, Jung-Hyun; Samal, Akshaya Kumar; Alsabban, Bedour

    2018-01-01

    The present invention uses a cobalt catalyst for carbon dioxide reforming of lower alkanes to synthesis gas having a cobalt catalyst on an oxide support where the supported cobalt catalyst has been modified with a boron precursor. The boron

  19. Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

    DEFF Research Database (Denmark)

    Walton, Alexander; Fester, Jakob; Bajdich, Michal

    2015-01-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

  20. Fischer-Tropsch synthesis: Support and cobalt cluster size effects on kinetics over Co/Al{sub 2}O{sub 3} and Co/SiO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wenping Ma; Gary Jacobs; Dennis E. Sparks; Muthu K. Gnanamani; Venkat Ramana Rao Pendyala; Chia H. Yen; Jennifer L.S. Klettlinger; Thomas M. Tomsik; Burtron H. Davis [University of Kentucky, Lexington, KY (USA). Center for Applied Energy Research

    2011-02-15

    The influence of support type and cobalt cluster size (i.e., with average diameters falling within the range of 8-40 nm) on the kinetics of Fischer-Tropsch synthesis (FT) were investigated by kinetic tests employing a CSTR and two Co/{gamma}-Al{sub 2}O{sub 3} catalysts having different average pore sizes, and two Co/SiO{sub 2} catalysts prepared on the same support but having different loadings. A kinetic model -r{sub CO}=kP{sup a}{sub co}P{sup b}{sub H2}/(1 + mP{sub H2O}/P{sub H2}) that contains a water effect constant 'm' was used to fit the experimental data obtained with all four catalysts. Kinetic parameters suggest that both support type and average Co particle size impact FT behavior. Cobalt cluster size influenced kinetic parameters such as reaction order, rate constant, and the water effect parameter.Decreasing the average Co cluster diameter by about 30% led to an increase in the intrinsic reaction rate constant k, defined on a per g of catalyst basis, by 62-102% for the {gamma}-Al{sub 2}O{sub 3} and SiO{sub 2}-supported cobalt catalysts. Moreover, less inhibition by adsorbed CO and greater H{sub 2} dissociation on catalysts having smaller Co particles was suggested by the higher a and lower b values obtained for the measured reaction orders. Irrespective of support type, the catalysts having smaller average Co particles were more sensitive to water. Comparing the catalysts having strong interactions between cobalt and support (Co/Al{sub 2}O{sub 3}) to the ones with weak interactions (Co/SiO{sub 2}), the water effect parameters were found to be positive (indicating a negative influence on CO conversion) and negative (denoting a positive effect on CO conversion), respectively. Greater a and a/b values were observed for both Al{sub 2}O{sub 3}-supported Co catalysts, implying greater inhibition of the FT rate by strongly adsorbed CO on Co/Al{sub 2}O{sub 3} relative to Co/SiO{sub 2}. 78 refs., 4 figs., 3 tabs.

  1. Genesis of Co/SiO2 catalysts : XAS study at the cobalt L-III,L- II absorption edges

    NARCIS (Netherlands)

    Bazin, D.; Kovacs, I.; Guczi, L.; Parent, P.; Laffon, C.; De Groot, F.; Ducreux, O.; Lynch, J.

    2000-01-01

    Silica-supported cobalt catalysts have been investigated by soft X-ray absorption techniques. Soft X-ray absorption spectra were collected at the Co LII,III edge during in situ reduction of calcined samples in a stream of hydrogen in the temperature range between 300 and 650°C. Using reference

  2. Relating FTS Catalyst Properties to Performance

    Science.gov (United States)

    Ma, Wenping; Ramana Rao Pendyala, Venkat; Gao, Pei; Jermwongratanachai, Thani; Jacobs, Gary; Davis, Burton H.

    2016-01-01

    During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of ?-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature

  3. Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

    Science.gov (United States)

    Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

    2011-11-01

    This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yu-Heng [Department; Pegis, Michael L. [Department; Mayer, James M. [Department; Stahl, Shannon S. [Department

    2017-11-07

    A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2 was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.

  5. Silylated Co/SBA-15 catalysts for Fischer-Tropsch synthesis

    International Nuclear Information System (INIS)

    Jia Lihong; Jia Litao; Li Debao; Hou Bo; Wang Jungang; Sun Yuhan

    2011-01-01

    A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N 2 physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH 3 ) 3 species even after calcinations and H 2 reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH 3 ) 3 for the re-adsorption of α-olefins. -- Graphical abstract: The silylation of an SBA-15 before cobalt impregnation enhanced the reducibility of cobalt oxides on an SBA-15-supported cobalt catalyst and consequently increased the catalytic activity for Fischer-Tropsch synthesis. Display Omitted

  6. Development of an Innovative XRD-DRIFTS Prototype Allowing Operando Characterizations during Fischer-Tropsch Synthesis over Cobalt-Based Catalysts under Representative Conditions

    Directory of Open Access Journals (Sweden)

    Scalbert Julien

    2015-03-01

    Full Text Available An original system combining both X-Ray Diffraction and diffuse reflectance infrared Fourier transform spectroscopy was developed with the aim to characterize Fischer-Tropsch catalysts in relevant reaction conditions. The catalytic properties of a model PtCo/silica catalyst tested with this prototype have shown to be in the same range of those obtained in similar conditions with classical fixed-bed reactors. No bulk cobalt oxidation nor sintering were observed on operando XRD patterns. The formation of linear carbonyls and adsorbed hydrocarbons species at the surface of the catalyst was observed on operando DRIFT spectra. The surface of the catalyst was also suspected to be covered with carbon species inducing unfavorable changes in selectivity.

  7. Fischer-Tropsch Catalyst for Aviation Fuel Production

    Science.gov (United States)

    DeLaRee, Ana B.; Best, Lauren M.; Bradford, Robyn L.; Gonzalez-Arroyo, Richard; Hepp, Aloysius F.

    2012-01-01

    As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

  8. NMR evidence of metal-support interaction in syngas conversion catalyst Co-TiO2

    International Nuclear Information System (INIS)

    Murty, A.N.; Seamster, M.; Thorpe, A.N.; Obermyer, R.T.; Rao, V.U.S.

    1990-01-01

    To examine the relation between catalytic and magnetic properties, the zero-field NMR spectra and hysteresis loops of cobalt supported on silica, alumina, magnesia, titania, and ZSM-5 with and without the promoter thoria were investigated. Cobalt was incorporated on the support by simple physical admixture of precipitated cobalt and support, and by aqueous impregnation technique. Our studies indicate that the particle sizes are consistently lower in the presence of thoria. Of all the catalysts examined, the Co/Th/TiO 2 catalyst exhibits a high saturation magnetization value---about 20% higher than pure cobalt. In addition, the NMR spectrum of the aqueous impregnation Co/TiO 2 catalyst is distinctly different from the rest. All the NMR lines are shifted to a higher frequency by about 4 MHz. These two features---enhancement of the magnetic moment of cobalt atoms and increases in the hyperfine field at the Co nucleus---clearly indicate that there occurs strong metal-support interaction between cobalt and titania support. The higher hydrocarbon yields observed by the earlier investigators with Co/TiO 2 catalysts might be related to this phenomenon

  9. Study on the structure of Co/ZrO2-SiO2 catalysts by XAFS

    International Nuclear Information System (INIS)

    Gao Haiyan; Xiang Hongwei; Li Yongwang; Sun Yuhan; Liu Tao; Xie Yaning; Hu Tiandou

    2002-01-01

    The Co-based catalysts have been extensively used in converting CO to longer chain hydrocarbons which can then be hydrocracked to diesel oil with high grade. SiO 2 is one of the most commonly used carriers for Co-based catalysts. It is showed that commercial silica carrier after modification can lead to much high reaction activity and selectivity to heavy hydrocarbons. But the structure of Co-based catalysts supported on the modified carrier has not been clearly understood. XAFS is used to investigate the change of structure of cobalt species in Co-based catalysts supported on modified carriers. The result from XAFS indicate that the structure of Co-based catalysts supported on modified carrier has certain change in comparison with Co-based catalyst supported on commercial silica. The interaction between carrier and metal is woken in the modified catalysts. Especially, the structure of catalysts after reduction have distinct difference. The extent of reduction in modified catalysts is much more than the catalyst supported on commercial silica. Cobalt species of the catalyst supported commercial silica after reduction dose exist mainly in the form of cobalt metal forms and may exist in the form of Co 2 SiO 4 surface compound

  10. High-Throughput Screening of Heterogeneous Catalysts for the Conversion of Furfural to Bio-Based Fuel Components

    Directory of Open Access Journals (Sweden)

    Roberto Pizzi

    2015-12-01

    Full Text Available The one-pot catalytic reductive etherification of furfural to 2-methoxymethylfuran (furfuryl methyl ether, FME, a valuable bio-based chemical or fuel, is reported. A large number of commercially available hydrogenation heterogeneous catalysts based on nickel, copper, cobalt, iridium, palladium and platinum catalysts on various support were evaluated by a high-throughput screening approach. The reaction was carried out in liquid phase with a 10% w/w furfural in methanol solution at 50 bar of hydrogen. Among all the samples tested, carbon-supported noble metal catalysts were found to be the most promising in terms of productivity and selectivity. In particular, palladium on charcoal catalysts show high selectivity (up to 77% to FME. Significant amounts of furfuryl alcohol (FA and 2-methylfuran (2-MF are observed as the major by-products.

  11. Supramolecular tetracluster-cobalt porphyrin: a four-electron transfer catalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Winnischofer, Herbert; Otake, Vesper Yoshiyuki; Dovidauskas, Sergio; Nakamura, Marcelo; Toma, Henrique Eisi; Araki, Koiti

    2004-01-01

    Electrocatalysis by CoTCP {CoTCP meso-tetrakis(4-pyridyl)porphynatocobalt(III)} coordinated to four [Ru 3 (μ 3 -O)(μ 2 -CH 3 CO 2 ) 6 (py) 2 ] + complexes in the four-electron reduction of dioxygen, has been unequivocally demonstrated in this work by using two types of electrostatically assembled films of CoTCP and anionic zinc or free-base meso-tetrakis(4-sulfonatophenyl)porphyrins (ZnTPPS or H 2 TPPS), as well as, by employing different electrode materials. An enhanced electrocatalytic activity has been observed, in spite of the fact that the typical bis-coordination of dioxygen to two cobalt porphyrin sites is precluded in such CoTCP/ZnTPPS or CoTCP/H 2 TPPS bilayered films. In addition, negligible ring currents have been observed in ring-disk voltammetry measurements, yielding straight Levich and Koutecky-Levich plots, whose slopes approached the theoretical 4e - curve in air, or in O 2 saturated solutions (pH 3-5). The use of gold instead of glassy carbon (GC) electrodes has not also significantly perturbed the mechanism. By ruling out any influence from the electrode materials, a well known critical point in the catalysis by cobalt porphyrins, the results have shown that CoTCP is acting as a four-electron transfer catalyst for dioxygen reduction. Also, by excluding the possibility of bis-coordination of dioxygen, it was shown that the electronic and supramolecular effects exerted by the peripheral ruthenium cluster complexes should be triggering the four-electron catalytic activity of the cobalt porphyrin center

  12. Performance of Cobalt-Based Fischer-Tropsch Synthesis Catalysts Using Dielectric-Barrier Discharge Plasma as an Alternative to Thermal Calcination

    International Nuclear Information System (INIS)

    Bai Suli; Huang Chengdu; Lv Jing; Li Zhenhua

    2012-01-01

    Co-based catalysts were prepared by using dielectric-barrier discharge (DBD) plasma as an alternative method to conventional thermal calcination. The characterization results of N 2 -physisorption, temperature programmed reduction (TPR), transmission electron microscope (TEM), and X-ray diffraction (XRD) indicated that the catalysts prepared by DBD plasma had a higher specific surface area, lower reduction temperature, smaller particle size and higher cobalt dispersion as compared to calcined catalysts. The DBD plasma method can prevent the sintering and aggregation of active particles on the support due to the decreased treatment time (0.5 h) at lower temperature compared to the longer thermal calcination at higher temperature (at 500° C for 5 h). As a result, the catalytic performance of the Fischer-Tropsch synthesis on DBD plasma treated Co/SiO 2 catalyst showed an enhanced activity, C 5+ selectivity and catalytic stability as compared to the conventional thermal calcined Co/SiO 2 catalyst.

  13. Novel catalysts and photoelectrochemical system for solar fuel production

    Science.gov (United States)

    Zhang, Yan

    Solar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption

  14. Highly efficient and stable catalyst for peroxynitrite decomposition

    Science.gov (United States)

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

    2001-01-01

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

  15. Highly efficient cobalt-doped carbon nitride polymers for solvent-free selective oxidation of cyclohexane

    Directory of Open Access Journals (Sweden)

    Yu Fu

    2017-04-01

    Full Text Available Selective oxidation of saturated hydrocarbons with molecular oxygen has been of great interest in catalysis, and the development of highly efficient catalysts for this process is a crucial challenge. A new kind of heterogeneous catalyst, cobalt-doped carbon nitride polymer (g-C3N4, was harnessed for the selective oxidation of cyclohexane. X-ray diffraction, Fourier transform infrared spectra and high resolution transmission electron microscope revealed that Co species were highly dispersed in g-C3N4 matrix and the characteristic structure of polymeric g-C3N4 can be retained after Co-doping, although Co-doping caused the incomplete polymerization to some extent. Ultraviolet–visible, Raman and X-ray photoelectron spectroscopy further proved the successful Co doping in g-C3N4 matrix as the form of Co(IIN bonds. For the selective oxidation of cyclohexane, Co-doping can markedly promote the catalytic performance of g-C3N4 catalyst due to the synergistic effect of Co species and g-C3N4 hybrid. Furthermore, the content of Co largely affected the activity of Co-doped g-C3N4 catalysts, among which the catalyst with 9.0 wt% Co content exhibited the highest yield (9.0% of cyclohexanone and cyclohexanol, as well as a high stability. Meanwhile, the reaction mechanism over Co-doped g-C3N4 catalysts was elaborated. Keywords: Selective oxidation of cyclohexane, Oxygen oxidant, Carbon nitride, Co-doping

  16. Application of Two Cobalt-Based Metal-Organic Frameworks as Oxidative Desulfurization Catalysts.

    Science.gov (United States)

    Masoomi, Mohammad Yaser; Bagheri, Minoo; Morsali, Ali

    2015-12-07

    Two new porous cobalt-based metal-organic frameworks, [Co6(oba)5(OH)2(H2O)2(DMF)4]n · 5DMF (TMU-10) and [Co3(oba)3(O) (Py)0.5] n · 4DMF · Py (TMU-12) have been synthesized by solvothermal method using a nonlinear dicarboxylate ligand. Under mild reaction conditions, these compounds exhibited good catalytic activity and reusability in oxidative desulfurization (ODS) reaction of model oil which was prepared by dissolving dibenzothiophene (DBT) in n-hexane. FT-IR and Mass analysis showed that the main product of DBT oxidation is its corresponding sulfone, which was adsorbed on the surfaces of catalysts. The activation energy was obtained as 13.4 kJ/mol.

  17. Surface science models of CoMoS hydrodesulfurisation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    De Jong, A.M.; De Beer, V.H.J.; Van Veen, J.A.R.; Niemantsverdriet, J.W. [Schuit Institute of Catalysis, Eindhoven University of Technology, Eindhoven (Netherlands)

    1997-07-01

    Characterization of supported catalysts with surface spectroscopic techniques is often limited due to restraints imposed by the support material. The use of flat conducting substrates as a model support offers a way to apply these techniques to their full potential. Such surface science models of silica and alumina supported CoMoS catalysts have been made by impregnating thin SiO{sub 2} and Al{sub 2}O{sub 3} films with a solution of nitrilotriacetic acid (NTA) complexes of cobalt and molybdenum. X-ray Photoelectron Spectroscopy (XPS) spectra indicate that the order in which cobalt and molybdenum transfer to the sulfided state is reversed with respect to oxidic Co and Mo systems prepared by conventional methods, implying that NTA complexation retards the sulfidation of cobalt to temperatures where MoS{sub 2} is already formed. Catalytic tests show that the CoMoS model catalysts exhibit activities for thiophene desulfurisation and product distributions similar to those of their high surface area counterparts. 25 refs.

  18. Hydrogen evolution catalyzed by cobalt diimine-dioxime complexes.

    Science.gov (United States)

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-05-19

    Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged 10 years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, that is, close to the thermodynamic equilibrium over a wide range of acid-base conditions in nonaqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly, we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts in the

  19. Comparison of Cobalt based Catalysts Supported on MWCNT and SBA-15 Supporters for Fischer-tropsch Synthesis by Using Novel Vortex Type Reactor

    International Nuclear Information System (INIS)

    Yakubov, A.; Shahrun, M.S.; Kutty, M.G.; Hamid, S.B.A.; Piven, V.

    2011-01-01

    10 and 40 wt% Co/ Multi wall Carbon Nano tubes (MWCNT) and 10 and 40 wt% Co/ Santa Barbara Amorphous-15 (SBA) catalysts were prepared via incipient wetness impregnation and characterized by Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy (SEM and EDX), N 2 adsorption-desorption (BET), X-ray Diffractometry (XRD), Transmission Electron Microscopy (TEM) and Temperature- Programmed Reduction and H 2 desorption TPD/RO. Co(NO 3 ) 2 * 6H 2 O was used as a cobalt precursor. 200 ml hastelloy autoclave reactor was implemented to see the performance of the catalysts. This report presents details about the catalyst synthesis and reactor study. (author)

  20. Synthesis and Characterization of Cobalt Containing Nanoparticles on Alumina A Potential Catalyst for Gas to Liquid Fuels Production

    Science.gov (United States)

    Cowen, Jonathan; Hepp, Aloysius F.

    2016-01-01

    Fisher-Tröpsch synthesis (FTS) is a century-old gas-to-liquid (GTL) technology that commonly employs cobalt (Co, on an oxide support) or iron (supported or not) species catalysts. It has been well established that the activity of the Co catalyst depends directly upon the number of surface Co atoms. The addition of promoter (mainly noble) metals has been widely utilized to increase the fraction of Co that is available for surface catalysis. Direct synthesis of Co nanoparticles is a possible alternative approach; our preliminary synthesis and characterization efforts are described. Materials were characterized by various transmission microscopies and energy dispersive spectroscopy. Tri-n-octylphosphine oxide (TOPO) and dicobalt octacarbonyl were heated under argon to a temperature of 180 deg with constant stirring for 1 hr. Quenching the reaction in toluene produced Co-containing nanoparticles with a diameter of 5 to 10 nm. Alternatively, an alumina support (SBA-200 Al2O3) was added; the reaction was further stirred and the temperature was decreased to 140 deg to reduce the rate of further growth/ripening of the nucleated Co nanoparticles. A typical size of Co-containing NPs was also found to be in the range of 5 to 10 nm. This can be contrasted with a range of 50 to 200 nm for conventionally-produced Co-Al2O3 Fischer-Tröpsch catalysts. This method shows great potential for production of highly dispersed catalysts that are either supported or unsupported.

  1. Structural and luminescence properties of GaN nanowires grown using cobalt phthalocyanine as catalyst

    Science.gov (United States)

    Yadav, Shivesh; Rodríguez-Fernández, Carlos; de Lima, Mauricio M.; Cantarero, Andres; Dhar, Subhabrata

    2015-12-01

    Catalyst free methods have usually been employed to avoid any catalyst induced contamination for the synthesis of GaN nanowires with better transport and optical properties. Here, we have used a catalytic route to grow GaN nanowires, which show good optical quality. Structural and luminescence properties of GaN nanowires grown by vapor-liquid-solid technique using cobalt phthalocyanine as catalyst are systematically investigated as a function of various growth parameters such as the growth temperature and III/V ratio. The study reveals that most of the nanowires, which are several tens of microns long, grow along [ 10 1 ¯ 0 ] direction. Interestingly, the average wire diameter has been found to decrease with the increase in III/V ratio. It has also been observed that in these samples, defect related broad luminescence features, which are often present in GaN, are completely suppressed. At all temperatures, photoluminescence spectrum is found to be dominated only by a band edge feature, which comprises of free and bound excitonic transitions. Our study furthermore reveals that the bound excitonic feature is associated with excitons trapped in certain deep level defects, which result from the deficiency of nitrogen during growth. This transition has a strong coupling with the localized vibrational modes of the defects.

  2. Effect study of the support in nickel and cobalt catalysts for obtaining hydrogen from ethanol steam reforming

    International Nuclear Information System (INIS)

    Silva, Sirlane Gomes da

    2013-01-01

    A range of oxide-supported metal catalysts have been investigated for the steam reforming of ethanol for the production of hydrogen and subsequent application in fuel cells. The catalysts were synthesized by the co-precipitation and internal gelification methods using cobalt and nickel as active metals supported on aluminum, zirconium, lanthanum and cerium oxides. After prepared and calcined at 550 Cº the solids were fully characterized by different techniques such as X-rays diffraction(DRX), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy, nitrogen adsorption (B.E.T), temperature-programmed reduction in H2 (TPR-H2) and thermogravimetric analysis. The catalytic tests were performed in a monolithic quartz reactor and submitted to different thermodynamic conditions of steam reforming of ethanol at temperatures varying from 500º C to 800 ºC. The product gas streams from the reactor were analyzed by an on-line gas chromatograph. The cobalt/nickel catalyst supported on a ceria-lanthania mixture (Co 10% / Ni 5% - CeO 2 La 2 O 3 ) showed good catalytic performance in hydrogen selectivity reaching a concentration greater than 65%, when compared to other catalytic systems such as: Co 10% / Ni5% - CeO 2 ; Co 10% / Ni 5% - CeO 2 ZrO 2 ; Co 10% / Ni 5% - ZrO 2 ; Co 10% / Ni 5% - La 2 O 3 ; Co 10% / Ni 5% - CeO 2 La 2 O 3 /K 2% ; Co 10 % / Ni 5% - CeO 2 La 2 O 3 / Na 2% ; Ni 10% / Co 5% - CeO 2 La 2 O 3 ; Co-Al 2 O 3 e Co-Al 2 O 3 CeO 2 . (author)

  3. Carbon-Based Oxamate Cobalt(III) Complexes as Bioenzyme Mimics for Contaminant Elimination in High Backgrounds of Complicated Constituents.

    Science.gov (United States)

    Li, Nan; Zheng, Yun; Jiang, Xuemei; Zhang, Ran; Pei, Kemei; Chen, Wenxing

    2017-10-12

    Complex wastewater with massive components is now a serious environmental issue facing humanity. Selective removal of low-concentration contaminants in mixed constituents holds great promise for increasing water supplies. Bioenzymes like horseradish peroxidase exhibit oxidizing power and selectivity. Here, we manufactured its mimic through immobilizing non-heme oxamate anionic cobalt(III) complex ([Co III (opba)] - , opba = o-phenylenebis(oxamate)) onto pyridine (Py) modified multiwalled carbon nanotubes ([Co III (opba)] - -Py-MWCNTs, MWCNTs = multiwalled carbon nanotubes), where MWCNTs captured substrates and Py functioned as the fifth ligand. We chose typical azo dye (C.I. Acid Red 1) and antibiotic (ciprofloxacin) as model substrates. Without •OH, this catalyst could detoxify target micropollutants efficiently at pH from 8 to 11. It also remained efficient in repetitive tests, and the final products were non-poisonous OH-containing acids. Combined with radical scavenger tests and electron paramagnetic resonance result, we speculated that high-valent cobalt-oxo active species and oxygen atom transfer reaction dominated in the reaction pathway. According to density functional theory calculations, the electron spin density distribution order showed that electron-withdrawing ligand was beneficial for inward pulling the excess electron and lowering the corresponding energy levels, achieving an electrophilic-attack enhancement of the catalyst. With target removal property and recyclability, this catalyst is prospective in water detoxication.

  4. Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

    International Nuclear Information System (INIS)

    Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

    1977-01-01

    Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

  5. Cobalt Oxide Catalysts Supported on CeO2–TiO2 for Ethanol Oxidation and N2O Decomposition.

    Czech Academy of Sciences Publication Activity Database

    Jirátová, Květa; Kovanda, F.; Balabánová, Jana; Koloušek, D.; Klegová, A.; Pacultová, K.; Obalová, L.

    2017-01-01

    Roč. 12, č. 1 (2017), s. 121-139 ISSN 1878-5190. [Pannonian Symposium on Catalysis. Siófok, 19.09.2016-23.09.2016] R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : cobalt oxide catalysts * ethanol total oxidation * N2O decomposition Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 1.264, year: 2016

  6. Synthesis and butadiene polymerization behaviors of cationic cobalt-based catalyst

    Directory of Open Access Journals (Sweden)

    Li Liu

    2017-01-01

    Full Text Available A series of cationic cobalt-based compounds bearing different neutral N-bearing ligands (1,10-phenanthroline, bipyridine, benzimidazole, terpyridine and anionic ligands (trifluoromethanesulfonate, methanesulfonate were synthesized and the simple compound, Co(Phen2Cl2, was also prepared as a reference compound. All the compounds were characterized along with infrared spectra analysis and some of them were further confirmed by single crystal X-ray crystallographic analysis. Upon activation with ethylaluminum sesquichloride, these cationic cobalt(II compounds showed high catalytic activities for butadiene polymerization. The detailed investigations were carried out to disclose the influence of various polymerization conditions, sterical and electronic parameters of the ligands on their performing activities of the compounds.

  7. Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

    KAUST Repository

    Sun, Xiaohui; Suarez, Alma I. Olivos; Meijerink, Mark; van Deelen, Tom; Ould-Chikh, Samy; Zečević, Jovana; de Jong, Krijn P.; Kapteijn, Freek; Gascon, Jorge

    2017-01-01

    The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size

  8. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Burtron H. Davis

    1999-01-01

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe(sub 3)O(sub 4). Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to(epsilon)(prime)-Fe(sub 2.2)C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to(chi)-Fe(sub 5)C(sub 2) and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe(sub 3)O(sub 4); however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94%(chi)-Fe(sub 5)C(sub 2), deactivated rapidly as the carbide was oxidized to Fe(sub 3)O(sub 4). No difference in activity, stability or deactivation rate was found for(chi)-Fe(sub 5)C(sub 2) and(epsilon)(prime)-Fe(sub 2.2)C

  9. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Burtron H. Davis

    1999-04-30

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe{sub 3}O{sub 4}. Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to {epsilon}{prime}-Fe{sub 2.2}C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to {chi}-Fe{sub 5}C{sub 2} and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe{sub 3}O{sub 4}; however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94% {chi}-Fe{sub 5}C{sub 2}, deactivated rapidly as the carbide was oxidized to Fe{sub 3}O{sub 4}. No difference in activity, stability or deactivation rate was found for {chi}-Fe{sub 5}C{sub 2} and {epsilon}{prime}-Fe{sub 2.2}C.

  10. Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes

    KAUST Repository

    Sun, Xiaohui

    2017-11-20

    A supported cobalt catalyst with atomically dispersed Co-Nx sites (3.5 wt% Co) in a mesoporous N-doped carbon matrix (named Co@mesoNC) is synthesized by hydrolysis of tetramethyl orthosilicate (TMOS) in a Zn/Co bimetallic zeolitic imidazolate framework (BIMZIF(Co,Zn)), followed by high-temperature pyrolysis and SiO2 leaching. A combination of TEM, XRD XPS and X-ray absorption spectroscopy studies confirm the absence of cobalt nanoparticles and indicate that these highly dispersed cobalt species are present in the form of Co-Nx. The exclusive formation of Co-Nx sites in the carbon matrix is attributed to the presence of a large amount of Zn and N in the BIMZIF precursor together with the presence of SiO2 in the pore space of this framework, extending the initial spatial distance between cobalt atoms and thereby impeding their agglomeration. The presence of SiO2 during high-temperature pyrolysis is proven crucial to create mesoporosity and a high BET area and pore volume in the N-doped carbon support (1780 m2 g−1, 1.54 cm3 g−1). This heterogeneous Co@mesoNC catalyst displays high activity and selectivity (>99%) for the selective hydrogenation of nitrobenzene to aniline at mild conditions (0.5–3 MPa, 343–383 K). When more challenging substrates (functionalized nitroarenes) are hydrogenated, the catalyst Co@mesoNC displays an excellent chemoselectivity to the corresponding substituted anilines.The presence of mesoporosity improves mass transport of reactants and/or products and the accessibility of the active Co-Nx sites, and greatly reduces deactivation due to fouling.

  11. Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes

    KAUST Repository

    Sun, Xiaohui; Olivos-Suarez, Alma I.; Osadchii, Dmitrii; Romero, Maria Jose Valero; Kapteijn, Freek; Gascon, Jorge

    2017-01-01

    A supported cobalt catalyst with atomically dispersed Co-Nx sites (3.5 wt% Co) in a mesoporous N-doped carbon matrix (named Co@mesoNC) is synthesized by hydrolysis of tetramethyl orthosilicate (TMOS) in a Zn/Co bimetallic zeolitic imidazolate framework (BIMZIF(Co,Zn)), followed by high-temperature pyrolysis and SiO2 leaching. A combination of TEM, XRD XPS and X-ray absorption spectroscopy studies confirm the absence of cobalt nanoparticles and indicate that these highly dispersed cobalt species are present in the form of Co-Nx. The exclusive formation of Co-Nx sites in the carbon matrix is attributed to the presence of a large amount of Zn and N in the BIMZIF precursor together with the presence of SiO2 in the pore space of this framework, extending the initial spatial distance between cobalt atoms and thereby impeding their agglomeration. The presence of SiO2 during high-temperature pyrolysis is proven crucial to create mesoporosity and a high BET area and pore volume in the N-doped carbon support (1780 m2 g−1, 1.54 cm3 g−1). This heterogeneous Co@mesoNC catalyst displays high activity and selectivity (>99%) for the selective hydrogenation of nitrobenzene to aniline at mild conditions (0.5–3 MPa, 343–383 K). When more challenging substrates (functionalized nitroarenes) are hydrogenated, the catalyst Co@mesoNC displays an excellent chemoselectivity to the corresponding substituted anilines.The presence of mesoporosity improves mass transport of reactants and/or products and the accessibility of the active Co-Nx sites, and greatly reduces deactivation due to fouling.

  12. Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Gang [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Yang, Ce [Chemical Science and Engineering Division, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Zhao, Wanpeng [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Li, Qianru [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Wang, Ning [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Li, Tao [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Zhou, Hua [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Chen, Hangrong [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; Shi, Jianlin [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China

    2017-11-06

    The introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications, however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs is investigated for the first time. It is found that the active cobalt-nitrogen sites tend to be selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for ORR and HER in acidic media. And the remarkably enhanced catalytic activities approaching that of benchmark Pt/C in acidic medium has been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic . Our finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.

  13. Reduction and reoxidation of cobalt Fischer-Tropsch catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hilmen, Anne-Mette

    1996-12-31

    The Fischer-Tropsch synthesis involves the hydrogenation of carbon monoxide to produce mainly hydrocarbons, water and carbon dioxide, but also alcohols, aldehydes and acids are formed. The distribution of these products is determined by the choice of catalyst and synthesis conditions. This thesis studies the reduction and reoxidation of 17%Co/Al{sub 2}O{sub 3} and 17%Co-1%Re/Al{sub 2}O{sub 3} by means of several characterization techniques. The effect of small amounts of Re on the reduction properties of Al{sub 2}O{sub 3}-supported Co catalysts has been studied by temperature-programmed reduction (TPR). An intimate mixture of CoAl{sub 2}O{sub 3} and Re/Al{sub 2}O{sub 3} catalysts showed a promoting effect of Re similar to that for co impregnated CoRe/Al{sub 2}O{sub 3}. A loose mixture of Co/Al{sub 2}O{sub 3} + Re/Al{sub 2}O{sub 3} did not show any effect of Re on the reduction of Co. But a promoting effect was observed if the mixture had been pre-treated with Ar saturated with water before the TPR. It is suggested that Re promotes the reduction of Co oxide by hydrogen spillover. It is shown that a high temperature TPK peak at 1200K assigned to Co aluminate is mainly caused by the diffusion of Co ions during the TPR and not during calcination. The Co particle size measured by x-ray diffraction on oxidized catalysts decreased compared to the particle size on the calcined catalysts, while the dispersion measured by volumetric chemisorption decreased somewhat after the oxidation-reduction treatment. The role of water in the deactivation of Co/Al{sub 2}O{sub 3} and CoRe/Al{sub 2}O{sub 3} Fischer-Tropsch catalysts has been extensively studied. There were significant differences in the reducibility of the phases formed for the two catalysts during exposure to H{sub 2}O/He. 113 refs., 76 figs., 18 tabs.

  14. Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

    KAUST Repository

    Cabán-Acevedo, Miguel

    2015-09-14

    The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS 2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm at overpotentials as low as 48mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n -p-p silicon micropyramids achieved photocurrents up to 35 mA cm at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

  15. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed

    2016-11-04

    The decoration of (photo)electrodes for efficient photoresponse requires the use of electrocatalysts with good dispersion and high transparency for efficient light absorption by the photoelectrode. As a result of the ease of thermal evaporation and particulate self-assembly growth, the phthalocyanine molecular species can be uniformly deposited layer-by-layer on the surface of substrates. This structure can be used as a template to achieve a tunable amount of catalysts, high dispersion of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a phthalocyanine metal precursor. Cobalt phthalocyanine (CoPc) films with different thicknesses were deposited by thermal evaporation on different substrates. The films were annealed at 400 °C in air to form a material with the cobalt oxide phase. The final Co oxide catalysts exhibit high transparency after thermal treatment. Their OER measurements demonstrate well expected mass activity for OER. Thermally evaporated and treated transition metal oxide nanoparticles are attractive for the functionalization of (photo)anodes for water oxidation.

  16. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    International Nuclear Information System (INIS)

    Kepenienė, V.; Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J.; Vaitkus, R.; Norkus, E.

    2016-01-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  17. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Kepenienė, V., E-mail: virginalisk@gmail.com [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Vaitkus, R. [Faculty of Chemistry, Vilnius University, Vilnius LT 03225 (Lithuania); Norkus, E. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania)

    2016-03-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  18. Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongting [Department; Xu, Zhuoran [Department; Chada, Joseph P. [Department; Carrero, Carlos A. [Department; Rosenfeld, Devon C. [The Dow Chemical Company, 2301 N. Brazosport Boulevard, Freeport, Texas 77541-3257, United States; Rogers, Jessica L. [The Dow Chemical Company, 2301 N. Brazosport Boulevard, Freeport, Texas 77541-3257, United States; Hermans, Ive [Department; Huber, George W. [Department

    2017-10-02

    Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH4OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased with 1-butene conversion. The catalysts were characterized by elemental analysis, N2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by elemental analysis. The surface content of pyridinic nitrogen with a binding energy of 398.4 ± 0.1 eV increased with ammonia treatment temperature as evidenced by deconvolution of N 1s XPS spectra.

  19. Investigation of sulfur-tolerant catalysts for selective synthesis of hydrocarbon liquids from coal-derived gases. Annual technical progress report, September 19, 1980-September 18, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Bartholomew, C.H.

    1981-10-31

    During the past contract year, considerable progress was made in characterization and activity/selectivity testing of iron and cobalt catalysts. Preparation of boride promoted cobalt and iron catalysts was refined and nearly completed. H/sub 2/ and CO adsorption and oxygen titration measurements were performed on a number of supported and unsupported catalysts, especially several boride promoted cobalt and iron catalysts. Activity/selectivity tests of 3 and 15% Fe/SiO/sub 2/ and Co/SiO/sub 2/ and of 6 borided cobalt and iron catalysts were completed. The product distributions for iron and cobalt boride catalysts are unusual and interesting. Boron promoted iron is more active and stable than iron/silica; cobalt boride has an unusually high selectivity for alcohols. Tests to determine effects of H/sub 2/S poisoning on activity/selectivity properties of 15% Co/SiO/sub 2/ indicate that a significant loss of activity occurs over a period of 24 to 28 h in the presence of 10 to 20 ppM H/sub 2/S. Product selectivity to liquids increased through a maximum during the gradual addition of sulfur. Reactant CO and H/sub 2/S interact partially to form COS which is less toxic than H/sub 2/S. H/sub 2/ and CO adsorption data were obtained for 3, 6 and 9% Co/ZSM-5 catalysts prepared and reactor tested by PETC. The unusual and interesting results suggest that metal-support interactions may have an important influence on reactant adsorption properties.

  20. Reactions of synthesis gas on silica supported transition metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Niemelae, M. [VTT Chemical Technology, Espoo (Finland). Lab. of Industrial Chemistry

    1997-12-31

    The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO{sub 2} catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO{sub 2} considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO{sub 2} appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO{sub 2} ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO{sub 2} catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh{sub 4}(CO){sub 12}/SiO{sub 2} from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes. (orig.) 69 refs.

  1. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.; Vagin, Sergei I.; Hammann, Markus; Zimmermann, Leander; Rieger, Bernhard

    2013-01-01

    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.

    2013-09-18

    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Nitrogen doped graphene supported palladium-cobalt as a promising catalyst for methanol oxidation reaction: Synthesis, characterization and electrocatalytic performance

    International Nuclear Information System (INIS)

    Kiyani, Roya; Rowshanzamir, Soosan; Parnian, Mohammad Javad

    2016-01-01

    In this work, palladium and palladium-cobalt supported on nitrogen doped graphene as anode materials in direct methanol fuel cells is reported. A simple and low temperature solvothermal method is used to directly prepare nanoflower-like NG and then, Pd and Pd−Co nanoparticles are precipitated onto the surface of NG using a modified polyol reduction method. The synthesized electrocatalysts are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) are used to measure electrocatalytic methanol oxidation activity and the durability of electrocatalysts. The results show that Pd−Co/NG has better electrocatalytic activity than Pd/NG toward methanol oxidation reaction (MOR) in alkaline media that is related at the presence of cobalt atoms. In addition, chronoamperometric results indicate that Pd−Co/NG is more stable than commercial Pt/C for MOR. - Highlights: • Nitrogen doped graphene (NG) was prepared by a simple solvothermal method. • Pd and Pd−Co nanoparticles were deposited on NG by polyol reduction method. • Promoting effects of cobalt over Pd/NG for MOR were investigated. • Higher activity and enhanced durability was observed for Pd−Co/NG catalyst.

  4. Mechanizm of propylene oxidation on modified cobalt-molybdenum catalysts

    International Nuclear Information System (INIS)

    Kutyrev, M.Yu.; Rozentuller, B.V.; Isaev, O.V.; Margolis, L.Ya.; Krylov, O.V.

    1977-01-01

    Effect is studied of additions of iron, copper, nickel, and vanadium oxides, introduced into cobalt, molybdate, on oxidation reactions of propylene to acrolein and acrylicacid. The principal parameters determining the activity and selectivity of oxidation of propylene and acrolein on modified cobalt molibdate are the structure, the type of Mo-O bond, and the nature of the electron transitions in the solid under the effect of adsorption of the reaction components

  5. In situ synthesis and catalytic application of reduced graphene oxide supported cobalt nanowires

    Science.gov (United States)

    Xu, Zhiqiang; Long, Qin; Deng, Yi; Liao, Li

    2018-05-01

    Controlled synthesis of magnetic nanocomposite with outstanding catalytic performances is a promising strategy in catalyst industry. We proposed a novel concept for fabrication of reduced graphene oxide-supported cobalt nanowires (RGO/Co-NWs) nanocomposite as high-efficient magnetic catalyst. Unlike the majority of experiments necessitating harsh synthesis conditions such as high-pressure, high-temperature and expensive template, here the RGO/Co-NWs were successfully prepared in aqueous solution under mild conditions with the assistance of external magnetic field. The synthetic process was facile and external magnetic force was adopted to induce the unidirectional self-assembly of cobalt crystals on graphene oxide to form RGO/Co-NWs. The possible formation mechanism laid on the fact that the dipole magnetic moments of the nanoparticles were aligned along the magnetic induction lines with the external magnetic field direction resulting in the formation of nanowires elongating in the direction of the magnetization axis. Simultaneously, a series of controlled reactions were conducted to illuminate the effect of graphene oxide, external magnetic field and PVP on the morphology and size of RGO/Co-NWs in the present approach. More importantly, the nanocomposite exhibited a high catalytic performance towards ammonia borane. Hence the novel nanocomposite holds a great potential for technological applications such as catalyst industry.

  6. Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.

    Science.gov (United States)

    Mei, Ruhuai; Sauermann, Nicolas; Oliveira, João C A; Ackermann, Lutz

    2018-06-27

    Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H 2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.

  7. Comprehensive characterisation of products from cobalt catalysed Fischer-Tropsch reaction

    Energy Technology Data Exchange (ETDEWEB)

    Marion, M.C.; Bertoncini, F.; Hugues, F.; Forestiere, A. [IFP, Vernaison (France)

    2006-07-01

    Fischer-Tropsch reaction synthesis has been studied in presence of supported cobalt catalysts. The experimental work has been performed by using a slurry pilot plant. All the gaseous and liquid products, including by-products recovered in the water phase produced, have been analysed in order to determine the whole products distribution and the catalyst selectivity. Apart from paraffin which are the main products obtained via cobalt-catalyzed Fischer-Tropsch synthesis, olefins and oxygenates by-products present also their own distribution. These detailed data are available thanks to new dedicated analytical methods developed in IFP laboratories. (orig.)

  8. Cu–Co–O nano-catalysts as a burn rate modifier for composite solid propellants

    Directory of Open Access Journals (Sweden)

    D. Chaitanya Kumar Rao

    2016-08-01

    Full Text Available Nano-catalysts containing copper–cobalt oxides (Cu–Co–O have been synthesized by the citric acid (CA complexing method. Copper (II nitrate and Cobalt (II nitrate were employed in different molar ratios as the starting reactants to prepare three types of nano-catalysts. Well crystalline nano-catalysts were produced after a period of 3 hours by the calcination of CA–Cu–Co–O precursors at 550 °C. The phase morphologies and crystal composition of synthesized nano-catalysts were examined using Scanning Electron Microscope (SEM, Energy Dispersive Spectroscopy (EDS and Fourier Transform Infrared Spectroscopy (FTIR methods. The particle size of nano-catalysts was observed in the range of 90 nm–200 nm. The prepared nano-catalysts were used to formulate propellant samples of various compositions which showed high reactivity toward the combustion of HTPB/AP-based composite solid propellants. The catalytic effects on the decomposition of propellant samples were found to be significant at higher temperatures. The combustion characteristics of composite solid propellants were significantly improved by the incorporation of nano-catalysts. Out of the three catalysts studied in the present work, CuCo-I was found to be the better catalyst in regard to thermal decomposition and burning nature of composite solid propellants. The improved performance of composite solid propellant can be attributed to the high crystallinity, low agglomeration and lowering the decomposition temperature of oxidizer by the addition of CuCo-I nano-catalyst.

  9. Catalyst systems and uses thereof

    Science.gov (United States)

    Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

    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.

  10. Carbon-supported co-pyridine as non-platinum cathode catalyst for alkaline membrane fuel cells

    International Nuclear Information System (INIS)

    Qiao, Jinli; Xu, Li; Liu, Yuyu; Xu, Pan; Shi, Jingjing; Liu, Shiyao; Tian, Binglun

    2013-01-01

    Development of high-performance cost-effective electrocatalyts that can replace Pt catalyst have been a central theme in polymer electrolyte membrane fuel cells (PEMFCs) including direct methanol fuel cells (DMFCs). Here we show that carbon-supported pyridine–cobalt nanoparticles (CoPy/C) can generate a high catalytic activity toward the oxygen reduction reaction (ORR). The catalysts are synthesized using cobalt sulfate heptahydrate (CoSO 4 ·7H 2 O) and pyridine (Py) as the Co and N precursors via a solid state reaction by heat-treatment in an inert atmosphere at 800 °C. In particular, the ORR kinetics on these catalyst materials are evaluated using rotating disk electrode (RDE) technique in electrolytes of various KOH concentrations, ranging from 0.05 to 12 M. The Koutecky–Levich equation analyses indicate that the transferred electron number, n, per oxygen molecule on CoPy/C electrode depend on the low negative ovevrpotentials in low KOH concentrations, whereas in high KOH concentrations the values of n for oxygen reduction depend on the high negative overpotentials, and varies between 3.5 and 4.0. These catalysts exhibit the superior methanol tolerance to commercial 40%Pt/C catalyst, and the negative effect of high KOH concentration is much less for CoPy/C than for Pt/C, suggesting the promising utilization of CoPy/C as electrocatalysts for alkaline polymer electrolyte membrane fuel cells

  11. Preparation and characterization of catalyst 20% Co/SBA-15

    International Nuclear Information System (INIS)

    Lima, L.A.; Nogueira, A.C.; Rodrigues, J.J.; Rodrigues, M.G.F.

    2012-01-01

    The utilization of molecular sieves as supports for cobalt catalysts are promising. SBA-15 is a class of mesoporous silicate with a high thermal stability and high degree of structural order, which confers an important feature for the catalytic process. It was prepared SBA-15 molecular sieve with molar composition: 1.0 TEOS: 0017P123: 5.7 HCl: 193 H2O. The deposition of cobalt on the substrate SBA-15 was performed by wet impregnation, using a solution of 0.1M cobalt nitrate. The materials were characterized by the techniques of X-Ray Diffraction (XRD), chemical analysis by X-Ray Spectrometry by Energy Dispersive (EDX), and nitrogen adsorption (BET). By XRD and BET verified the formation of SBA-15, and after the impregnation there was no change in the structure, with EDX showed that the impregnation method is efficient, the sample showed cobalt content close to the nominal value. (author)

  12. Controllable synthesis of hierarchical nickel cobalt sulfide with enhanced electrochemical activity

    Science.gov (United States)

    Tie, Jinjin; Han, Jiaxi; Diao, Guiqiang; Liu, Jiwen; Xie, Zhuopeng; Cheng, Gao; Sun, Ming; Yu, Lin

    2018-03-01

    The composition of nickel cobalt sulfide has great influence on its electrochemical performance. Herein, the nickel cobalt sulfide with different composition and mixed phase were synthesized by one-step solvothermal method through changing the molar ratio of Ni to Co in the reaction system. The electrochemical measurements showed that the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co to be 1.5:1.5 (NCS-2) demonstrates the superior pseudocapacitive performance with a high specific capacitance (6.47 F cm-2 at 10 mA cm-2) and a favorable Coulombic efficiency (∼99%). Whereas, when applied as the catalyst for hydrogen evolution reaction in 1 M KOH aqueous electrolyte, the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co is 1:2 (NCS-1) displays better catalytic activity, and it requires a relatively lower overpotential of 282 mV to deliver the current density of 10 mA cm-2.

  13. Alkali promotion effect in Fischer-Tropsch cobalt-alumina catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Eliseev, O.L.; Tsapkina, M.V.; Davydov, P.E.; Kazantsev, R.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry; Belousova, O.S.; Lapidus, A.L. [Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation)

    2011-07-01

    Promoting Co-alumina Fischer-Tropsch synthesis catalysts with alkali and alkaline-earth metals was studied. XRD, oxygen titration and CO chemisorption were used for the characterization of the catalysts. The best results in terms of catalyst selectivity and long-chain alkanes content in synthesized products were obtained with K-promoted catalyst. Catalytic performance strongly depends on K:Co atomic ratio as well as preparation procedure. Effect of K loading on selectivities is non-linear with extreme point at K:Co=0.01. Significant increase in C{sub 5+} selectivity of K-promoted catalyst may be explained as a result of strong CO adsorption on the catalyst surface, as was confirmed in CO chemisorption experiments. (orig.)

  14. Investigation of Thin Layered Cobalt Oxide Nano-Islands on Gold

    Science.gov (United States)

    Bajdich, Michal; Walton, Alex S.; Fester, Jakob; Arman, Mohammad A.; Osiecki, Jacek; Knudsen, Jan; Vojvodic, Aleksandra; Lauritsen, Jeppe V.

    2015-03-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER), but the synergistic effect of contact with gold is yet to be fully understood. The synthesis of three distinct types of thin-layered cobalt oxide nano-islands supported on a single crystal gold (111) substrate is confirmed by combination of STM and XAS methods. In this work, we present DFT+U theoretical investigation of above nano-islands using several previously known structural models. Our calculations confirm stability of two low-oxygen pressure phases: (a) rock-salt Co-O bilayer and (b) wurtzite Co-O quadlayer and single high-oxygen pressure phase: (c) O-Co-O trilayer. The optimized geometries agree with STM structures and calculated oxidation states confirm the conversion from Co2+ to Co3+ found experimentally in XAS. The O-Co-O trilayer islands have the structure of a single layer of CoOOH proposed to be the true active phase for OER catalyst. For that reason, the effect of water on the Pourbaix stabilities of basal planes and edge sites is fully investigated. Lastly, we also present the corresponding OER theoretical overpotentials.

  15. Catalyst design for clean and efficient fuels

    DEFF Research Database (Denmark)

    Šaric, Manuel

    cobalt promoted MoS2 catalyst. Reactivity of a series of model molecules, found in oil prior to desulfurization, is studied on cobalt promoted MoS2. Such an approach has the potential to explain the underlying processes involved in the removal of sulfur at each specific site of the catalyst. The goal...... is to identify which sites are active towards specific molecules and in getting insight to what the ideal catalyst should look like in terms of morphology. Dimethyl carbonate is an environmentally benign compound that can be used as a solvent and precursor in chemical synthesis or as a fuel and fuel additive...... processes currently used. It is found that noble metals can be used as electrocatalysts for the synthesis of dimethyl carbonate, significantly lowering the potential when using copper instead of gold. Besides being active, copper was found to be selective towards dimethyl carbonate. A non-selective catalyst...

  16. Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

    Science.gov (United States)

    Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

    2018-03-26

    Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Facile and large-scale synthesis of high quality few-layered graphene nano-platelets via methane decomposition over unsupported iron family catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Awadallah, Ahmed E., E-mail: ahmedelsayed_epri@yahoo.com [Process Development Division, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Aboul-Enein, Ateyya A. [Process Development Division, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Kandil, Usama F. [Petroleum Application Department, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Taha, Mahmoud Reda [Department of Civil Engineering, University of New Mexico, Albuquerque, NM 87131 (United States)

    2017-04-15

    High quality few-layered graphene nano-platelets (GNPs) were successfully prepared via catalytic chemical vapor deposition of methane under ambient pressure using substrate-free unsupported iron, cobalt, and nickel metallic sheets as catalysts. The bulk catalysts were prepared via combustion method using citric acid as a fuel. Various analytical techniques, including high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), temperature programmed reduction (TPR) and Raman spectroscopy were employed to characterize the fresh and reduced catalysts and to identify the morphological structure of the as-grown GNPs. TEM images of the reduced metal catalysts showed that polycrystalline metallic sheets were easily produced after complete reduction of unsupported metal oxides. The data demonstrated that the formation of zero-valent metallic sheets could effectively promote the growth of GNPs on their surfaces. The unsupported Ni catalyst exhibits higher catalytic growth activity in terms of GNPs yield (254 wt%) compared with all other catalysts. Raman spectra and TEM results established that a few layers of GNPs with high crystallinity and good graphitization were produced. TGA results further demonstrated that the as-grown GNPs exhibit significantly higher thermal stability in air atmosphere compared with other synthesis methods. - Highlights: • Few-layered graphene nanoplatelets were prepared via methane catalytic decomposition. • Metallic sheets of iron group metals were used as novel catalysts. • The surfaces of metallic sheets were found to be very effective for GNPs growth. • The number of layers is dependent on the morphological structure of the catalysts. • The unsupported metallic Ni catalyst exhibited higher catalytic growth activity.

  18. Perfluorinated cobalt phthalocyanine effectively catalyzes water electrooxidation

    KAUST Repository

    Morlanes, Natalia Sanchez

    2014-12-08

    Efficient electrocatalysis of water oxidation under mild conditions at neutral pH was achieved by a fluorinated cobalt phthalocyanine immobilized on fluorine-doped tin oxide (FTO) surfaces with an onset potential at 1.7 V vs. RHE. Spectroscopic, electrochemical, and inhibition studies indicate that phthalocyanine molecular species are the operational active sites. Neither free cobalt ions nor heterogeneous cobalt oxide particles or films were observed. During long-term controlled-potential electrolysis at 2 V vs. RHE (phosphate buffer, pH 7), electrocatalytic water oxidation was sustained for at least 8 h (TON ≈ 1.0 × 105), producing about 4 μmol O2 h-1 cm-2 with a turnover frequency (TOF) of about 3.6 s-1 and no measurable catalyst degradation.

  19. Functionalized Natural Carbon-Supported Nanoparticles as Excellent Catalysts for Hydrocarbon Production.

    Science.gov (United States)

    Sun, Jian; Guo, Lisheng; Ma, Qingxiang; Gao, Xinhua; Yamane, Noriyuki; Xu, Hengyong; Tsubaki, Noritatsu

    2017-02-01

    We report a one-pot and eco-friendly synthesis of carbon-supported cobalt nanoparticles, achieved by carbonization of waste biomass (rice bran) with a cobalt source. The functionalized biomass provides carbon microspheres as excellent catalyst support, forming a unique interface between hydrophobic and hydrophilic groups. The latter, involving hydroxyl and amino groups, can catch much more active cobalt nanoparticles on surface for Fischer-Tropsch synthesis than chemical carbon. The loading amount of cobalt on the final catalyst is much higher than that prepared with a chemical carbon source, such as glucose. The proposed concept of using a functionalized natural carbon source shows great potential compared with conventional carbon sources, and will be meaningful for other fields concerning carbon support, such as heterogeneous catalysis or electrochemical fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  1. Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

    International Nuclear Information System (INIS)

    Fester, J.; García-Melchor, M.; Walton, A. S.; Bajdich, M.

    2017-01-01

    Here, transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the important assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions.

  2. Cobalt and KNO3 supported on alumina catalysts for diesel soot combustion

    International Nuclear Information System (INIS)

    Grzona, Claudia B.; Lick, Ileana D.; Castellon, Enrique Rodriguez; Ponzi, Marta I.; Ponzi, Esther N.

    2010-01-01

    The catalytic combustion of diesel soot was studied in the presence of fresh and aged catalysts: Co/Al 2 O 3 , KNO 3 /Al 2 O 3 and Co/KNO 3 /Al 2 O 3 . The catalysts were prepared by impregnation using nitrate solutions. The catalysts were characterized by X-ray diffraction, thermal programmed reduction, vibrational spectroscopy and X-ray photoelectron spectroscopy. Fresh and aged catalysts present high activity in presence of O 2 and O 2 /NO. The values of the combustion temperature decrease more than 200 deg. C with respect to that observed in the process without catalysis. The activity is associated with the presence of KNO 3 and the role of this salt can be attributed to the contribution of NO 3 - /NO 2 - redox cycle.

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

    Science.gov (United States)

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

    2017-10-16

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

  4. Fischer-Tropsch Performance of an SiO2-Supported Co-Based Catalyst Prepared by Hydrogen Dielectric-Barrier Discharge Plasma

    International Nuclear Information System (INIS)

    Fu Tingjun; Huang Chengdu; Lv Jing; Li Zhenhua

    2014-01-01

    A silica-supported cobalt catalyst was prepared by hydrogen dielectric-barrier discharge (H 2 -DBD) plasma. Compared to thermal hydrogen reduction, H 2 -DBD plasma treatment can not only fully decompose the cobalt precursor but also partially reduce the cobalt oxides at lower temperature and with less time. The effect of the discharge atmosphere on the property of the plasma-prepared catalyst and the Fischer-Tropsch synthesis activity was studied. The results indicate that H 2 -DBD plasma treatment is a promising alternative for preparing Co/SiO 2 catalysts from the viewpoint of energy savings and efficiency

  5. Cobalt

    Science.gov (United States)

    Slack, John F.; Kimball, Bryn E.; Shedd, Kim B.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Cobalt is a silvery gray metal that has diverse uses based on certain key properties, including ferromagnetism, hardness and wear-resistance when alloyed with other metals, low thermal and electrical conductivity, high melting point, multiple valences, and production of intense blue colors when combined with silica. Cobalt is used mostly in cathodes in rechargeable batteries and in superalloys for turbine engines in jet aircraft. Annual global cobalt consumption was approximately 75,000 metric tons in 2011; China, Japan, and the United States (in order of consumption amount) were the top three cobalt-consuming countries. In 2011, approximately 109,000 metric tons of recoverable cobalt was produced in ores, concentrates, and intermediate products from cobalt, copper, nickel, platinum-group-element (PGE), and zinc operations. The Democratic Republic of the Congo (Congo [Kinshasa]) was the principal source of mined cobalt globally (55 percent). The United States produced a negligible amount of byproduct cobalt as an intermediate product from a PGE mining and refining operation in southeastern Montana; no U.S. production was from mines in which cobalt was the principal commodity. China was the leading refiner of cobalt, and much of its production came from cobalt ores, concentrates, and partially refined materials imported from Congo (Kinshasa).The mineralogy of cobalt deposits is diverse and includes both primary (hypogene) and secondary (supergene) phases. Principal terrestrial (land-based) deposit types, which represent most of world’s cobalt mine production, include primary magmatic Ni-Cu(-Co-PGE) sulfides, primary and secondary stratiform sediment-hosted Cu-Co sulfides and oxides, and secondary Ni-Co laterites. Seven additional terrestrial deposit types are described in this chapter. The total terrestrial cobalt resource (reserves plus other resources) plus past production, where available, is calculated to be 25.5 million metric tons. Additional resources of

  6. Low temperature incineration of mixed wastes using bulk metal oxide catalysts

    International Nuclear Information System (INIS)

    Gordon, M.J.; Gaur, S.; Kelkar, S.; Baldwin, R.M.

    1996-01-01

    Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose. This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal-redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T<650C, low oxygen partial pressures). Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide

  7. Carbon-encapsulated nickel-cobalt alloys nanoparticles fabricated via new post-treatment strategy for hydrogen evolution in alkaline media

    Science.gov (United States)

    Guo, Hailing; Youliwasi, Nuerguli; Zhao, Lei; Chai, Yongming; Liu, Chenguang

    2018-03-01

    This paper addresses a new post-treatment strategy for the formation of carbon-encapsulated nickel-cobalt alloys nanoparticles, which is easily controlled the performance of target products via changing precursor composition, calcination conditions (e.g., temperature and atmosphere) and post-treatment condition. Glassy carbon electrode (GCE) modified by the as-obtained carbon-encapsulated mono- and bi-transition metal nanoparticles exhibit excellent electro-catalytic activity for hydrogen production in alkaline water electrolysis. Especially, Ni0.4Co0.6@N-Cs800-b catalyst prepared at 800 °C under an argon flow exhibited the best electrocatalytic performance towards HER. The high HER activity of the Ni0.4Co0.6@N-Cs800-b modified electrode is related to the appropriate nickel-cobalt metal ratio with high crystallinity, complete and homogeneous carbon layers outside of the nickel-cobalt with high conductivity and the synergistic effect of nickel-cobalt alloys that also accelerate electron transfer process.

  8. Catalytic hydrolysis of ammonia borane via cobalt palladium nanoparticles.

    Science.gov (United States)

    Sun, Daohua; Mazumder, Vismadeb; Metin, Önder; Sun, Shouheng

    2011-08-23

    Monodisperse 8 nm CoPd nanoparticles (NPs) with controlled compositions were synthesized by the reduction of cobalt acetylacetonate and palladium bromide in the presence of oleylamine and trioctylphosphine. These NPs were active catalysts for hydrogen generation from the hydrolysis of ammonia borane (AB), and their activities were composition dependent. Among the 8 nm CoPd catalysts tested for the hydrolysis of AB, the Co(35)Pd(65) NPs exhibited the highest catalytic activity and durability. Their hydrolysis completion time and activation energy were 5.5 min and 27.5 kJ mol(-1), respectively, which were comparable to the best Pt-based catalyst reported. The catalytic performance of the CoPd/C could be further enhanced by a preannealing treatment at 300 °C under air for 15 h with the hydrolysis completion time reduced to 3.5 min. This high catalytic performance of Co(35)Pd(65) NP catalyst makes it an exciting alternative in pursuit of practical implementation of AB as a hydrogen storage material for fuel cell applications. © 2011 American Chemical Society

  9. 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.

  10. Mechanistic Studies of Cobalt-Catalyzed C(sp2)-H Borylation of Five-Membered Heteroarenes with Pinacolborane.

    Science.gov (United States)

    Obligacion, Jennifer V; Chirik, Paul J

    2017-07-07

    Studies into the mechanism of cobalt-catalyzed C(sp 2 )-H borylation of five-membered heteroarenes with pinacolborane (HBPin) as the boron source established the catalyst resting state as the trans -cobalt(III) dihydride boryl, ( iPr PNP)Co(H) 2 (BPin) ( iPr PNP = 2,6-( i Pr 2 PCH 2 ) 2 (C 5 H 3 N)), at both low and high substrate conversions. The overall first-order rate law and observation of a normal deuterium kinetic isotope effect on the borylation of benzofuran versus benzofuran-2- d 1 support H 2 reductive elimination from the cobalt(III) dihydride boryl as the turnover-limiting step. These findings stand in contrast to that established previously for the borylation of 2,6-lutidine with the same cobalt precatalyst, where borylation of the 4-position of the pincer occurred faster than the substrate turnover and arene C-H activation by a cobalt(I) boryl is turnover-limiting. Evaluation of the catalytic activity of different cobalt precursors in the C-H borylation of benzofuran with HBPin established that the ligand design principles for C- H borylation depend on the identities of both the arene and the boron reagent used: electron-donating groups improve catalytic activity of the borylation of pyridines and arenes with B 2 Pin 2 , whereas electron-withdrawing groups improve catalytic activity of the borylation of five-membered heteroarenes with HBPin. Catalyst deactivation by P-C bond cleavage from a cobalt(I) hydride was observed in the C-H borylation of arene substrates with C-H bonds that are less acidic than those of five-membered heteroarenes using HBPin and explains the requirement of B 2 Pin 2 to achieve synthetically useful yields with these arene substrates.

  11. Nanostructured Co3O4 grown on nickel foam: An efficient and readily recyclable 3D catalyst for heterogeneous peroxymonosulfate activation.

    Science.gov (United States)

    Yuan, Ruixia; Hu, Lin; Yu, Peng; Wang, Huaiyuan; Wang, Zhaohui; Fang, Jingyun

    2018-05-01

    Cobalt-based heterogeneous catalyst has been recognized as one of most efficient activators for peroxymonosulfate (PMS) decomposition, but usually suffers from the poor stability and difficulty to recover and reuse. Here easily recyclable cobalt oxide (Co 3 O 4 ) nanowires and nanoflowers grown on nickel foam (NF) are fabricated by a hydrothermal and calcination method. The prepared 3D Co 3 O 4 /NF catalyst is characterized and applied as a heterogeneous catalyst for PMS activation to generate sulfate radicals for decomposition of Acid Orange 7 (AO7). The results show that the AO7 degradation rate increases with cobalt loading and PMS dosage, but decreases with the increase of solution pH. The Co 3 O 4 /NF catalyst using 2 mM Co(NO 3 ) 2 ·6H 2 O as cobalt source exhibits highest activity, and almost complete decolorization could be achieved within 30 min. The diverse effects of coexisting anions (SO 4 2- , HCO 3 - , NO 3 - and Cl - ) on AO7 degradation are observed and explained. After 10 consecutive runs, excellent catalytic reactivity of the catalyst remains while the level of leached cobalt during the catalyst usage is much lower than the maximum allowable concentration in drinking and natural water. More importantly, the macroscopic Co 3 O 4 /NF catalyst shows advantage of easy recycling after application compared to traditional catalysts. It is believed that the as-prepared Co 3 O 4 /NF is promising to be an effective and green heterogeneous catalyst for PMS activation to degrade organic pollutants for environmental application. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  13. Synthesis of Co/MCM-41catalysts and characterization by XRD, EDX, DTA/TG, SEM and TEM

    International Nuclear Information System (INIS)

    Sousa, B.V.; Rodrigues, M.G.F.

    2009-01-01

    Full text: In this work, molecular sieve MCM-41 was prepared as well as the Co/MCM-41 catalyst, via humid impregnation with concentration of 5 wt.% and 10 wt.% Co/MCM- 41. The attainment of the mesoporous molecular sieve, Si-MCM-41, was confirmed by the x-ray diffractogram. It was verified that after the calcination all the bromine (Br) was removed indicating that the calcination process removed all surfactant in the mesoporous structure. XRD and EDX analyses indicated that cobalt was found in the form of Co3O2 in the Co/MCM-41 catalysts. The diffraction standards showed that the impregnation and calcination processes caused changes in the structure only for catalyst with 10 wt.% Co/MCM-41. The DTA/TG curves showed that cobalt nitrate was totally decomposed on the MCM-41. From the images of SEM, it was possible to observe that the Co/MCM-41 catalysts were composed by clusters of small crystals. The images obtained from TEM showed clearly the presence of metal cobalt particles in a well dispersed form for catalyst with 5 wt.% Co/MCM41, except for the catalyst with 10 wt.% Co/MCM41. (author)

  14. Mobilization and Defense Management Technical Reports Series. Critical Non-Fuel Minerals in Mobilization with Case Studies on Cobalt and Titanium.

    Science.gov (United States)

    1983-04-01

    Affairs Comarce Science and Transportation House Comittees Science Rsearch and Tecnology Interstate and Foreign Commrce hnting, Finance, and Urban...cobalt include cutting tools, jet engine parts, electrical devices, permanent magnets, catalysts, paint pigmnts, and paint dryers . 1 The U.S. is the...in the superalloy field. Subtittesfor cobalt as a catalyst or as a dryer in paints are usually not effective. In dryer iUcations,, manganame and lead

  15. Efficient direct coal liquefaction of a premium brown coal catalyzed by cobalt-promoted fumed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Trautmann, M.; Loewe, A.; Traa, Y. [Stuttgart Univ. (Germany). Inst. of Chemical Technology

    2013-11-01

    The search for alternatives in the fuel sector is an important technological challenge. An interim solution could be provided by direct coal liquefaction. Hydrogen economy and the lack of an efficient catalyst are the main obstacles for this process. We used a premium German brown coal with a high H/C molar ratio of 1.25 and nanostructured cobalt catalysts to improve the efficiency of direct coal liquefaction. We were able to recover and recycle the catalyst efficiently and reached good brown coal conversions and oil yields with single-stage coal liquefaction. The oil quality observed almost reached that of a conventional crude oil considering higher heating value (HHV), H/C molar ratio and aliphatic content. (orig.)

  16. Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

    Science.gov (United States)

    Shah, Pinakin M.

    1990-01-01

    An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

  17. Chemical nature of catalysts of oxide nanoparticles in environment

    Indian Academy of Sciences (India)

    Carbon nanostructures (CNS) are often grown using oxide nanoparticles as catalyst in chemical vapour deposition and these oxides are not expected to survive as such during growth. In the present study, the catalysts of cobalt- and nickel oxide-based nanoparticles of sizes varying over a range have been reduced at 575 ...

  18. Highly Stable and Active Catalyst for Sabatier Reactions

    Science.gov (United States)

    Hu, Jianli; Brooks, Kriston P.

    2012-01-01

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

  19. Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

    2017-06-28

    Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

  20. Fischer-Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    A.R. de la Osa; A. De Lucas; A. Romero; J.L. Valverde; P. Sanchez [University of Castilla-La Mancha, Ciudad Real (Spain). Chemical Engineering Department

    2011-05-15

    The effects of reaction conditions on the Fischer-Tropsch activity and product distribution of an alkali-earth metal promoted cobalt based catalyst were studied. The influence of the promoter on the reducibility and cobalt particle size was studied by different techniques, including N{sub 2} adsorption, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption and acid-base titrations. Experiments were carried out on a bench-scale fixed bed reactor and catalysts were prepared by incipient wetness impregnation. It was observed that addition of a small amount of calcium oxide as a promoter (0.6 wt.%) improved the cobalt oxide reducibility and reduced the formation of cobalt-aluminate species. A positive correlation between basicity and particle size was observed. In terms of FTS results, CO conversion and C{sub 5}{sup +} selectivity were found to be enhanced by the addition of this promoter. It was important to note that the addition of calcium shifted the distribution to mainly C{sub 16}-C{sub 18} hydrocarbons fraction, which could be greatly considered for a diesel formulation. Furthermore, the variation of the reaction conditions seemed to influence product distribution in a lesser extent than unpromoted catalyst. Also, a displacement of hydrocarbon distribution to higher molecular weight with decreasing space velocity and temperature was observed. Moreover, the addition of calcium to the cobalt based catalyst was found to greatly maintain selectivity to C{sub 5}{sup +} for a wide range of H{sub 2}/CO molar ratios. 60 refs., 10 figs., 5 tabs.

  1. Cobalt and sulfur co-doped nano-size TiO2 for photodegradation of various dyes and phenol

    KAUST Repository

    Siddiqa, Asima; Masih, Dilshad; Anjum, Dalaver H.; Siddiq, Muhammad

    2015-01-01

    Various compositions of cobalt and sulfur co-doped titania nano-photocatalyst are synthesized via sol–gel method. A number of techniques including X-ray diffraction (XRD), ultraviolet–visible (UV–Vis), Rutherford backscattering spectrometry (RBS), thermal gravimetric analysis (TGA), Raman, N2 sorption, electron microscopy are used to examine composition, crystalline phase, morphology, distribution of dopants, surface area and optical properties of synthesized materials. The synthesized materials consisted of quasispherical nanoparticles of anatase phase exhibiting a high surface area and homogeneous distribution of dopants. Cobalt and sulfur co-doped titania demonstrated remarkable structural and optical properties leading to an efficient photocatalytic activity for degradation of dyes and phenol under visible light irradiations. Moreover, the effect of dye concentration, catalyst dose and pH on photodegradation behavior of environmental pollutants and recyclability of the catalyst is also examined to optimize the activity of nano-photocatalyst and gain a better understanding of the process.

  2. Cobalt and sulfur co-doped nano-size TiO2 for photodegradation of various dyes and phenol

    KAUST Repository

    Siddiqa, Asima

    2015-11-01

    Various compositions of cobalt and sulfur co-doped titania nano-photocatalyst are synthesized via sol–gel method. A number of techniques including X-ray diffraction (XRD), ultraviolet–visible (UV–Vis), Rutherford backscattering spectrometry (RBS), thermal gravimetric analysis (TGA), Raman, N2 sorption, electron microscopy are used to examine composition, crystalline phase, morphology, distribution of dopants, surface area and optical properties of synthesized materials. The synthesized materials consisted of quasispherical nanoparticles of anatase phase exhibiting a high surface area and homogeneous distribution of dopants. Cobalt and sulfur co-doped titania demonstrated remarkable structural and optical properties leading to an efficient photocatalytic activity for degradation of dyes and phenol under visible light irradiations. Moreover, the effect of dye concentration, catalyst dose and pH on photodegradation behavior of environmental pollutants and recyclability of the catalyst is also examined to optimize the activity of nano-photocatalyst and gain a better understanding of the process.

  3. Catalytic activity of dual catalysts system based on nano-manganese oxide and cobalt octacyanophthalocyanine toward four-electron reduction of oxygen in alkaline media

    International Nuclear Information System (INIS)

    Zhang, Dun; Chi, Dahe; Okajima, Takeyoshi; Ohsaka, Takeo

    2007-01-01

    The electrocatalysis of the dual functional catalysts system composed of electrolytic nano-manganese oxide (nano-MnOx) and cobalt octacyanophthalocyanine (CoPcCN) toward 4-electron reduction of oxygen (O 2 ) in alkaline media was studied. Nano-MnOx electrodeposited on the CoPcCN monolayer-modified glassy carbon (GC) electrode was clarified as the nano-rods with ca. 10-20 nm diameter by scanning electron microscopy. The peak current for O 2 reduction at the dual catalysts-modified GC electrode increases largely and the peak potential shifts by ca. 160 mV to the positive direction in cyclic voltammograms compared with those obtained at the bare GC electrode. The Koutecky-Levich plots indicate that the O 2 reduction at the dual catalysts-modified GC electrode is an apparent 4-electron process. Collection efficiencies obtained at the dual catalysts-modified GC electrode are much lower than those at the GC electrode and are almost similar to those at the Pt nano-particles modified GC electrode. The obtained results demonstrate that the dual catalysts system possesses a bifuctional catalytic activity for redox-mediating 2-electron reduction of O 2 to HO 2 - by CoPcCN as well as catalyzing the disproportionation of HO 2 - to OH - and O 2 by nano-MnOx, and enables an apparent 4-electron reduction of O 2 at a relatively low overpotential in alkaline media. In addition, it has been found that the cleaning of the dual catalysts-modified electrode by soaking in 0.1 M sulfuric acid solution enhances its catalytic activity toward the reduction of O 2

  4. Nickel/cobalt layered double hydroxide hollow microspheres with hydrangea-like morphology for high-performance supercapacitors

    International Nuclear Information System (INIS)

    Tao, Yan; Ruiyi, Li; Tingting, Yang; Zaijun, Li

    2015-01-01

    Graphical abstract: We report a new template synthesis of nickel/cobalt layered double hydroxides (Ni/Co-LDH) without any adscititious alkali source, oxidant and step for removal of the template. The perfect match between generation rate of Ni/Co-LDH nanoflakes and removal rate of template creates elaborate three-dimensional architecture with well-defined hollow interior and hydrangea-like exterior. The unique structure improves faradaic redox reaction and mass transfer during the redox process, thus the Ni/Co-LDH electrode provides excellent electrochemical performance for supercapacitors. - Highlights: • The study demonstrated a new strategy for template synthesis of Ni/Co-LDH without any adscititious alkali source, oxidant and step for removal of the template. • The perfect match between generation rate of Ni/Co-LDH nanoflakes and removal rate of SiO 2 template create hollow microspheres with hydrangea-like morphology. • The unique structure of Ni/Co-LDH will greatly improve faradaic redox reaction and mass transfer during the redox process. • The Ni/Co-LDH electrode displays high specific capacitance, good charge/discharge capability, large energy density and superior cycle stability. • The study provides a prominent approach to fabricate various hollow nanomaterials for supercapacitors, Li-ion batteries, catalyst and sensors. - Abstract: Electroactive materials with hollow nanostructures received great attractiveness due to large surface area, low density and superior structure permeablity. The paper reported a new template synthesis of nickel/cobalt layered double hydroxides (Ni/Co-LDH) without any adscititious alkali source, oxidant and step for removal of the template. Nickel nitrate, cobalt nitrate and SiO 2 nanosphere were dispersed in an ethanol solution. Then, the mixed soution was heated at 160 °C for 6 h to obtain Ni/Co-LDH product. During the process, ethanol and nitrate underwent a redox reaction releasing hydroxide ions, which will react

  5. Combined XRD and XANES studies of a Re-promoted Co/γ-Al2O3 catalyst at Fischer–Tropsch synthesis conditions

    DEFF Research Database (Denmark)

    Rønning, Magnus; Tsakoumis, Nikolaos E.; Voronov, Alexey

    2010-01-01

    A cobalt based Fischer–Tropsch catalyst was studied during the initial stages of the reaction at industrially relevant conditions. The catalyst consists of 20wt% cobalt supported on γ-Al2O3 and promoted by 1wt% of rhenium. X-ray diffraction (XRD) in combination with X-ray absorption near edge...

  6. Recycling of spent hydroprocessing catalysts: EURECAT technology

    Energy Technology Data Exchange (ETDEWEB)

    Berrebi, G.; Dufresne, P.; Jacquier, Y. (EURECAT-European Reprocessing Catalysts, La Voulte sur Rhone (France))

    1994-04-01

    Disposal of spent catalyst is a growing concern for all refiners. Environmental regulations are becoming stricter and stricter and there are State recommendations to develop disposal routes which would emphasize recycling as much as possible, and processing the wastes as near as possible to the production center. In this context, EURECAT has developed a recycling process for the hydroprocessing catalysts used in the oil refineries (NiMo, CoMo, NiW on alumina or mixed alumina silica). The process starts with a regeneration of the catalyst to eliminate hydrocarbons, carbon and sulfur. After a caustic roasting, the material is leached to obtain a solution containing mainly molybdenum (or tungsten) and vanadium, and a solid containing essentially alumina, cobalt and/or nickel. Molybdenum and vanadium are separated by an ion exchange resin technique. The solid is processed in an arc furnace to separate the alumina. Nickel and cobalt are separated by conventional solvent extraction to obtain pure metal. Alumina is disposed of as an inert slag. The strength of the process lies in the combination of proven technologies applied by companies whose reliability in their respective field is well known. The aspects concerning spent catalyst handling, packaging and transport are also discussed. 13 refs., 2 figs., 2 tabs.

  7. Cobalt and KNO{sub 3} supported on alumina catalysts for diesel soot combustion

    Energy Technology Data Exchange (ETDEWEB)

    Grzona, Claudia B. [25 de mayo 284, INTEQUI-CONICET-UNSL, Facultad de Ingenieria y Ciencias Economico-Sociales, Villa Mercedes, 5730 (Argentina); Lick, Ileana D. [Calle 47 No 257, CINDECA (CCT-LaPlata-CONICET-UNLP), Departamento de Quimica, Facultad de Ciencias Exactas, La Plata, 1900 (Argentina); Castellon, Enrique Rodriguez [Departamento de Quimica Inorganica, Cristalografia y Mineralogia, Facultad de Ciencias, Universidad de Malaga, Campus de Teatinos, Malaga, 29071 (Spain); Ponzi, Marta I. [25 de mayo 284, INTEQUI-CONICET-UNSL, Facultad de Ingenieria y Ciencias Economico-Sociales, Villa Mercedes, 5730 (Argentina); Ponzi, Esther N., E-mail: eponzi@quimica.unlp.edu.ar [Calle 47 No 257, CINDECA (CCT-LaPlata-CONICET-UNLP), Departamento de Quimica, Facultad de Ciencias Exactas, La Plata, 1900 (Argentina)

    2010-10-01

    The catalytic combustion of diesel soot was studied in the presence of fresh and aged catalysts: Co/Al{sub 2}O{sub 3}, KNO{sub 3}/Al{sub 2}O{sub 3} and Co/KNO{sub 3}/Al{sub 2}O{sub 3}. The catalysts were prepared by impregnation using nitrate solutions. The catalysts were characterized by X-ray diffraction, thermal programmed reduction, vibrational spectroscopy and X-ray photoelectron spectroscopy. Fresh and aged catalysts present high activity in presence of O{sub 2} and O{sub 2}/NO. The values of the combustion temperature decrease more than 200 deg. C with respect to that observed in the process without catalysis. The activity is associated with the presence of KNO{sub 3} and the role of this salt can be attributed to the contribution of NO{sub 3}{sup -}/NO{sub 2}{sup -} redox cycle.

  8. Cobalt nanoparticles as reusable catalysts for reduction of 4 ...

    Indian Academy of Sciences (India)

    33

    active and ordered structures of cobalt nanoparticles. The air stable ... same surfactant was found to reduce p-nitrophenol but lose their catalytic efficiency after recovery. Based on chemical and ... industrial sources.11-13 The US Environmental Protection Agency has reported nitrophenols as one of the most hazardous and ...

  9. Some problems of manufacturing and industrial application of CoMo-Al2O3 catalyst

    International Nuclear Information System (INIS)

    Walendziewski, J.

    1991-01-01

    The monograph presents results of studies of some selected problems relating to CoMo-Al 2 O 3 catalyst: method of production alumina support and catalyst; application of catalyst in the selected hydro refining processes; physicochemical properties of the used catalyst; reclamation of metal compounds from the spent catalyst. Results of investigations of catalyst preparation illustrate how the physicochemical properties of alumina support and catalyst, mainly porous structure could be controlled by the selection of raw materials and parameters of aluminum hydroxide precipitation, method of forming and calcination temperature of support. Application of the catalyst of modified porous structure has shown its high activity in hydro refining process of light cracking catalytic oil (over 95% hydrodesulphurization) and mild hydro cracking process of vacuum gas oil (sulphur content in product below 0.03% wt.). As an effect of studying of hydro refining process of aromatic hydrocarbon fraction it has been found that H 2 S concentration in reaction mixture is the main factor influencing process selectivity. Some effect on the selectivity exerts also other process parameters and chemical composition of the catalyst - cobalt molybdenum content ratio and promoters content. Long term exploitation of the domestic CoMo-Al 2 O 3 catalyst in hydrodesulphurization process indicates its satisfied thermal stability although results in deteriorating of mechanical resistance, lowering of specific surface area, increase in mean pore radius and decrease in acidity of catalyst. In the last chapter of the monograph the results of investigations of reclamation of metal compounds (molybdic acid, aluminum hydroxide, cobalt carbonate) from the spent catalyst as well as an original technology of manufacture of the fresh one using these compounds have been presented. (author). 338 refs, 31 figs, 32 tabs

  10. Alkylation of isobutane by butenes on a cobalt-containing zeolite catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Vasil`ev, A.N.; Galinskii, A.A. [Inst. of Bioorganic Chemistry and Petrochemistry, Kiev (Ukraine)

    1995-05-10

    It is shown that the polycationic form of a faujasite-type zeolite, CoLaCaNaY, exhibits high catalytic activity in alkylation of isobutane by butenes. The service life of the catalyst, which terminates when oxidative regeneration is necessary, is significantly extended.

  11. Process for obtaining cobalt and lanthanum nickelate

    International Nuclear Information System (INIS)

    Tapcov, V.; Samusi, N.; Gulea, A.; Horosun, I.; Stasiuc, V.; Petrenco, P.

    1999-01-01

    The invention relates to the process for obtaining polycrystalline ceramics of cobalt and lanthanum nickelate with the perovskite structure from coordinative hetero metallic compounds. The obtained products can be utilized in the industry in the capacity of catalysts. Summary of the invention consists in obtaining polycrystalline ceramics LaCoO 3 and LaNiO 3 with the perovskite structure by pyrolysis of the parent compounds, namely, the coordinative hetero metallic compounds of the lanthanum cobalt or lanthanum nickel. The pyrolysis of the parent compound runs during one hour at 800 C. The technical result of the invention consists in lowering the temperature of the parent compound pyrolysis containing the precise ratio of metals necessary for ceramics obtaining

  12. Metal-Organic-Framework mediated supported-cobalt catalysts in multiphase hydrogenation reactions

    OpenAIRE

    Sun, X.

    2017-01-01

    The production of most industrially important chemicals involves catalysis. Depending on the difference in phases between the catalysts and reactants, one distinguishes homogenous catalysis and heterogeneous catalysis, with the latter being more attractive in real applications, due to the easy separation of products from catalysts and reusing the latter. In spite of the research and development of heterogeneous catalysts for decades, the exploration for catalysts system with outstanding activ...

  13. Characterization of Catalyst Materials for Production of Aerospace Fuels

    Science.gov (United States)

    Best, Lauren M.; De La Ree, Ana B.; Hepp, Aloysius F.

    2012-01-01

    Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

  14. Reduced cobalt phases of ZrO2 and Ru/ZrO2 promoted cobalt catalysts and product distributions from Fischer–Tropsch synthesis

    International Nuclear Information System (INIS)

    Kangvansura, Praewpilin; Schulz, Hans; Suramitr, Anwaraporn; Poo-arporn, Yingyot; Viravathana, Pinsuda; Worayingyong, Attera

    2014-01-01

    Highlights: • Ru/ZrO 2 , ZrO 2 promoted Co/SiO 2 for FTS were reduced by time resolved XANES. • Reduced catalysts resulted from XANES reduction showed the mixed phases of Co, CoO. • The highest percentages of CoO resulted from the high ZrO 2 promoted Co/SiO 2 . • Product distributions of 1-alkenes, iso-alkanes indicated sites for FTS and the 2° reaction. • Alkene readsorption were high corresponding to the high CoO forming branched alkanes. - Abstract: Co/SiO 2 catalysts were promoted with 4% and 8% ZrO 2 . Small amounts (0.07%) of Ru were impregnated onto 4%ZrO 2 /Co/SiO 2 . Catalysts resulting from time-resolved XANES reduction showed mixed phases of Co and CoO, with the highest percentages of Co resulting from Ru/4%ZrO 2 /Co/SiO 2 and the highest percentages of CoO resulting from 8%ZrO 2 /Co/SiO 2 . Product distributions of n-alkanes, iso-alkanes and alkenes during Fischer–Tropsch Synthesis (FTS) were used to investigate the catalyst performance of 4%ZrO 2 /Co/SiO 2 8%ZrO 2 /Co/SiO 2 and Ru/4%ZrO 2 /Co/SiO 2 . FTS steady state was studied by growth probabilities of n-alkane products. No 1-alkene was produced from Ru/4%ZrO 2 /Co/SiO 2 , indicating high availability of Fischer–Tropsch sites for long chain hydrocarbon growth, despite high methanation. Branched alkanes produced from the secondary reaction were related to the high CoO percentages on 8%ZrO 2 /Co/SiO 2 . Alkene readsorption sites were high, corresponding to the high CoO percentages, causing a high probability of forming branched alkane products

  15. The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

    2007-02-01

    The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

  16. Synthesis of subnanometer-diameter vertically aligned single-walled carbon nanotubes with copper-anchored cobalt catalysts

    Science.gov (United States)

    Cui, Kehang; Kumamoto, Akihito; Xiang, Rong; An, Hua; Wang, Benjamin; Inoue, Taiki; Chiashi, Shohei; Ikuhara, Yuichi; Maruyama, Shigeo

    2016-01-01

    We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high-quality SWNTs are expected to pave the way to replace silicon for next-generation optoelectronic and photovoltaic devices.We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high

  17. Cobalt ferrite nanoparticles under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Saccone, F. D.; Ferrari, S.; Grinblat, F.; Bilovol, V. [Instituto de Tecnologías y Ciencias de la Ingeniería, “Ing. H. Fernández Long,” Av. Paseo Colón 850 (1063), Buenos Aires (Argentina); Errandonea, D., E-mail: daniel.errandonea@uv.es [Departamento de Fisica Aplicada, Institut Universitari de Ciència dels Materials, Universitat de Valencia, c/ Doctor Moliner 50, E-46100 Burjassot, Valencia (Spain); Agouram, S. [Departamento de Física Aplicada y Electromagnetismo, Universitat de València, 46100 Burjassot, Valencia (Spain)

    2015-08-21

    We report by the first time a high pressure X-ray diffraction and Raman spectroscopy study of cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles carried out at room temperature up to 17 GPa. In contrast with previous studies of nanoparticles, which proposed the transition pressure to be reduced from 20–27 GPa to 7.5–12.5 GPa (depending on particle size), we found that cobalt ferrite nanoparticles remain in the spinel structure up to the highest pressure covered by our experiments. In addition, we report the pressure dependence of the unit-cell parameter and Raman modes of the studied sample. We found that under quasi-hydrostatic conditions, the bulk modulus of the nanoparticles (B{sub 0} = 204 GPa) is considerably larger than the value previously reported for bulk CoFe{sub 2}O{sub 4} (B{sub 0} = 172 GPa). In addition, when the pressure medium becomes non-hydrostatic and deviatoric stresses affect the experiments, there is a noticeable decrease of the compressibility of the studied sample (B{sub 0} = 284 GPa). After decompression, the cobalt ferrite lattice parameter does not revert to its initial value, evidencing a unit cell contraction after pressure was removed. Finally, Raman spectroscopy provides information on the pressure dependence of all Raman-active modes and evidences that cation inversion is enhanced by pressure under non-hydrostatic conditions, being this effect not fully reversible.

  18. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  19. Application in industry and energy production of active carbon/cobalt catalyst for nitrogen oxide neutralization

    International Nuclear Information System (INIS)

    Mekhandzhiev, D.; Nikolov, R.; Lyutskanov, L.; Dushanov, D.; Lakov, L.

    1997-01-01

    A new material for neutralization of nitrogen oxides is presented. Two or three metals containing catalysts with a good activity and selectivity towards NO x have been obtained. Preparation of carbon catalysts by deposition of the active phase precursor on the initial carbon material prior to activation is considered as the most promising method. An active carbon-based catalyst (AC/Co) has been synthesized Apricot shells preliminary impregnated with a water-alcohol solution of Co nitrate have been used as initial carbon material. after drying they have been subjected to one-phase steam pyrolysis using a fix-bed reactor. The catalyst thus obtained has a specific surface area (BET) of 53 m 2 g -1 , a favorable mesopore volume/total volume ratio (about 0.85) determined by nitrogen adsorption, a suitable mesopore distribution, about 70% of the mesopores being characterized by r p larger than 25 A and a high dispersion of the Co oxide phase. In addition the catalyst possesses the necessary mechanical resistance. The catalyst has exhibited a high activity with respect to NO x reduction with CO at low temperatures (at 150-250 o C which are the temperatures of industrial flue gases, nO conversion up to 60-95% occurs) and a high selectivity. No presence of H 2 O has been established over the whole temperature range (100-300 o C). An additional advantage of the catalyst is the fact that the amount of CO above 150 o C is lower than the stoichiometric which indicates parallel participation in the process of both the active phase and the support (active carbon) It is also important that the presented catalyst has a low price due to the use of waste products from agriculture and the elimination of special thermal treatment of the supported Co nitrate. There are possibilities of using of other organic wastes from agriculture as well as wastes obtained during flotation of coal. (author)

  20. Effect of CO{sub 2} and H{sub 2}O content in syngas on activity and selectivity of a cobalt based Fischer-Tropsch synthesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Poehlmann, F.; Kaiser, P.; Kern, C.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2013-11-01

    When liquid hydrocarbons are to be used as CO{sub 2} neutral storage media for electrical energy, it is necessary to convert CO{sub 2} from e.g. flue gas and hydrogen from water electrolysis to synthesis gas (CO/H{sub 2}). This can be achieved by a high temperature reverse water gas shift (RWGS) reaction. Due to thermodynamic limitations, the product gas of RWGS reactors operated at technically feasible temperatures of around 900 C will always contain significant amounts of water and carbon dioxide, which can influence the activity of Fischer-Tropsch synthesis (FTS) catalysts for the actual hydrocarbon production. In this study, a commercial cobalt catalyst was investigated under low temperature FTS conditions (2.5 MPa, 215 C) regard to activity and selectivity in the presence of H{sub 2}O and CO{sub 2}. A continuous flow apparatus including a fixed-bed reactor for the synthesis step was used to conduct all experiments. The experimental data reveals that the CO/CO{sub 2}-ratio does not affect the activity and product selectivity until the CO{sub 2}-concentration reaches 75 vol.-% (CO{sub 2}/(CO+CO{sub 2})). On increasing the carbon dioxide concentration to 100 vol.-% (H{sub 2}/CO{sub 2} = 2), the methane selectivity rose up to 70 % and even above. Addition of water caused an initial loss of activity. After the initial loss of activity the FT catalyst activity was found to remain constant, irrespectively of if the water was removed from the feed or not. Thus, the deactivation was permanent. (orig.)

  1. A combined in situ XAS-XRPD-Raman study of Fischer-Tropsch synthesis over a carbon supported Co catalyst

    DEFF Research Database (Denmark)

    Tsakoumis, Nikolaos E.; Dehghan, Roya; Johnsen, Rune

    2013-01-01

    A cobalt based Fischer-Tropsch synthesis (FTS) catalyst, supported on a carbon nanofibers/carbon felt composite (Co/CNF/CF) was studied in situ at realistic conditions. The catalyst was monitored by Xray absorption spectroscopy (XAS), high-resolution X-ray powder diffraction (HR-XRPD) and Raman...... spectroscopy, while changes in the gas phase were observed by mass spectrometry (MS). Transmission electron microscopy (TEM) was also applied to characterise the catalyst. The catalyst has a bimodal particle size distribution and exhibits a high deactivation rate. During the in situ study the catalyst appears...... to reduce further at the induction period of FTS, while crystallite growth is been detected in the same period. At steady state FTS the amount of metallic Co is constant. A change in the volumetric flow towards higher conversions did not affect the degree of reduction or the crystallite size of the catalyst...

  2. CoFe2O4 magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water

    International Nuclear Information System (INIS)

    Deng, Jing; Shao, Yisheng; Gao, Naiyun; Tan, Chaoqun; Zhou, Shiqing; Hu, Xuhao

    2013-01-01

    Highlights: • CoFe 2 O 4 MNPs tested as heterogeneous catalyst for the activation of oxone. • The catalytic performance was typically affected by several key operating parameters. • The catalyst exhibited good stability and easily recovered with excellent reusability. • Degradation pathway was proposed according to the results of LC-MS/MS analysis. -- Abstract: A magnetic nanoscaled catalyst cobalt ferrite (CoFe 2 O 4 ) was successfully prepared and used for the activation of oxone to generate sulfate radicals for the degradation of diclofenac. The catalyst was characterized by transmission electron microscopy, X-ray diffractometry, Fourier transform infrared spectroscopy and vibrating sample magnetometer. The effects of calcination temperature, initial pH, catalyst and oxone dosage on the degradation efficiency were investigated. Results demonstrated that CoFe 2 O 4 -300 exhibited the best catalytic performance and almost complete removal of diclofenac was obtained in 15 min. The degradation efficiency increased with initial pH decreasing in the pH range of 5–9. The increase of catalyst and oxone dosage both had the positive effect on the degradation of diclofenac. Moreover, CoFe 2 O 4 could retain high degradation efficiency even after being reused for five cycles. Finally, the major diclofenac degradation intermediates were identified and the primary degradation pathways were proposed

  3. Engineering Interfacial Energetics: A Novel Hybrid System of Metal Oxide Quantum Dots and Cobalt Complex for Photocatalytic Water Oxidation

    International Nuclear Information System (INIS)

    Niu, Fujun; Shen, Shaohua; Wang, Jian; Guo, Liejin

    2016-01-01

    Graphical abstract: A cobalt complex engineers the interfacial energetics of metal oxide quantum dots (n- or p-type) and electrolytes for highly efficient O_2 generation under visible light irradiation. - Highlights: • A noble-metal-free hybrid photocatalytic system using a single-site cobalt catalyst was developed for O_2 generation. • Considerable activity and excellent stability for O_2 production were achieved by this novel system. • CoSlp engineered the QDs/electrolyte interfacical energetics for efficient hole transfer. - Abstract: Here we reported a novel hybrid photocatalytic water oxidation system, containing metal oxide (n-Fe_2O_3 or p-Co_3O_4) quantum dots (QDs) as light harvester, a salophen cobalt(II) complex (CoSlp) as redox catalyst and persulfate (S_2O_8"2"−) as sacrificial electron acceptor, for oxygen generation from fully aqueous solution. The n-Fe_2O_3 QDs/CoSlp and p-Co_3O_4 QDs/CoSlp systems exhibited good O_2 evolution performances, giving turnover numbers (TONs) of ca. 33 and ca. 35 over CoSlp after visible light irradiation for 72 h, respectively. The excellent photocatalytic performance could be ascribed to the efficient hole transfer from QDs to CoSlp catalyst, leading to reduced photogenerated charge recombination, as well as the CoSlp engineered interfacial band bending of QDs, increasing the driving force or decreasing the energy barrier for hole transfer and then benefiting the following O_2 generation at the QDs/electrolyte interface. The present work successfully demonstrated a novel hybrid system for photocatalytic O_2 evolution from fully aqueous solution; and the essential role of cobalt complexes in engineering the interfacial energetics of semiconductors (n- or p-type) and electrolytes could be informative for designing efficient systems for solar water splitting.

  4. Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NOx with methane

    International Nuclear Information System (INIS)

    Pieterse, J.A.Z.; Van den Brink, R.W.; Booneveld, S.; De Bruijn, F.A.

    2003-01-01

    Selective catalytic reduction of NO with CH 4 was studied over ZSM-5, MOR, FER and BEA zeolite-based cobalt (Co) and palladium (Pd) catalysts in the presence of oxygen and water. As compared to other catalytic systems reported in literature for CH 4 -SCR in the presence of water, zeolite supported Co-Pd combination catalysts are very active and selective. The most active catalysts, based on MOR and ZSM-5, are characterised by well-dispersed Pd ions in the zeolite that activate methane. Wet ion exchange is a good method to achieve high dispersion of Pd provided that it is carried out in a competitive manner. The presence of cobalt (Co 3 O 4 , Co-oxo ions) boosts SCR activity by oxidising NO to NO 2 . The activity of the zeolite-based Co-Pd combination catalysts decreases with prolonged times on stream. The severity of the deactivation was found to be different for different zeolite topologies. The characterisation and evaluation of freshly calcined catalysts and spent catalysts show two things that occur during reaction: (1) zeolite solvated metal cations disappear in favour of (inactive) metal oxides and presumably larger metal entities, i.e. loss of dispersion; (2) loss of crystallinity affiliated with steam-dealumination and the concomitant formation of extra-framework aluminium (EFAL) in the presence of water. Both phenomena strongly depend on the (reaction) temperature. The deactivation of Co-Pd-zeolite resembles the deactivation of Pd-zeolite. Hence, future research could encompass the stabilisation of Pd (cations) in the zeolite pores by exploring additives other than cobalt. For this, detailed understanding on the siting of Pd in zeolites is important

  5. Highly selective cobalt-catalyzed hydrovinylation of styrene

    NARCIS (Netherlands)

    Grutters, M.M.P.; Müller, C.; Vogt, D.

    2006-01-01

    The hydrovinylation reaction is a codimerization of a 1,3-diene or vinyl arene and ethene with great potential for fine chemicals and pharmaceuticals. For the first time, enantioselective cobalt-catalyzed hydrovinylations of styrene were achieved with a cobalt-based system bearing a chiral

  6. Cobalt-Doped Carbon Gels as Electro-Catalysts for the Reduction of CO2 to Hydrocarbons

    Directory of Open Access Journals (Sweden)

    Abdalla Abdelwahab

    2017-01-01

    Full Text Available Two original series of carbon gels doped with different cobalt loadings and well-developed mesoporosity, aerogels and xerogels, have been prepared, exhaustively characterized, and tested as cathodes for the electro-catalytic reduction of CO2 to hydrocarbons at atmospheric pressure. Commercial cobalt and graphite sheets have also been tested as cathodes for comparison. All of the doped carbon gels catalyzed the formation of hydrocarbons, at least from type C1 to C4. The catalytic activity depends mainly on the metal loading, nevertheless, the adsorption of a part of the products in the porous structure of the carbon gel cannot be ruled out. Apparent faradaic efficiencies calculated with these developed materials were better that those obtained with a commercial cobalt sheet as a cathode, especially considering the much lower amount of cobalt contained in the Co-doped carbon gels. The cobalt-carbon phases formed in these types of doped carbon gels improve the selectivity to C3-C4 hydrocarbons formation, obtaining even more C3 hydrocarbons than CH4 in some cases.

  7. Cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond alkenylation by alkynes.

    Science.gov (United States)

    Grigorjeva, Liene; Daugulis, Olafs

    2014-09-15

    A method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed C(sp(2))-H bond alkenylation by alkynes was developed. The method shows excellent functional-group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2⋅4 H2O catalyst, Mn(OAc)2 co-catalyst, and oxygen (from air) as a terminal oxidant. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Speciation analysis of cobalt in foods by high-performance liquid chromatography and neutron activation analysis

    International Nuclear Information System (INIS)

    Muto, Toshio; Koyama, Motoko

    1994-01-01

    A combined method by coupling high-performance liquid chromatography (HPLC, as a separation method) with neutron activation analysis (as a detection method) have been applied to the speciation analysis of cobalt in daily foods (e.g. egg, fish and milk). Cobalt species including free cobalt, vitamin B 12 and protein-bound cobalt were separated with a preparative HPLC and a centrifuge. Subsequently, the determination of cobalt in the separated species was made by neutron activation analysis. The results showed that the content of the total cobalt in the foods was found to lie in the range 0.4-11ng/g(0.4-11ppb) based on wet weight. The compositions of free cobalt, vitamin B 12 and protein-bound cobalt were ranged 16-43%, 55-73%, 2.3-17%, respectively. These experimental evidences suggest that the combination of HPLC and neutron activation analysis is expected to be a useful tool for speciation analysis of trace elements in biological as well as environmental materials. (author)

  9. Palladium-alloy catalysts as ethanol tolerant cathodes for direct alcohol fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie; Varela, F.J.R. [Centro de Investigacion y de Estudios Avanzados, Coahuila (Mexico). Unidad Saltillo

    2008-07-01

    Recent studies have demonstrated that electroactive palladium (Pd) and Pd-alloy catalysts prepared using a sputtering technique possess a similar degree of activity as platinum (Pt) electrodes. This study demonstrated that Pd and Pd-alloys show a high degree of tolerance to ethanol during oxygen reduction reaction (ORR) processes. The onset potential of the ORR process in the presence of 0.5M of ethanol decreased by only 33 mV and 18 mV on Pd and Pd-cobalt (Co) catalysts. Linear sweep voltammetry experiments showed that no peak current density caused by the electro-oxidation of ethanol was observed in the Pd-based catalysts. The selective behaviour of the Pd and Pd-Co catalysts was attributed to a slow rate of adsorption of the ethanol as well as the presence of reaction intermediates on the catalytic surface. Results suggested that the Pd and Pd-Co catalysts are suitable candidates for direct alcohol fuel cell applications. 10 refs., 2 figs.

  10. New perspectives in the Fischer-Tropsch synthesis using cobalt supported on mesoporous molecular sieves; Novas perspectivas na sintese de Fischer-Tropsch usando cobalto suportado em peneiras moleculares mesoporosas

    Energy Technology Data Exchange (ETDEWEB)

    Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. de Engenharia Quimica; Fernandes Junior, V.J.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. de Quimica

    2004-07-01

    The conversion of synthesis gas to liquid products via Fischer-Tropsch synthesis (FTS) is an important process in the generation of clean fuels of sulfur and nitrogen compounds. Catalysts based on iron are very used in the conventional process due its cheap manufacture price. Recently the use of cobalt as promoter gave good results. MCM-41 mesoporous materials were discovered by Mobil scientists in the nineties and ever since they have great successes as support and catalyst in several processes of the oil industry as catalytic cracking, reformer and hydrotreating. In this work are presented new alternatives for FTS with the use of cobalt supported on molecular sieves of the type MCM-41. A comparative study with the usual catalysts based on silica was accomplished with different levels of cobalt. (author)

  11. An EXAFS study of the structure of Co-Mo hydrodesulfurization catalysts

    International Nuclear Information System (INIS)

    Clausen, B.S.; Topsoe, H.; Candia, R.; Villadsen, J.; Lengeler, B.

    1981-05-01

    By analysing the extended X-ray absorption fine structure (EXAFS) of the Mo absorption edge, structural information about both calcined and sulfided Mo/Al 2 O 3 and Co-Mo/Al 2 O 3 catalysts has been obtained. The calcined catalysts show only one strong backscatterer peak in the radial distribution function, which indicates that molybdenum is present in a highly disordered structure. For the Co-Mo/Al 2 O 3 catalyst the presence of cobalt seems to have some effect on the immediate surroundings of molybdenum. Upon sulfiding the catalysts, an ordering of the molybdenum-containing phase takes place as evidenced by the observation of a contribution from the second coordination shell. From a comparison with EXAFS data obtained on well-crystallized MoS 2 it is concluded that the molybdenum atoms in the catalysts are present in MoS 2 -like structures. Furthermore, from a comparison of the amplitude of the Mo-backscatterer peak it is found that these MoS 2 -like structures are ordered in very small domains. (orig.)

  12. Full Scale Alternative Catalyst Testing for Bosch Reactor Optimization

    Science.gov (United States)

    Barton, Katherine; Abney, Morgan B.

    2011-01-01

    Current air revitalization technology onboard the International Space Station (ISS) cannot provide complete closure of the oxygen and hydrogen loops. This makes re-supply necessary, which is possible for missions in low Earth orbit (LEO) like the ISS, but unviable for long term space missions outside LEO. In comparison, Bosch technology reduces carbon dioxide with hydrogen, traditionally over a steel wool catalyst, to create water and solid carbon. The Bosch product water can then be fed to the oxygen generation assembly to produce oxygen for crew members and hydrogen necessary to reduce more carbon dioxide. Bosch technology can achieve complete oxygen loop closure, but has many undesirable factors that result in a high energy, mass, and volume system. Finding a different catalyst with an equal reaction rate at lower temperatures with less catalyst mass and longer lifespan would make a Bosch flight system more feasible. Developmental testing of alternative catalysts for the Bosch has been performed using the Horizontal Bosch Test Stand. Nickel foam, nickel shavings, and cobalt shavings were tested at 500 C and compared to the original catalyst, steel wool. This paper presents data and analysis on the performance of each catalyst tested at comparable temperatures and recycle flow rates.

  13. Sulphonated cobalt phthalocyanine-MCM-41: An active photocatalyst for degradation of 2,4-dichlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zanjanchi, M.A., E-mail: zanjanchi@guilan.ac.ir [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Namjoo St., Rasht 41335 (Iran, Islamic Republic of); Ebrahimian, A.; Arvand, M. [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Namjoo St., Rasht 41335 (Iran, Islamic Republic of)

    2010-03-15

    The photocatalytic activity of sulphonated cobalt phthalocyanine immobilized onto MCM-41 was investigated for decomposition of 2,4-dichlorophenol (2,4-DCP) in aqueous solutions. Immobilization of anion sulpho-cobalt phthalocyanine to the walls of MCM-41 was performed by pre-anchorage of 3-(aminopropyl)-triethoxysilane (APTES) onto MCM-41 via post-synthesis method. X-ray diffraction, nitrogen physisorption, diffuse reflectance spectroscopy, energy-dispersive X-ray and FT-IR methods were used to characterize the product. Photocatalytic efficiency of the prepared catalyst for degradation of 2,4-DCP was tested under illumination of UV-A and visible light. The results obtained reveal that the photocatalyst is very active in degradation of 2,4-DCP. The photodegradation process is completed within 3 h using a dose of 0.6 g/L of the catalyst under UV irradiation. The reactions follow a pseudo-first-order kinetics and the observed rate constant values change with 2,4-DCP concentrations. The reproducibility of the catalyst was tested. The reaction intermediates were identified by gas chromatoghraphy-mass spectrometery (GC-MS) technique.

  14. Cobalt-Doped Nickel Phosphite for High Performance of Electrochemical Energy Storage.

    Science.gov (United States)

    Li, Bing; Shi, Yuxin; Huang, Kesheng; Zhao, Mingming; Qiu, Jiaqing; Xue, Huaiguo; Pang, Huan

    2018-03-01

    Compared to single metallic Ni or Co phosphides, bimetallic Ni-Co phosphides own ameliorative properties, such as high electrical conductivity, remarkable rate capability, upper specific capacity, and excellent cycle performance. Here, a simple one-step solvothermal process is proposed for the synthesis of bouquet-like cobalt-doped nickel phosphite (Ni 11 (HPO 3 ) 8 (OH) 6 ), and the effect of the structure on the pseudocapacitive performance is investigated via a series of electrochemical measurements. It is found that when the cobalt content is low, the glycol/deionized water ratio is 1, and the reaction is under 200 °C for 20 h, the morphology of the sample is uniform and has the highest specific surface area. The cobalt-doped Ni 11 (HPO 3 ) 8 (OH) 6 electrode presents a maximum specific capacitance of 714.8 F g -1 . More significantly, aqueous and solid-state flexible electrochemical energy storage devices are successfully assembled. The aqueous device shows a high energy density of 15.48 mWh cm -2 at the power density of 0.6 KW cm -2 . The solid-state device shows a high energy density of 14.72 mWh cm -2 at the power density of 0.6 KW cm -2 . These excellent performances confirm that the cobalt-doped Ni 11 (HPO 3 ) 8 (OH) 6 are promising materials for applications in electrochemical energy storage devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic ...

    Indian Academy of Sciences (India)

    been prepared by a general method and these have been characterized by analytical, spectroscopic, electro- chemical and ... alkylaromatics, alkenes and alcohols.1 Several indus- .... us to obtain the cobalt(III)-oxo clusters in good to very.

  16. CoFe{sub 2}O{sub 4} magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Jing [State Key Laboratory of Pollution Control Reuse, Tongji University, Shanghai 200092 (China); Shao, Yisheng, E-mail: shaoyisheng2011@163.com [State Key Laboratory of Pollution Control Reuse, Tongji University, Shanghai 200092 (China); China Academy of Urban Planning and Design, Beijing 100037 (China); Gao, Naiyun; Tan, Chaoqun; Zhou, Shiqing; Hu, Xuhao [State Key Laboratory of Pollution Control Reuse, Tongji University, Shanghai 200092 (China)

    2013-11-15

    Highlights: • CoFe{sub 2}O{sub 4} MNPs tested as heterogeneous catalyst for the activation of oxone. • The catalytic performance was typically affected by several key operating parameters. • The catalyst exhibited good stability and easily recovered with excellent reusability. • Degradation pathway was proposed according to the results of LC-MS/MS analysis. -- Abstract: A magnetic nanoscaled catalyst cobalt ferrite (CoFe{sub 2}O{sub 4}) was successfully prepared and used for the activation of oxone to generate sulfate radicals for the degradation of diclofenac. The catalyst was characterized by transmission electron microscopy, X-ray diffractometry, Fourier transform infrared spectroscopy and vibrating sample magnetometer. The effects of calcination temperature, initial pH, catalyst and oxone dosage on the degradation efficiency were investigated. Results demonstrated that CoFe{sub 2}O{sub 4}-300 exhibited the best catalytic performance and almost complete removal of diclofenac was obtained in 15 min. The degradation efficiency increased with initial pH decreasing in the pH range of 5–9. The increase of catalyst and oxone dosage both had the positive effect on the degradation of diclofenac. Moreover, CoFe{sub 2}O{sub 4} could retain high degradation efficiency even after being reused for five cycles. Finally, the major diclofenac degradation intermediates were identified and the primary degradation pathways were proposed.

  17. Effect of support surface treatment on the synthesis, structure, and performance of Co/CNT Fischer-Tropsch catalysts

    NARCIS (Netherlands)

    Eschemann, Thomas O.; Lamme, Wouter S.; Manchester, Rene L.; Parmentier, Tanja E.; Cognigni, Andrea; Ronning, Magnus; de Jong, Krijn P.

    We report the preparation of supported cobalt catalysts (9 wt% Co) on untreated (CNT) and surface-oxidized (CNT-ox) carbon nanotube materials by incipient wetness impregnation with solutions of cobalt nitrate in water, ethanol, or 1-propanol. The results show that by a judicious selection of solvent

  18. Highly dispersed metal catalyst

    Science.gov (United States)

    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.

  19. Synergistic Effect of Copper and Cobalt in Cu-Co-O Composite Nanocatalyst for Catalytic Ozonation

    International Nuclear Information System (INIS)

    Dong, Yuming; Wu, Lina; Wang, Guangli; Zhao, Hui; Jiang, Pingping; Feng, Cuiyun

    2013-01-01

    A novel Cu-Co-O composite nanocatalyst was designed and prepared for the ozonation of phenol. A synergistic effect of copper and cobalt was observed over the Cu-Co-O composite nanocatalyst, which showed higher activity than either copper or cobalt oxide alone. In addition, the Cu-Co-O composite revealed good activity in a wide initial pH range (4.11-8.05) of water. The fine dispersion of cobalt on the surface of copper oxide boosted the interaction between catalyst and ozone, and the surface Lewis acid sites on the Cu-Co-O composite were determined as the active sites. The Raman spectroscopy also proved that the Cu-Co-O composite was quite sensitive to the ozone. The trivalent cobalt in the Cu-Co-O composite was proposed as the valid state

  20. Amorphous nickel/cobalt tungsten sulfide electrocatalysts for high-efficiency hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lun [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Wu, Xinglong, E-mail: hkxlwu@nju.edu.cn [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Department of Physics, NingBo University, NingBo 315001 (China); Zhu, Xiaoshu [Center for Analysis and Testing, Nanjing Normal University, Nanjing 210093 (China); He, Chengyu; Meng, Ming; Gan, Zhixing [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Chu, Paul K. [Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China)

    2015-06-30

    Graphical abstract: - Highlights: • Amorphous nickel/cobalt tungsten sulfides were synthesized by a thermolytic process. • Amorphous NiWS and CoWS could realize hydrogen evolution efficiently. • Ni/Co promotion and annealing alter the porous structure and chemical bonding states. • Active sites on the surface of amorphous WS{sub x} are increased with Ni or Co doping. • Amorphous NiWS and CoWS have immense potentials in water splitting devices. - Abstract: The hydrogen evolution reaction (HER), an appealing solution for future energy supply, requires efficient and inexpensive electrocatalysts with abundant active surface sites. Although crystalline MoS{sub 2} and WS{sub 2} are promising candidates, their activity is dominated by edge sites. Amorphous tungsten sulfide prepared so far lacks the required active sites and its application has thus been hampered. In this work, nickel and cobalt incorporated amorphous tungsten sulfide synthesized by a thermolytic process is demonstrated to enhance the HER efficiency dramatically. The amorphous nickel tungsten sulfide (amorphous NiWS) annealed at 210 °C delivers the best HER performance in this system boasting a Tafel slope of 55 mV per decade and current density of 8.6 mA cm{sup −2} at 250 mV overpotential in a sustained test for 24 h. The introduction of Ni or Co into the catalyst and subsequent thermal treatment alters the porous structure and chemical bonding states thereby increasing the density of active sites on the surface.

  1. Engineering phase transformation of cobalt selenide in carbon cages and the phases’ bifunctional electrocatalytic activity for water splitting

    Science.gov (United States)

    Gao, Jiaojiao; Liu, Li; Qiu, Hua-Jun; Wang, Yu

    2017-08-01

    Using Co-based metal-organic frameworks as the precursor, we synthesized cobalt selenide (CoSe2) nanoparticles imbedded in carbon cages. By simply controlling the annealing conditions, phase transformation of CoSe2 from the orthorhombic phase to the cubic phase has been realized. Benefitting from the metallic character, the cubic phase CoSe2 shows greatly enhanced electrocatalytic activity for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). The as-prepared cubic phase CoSe2 electrode possesses onset overpotentials of 43 and 200 mV, and Tafel slopes of 51 and 83 mV dec-1 for HER and OER, respectively, which are remarkably superior to that of the orthorhombic phase CoSe2 catalyst and comparable to those of commercial noble-metal catalysts. In addition, the cubic phase CoSe2 electrode also demonstrates excellent stability after long-term operations. Our work not only provides a high performance catalyst for water splitting, but also introduces a new route to the design of a highly efficient catalyst by phase transformation.

  2. Surface-oxidized cobalt phosphide used as high efficient electrocatalyst in activated carbon air-cathode microbial fuel cell

    Science.gov (United States)

    Yang, Tingting; Wang, Zhong; Li, Kexun; Liu, Yi; Liu, Di; Wang, Junjie

    2017-09-01

    Herein, we report a simplistic method to fabricate the surface-oxidized cobalt phosphide (CoP) nanocrystals (NCs), which is used as electrocatalyst for oxygen reduction reaction (ORR) in microbial fuel cell (MFC) for the first time. The corallite-like CoP NCs are successfully prepared by a hydrothermal reaction following a phosphating treatment in N2 atmosphere. When used as an ORR catalyst, cobalt phosphide shows comparable onset potential, inferior resistance, as well as a small Tafel slope with long-term stability in neutral media. The maximum power density of MFC embellished with 10% CoP reached 1914.4 ± 59.7 mW m-2, which is 108.5% higher than the control. The four-electron pathway, observed by the RDE, plays a crucial role in electrochemical catalytic activity. In addition, material characterizations indicate that the surface oxide layer (CoOx) around the metallic CoP core is important and beneficial for ORR. Accordingly, it can be expected that the as-synthesized CoP will be a promising candidate of the non-precious metal ORR electrocatalysts for electrochemical energy applications.

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

    International Nuclear Information System (INIS)

    Cronauer, D.C.

    2011-01-01

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

  4. Electrochemical Cobalt-Catalyzed C-H Activation.

    Science.gov (United States)

    Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

    2018-06-19

    Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Surprisingly facile CO2 insertion into cobalt alkoxide bonds: A theoretical investigation

    Directory of Open Access Journals (Sweden)

    Willem K. Offermans

    2015-07-01

    Full Text Available Exploiting carbon dioxide as co-monomer with epoxides in the production of polycarbonates is economically highly attractive. More effective catalysts for this reaction are intensively being sought. To promote better understanding of the catalytic pathways, this study uses density functional theory calculations to elucidate the reaction step of CO2 insertion into cobalt(III–alkoxide bonds, which is also the central step of metal catalysed carboxylation reactions. It was found that CO2 insertion into the cobalt(III–alkoxide bond of [(2-hydroxyethoxyCoIII(salen(L] complexes (salen = N,N”-bis(salicyliden-1,6-diaminophenyl is exothermic, whereby the exothermicity depends on the trans-ligand L. The more electron-donating this ligand is, the more exothermic the insertion step is. Interestingly, we found that the activation barrier decreases with increasing exothermicity of the CO2 insertion. Hereby, a linear Brønsted–Evans–Polanyi relationship was found between the activation energy and the reaction energy.

  6. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Roenning, Magnus

    2000-07-01

    rhenium atoms, leading to weaker metal - support interactions in the bimetallic sample than what is observed for the monometallic sample. Cobalt does not catalyse the reduction of rhenium and more than six hours reduction at 450{sup o}C is required for complete reduction of accessible rhenium. The influence of pretreatment temperature on the metal function of a commercial Pt-Re/Al{sub 2}O{sub 3} reforming catalyst (EUROPT-4) was studied by X-ray absorption spectroscopy. By simultaneously examining the rhenium L{sub III} and platinum L{sub III} EXAFS data, the bimetallic interaction and the metal - support interaction can be distinguished from the overall spectrum. The results show that if the catalyst is dried in air at temperatures {<=} 500{sup o}C before reduction at 480{sup o}C, bimetallic particles of platinum and rhenium are formed. Drying at higher temperatures and in absence of air inhibits the transport of mobile (rhenium) species on the surface causing no intimate contact between the two metals. Platinum L{sub III} EXAFS data show that the average particle size of the bimetallic particles on the alumina surface is less than 10 A. The results from the rhenium L{sub III} EXAFS analysis confirm that rhenium is not completely reduced to metallic rhenium after reduction, with a significant fraction of the rhenium present in low, positive oxidation states and in intimate contact with the support. The EXAFS data are consistent with a structural model of flat rhenium metal particles with smaller platinum particles situated at the boundary of the rhenium particles. Ethene adsorption and subsequent dehydrogenation on the hexagonally reconstructed Pt(100)-hex-R0.7{sup o} surface has been investigated using scanning tunnelling microscopy (STM) and low energy electron diffraction (LEED). The results show that heterogeneous nucleation of the (1x1) domains occur when the hexagonal reconstruction is lifted during ethene adsorption on Pt(100). The (1x1) domains are highly

  7. Functionalized Cobalt Triarylcorrole Covalently Bonded with Graphene Oxide: A Selective Catalyst for the Two- or Four-Electron Reduction of Oxygen.

    Science.gov (United States)

    Tang, Jijun; Ou, Zhongping; Guo, Rui; Fang, Yuanyuan; Huang, Dong; Zhang, Jing; Zhang, Jiaoxia; Guo, Song; McFarland, Frederick M; Kadish, Karl M

    2017-08-07

    A cobalt triphenylcorrole (CorCo) was covalently bonded to graphene oxide (GO), and the resulting product, represented as GO-CorCo, was characterized by UV-vis, FT-IR, and micro-Raman spectroscopy as well as by HRTEM, TGA, XRD, XPS, and AFM. The electrocatalytic activity of GO-CorCo toward the oxygen reduction reaction (ORR) was then examined in air-saturated 0.1 M KOH and 0.5 M H 2 SO 4 solutions by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and/or a rotating ring-disk electrode. An overall 4-electron reduction of O 2 is obtained in alkaline media while under acidic conditions a 2-electron process is seen. The ORR results thus indicate that covalently bonded GO-CoCor can be used as a selective catalyst for either the 2- or 4-electron reduction of oxygen, the prevailing reaction depending upon the acidity of the solution.

  8. Nickel and cobalt filled multiwalled carbon nantubes : structural transformation under heavy ion irradiation and high pressure

    International Nuclear Information System (INIS)

    Misra, D.S.; Misra, A.; Tyagi, Pawan K.; Karamakar, S.; Sharma, Surinder M.

    2006-01-01

    Full text: The nickel and cobalt nano wires of diameters ranging from 5-15 nm are formed inside the multiwalled carbon nantubes using microwave plasma chemical vapor deposition in our laboratory. The nano wires inside the tubes are found to have a perfect crystalline structure and the crystalline planes of (111) orientations are aligned for FCC nickel and cobalt in a particular fashion. We find that the cobalt can exist either in FCC or HCP phase in confinement depending upon the diameter of the tubes. The irradiation of these nanowires with high energy Au + ions alter the orientation of the crystalline planes and generate various types of domains and defects in the nanowires. The complete amorphization of the walls of the nano tubes is observed at the fluence of 5x10 13 /cm 2 and results in amorphization of nickel nano wires as well. The cobalt nano wires have FCC structure in ambient conditions and transform to HCP cobalt irreversibly when subjected to high pressure of ∼9 GPa. Multi-walled carbon nano tubes that encapsulate the cobalt nano wires do not undergo any other structural transformation with pressure except partial reversible amorphization beyond 9 GPa

  9. Catalysts for Efficient Production of Carbon Nanotubes

    Science.gov (United States)

    Sun, Ted X.; Dong, Yi

    2009-01-01

    Several metal alloys have shown promise as improved catalysts for catalytic thermal decomposition of hydrocarbon gases to produce carbon nanotubes (CNTs). Heretofore almost every experiment on the production of carbon nanotubes by this method has involved the use of iron, nickel, or cobalt as the catalyst. However, the catalytic-conversion efficiencies of these metals have been observed to be limited. The identification of better catalysts is part of a continuing program to develop means of mass production of high-quality carbon nanotubes at costs lower than those achieved thus far (as much as $100/g for purified multi-wall CNTs or $1,000/g for single-wall CNTs in year 2002). The main effort thus far in this program has been the design and implementation of a process tailored specifically for high-throughput screening of alloys for catalyzing the growth of CNTs. The process includes an integral combination of (1) formulation of libraries of catalysts, (2) synthesis of CNTs from decomposition of ethylene on powders of the alloys in a pyrolytic chemical-vapor-decomposition reactor, and (3) scanning- electron-microscope screening of the CNTs thus synthesized to evaluate the catalytic efficiencies of the alloys. Information gained in this process is put into a database and analyzed to identify promising alloy compositions, which are to be subjected to further evaluation in a subsequent round of testing. Some of these alloys have been found to catalyze the formation of carbon nano tubes from ethylene at temperatures as low as 350 to 400 C. In contrast, the temperatures typically required for prior catalysts range from 550 to 750 C.

  10. Study of high coercive force films made by vacuum deposition of cobalt onto chromium

    International Nuclear Information System (INIS)

    Randet, Denis

    1969-01-01

    A new method to make high coercive force films, by successive evaporations of chromium and cobalt, was demonstrated in 1966 at the 'Laboratoire d'Electronique et de Technologie de l'Informatique'. This work first contains a description of the magnetic properties of these films according to the conditions of preparation. These properties, which are isotropic in the plane of the film, are then related to the crystallographic structure of chromium and cobalt, in particular through electron microscopy. It is concluded that the coercive force is essentially due to the high magneto-crystalline anisotropy of cobalt in its hexagonal phase and depends, altogether with the shape of the hysteresis loop, on the magnetostatic coupling between the grains, which varies according to their dimensions. The chromium underlayer, if its surface is free enough of oxygen contamination, induces the growth of the hexagonal phase and influences the grain size of cobalt by a sort of epitaxy. At last, the behaviour of the Co/Cr films as a magnetic recording material is briefly examined and discussed. (author) [fr

  11. Boron-capped tris(glyoximato) cobalt clathrochelate as a precursor for the electrodeposition of nanoparticles catalyzing H2 evolution in water.

    Science.gov (United States)

    Anxolabéhère-Mallart, Elodie; Costentin, Cyrille; Fournier, Maxime; Nowak, Sophie; Robert, Marc; Savéant, Jean-Michel

    2012-04-11

    Electrochemical investigation of a boron-capped tris(glyoximato)cobalt clathrochelate complex in the presence of acid reveals that the catalytic activity toward hydrogen evolution results from an electrodeposition of cobalt-containing nanoparticles on the electrode surface at a modest cathodic potential. The deposited particles act as remarkably active catalysts for H(2) production in water at pH 7. © 2012 American Chemical Society

  12. Electrocatalytic performance evaluation of cobalt hydroxide and cobalt oxide thin films for oxygen evolution reaction

    Science.gov (United States)

    Babar, P. T.; Lokhande, A. C.; Pawar, B. S.; Gang, M. G.; Jo, Eunjin; Go, Changsik; Suryawanshi, M. P.; Pawar, S. M.; Kim, Jin Hyeok

    2018-01-01

    The development of an inexpensive, stable, and highly active electrocatalyst for oxygen evolution reaction (OER) is essential for the practical application of water splitting. Herein, we have synthesized an electrodeposited cobalt hydroxide on nickel foam and subsequently annealed in an air atmosphere at 400 °C for 2 h. In-depth characterization of all the films using X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) techniques, which reveals major changes for their structural, morphological, compositional and electrochemical properties, respectively. The cobalt hydroxide nanosheet film shows high catalytic activity with 290 mV overpotential at 10 mA cm-2 and 91 mV dec-1 Tafel slope and robust stability (24 h) for OER in 1 M KOH electrolyte compared to cobalt oxide (340 mV). The better OER activity of cobalt hydroxide in comparison to cobalt oxide originated from high active sites, enhanced surface, and charge transport capability.

  13. Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst.

    Science.gov (United States)

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

    2015-06-08

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

  14. Cobalt oxide-molybdenum oxide-aluminum oxide catalyst : II. The structure of the catalyst

    NARCIS (Netherlands)

    Lipsch, J.M.J.G.; Schuit, G.C.A.

    1969-01-01

    The structure of the \\"Co molybdate on alumina\\" catalyst was investigated. Infrared spectra show that the Mo is present as MoO3. Reflection spectra lead to the conclusion that the Co is distributed throughout the bulk of the alumina as CoAl2O4, whereas the MoO3 is spread over the carrier surface,

  15. Evaluation of functionalized silica's for the adsorptive recovery of homogeneous catalysts through interaction with the metal centre

    NARCIS (Netherlands)

    Djekic, T.; Ham, van der A.G.J.; Haan, de A.B.

    2007-01-01

    The goal of this paper is the evaluation of functionalized silica's for the recovery of homogeneous catalysts by adsorption via its metal centre. As model catalysts, we selected bis(triphenylphosphine)cobalt(II)dichloride (CoCl2(PPh3)2), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2)

  16. Establishing efficient cobalt based catalytic sites for oxygen evolution on a Ta3N5 photocatalyst

    KAUST Repository

    Nurlaela, Ela; Ould-Chikh, Samy; Llorens, Isabelle; Hazemann, Jean-louis; Takanabe, Kazuhiro

    2015-01-01

    In a photocatalytic suspension system with a powder semiconductor, the interface between the photocatalyst semiconductor and catalyst should be constructed to minimize resistance for charge transfer of excited carriers. This study demonstrates an in-depth understanding of pretreatment effects on the photocatalytic O2 evolution reaction (OER) activity of visible-light-responsive Ta3N5 decorated with CoOx nanoparticles. The CoOx/Ta3N5 sample was synthesized by impregnation followed by sequential heat treat-ments under NH3 flow and air flow at various temperatures. Various characterization techniques, including X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and X-ray photoelectron spec-troscopy (XPS), were used to clarify the state and role of cobalt. No improvement in photocatalytic activity for OER over the bare Ta3N5 was observed for the as-impregnated CoOx/Ta3N5, likely because of insufficient contact between CoOx and Ta3N5. When the sample was treated in NH3 at high temperature, a substantial improvement in the photocatalytic activity was observed. After NH3 treatment at 700 °C, the Co0-CoOx core-shell agglomerated cobalt structure was identified by XAS and STEM. No metallic cobalt species was evident after the photocatalytic OER, indicating that the metallic cobalt itself is not essential for the reaction. Accordingly, mild oxidation (200 °C) of the NH3-treated CoOx/Ta3N5 sample enhanced photocatalytic OER activity. Oxidation at higher temperatures drastically eliminated the photocatalytic activity, most likely because of unfavorable Ta3N5 oxidation. These results suggest that the intimate contact between cobalt species and Ta3N5 facilitated at high temperature is beneficial to enhancing hole transport and that the cobalt oxide provides electrocatalytic sites for OER.

  17. Establishing efficient cobalt based catalytic sites for oxygen evolution on a Ta3N5 photocatalyst

    KAUST Repository

    Nurlaela, Ela

    2015-08-05

    In a photocatalytic suspension system with a powder semiconductor, the interface between the photocatalyst semiconductor and catalyst should be constructed to minimize resistance for charge transfer of excited carriers. This study demonstrates an in-depth understanding of pretreatment effects on the photocatalytic O2 evolution reaction (OER) activity of visible-light-responsive Ta3N5 decorated with CoOx nanoparticles. The CoOx/Ta3N5 sample was synthesized by impregnation followed by sequential heat treat-ments under NH3 flow and air flow at various temperatures. Various characterization techniques, including X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and X-ray photoelectron spec-troscopy (XPS), were used to clarify the state and role of cobalt. No improvement in photocatalytic activity for OER over the bare Ta3N5 was observed for the as-impregnated CoOx/Ta3N5, likely because of insufficient contact between CoOx and Ta3N5. When the sample was treated in NH3 at high temperature, a substantial improvement in the photocatalytic activity was observed. After NH3 treatment at 700 °C, the Co0-CoOx core-shell agglomerated cobalt structure was identified by XAS and STEM. No metallic cobalt species was evident after the photocatalytic OER, indicating that the metallic cobalt itself is not essential for the reaction. Accordingly, mild oxidation (200 °C) of the NH3-treated CoOx/Ta3N5 sample enhanced photocatalytic OER activity. Oxidation at higher temperatures drastically eliminated the photocatalytic activity, most likely because of unfavorable Ta3N5 oxidation. These results suggest that the intimate contact between cobalt species and Ta3N5 facilitated at high temperature is beneficial to enhancing hole transport and that the cobalt oxide provides electrocatalytic sites for OER.

  18. Computational Modeling of Cobalt-Based Water Oxidation: Current Status and Future Challenges

    Directory of Open Access Journals (Sweden)

    Mauro Schilling

    2018-04-01

    Full Text Available A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context, mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysts. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability toward real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

  19. Selective propene oxidation on mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    James, David William

    2002-01-01

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

  20. Key technology studies of GY-20 and GY-40 High-capacity cobalt-60 transport casks

    International Nuclear Information System (INIS)

    Liu Huifang; Zhang Xin

    2012-01-01

    GY-20 and GY-40 high-capacity cobalt-60 transport casks are used to transport cobalt-60 industrial irradiators and cobalt-60 bundles. The radioactive contents have special features of high-activity and high residual heat, so only a few countries such as Canada, England and Russia have design capacity. The key technologies and corresponding solutions were studied for the design and manufacture of the cask taking into account the structural, thermal, mechanics and shield requests. A series of tests prove that the cask structure design, design criteria for lead coating structure and quality control measurements are reasonable and effective, and the cask shield integrity can be ensured for all conditions. The casks have ability to transport high-activity sealed sources safely, and the design of cask satisfies the requirement of design code and standard. It can provide reference for other B type package. (authors)

  1. Synthesis and Characterization of Carbon nanofibers on Co and Cu Catalysts by Chemical Vapor Deposition

    International Nuclear Information System (INIS)

    Park, Eunsil; Kim, Jongwon; Lee, Changseop

    2014-01-01

    This study reports on the synthesis of carbon nanofibers via chemical vapor deposition using Co and Cu as catalysts. In order to investigate the suitability of their catalytic activity for the growth of nanofibers, we prepared catalysts for the synthesis of carbon nanofibers with Cobalt nitrate and Copper nitrate, and found the optimum concentration of each respective catalyst. Then we made them react with Aluminum nitrate and Ammonium Molybdate to form precipitates. The precipitates were dried at a temperature of 110 .deg. C in order to be prepared into catalyst powder. The catalyst was sparsely and thinly spread on a quartz tube boat to grow carbon nanofibers via thermal chemical vapor deposition. The characteristics of the synthesized carbon nanofibers were analyzed through SEM, EDS, XRD, Raman, XPS, and TG/DTA, and the specific surface area was measured via BET. Consequently, the characteristics of the synthesized carbon nanofibers were greatly influenced by the concentration ratio of metal catalysts. In particular, uniform carbon nanofibers of 27 nm in diameter grew when the concentration ratio of Co and Cu was 6:4 at 700 .deg. C of calcination temperature; carbon nanofibers synthesized under such conditions showed the best crystallizability, compared to carbon nanofibers synthesized with metal catalysts under different concentration ratios, and revealed 1.26 high amorphicity as well as 292 m 2 g -1 high specific surface area

  2. High aspect ratio catalytic reactor and catalyst inserts therefor

    Science.gov (United States)

    Lin, Jiefeng; Kelly, Sean M.

    2018-04-10

    The present invention relates to high efficient tubular catalytic steam reforming reactor configured from about 0.2 inch to about 2 inch inside diameter high temperature metal alloy tube or pipe and loaded with a plurality of rolled catalyst inserts comprising metallic monoliths. The catalyst insert substrate is formed from a single metal foil without a central supporting structure in the form of a spiral monolith. The single metal foil is treated to have 3-dimensional surface features that provide mechanical support and establish open gas channels between each of the rolled layers. This unique geometry accelerates gas mixing and heat transfer and provides a high catalytic active surface area. The small diameter, high aspect ratio tubular catalytic steam reforming reactors loaded with rolled catalyst inserts can be arranged in a multi-pass non-vertical parallel configuration thermally coupled with a heat source to carry out steam reforming of hydrocarbon-containing feeds. The rolled catalyst inserts are self-supported on the reactor wall and enable efficient heat transfer from the reactor wall to the reactor interior, and lower pressure drop than known particulate catalysts. The heat source can be oxygen transport membrane reactors.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-04-11

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

  4. Synthesis of carbon nanotubes using the cobalt nanocatalyst by thermal chemical vapor deposition technique

    Energy Technology Data Exchange (ETDEWEB)

    Madani, S.S. [Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Zare, K. [Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Department of Chemistry, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Ghoranneviss, M. [Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Salar Elahi, A., E-mail: Salari_phy@yahoo.com [Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of)

    2015-11-05

    The three main synthesis methods of Carbon nanotubes (CNTs) are the arc discharge, the laser ablation and the chemical vapour deposition (CVD) with a special regard to the latter one. CNTs were produced on a silicon wafer by Thermal Chemical Vapor Deposition (TCVD) using acetylene as a carbon source, cobalt as a catalyst and ammonia as a reactive gas. The DC-sputtering system was used to prepare cobalt thin films on Si substrates. A series of experiments was carried out to investigate the effects of reaction temperature and deposition time on the synthesis of the nanotubes. The deposition time was selected as 15 and 25 min for all growth temperatures. Energy Dispersive X-ray (EDX) measurements were used to investigate the elemental composition of the Co nanocatalyst deposited on Si substrates. Atomic Force Microscopy (AFM) was used to characterize the surface topography of the Co nanocatalyst deposited on Si substrates. The as-grown CNTs were characterized under Field Emission Scanning Electron Microscopy (FESEM) to study the morphological properties of CNTs. Also, the grown CNTs have been investigated by High Resolution Transmission Electron Microscopy (HRTEM) and Raman spectroscopy. The results demonstrated that increasing the temperature leads to increasing the diameter of CNTs. The ideal reaction temperature was 850 °C and the deposition time was 15 min. - Graphical abstract: FESEM images of CNTs grown on the cobalt catalyst at growth temperatures of (a) 850 °C, (b) 900 °C, (c) 950 °C and (d) 1000 °C during the deposition time of 15 min. - Highlights: • Carbon nanotubes (CNTs) were produced on a silicon wafer by TCVD technique. • EDX and AFM were used to investigate the elemental composition and surface topography. • FESEM was used to study the morphological properties of CNTs. • The grown CNTs have been investigated by HRTEM and Raman spectroscopy.

  5. Synthesis of trans-disubstituted alkenes by cobalt-catalyzed reductive coupling of terminal alkynes with activated alkenes.

    Science.gov (United States)

    Mannathan, Subramaniyan; Cheng, Chien-Hong

    2012-09-10

    A cobalt-catalyzed reductive coupling of terminal alkynes, RC≡CH, with activated alkenes, R'CH=CH(2), in the presence of zinc and water to give functionalized trans-disubstituted alkenes, RCH=CHCH(2)CH(2)R', is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl(2)/P(OMe)(3)/Zn catalyst system to afford 1,2-trans-disubstituted alkenes with high regio- and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl(2)/P(OPh)(3)/Zn system providing a mixture of 1,2-trans- and 1,1-disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3-enynes and acetylene gas with alkenes. Furthermore, a phosphine-free cobalt-catalyzed reductive coupling of terminal alkynes with enones, affording 1,2-trans-disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air-stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Cobalt-Catalyzed, Aminoquinoline-Directed sp2 C-H Bond Alkenylation by Alkynes**

    Science.gov (United States)

    Grigorjeva, Liene; Daugulis, Olafs

    2014-01-01

    We have developed a method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed sp2 C-H bond alkenylation by alkynes. Method shows excellent functional group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2*4H2O catalyst, Mn(OAc)2 cocatalyst, and oxygen from air as a terminal oxidant. PMID:25060365

  7. Novel type of carbon-supported catalysts. I.Preparation and characterization

    NARCIS (Netherlands)

    van Doorn, J.; Staugaard, P.; Moulijn, J.A.; Beer, de V.H.J.

    1989-01-01

    The exposure of CoO/Al2O3 catalysts to carbon monoxide leads, after reduction to cobalt metal, to the formation of filamentary carbon in addition to a less reactive form of deposited carbon. The filament diameters were determined by scanning electron microscopy. The carbon content was determined by

  8. Morphology Changes of Co Catalyst Nanoparticles at the Onset of Fischer-Tropsch Synthesis

    DEFF Research Database (Denmark)

    Høydalsvik, Kristin; Fløystad, Jostein B.; Voronov, Alexey

    2014-01-01

    Cobalt nanoparticles play an important role as catalysts for the Fischer-Tropsch synthesis, which is an attractive route for production of synthetic fuels. It is of particular interest to understand the varying conversion rate during the first hours after introducing synthesis gas (H-2 and CO......) to the system. To this end, several in situ characterization studies have previously been done on both idealized model systems and commercially relevant catalyst nanoparticles, using bulk techniques, such as X-ray powder diffraction and X-ray absorption spectroscopy. Since catalysis takes place at the surface...... of the cobalt particles, it is important to develop methods to gain surface-specific structural information under realistic processing conditions. We addressed this challenge using small-angle X-ray scattering (SAXS), a technique exploiting the penetrating nature of X-rays to provide information about particle...

  9. Cobalt carbide nanoprisms for direct production of lower olefins from syngas

    Science.gov (United States)

    Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

    2016-10-01

    Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

  10. Hydrogen or synthesis gas production via the partial oxidation of methane over supported nickel-cobalt catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Alaric C.W. [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Chen, Luwei; Lin, Jianyi [Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Kee Leong, Weng [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Johnson, Brian F.G.; Khimyak, Tetyana [University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW (United Kingdom)

    2007-05-15

    Activity, selectivity, and coking-resistance of a series of Ni{sub x}Co{sub y} (where x,y are the respective metal loadings of 0, 1, 2 or 3 wt.%; x+y=3) bimetallic catalysts supported on CaAl{sub 2}O{sub 4}/Al{sub 2}O{sub 3} have been studied for hydrogen/synthesis gas production via the catalytic partial oxidation (CPO) of methane. Catalysts were characterized by temperature programmed reduction (TPR), transmission electron microscopy (TEM) and X-ray fluorescence multi-element analysis (XRF). Their activity for the partial oxidation of methane to hydrogen and carbon monoxide (at 1 bar, gas hourly space velocity (GHSV) of 144,000cm{sup 3}g{sup -1}h{sup -1} and CH{sub 4}/O{sub 2} molar ratio of 2) was investigated, and coke deposited on the spent catalysts was studied by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA). The activity was found to decrease in the order of Ni{sub 2}Co>Ni{sub 3}>NiCo{sub 2}>>Co{sub 3}, while CO and H{sub 2} selectivities were found to be in the order ofNi{sub 2}Co>Ni{sub 3}{approx}NiCo{sub 2}>Co{sub 3}. Ni{sub 2}Co is also shown to be more resistant to coking as compared to Ni{sub 3}, which is a current catalyst of choice. Results show that not only does Ni{sub 2}Co have the highest activity and selectivity among all the catalysts tested, it is also relatively resistant to coking. This finding would be helpful for catalyst design to achieve high coking resistivity catalysts for hydrogen production from CPO of methane. (author)

  11. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel

    Science.gov (United States)

    Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

    2016-01-01

    Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially ‘clean’ strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2•- radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO-) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems

  12. Evaluation of functionalized silica¿s for the adsorptive recovery of homogenous catalysts through interaction with the metal centre

    NARCIS (Netherlands)

    Djekic, T.; van der Ham, Aloysius G.J.; de Haan, A.B.

    2007-01-01

    The goal of this paper is the evaluation of functionalized silica's for the recovery of homogeneous catalysts by adsorption via its metal centre. As model catalysts, we selected bis(triphenylphosphine)cobalt(II)dichloride (CoCl2(PPh3)2), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2)

  13. Synthesis of Single-Walled Carbon Nanotubes: Effects of Active Metals, Catalyst Supports, and Metal Loading Percentage

    Directory of Open Access Journals (Sweden)

    Wei-Wen Liu

    2013-01-01

    Full Text Available The effects of active metals, catalyst supports, and metal loading percentage on the formation of single-walled carbon nanotubes (SWNTs were studied. In particular, iron, cobalt, and nickel were investigated for SWNTs synthesis. Iron was found to grow better-quality SWNTs compared to cobalt and nickel. To study the effect of catalyst supports, magnesium oxide, silicon oxide, and aluminium oxide were chosen for iron. Among the studied supports, MgO was identified to be a suitable support for iron as it produced SWNTs with better graphitisation determined by Raman analysis. Increasing the iron loading decreased the quality of SWNTs due to extensive agglomeration of the iron particles. Thus, lower metal loading percentage is preferred to grow better-quality SWNTs with uniform diameters.

  14. Catalysts with Cerium in a Membrane Reactor for the Removal of Formaldehyde Pollutant from Water Effluents

    Directory of Open Access Journals (Sweden)

    Mirella Gutiérrez-Arzaluz

    2016-05-01

    Full Text Available We report the synthesis of cerium oxide, cobalt oxide, mixed cerium, and cobalt oxides and a Ce–Co/Al2O3 membrane, which are employed as catalysts for the catalytic wet oxidation (CWO reaction process and the removal of formaldehyde from industrial effluents. Formaldehyde is present in numerous waste streams from the chemical industry in a concentration low enough to make its recovery not economically justified but high enough to create an environmental hazard. Common biological degradation methods do not work for formaldehyde, a highly toxic but refractory, low biodegradability substance. The CWO reaction is a recent, promising alternative that also permits much lower temperature and pressure conditions than other oxidation processes, resulting in economic benefits. The CWO reaction employing Ce- and Co-containing catalysts was carried out inside a slurry batch reactor and a membrane reactor. Experimental results are reported. Next, a mixed Ce–Co oxide film was supported on an γ-alumina membrane used in a catalytic membrane reactor to compare formaldehyde removal between both types of systems. Catalytic materials with cerium and with a relatively large amount of cerium favored the transformation of formaldehyde. Cerium was present as cerianite in the catalytic materials, as indicated by X-ray diffraction patterns.

  15. Ultrafine Cobalt Sulfide Nanoparticles Encapsulated Hierarchical N-doped Carbon Nanotubes for High-performance Lithium Storage

    International Nuclear Information System (INIS)

    Li, Xiaoyan; Fu, Nianqing; Zou, Jizhao; Zeng, Xierong; Chen, Yuming; Zhou, Limin; Lu, Wei; Huang, Haitao

    2017-01-01

    Graphical abstract: Ultrafine cobalt sulfide nanoparticles encapsulated in hierarchical N-doped carbon nanotubes show exceptional lithium ion storage as anodes. - Abstract: Nanostructured cobalt sulfide based materials with rational design are attractive for high-performance lithium-ion batteries. In this work, we report a multistep method to synthesize ultrafine cobalt sulfide nanoparticles encapsulated in hierarchical N-doped carbon nanotubes (CoS x @HNCNTs). Co-based zeolitic imidazolate framework (ZIF-67) nanotubes are obtained from the reaction between electrospun polyacrylonitrile/cobalt acetate and 2-methylimidazole, followed by the dissolution of template. Next, a combined calcination and sulfidation process is employed to convert the ZIF-67 nanotubes to CoS x @HNCNTs. Benefited from the compositional and structural features, the as-prepared nanostructured hybrid materials deliver superior lithium storage properties with high capacity of 1200 mAh g −1 at 0.25 A g −1 . More importantly, a remarkable capacity of 1086 mAh g −1 can be maintained after 100 cycles at the current density of 0.5 A g −1 . Even at a high rate of 5 A g −1 , a reversible capacity of 592 mAh g −1 after 1600 cycles can still be achieved.

  16. Ammonia synthesis with barium-promoted iron–cobalt alloys supported on carbon

    DEFF Research Database (Denmark)

    Hagen, Stefan; Barfod, Rasmus; Fehrmann, Rasmus

    2003-01-01

    Iron–cobalt alloys supported on carbon were investigated as ammonia synthesis catalysts. Barium was found to have a promoting effect for Fe with an optimum atomic ratio Ba/Fe of 0.35. At this Ba loading, a local maximum for the NH3 synthesis activity was found at 4 wt% Co by varying the Fe/Co ratio....... Samples containing only Co and no Fe, however, yielded by far the most active catalysts (7.0 μmol (NH3) g−1 s−1, 673 K, 10 bar). Barium was a very efficient promoter for Co, increasing the NH3 synthesis activity by more than two orders of magnitude compared to the unpromoted Co samples, while...

  17. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed; Shinagawa, Tatsuya; Stegenburga, Liga; Takanabe, Kazuhiro

    2016-01-01

    of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a

  18. Topotactic Synthesis of Porous Cobalt Ferrite Platelets from a Layered Double Hydroxide Precursor and Their Application in Oxidation Catalysis.

    Science.gov (United States)

    Ortega, Klaus Friedel; Anke, Sven; Salamon, Soma; Özcan, Fatih; Heese, Justus; Andronescu, Corina; Landers, Joachim; Wende, Heiko; Schuhmann, Wolfgang; Muhler, Martin; Lunkenbein, Thomas; Behrens, Malte

    2017-09-12

    Monocrystalline, yet porous mosaic platelets of cobalt ferrite, CoFe 2 O 4 , can be synthesized from a layered double hydroxide (LDH) precursor by thermal decomposition. Using an equimolar mixture of Fe 2+ , Co 2+ , and Fe 3+ during co-precipitation, a mixture of LDH, (Fe II Co II ) 2/3 Fe III 1/3 (OH) 2 (CO 3 ) 1/6 ⋅m H 2 O, and the target spinel CoFe 2 O 4 can be obtained in the precursor. During calcination, the remaining Fe II fraction of the LDH is oxidized to Fe III leading to an overall Co 2+ :Fe 3+ ratio of 1:2 as required for spinel crystallization. This pre-adjustment of the spinel composition in the LDH precursor suggests a topotactic crystallization of cobalt ferrite and yields phase pure spinel in unusual anisotropic platelet morphology. The preferred topotactic relationship in most particles is [111] Spinel ∥[001] LDH . Due to the anion decomposition, holes are formed throughout the quasi monocrystalline platelets. This synthesis approach can be used for different ferrites and the unique microstructure leads to unusual chemical properties as shown by the application of the ex-LDH cobalt ferrite as catalyst in the selective oxidation of 2-propanol. Compared to commercial cobalt ferrite, which mainly catalyzes the oxidative dehydrogenation to acetone, the main reaction over the novel ex-LDH cobalt is dehydration to propene. Moreover, the oxygen evolution reaction (OER) activity of the ex-LDH catalyst was markedly higher compared to the commercial material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Fracture and Residual Characterization of Tungsten Carbide Cobalt Coatings on High Strength Steel

    National Research Council Canada - National Science Library

    Parker, Donald S

    2003-01-01

    Tungsten carbide cobalt coatings applied via high velocity oxygen fuel thermal spray deposition are essentially anisotropic composite structures with aggregates of tungsten carbide particles bonded...

  20. In situ IR studies of Co and Ce doped Mn/TiO{sub 2} catalyst for low-temperature selective catalytic reduction of NO with NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng, E-mail: ouyangfh@hit.edu.cn

    2015-12-01

    Highlights: • A SCR mechanistic pathway over Mn–Co–Ce/TiO{sub 2} is proposed. • The cobalt oxide produces lots of Brønsted acid sites, which favor to the adsorption of coordinated NH{sub 3} through NH{sub 3} migration. • Ce addition improves amide ions formation to reach best NO reduction selectivity. • At low-temperature coordinated NH{sub 3} reacts with NO{sub 2}{sup −}, or amide reacts with NO (ad) or NO (g) to form N{sub 2}. At high temperature, the reaction also occurs between coordinated NH{sub 3} and nitrate species. - Abstract: The Mn–Co–Ce/TiO{sub 2} catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH{sub 3} in the presence of oxygen. The adsorption and co-adsorption of NH{sub 3}, NO and O{sub 2} on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH{sub 3} through NH{sub 3} migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn–Co–Ce/TiO{sub 2} was proposed. At low-temperature SCR reaction, coordinated NH{sub 3} reacted with NO{sub 2}{sup −}, and amide reacted with NO (ad) or NO (g) to form N{sub 2}. NO{sub 2} was related to the formation of nitrite on Co-contained catalysts and the generation of −NH{sub 2}{sup −} on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH{sub 3} and nitrate species, resulting in N{sub 2}O yield increase.

  1. Wear and creep of highly crosslinked polyethylene against cobalt chrome and ceramic femoral heads.

    Science.gov (United States)

    Galvin, A L; Jennings, L M; Tipper, J L; Ingham, E; Fisher, J

    2010-10-01

    The wear and creep characteristics of highly crosslinked ultrahigh-molecular-weight polyethylene (UHMWPE) articulating against large-diameter (36mm) ceramic and cobalt chrome femoral heads have been investigated in a physiological anatomical hip joint simulator for 10 million cycles. The crosslinked UHMWPE/ceramic combination showed higher volume deformation due to creep plus wear during the first 2 million cycles, and a steady-state wear rate 40 per cent lower than that of the crosslinked UHMWPE/cobalt chrome combination. Wear particles were isolated and characterized from the hip simulator lubricants. The wear particles were similar in size and morphology for both head materials. The particle isolation methodology used could not detect a statistically significant difference between the particles produced by the cobalt chrome and alumina ceramic femoral heads.

  2. Lanthanum cobalt oxides as models for La-promoted Co/{gamma}-Al{sub 2}O{sub 3} catalys

    Energy Technology Data Exchange (ETDEWEB)

    Hansteen, Ole Henrik

    1998-12-31

    Cobalt supported on {gamma}-Al{sub 2}O{sub 3} have for a long time been interesting catalysts for the synthesis of hydrocarbons by hydrogenation of carbonmonoxide, the so-called Fischer-Tropsch synthesis. The reduction and catalytic properties of these catalysts are largely improved by addition of promotors like rhenium and lanthanum. This thesis attempts to provide additional knowledge to the nature of the reduction processes from metal oxides via partially reduced phases into metal and to the large degree of interaction/reaction between the catalyst components. It focuses on detailed studies of model oxides in the La-Co-O and Co-Al-O systems under reducing conditions typically used for the synthesis of the catalysts. 132 refs., 41 figs., 16 tabs.

  3. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jie; Chen, Jinwei, E-mail: jwchen@scu.edu.cn; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin, E-mail: rl.wang@scu.edu.cn

    2016-12-15

    Graphical abstract: A hybrid catalyst was prepared via a quite green and simple method to achieve an one-pot synthesis of the N-doping carbon, tungsten carbides, and iron/cobalt carbides. It exhibited comparable electrocatalytic activity, higher durability and ability to methanol tolerance compared with commercial Pt/C to ORR. - Highlights: • A novel type of hybrid Fe/Co/WC@NC catalysts have been successfully synthesized. • The hybrid catalyst also exhibited better durability and methanol tolerance. • Multiple effective active sites of Fe{sub 3}C, Co{sub 3}C, WC, and NC help to improve catalytic performance. - Abstract: This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe{sub 3}C and Co{sub 3}C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe{sub 3}C, and Co{sub 3}C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

  4. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    International Nuclear Information System (INIS)

    Qi, B.; Andrew, J. S.; Arnold, D. P.

    2017-01-01

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe_6_6Co_3_4) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe_2O_4) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  5. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    Energy Technology Data Exchange (ETDEWEB)

    Qi, B. [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States); Andrew, J. S. [University of Florida, Department of Materials Science and Engineering (United States); Arnold, D. P., E-mail: darnold@ufl.edu [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States)

    2017-03-15

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe{sub 66}Co{sub 34}) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  6. Development and functionalization of magnetic nanoparticles as powerful and green catalysts for organic synthesis

    Directory of Open Access Journals (Sweden)

    Ahmed M. Abu-Dief

    2018-03-01

    Full Text Available Magnetic nanoparticles are a highly worthy reactant for the correlation of homogeneous inorganic and organic containing catalysts. This review deals with the very recent main advances in the development of various nano catalytic systems by the immobilization of homogeneous catalysts onto magnetic nanoparticles. Catalytic fields include the use of mainly cobalt, nickel, copper, and zinc ferrites, as well as their mixed-metal combinations with Cr, Cd, Mn and sometimes some lanthanides. The ferrite nanomaterials are obtained mainly by co-precipitation and hydrothermal methods, sometimes by the sonochemical technique, micro emulsion and flame spray synthesis route. Catalytic processes with application of ferrite nanoparticles include degradation (in particular photocatalytic, reactions of dehydrogenation, oxidation, alkylation, C–C coupling, among other processes. Ferrite nano catalysts can be easily recovered from reaction systems and reused up to several runs almost without loss of catalytic activity. Finally, we draw conclusions and present a futurity outlook for the further development of new catalytic systems which are immobilized onto magnetic nanoparticles.

  7. Metal-Carbon-CNF Composites Obtained by Catalytic Pyrolysis of Urban Plastic Residues as Electro-Catalysts for the Reduction of CO2

    Directory of Open Access Journals (Sweden)

    Jesica Castelo-Quibén

    2018-05-01

    Full Text Available Metal–carbon–carbon nanofibers composites obtained by catalytic pyrolysis of urban plastic residues have been prepared using Fe, Co or Ni as pyrolitic catalysts. The composite materials have been fully characterized from a textural and chemical point of view. The proportion of carbon nanofibers and the final content of carbon phases depend on the used pyrolitic metal with Ni being the most active pyrolitic catalysts. The composites show the electro-catalyst activity in the CO2 reduction to hydrocarbons, favoring all the formation of C1 to C4 hydrocarbons. The tendency of this activity is in accordance with the apparent faradaic efficiencies and the linear sweep voltammetries. The cobalt-based composite shows high selectivity to C3 hydrocarbons within this group of compounds.

  8. Manganese and Iron Catalysts in Alkyd Paints and Coatings

    Directory of Open Access Journals (Sweden)

    Ronald Hage

    2016-04-01

    Full Text Available Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification as carcinogens under the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals legislation. Alternative driers, for example manganese and iron soaps, have been applied for this purpose. However, relatively poor curing capabilities make it necessary to increase the level of metal salts to such a level that often coloring of the paint formulation occurs. More recent developments include the application of manganese and iron complexes with a variety of organic ligands. This review will discuss the chemistry of alkyd resin curing, the applications and reactions of cobalt-soaps as curing agents, and, subsequently, the paint drying aspects and mechanisms of (model alkyd curing using manganese and iron catalysts.

  9. Nano copper and cobalt ferrites as heterogeneous catalysts for the ...

    Indian Academy of Sciences (India)

    logically active natural products were found to contain substituted ... pH of the solution was increased to ... weak which indicate that the residual carbon has mostly burnt away .... imidazole. 3.1a Comparison of effect of the present catalysts with.

  10. Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

    Science.gov (United States)

    Ghampson, Isaac Tyrone

    The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the

  11. Feasibility Study for Cobalt Bundle Loading to CANDU Reactor Core

    International Nuclear Information System (INIS)

    Park, Donghwan; Kim, Youngae; Kim, Sungmin

    2016-01-01

    CANDU units are generally used to produce cobalt-60 at Bruce and Point Lepreau in Canada and Embalse in Argentina. China has started production of cobalt-60 using its CANDU 6 Qinshan Phase III nuclear power plant in 2009. For cobalt-60 production, the reactor’s full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel burn-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. Several studies have been performed to produce cobalt-60 using adjuster rod at Wolsong nuclear power plant. This study proposed new concept for producing cobalt-60 and performed the feasibility study. Bundle typed cobalt loading concept is proposed and evaluated the feasibility to fuel management without physics and system design change. The requirement to load cobalt bundle to the core was considered and several channels are nominated. The production of cobalt-60 source is very depend on the flux level and burnup directly. But the neutron absorption characteristic of cobalt bundle is too high, so optimizing design study is needed in the future

  12. Feasibility Study for Cobalt Bundle Loading to CANDU Reactor Core

    Energy Technology Data Exchange (ETDEWEB)

    Park, Donghwan; Kim, Youngae; Kim, Sungmin [KHNP Central Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    CANDU units are generally used to produce cobalt-60 at Bruce and Point Lepreau in Canada and Embalse in Argentina. China has started production of cobalt-60 using its CANDU 6 Qinshan Phase III nuclear power plant in 2009. For cobalt-60 production, the reactor’s full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel burn-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. Several studies have been performed to produce cobalt-60 using adjuster rod at Wolsong nuclear power plant. This study proposed new concept for producing cobalt-60 and performed the feasibility study. Bundle typed cobalt loading concept is proposed and evaluated the feasibility to fuel management without physics and system design change. The requirement to load cobalt bundle to the core was considered and several channels are nominated. The production of cobalt-60 source is very depend on the flux level and burnup directly. But the neutron absorption characteristic of cobalt bundle is too high, so optimizing design study is needed in the future.

  13. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    Science.gov (United States)

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

    A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  14. Ferromagnetic resonance of cobalt nanoparticles used as a catalyst for the carbon nanotubes synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Duraia, El-Shazly M. [Suez Canal University, Faculty of Science, Physics Department, Ismailia (Egypt); Al-Farabi Kazakh National University, Almaty (Kazakhstan); Institute of Physics and Technology, Almaty (Kazakhstan)], E-mail: duraia_physics@yahoo.com; Abdullin, Kh.A. [Institute of Physics and Technology, Almaty (Kazakhstan)

    2009-12-15

    Catalyst is considered to be the most crucial parameter for the growth of carbon nanotubes. In this work we study the ferromagnetic resonance (FMR) spectra of the catalyst nanoclusters. Moreover we report for the first time the angle FMR studies of catalyst particles with and without CNT layer. The dependencies of the FMR spectra, X-ray diffraction (XRD) patterns, Raman spectra and morphology of the CNT layers on the growth conditions are discussed.

  15. A simple synthetic route of N-doped mesoporous carbon derived from casein extracted with cobalt ions for high rate performance supercapacitors

    International Nuclear Information System (INIS)

    Jia, Shaopei; Wang, Yanhui; Tian, Pengfei; Zhou, Shuyu; Cai, Haixia; Gao, Hongwei; Zang, Jianbing

    2017-01-01

    Highlights: •NMC is prepared by pyrolysis of cobalt-containing casein. •Cobalt-containing casein is extracted from the pure milk by cobalt ions. •The cobalt element increases the specific surface area and the N doping amount. •NMC exhibits high specific capacitance, high rate capability, and excellent cycling stability. -- Abstract: Nitrogen-doped mesoporous carbon (NMC) was synthesized via pyrolysis of cobalt-containing casein obtained by extraction from pure milk with the auxiliary of cobalt ions. The cobalt element in casein promoted specific surface area and N element doping amount of casein-derived porous carbon. The N-doped porous carbon obtained by carbonization at 800 °C (NPC-800) possessed a specific surface area of ∼886.7 m 2 g −1 , and the mesoporous size was centered at 2.7 and 7 nm. X-ray photoelectron spectroscopy analysis showed that the nitrogen content of NPC-800 was 3.29 at%. The NPC-800 was explored as a symmetric supercapacitor, which exhibited specific capacity of 380 F g −1 at a current density of 0.5 A g −1 , 218 F g −1 at a current density of 20 A g −1 , and high capacitance retention of 91.3% after charging/discharging 5,000 cycles.

  16. Computational Modeling of Cobalt-based Water Oxidation: Current Status and Future Challenges

    Science.gov (United States)

    Schilling, Mauro; Luber, Sandra

    2018-04-01

    A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysis. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability towards real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

  17. Catalytic co-pyrolysis of paper biomass and plastic mixtures (HDPE (high density polyethylene), PP (polypropylene) and PET (polyethylene terephthalate)) and product analysis

    International Nuclear Information System (INIS)

    Chattopadhyay, Jayeeta; Pathak, T.S.; Srivastava, R.; Singh, A.C.

    2016-01-01

    Catalytic co-pyrolysis of biomass and plastics (HDPE (high density polyethylene), PP (polypropylene) and PET (polyethylene terephthalate)) has been performed in a fixed-bed reactor in presence of cobalt based alumina, ceria and ceria-alumina catalysts to analyze the product distribution and selectivity. Catalysts are synthesized using co-precipitation method and characterized by BET (Brunauer–Emmett–Teller) surface area and XRD analysis. The effect of catalytic co-pyrolysis at different temperature with product distribution has been evaluated. The results have clearly shown the synergistic effect between biomass and plastics, the liquid products gradually increases forming with rise in the plastic content in the blend. Gaseous products have yielded most during pyrolysis of blend having biomass/plastics ratio of 5:1 with the presence of 40% Co/30% CeO_2/30% Al_2O_3 catalyst with hydrogen gas production touched its peak of 47 vol%. Catalytic performance enhanced with increase with the cobalt loading, with best performance attributing to 40% Co/30% CeO_2/30% Al_2O_3 catalyst. - Highlights: • Catalytic co-pyrolysis of biomass and plastics (HDPE, PP & PET) blends in fixed-bed reactor. • Strong synergistic effect evident between biomass and plastics. • Solid residue diminished with application of catalysts. • Aromatics and olefins production increases with higher plastic content. • More hydrogen production with application of catalysts with higher cobalt content.

  18. Small-Scale Coal-Biomass to Liquids Production Using Highly Selective Fischer-Tropsch Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Gangwal, Santosh K. [Southern Research Institute, Durham, NC (United States); McCabe, Kevin [Southern Research Institute, Durham, NC (United States)

    2015-04-30

    The research project advanced coal-to-liquids (CTL) and coal-biomass to liquids (CBTL) processes by testing and validating Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to convert gasifier syngas predominantly to gasoline, jet fuel and diesel range hydrocarbon liquids, thereby eliminating expensive wax upgrading operations The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream testing/demonstration. Southern Research designed, installed and commissioned a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport integrated gasifier (TRIGTM). The test-rig was designed to receive up to 5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of 2 to 4 L/day. It employed a 2-inch diameter boiling water jacketed fixed-bed heat-exchange FT reactor incorporating Chevron’s catalyst in Intramicron’s high thermal conductivity micro-fibrous entrapped catalyst (MFEC) packing to efficiently remove heat produced by the highly exothermic FT reaction.

  19. Developing high coercivity in large diameter cobalt nanowire arrays

    Science.gov (United States)

    Montazer, A. H.; Ramazani, A.; Almasi Kashi, M.; Zavašnik, J.

    2016-11-01

    Regardless of the synthetic method, developing high magnetic coercivity in ferromagnetic nanowires (NWs) with large diameters has been a challenge over the past two decades. Here, we report on the synthesis of highly coercive cobalt NW arrays with diameters of 65 and 80 nm, which are embedded in porous anodic alumina templates with high-aspect-ratio pores. Using a modified electrochemical deposition method enabled us to reach room temperature coercivity and remanent ratio up to 3000 Oe and 0.70, respectively, for highly crystalline as-synthesized hcp cobalt NW arrays with a length of 8 μm. The first-order reversal curve (FORC) analysis showed the presence of both soft and hard magnetic phases along the length of the resulting NWs. To develop higher coercive fields, the length of the NWs was then gradually reduced in order from bottom to top, thereby reaching NW sections governed by the hard phase. Consequently, this resulted in record high coercivities of 4200 and 3850 Oe at NW diameters of 65 and 80 nm, respectively. In this case, the FORC diagrams confirmed a significant reduction in interactions between the magnetic phases of the remaining sections of NWs. At this stage, x-ray diffraction (XRD) and dark-field transmission electron microscopy analyses indicated the formation of highly crystalline bamboo-like sections along the [0 0 2] direction during a progressive pulse-controlled electrochemical growth of NW arrays under optimized parameters. Our results both provide new insights into the growth process, crystalline characteristics and magnetic phases along the length of large diameter NW arrays and, furthermore, develop the performance of pure 3d transition magnetic NWs.

  20. High-throughput heterogeneous catalyst research

    Science.gov (United States)

    Turner, Howard W.; Volpe, Anthony F., Jr.; Weinberg, W. H.

    2009-06-01

    With the discovery of abundant and low cost crude oil in the early 1900's came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them. Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems. We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the

  1. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    Directory of Open Access Journals (Sweden)

    I. V. Derevich

    2017-01-01

    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  2. Cerium Modified Pillared Montmorillonite Supported Cobalt Catalysts for Fischer Tropsch Synthesis

    International Nuclear Information System (INIS)

    Ahmad, N.; Ali, Z.; Abbas, S. M.; Hussain, F.

    2015-01-01

    Fischer-Tropsch (FT) synthesis was accomplished over Al-pillared Montmorillonite supported 20 wt% Co modified with different weight% of cerium catalysts. These catalysts were prepared by impregnation method while structural characterizations of the prepared samples were performed by XRD, TPR, NH/sub 3/TPD, TGA, BET, XRF and SEM techniques. The Fischer Tropsch reaction was studied in fixed bed micro catalytic reactor at temperature range of 220, 260 and 275 degree C and at different pressure (1, 5 and 10 bars). From the activity results, it was found that by pillaring NaMMT with Al higher catalytic activity and lower methane selectivity of NaMMT was achieved. Furthermore, the results of FT synthesis reaction revealed that cerium incorporation increased the dispersion of Co/sub 3/O/sub 4/ on the surface and consequently resulted in enhanced catalytic activity. Additionally, the C/sub 5/-C/sub 12/ hydrocarbons and methane selectivity increased while C/sub 22+/ hydrocarbons selectivity was decreased over cerium modified catalysts. Higher reaction temperature (>220 degree C) resulted in significant enhancement in CO conversion and methane selectivity. Though, increase in pressure from 1 to 10 bars eventually resulted in increase in C/sub 5+/ hydrocarbons and decrease in methane and C/sub 2/-C/sub 5/ hydrocarbons selectivity. (author)

  3. Novel, high-activity hydroprocessing catalysts: Iron group phosphides

    Science.gov (United States)

    Wang, Xianqin

    A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe2P, CoP and NO, were also prepared on a silica (SiO2) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N2 BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370°C). The reactivity studies showed that the nickel phosphide (Ni2P/SiO2) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/gamma-Al 2O3 catalyst at the same conditions, Ni2P/silica had a substantially higher HDS activity (100% vs. 76%) and HDN activity (82% vs. 38%). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni2P/SiO 2, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni2P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni2P/SiO2 sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an alpha-H activation

  4. Cobalt: A vital element in the aircraft engine industry

    Science.gov (United States)

    Stephens, J. R.

    1981-01-01

    Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.

  5. Construction of Bifunctional Co/H-ZSM-5 Catalysts for the Hydrodeoxygenation of Stearic Acid to Diesel-range Alkanes.

    Science.gov (United States)

    Wu, Guangjun; Zhang, Nan; Dai, Weili; Guan, Naijia; Li, Landong

    2018-04-27

    Bifunctional Co/H-ZSM-5 zeolites were prepared by surface organometallic chemistry grafting route, namely by the stoichiometric reaction between cobaltocene and the Brønsted acid sites in zeolites, and applied to the model reaction of stearic acid catalytic hydrodeoxygenation. Cobalt species existed in the form of isolated Co2+ ions at exchange positions after grafting, transformed to CoO species on the surface of zeolite and stabilized inside zeolite channels upon calcination in air, and finally reduced to metallic cobalt species of homogeneous clusters of ca. 1.5 nm by hydrogen. During this process, the Brønsted acid sites of H-ZSM-5 zeolites could be preserved with acid strength slightly reduced. The as-prepared bifunctional catalyst exhibited a ~16 times higher activity in stearic acid hydrodeoxygenation (2.11 gSAgcat-1h-1) than the reference catalyst (0.13 gSAgcat-1h-1) prepared by solid-state ion exchange, and a high C18/C17 ratio of ~24 was achieved as well. The remarkable hydrodeoxygenation performance of bifunctional Co/H-ZSM-5 could be explained from the effective synergy between the uniformed metallic cobalt clusters and the Brønsted acid sites in H-ZSM-5 zeolite. The simplified reaction network and kinetics of stearic acid hydrodeoxygenation catalyzed by the as-prepared bifunctional Co/H-ZSM-5 zeolites were also investigated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Catalytic performance of activated carbon supported cobalt catalyst for CO2 reforming of CH4.

    Science.gov (United States)

    Zhang, Guojie; Su, Aiting; Du, Yannian; Qu, Jiangwen; Xu, Ying

    2014-11-01

    Syngas production by CO2 reforming of CH4 in a fixed bed reactor was investigated over a series of activated carbon (AC) supported Co catalysts as a function of Co loading (between 15 and 30wt.%) and calcination temperature (Tc=300, 400 or 500°C). The catalytic performance was assessed through CH4 and CO2 conversions and long-term stability. XRD and SEM were used to characterize the catalysts. It was found that the stability of Co/AC catalysts was strongly dependent on the Co loading and calcination temperature. For the loadings (25wt.% for Tc=300°C), stable activities have been achieved. The loading of excess Co (>wt.% 25) causes negative effects not only on the performance of the catalysts but also on the support surface properties. In addition, the experiment showed that ultrasound can enhance and promote dispersion of the active metal on the carrier, thus improving the catalytic performance of the catalyst. The catalyst activity can be long-term stably maintained, and no obvious deactivation has been observed in the first 2700min. After analyzing the characteristics, a reaction mechanism for CO2 reforming of CH4 over Co/AC catalyst was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. High-throughput technology for novel SO2 oxidation catalysts

    International Nuclear Information System (INIS)

    Loskyll, Jonas; Stoewe, Klaus; Maier, Wilhelm F

    2011-01-01

    We review the state of the art and explain the need for better SO 2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO 2 to SO 3 . High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO 2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO 2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO 3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations. (topical review)

  8. Recuperação de metais de catalisadores de hidrorrefino usados via fusão com KHSO4 Recovery of elements from spent hydrorefining catalysts after fusion with KHSO4

    Directory of Open Access Journals (Sweden)

    Julio Carlos Afonso

    2006-07-01

    Full Text Available This work describes a process for metal recovery from spent NiMo and CoMo/Al2O3 commercial hydrorefining catalysts. The samples were treated by fusion with potassium hydrogen sulfate (5 h, 600 ºC with a KHSO4/catalyst mass ratio of 10:1. After fusion the solid was solubilized in water (100 ºC, leaving silicon compounds as residue. Losses of nickel and cobalt may reach 16 wt% of the amount present in the sample, depending on the silicon content. Soluble metals were isolated by selective precipitation techniques (nickel, cobalt, aluminum or by solvent extraction with methyl-isobutyl ketone (molybdenum in a hydrochloric acid medium. All metals were recovered in very good yields except for nickel and cobalt in the presence of considerable amounts of silicon. Soluble wastes consist of potassium/sodium sulfates/chlorides. Solid wastes correspond to about 4 wt% of the catalyst and can be discarded in industrial dumps.

  9. Nano-aggregates of cobalt nickel oxysulfide as a high-performance electrode material for supercapacitors

    Science.gov (United States)

    Liu, Lifeng

    2013-11-01

    Nano-aggregates of cobalt nickel oxysulfide (CoNi)OxSy have been synthesized by hydrothermal processing and exhibited specific and areal capacitance as high as 592 F g-1 and 1628 mF cm-2, respectively, at a current density of 0.5 A g-1/1.375 mA cm-2. They also show high capacitance retention upon extended cycling at high rates.Nano-aggregates of cobalt nickel oxysulfide (CoNi)OxSy have been synthesized by hydrothermal processing and exhibited specific and areal capacitance as high as 592 F g-1 and 1628 mF cm-2, respectively, at a current density of 0.5 A g-1/1.375 mA cm-2. They also show high capacitance retention upon extended cycling at high rates. Electronic supplementary information (ESI) available: Experimental details; supplementary tables. See DOI: 10.1039/c3nr03533f

  10. Carbon nanotubes/cobalt sulfide composites as potential high-rate and high-efficiency supercapacitors

    Science.gov (United States)

    Chen, Chia-Ying; Shih, Zih-Yu; Yang, Zusing; Chang, Huan-Tsung

    2012-10-01

    We have prepared carbon nanotube (CNT)/cobalt sulfide (CoS) composites from cobalt nitrate, thioacetamide, and CNTs in the presence of poly(vinylpyrrolidone). CNT/CoS composites are deposited onto fluorine-doped tin oxide glass substrates and then subjected to simple annealing at 300 °C for 0.5 h to fabricate CNT/CoS electrodes. Data collected from Raman spectroscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and d-spacing reveal the changes in the CoS structures and crystalline lattices after annealing. Cyclic voltammetry results reveal that the annealed CNT/CoS composite electrodes yield values of 2140 ± 90 and 1370 ± 50 F g-1 for specific capacitance at scan rates of 10 and 100 mV s-1, respectively. To the best of our knowledge, the annealed CNT/CoS composite electrodes provide higher specific capacitance relative to other reported ones at a scan rate of 100 mV s-1. CNT/CoS composite electrodes yield a power density of 62.4 kW kg-1 at a constant discharge current density of 217.4 A g-1. With such a high-rate capacity and power density, CNT/CoS composite supercapacitors demonstrate great potential as efficient energy storage devices.

  11. Phosphorus introduction mechanism in electrodeposited cobalt films

    International Nuclear Information System (INIS)

    Kravtchenko, Jean-Francois

    1973-01-01

    The cathodic reduction of hypophosphite, phosphite and phosphate ions was studied using chrono-potentiometry and voltammetry. Then cobalt was deposited at constant current from a bath containing one of these three compounds. The current, while giving an electrodeposition of cobalt, also enhances at the same time a chemical deposition of cobalt. It is shown that high coercive forces in cobalt films are much more related to this chemical deposition than to the simple fact that the films contain some phosphorus. (author) [fr

  12. Electroplated zinc-cobalt alloy

    International Nuclear Information System (INIS)

    Carpenter, D.E.O.S.; Farr, J.P.G.

    2005-01-01

    Recent work on the deposition and use of ectrodeposited zinc-cobalt alloys is surveyed. Alloys containing lower of Nuclear quantities of cobalt are potentially more useful. The structures of the deposits is related to their chemical and mechanical properties. The inclusion of oxide and its role in the deposition mechanism may be significant. Chemical and engineering properties relate to the metallurgical structure of the alloys, which derives from the mechanism of deposition. The inclusion of oxides and hydroxides in the electroplate may provide evidence for this mechanism. Electrochemical impedance measurements have been made at significant deposition potentials, in alkaline electrolytes. These reveal a complex electrode behaviour which depends not only on the electrode potential but on the Co content of the electrolyte. For the relevant range of cathodic potential zinc-cobalt alloy electrodeposition occurs through a stratified interface. The formation of an absorbed layer ZnOH/sup +/ is the initial step, this inhibits the deposition of cobalt at low cathodic potentials, so explaining its 'anomalous deposition'. A porous layer of zinc forms on the adsorbed ZnOH/sup +/ at underpotential. As the potential becomes more cathodic, cobalt co- deposits from its electrolytic complex forming a metallic solid solution of Co in Zn. In electrolytes containing a high concentration of cobalt a mixed entity (ZnCo)/sub +/ is assumed to adsorb at the cathode from which a CoZn intermetallic deposits. (author)

  13. Extraction Of Cobalt From Spent CMB Catalyst Using Supercritical CO2

    Directory of Open Access Journals (Sweden)

    Joo S.-H.

    2015-06-01

    Full Text Available The metal extraction from spent CMB catalyst using supercritical CO2(scCO2 was investigated with single organic system, binary organic system and ternary organic system to extract metal ions. Leaching solution of spent CMB catalyst containing 389 mg L−1 Co2+, 187 mg L−1 Mn2+, 133 mg L−1 Na+, 14.97 mg L−1 Ca2+ and 13.2 mg L−1 Mg2+. The method consists of scCO2/ligands complexation process and metal extraction process at 60°C and 200bar. The result showed the Co and Mn was selectively extracted from Mg, Ca and Na in the ternary system of mixture of Cyanex272, DEA and Alamine304-I.

  14. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Science.gov (United States)

    Albayati, Talib M.; Doyle, Aidan M.

    2015-02-01

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  15. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Albayati, Talib M., E-mail: talib-albyati@yahoo.com [University of Technology, Department of Chemical Engineering (Iraq); Doyle, Aidan M., E-mail: a.m.doyle@mmu.ac.uk [Manchester Metropolitan University, Division of Chemistry and Environmental Science (United Kingdom)

    2015-02-15

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  16. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    International Nuclear Information System (INIS)

    Albayati, Talib M.; Doyle, Aidan M.

    2015-01-01

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction

  17. Highly Dispersed Alloy Catalyst for Durability

    Energy Technology Data Exchange (ETDEWEB)

    Murthi, Vivek S.; Izzo, Elise; Bi, Wu; Guerrero, Sandra; Protsailo, Lesia

    2013-01-08

    Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them with existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.

  18. Pharmacokinetics of inorganic cobalt and a vitamin B12 supplement in the Thoroughbred horse: Differentiating cobalt abuse from supplementation.

    Science.gov (United States)

    Hillyer, L L; Ridd, Z; Fenwick, S; Hincks, P; Paine, S W

    2018-05-01

    While cobalt is an essential micronutrient for vitamin B 12 synthesis in the horse, at supraphysiological concentrations, it has been shown to enhance performance in human subjects and rats, and there is evidence that its administration in high doses to horses poses a welfare threat. Animal sport regulators currently control cobalt abuse via international race day thresholds, but this work was initiated to explore means of potentially adding to application of those thresholds since cobalt may be present in physiological concentrations. To devise a scientific basis for differentiation between presence of cobalt from bona fide supplementation and cobalt doping through the use of ratios. Six Thoroughbred horses were given 10 mL vitamin B 12 /cobalt supplement (Hemo-15 ® ; Vetoquinol, Buckingham, Buckinghamshire, UK., 1.5 mg B 12 , 7 mg cobalt gluconate = 983 μg total Co) as an i.v. bolus then an i.v. infusion (15 min) of 100 mg cobalt chloride (45.39 mg Co) 6 weeks later. Pre-and post-administration plasma and urine samples were analysed for cobalt and vitamin B 12 . Urine and plasma samples were analysed for vitamin B 12 using an immunoassay and cobalt concentrations were measured via ICP-MS. Baseline concentrations of cobalt in urine and plasma for each horse were subtracted from their cobalt concentrations post-administration for the PK analysis. Compartmental analysis was used for the determination of plasma PK parameters for cobalt using commercially available software. On administration of a vitamin B 12 /cobalt supplement, the ratio of cobalt to vitamin B 12 in plasma rapidly increased to approximately 3 and then rapidly declined below a ratio of 1 and then back to near baseline over the next week. On administration of 100 mg cobalt chloride, the ratio initially exceeded 10 in plasma and then declined with the lower 95% confidence interval remaining above a ratio of 1 for 7 days. For two horses with extended sampling, the plasma ratio remained above one for

  19. Technology development for cobalt F-T catalysts. Quarterly technical progress report No. 12, July 1, 1995--September 30, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Singleton, A.H.

    1996-03-21

    The investigation of the effect of certain promoters (Fe, Pd, and Ru) on the deactivation characteristics of Co catalysts during F-T synthesis was continued during this reporting period. All catalysts were tested first at 220{degrees}C, then at higher temperatures from 240 to 280{degrees}C, while monitoring their deactivation. The choice of these promoters was based on their intrinsic ability to enhance the hydrogenation reactions while slowing down the Boudouard reaction under the conditions used in F-T synthesis. Olefin hydrogenation and CO dissociation reactions were used individually to investigate further the nature of the deactivation process of these catalyst during F-T synthesis. Hydrogenation of isobutene (IB) was carried out in the presence of CO between 120 and 180{degrees}C and atmospheric pressure. CO dissociation activities of the catalysts were measured using a pulse technique at 2.5 atm and at temperatures between 180 and 280{degrees}C with intermittent H{sub 2} bracketing at 350{degrees}C. Promotion with high loadings of Fe or Pd resulted in catalysts with relatively lower activity and higher methane selectivity. The deactivation process and rate for catalysts containing Pd or Fe were similar to those of the non-promoted or Ru-promoted alumina-supported Co catalysts tested previously. The only exception was Co.068 with 1% Pd which had adequate activity and selectivity as well as lower deactivation rate at the various temperatures tested.

  20. Fabrication, microstructure, and mechanical properties of high strength cobalt sub-micron structures

    International Nuclear Information System (INIS)

    Jin Sumin; Burek, Michael J.; Evans, Robert D.; Jahed, Zeinab; Leung, Michael C.; Evans, Neal D.; Tsui, Ting Y.

    2012-01-01

    The mechanical properties exhibited by sub-micron scale columnar structures of cobalt, fabricated by electron beam lithography and electroplating techniques, were investigated through uniaxial compression. Transmission electron microscopy analyses show these specimens possess a microstructure with sub-micron grains which are elongated and aligned near to the pillar loading axis. In addition, small nanocrystalline cobalt crystals are also present within the columnar structure. These specimens display exceptional mechanical strength comparable with both bulk polycrystalline and nanocrystalline cobalt deposited by electroplating. Size-dependent softening with shrinking sample dimensions is also observed in this work. Additionally, the strength of these sub-micron structures appears to be strain rate sensitive and comparable with bulk nanocrystalline cobalt specimens.

  1. Phosphorene Co-catalyst Advancing Highly Efficient Visible-Light Photocatalytic Hydrogen Production.

    Science.gov (United States)

    Ran, Jingrun; Zhu, Bicheng; Qiao, Shi-Zhang

    2017-08-21

    Transitional metals are widely used as co-catalysts boosting photocatalytic H 2 production. However, metal-based co-catalysts suffer from high cost, limited abundance and detrimental environment impact. To date, metal-free co-catalyst is rarely reported. Here we for the first time utilized density functional calculations to guide the application of phosphorene as a high-efficiency metal-free co-catalyst for CdS, Zn 0.8 Cd 0.2 S or ZnS. Particularly, phosphorene modified CdS shows a high apparent quantum yield of 34.7 % at 420 nm. This outstanding activity arises from the strong electronic coupling between phosphorene and CdS, as well as the favorable band structure, high charge mobility and massive active sites of phosphorene, supported by computations and advanced characterizations, for example, synchrotron-based X-ray absorption near edge spectroscopy. This work brings new opportunities to prepare highly-active, cheap and green photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Cobalt-catalyzed hydrogenation of esters to alcohols: unexpected reactivity trend indicates ester enolate intermediacy.

    Science.gov (United States)

    Srimani, Dipankar; Mukherjee, Arup; Goldberg, Alexander F G; Leitus, Gregory; Diskin-Posner, Yael; Shimon, Linda J W; Ben David, Yehoshoa; Milstein, David

    2015-10-12

    The atom-efficient and environmentally benign catalytic hydrogenation of carboxylic acid esters to alcohols has been accomplished in recent years mainly with precious-metal-based catalysts, with few exceptions. Presented here is the first cobalt-catalyzed hydrogenation of esters to the corresponding alcohols. Unexpectedly, the evidence indicates the unprecedented involvement of ester enolate intermediates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Recovery of Cobalt as Cobalt Oxalate from Cobalt Tailings Using Moderately Thermophilic Bioleaching Technology and Selective Sequential Extraction

    Directory of Open Access Journals (Sweden)

    Guobao Chen

    2016-07-01

    Full Text Available Cobalt is a very important metal which is widely applied in various critical areas, however, it is difficult to recover cobalt from minerals since there is a lack of independent cobalt deposits in nature. This work is to provide a complete process to recover cobalt from cobalt tailings using the moderately thermophilic bioleaching technology and selective sequential extraction. It is found that 96.51% Co and 26.32% Cu were extracted after bioleaching for four days at 10% pulp density. The mean compositions of the leach solutions contain 0.98 g·L−1 of Co, 6.52 g·L−1 of Cu, and 24.57 g·L−1 of Fe (III. The copper ion was then recovered by a solvent extraction process and the ferric ions were selectively removed by applying a goethite deironization process. The technological conditions of the above purification procedures were deliberately discussed. Over 98.6% of copper and 99.9% of ferric ions were eliminated from the leaching liquor. Cobalt was finally produced as cobalt oxalate and its overall recovery during the whole process was greater than 95%. The present bioleaching process of cobalt is worth using for reference to deal with low-grade cobalt ores.

  4. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    International Nuclear Information System (INIS)

    Ramesh, Thimmasandra Narayan

    2010-01-01

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co 3 O 4 . The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co 3 O 4 phase.

  5. Co, Fe and Ni catalysts supported on coke for direct coal liquefaction

    International Nuclear Information System (INIS)

    Jimenez, Jose A; Villalba, Oscar A; Rodriguez, Luis I; Hernandez, Orlando; Agamez, Yasmin Y; Dias Jose de Jesus

    2008-01-01

    Transition metal catalysts supported on coke were prepared by impregnation with a solution of complex of metal-thiourea, that is produced from salt precursors of cobalt chloride, Nickel chloride or iron sulfate and ammonium. sulphide formation on the support surface was generated by decomposition of the metal complex. The catalysts obtained were used in direct coal liquefaction of a medium volatile bituminous coal (Yerbabuena N 1) from Cundinamarca using a 250 Ml, Parr reactor at 723 K and a hydrogen-donor solvent. The catalytic results show, for all samples, both a good coal conversion and an enhancement of the yield of oils, this indicates that the proposed preparation method of catalyst is effective and that eventually the H 2 S sulphidation conventional process could be replaced

  6. Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

    Science.gov (United States)

    Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

    2017-05-01

    Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH) 2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Advanced development of catalysts by using the high-brilliance synchrotron radiation in SPring-8

    International Nuclear Information System (INIS)

    2006-10-01

    The advanced development of catalysts by using the high-brilliance synchrotron radiation in SPring-8 is described: (1) the industrial use of SPring-8, (2) the analytical methods of catalyst using SPring-8 (XAFS, powder X-ray diffraction, thin film X-ray scattering, X-ray imaging, infrared analysis, X-ray fluorescence analysis, and photoelectron spectroscopy etc.), (3) the history of synchrotron radiation and catalyst investigations, (4) the new advanced measuring methods of catalyst using synchrotron radiation (various X-ray spectroscopic methods, and application of XAFS to highly-disperse systems of catalyst), and (5) the new advanced development of catalysts using synchrotron radiation and its applications (motor-car catalysts, light catalysts, fuel cells, nanotechnology, and trace amounts of catalyst in wastes). (M.H.)

  8. Following the Formation of Active Co(III) Sites in Cobalt Substituted Aluminophosphates Catalysts by In-Situ Combined UV-VIS/XAFS/XRD Technique

    International Nuclear Information System (INIS)

    Sankar, Gopinathan; Fiddy, Steven; Harvey, Ian; Hayama, Shusaku; Bushnell-Wye, Graham; Beale, Andrew M.

    2007-01-01

    Cobalt substituted aluminophosphates, CoAlPO-34 (Chabazite structure) and DAF-8 (Phillipsite structure) were investigated by in situ combined XRD/EXAFS/UV-VIS technique. In-situ combined XRD, Co K-edge EXAFS and UV-Vis measurements carried out during the calcination process reveal that CoAlPO-34 containing 10 wt percent cobalt is stable and the cobalt ions are converted from Co(II) in the as synthesised form to Co(III); DAF-8 containing about 25 percent cobalt is not stable and does not show change in oxidation state

  9. Blood doping by cobalt. Should we measure cobalt in athletes?

    Directory of Open Access Journals (Sweden)

    Guidi Gian

    2006-07-01

    Full Text Available Abstract Background Blood doping is commonplace in competitive athletes who seek to enhance their aerobic performances through illicit techniques. Presentation of the hypothesis Cobalt, a naturally-occurring element with properties similar to those of iron and nickel, induces a marked and stable polycythemic response through a more efficient transcription of the erythropoietin gene. Testing the hypothesis Although little information is available so far on cobalt metabolism, reference value ranges or supplementation in athletes, there is emerging evidence that cobalt is used as a supplement and increased serum concentrations are occasionally observed in athletes. Therefore, given the athlete's connatural inclination to experiment with innovative, unfair and potentially unhealthy doping techniques, cobalt administration might soon become the most suited complement or surrogate for erythropoiesis-stimulating substances. Nevertheless, cobalt administration is not free from unsafe consequences, which involve toxic effects on heart, liver, kidney, thyroid and cancer promotion. Implications of the hypothesis Cobalt is easily purchasable, inexpensive and not currently comprehended within the World Anti-Doping Agency prohibited list. Moreover, available techniques for measuring whole blood, serum, plasma or urinary cobalt involve analytic approaches which are currently not practical for antidoping laboratories. Thus more research on cobalt metabolism in athletes is compelling, along with implementation of effective strategies to unmask this potentially deleterious doping practice

  10. Basic study of catalyst aging in the H-coal process

    Energy Technology Data Exchange (ETDEWEB)

    Cable, T.L.; Massoth, F.E.; Thomas, M.G.

    1985-04-01

    Samples of CoMo/Al/sub 2/O/sub 3/ catalysts used in an H-coal process demonstration run were studied to determine causes of catalyst deactivation. Physical and surface properties of the aged and regenerated catalysts were examined. Model compounds were used to assess four catalyst activity functions, viz., hydrodesulfurization (HDS), hydrogenation, cracking and hydrodeoxygenation (HDO). Other tests were performed to study the effects of coke and metals separately on the four catalyst activity functions. Catalyst coke content and metal deposits first increased rapidly, then more gradually with exposure time in the process run. Surface area and pore volume markedly decreased with exposure time. Catalyst activities of aged catalysts showed a rapid decline with exposure time. One-day exposure to coal resulted in significant losses in HDS and hydrogenation activities and nearly complete loss in cracking and HDO activities. Although metal deposits caused some permanent catalyst deactivation, coke had a much greater effect. Regenerated catalysts showed less recovery of catalytic activity as processing time increased. These results agreed well with product inspections from the process run. Oxygen chemisorption on aged-regenerated catalysts decreased with catalyst exposure time, indicating a significant loss of active sites. However, ESCA results showed no evidence of extensive sintering of the active MoS/sub 2/ phase. Permanent deactivation of the longer-time exposed catalysts can be ascribed, at least partly, to lateral growth of the active molybdenum sulfide phase. In addition, some loss in cobalt promotion occurred early in the process, which may account for the rapid loss in HDS and HDO activity in regenerated catalysts. 24 references.

  11. Novel catalytic route to bulk production of high purity carbon nanotube

    International Nuclear Information System (INIS)

    Dasgupta, Kinshuk; Venugopalan, Ramani; Dey, G. K.; Sathiyamoorthy, D.

    2008-01-01

    Carbon nanotubes have been synthesized by catalytic chemical vapour deposition of acetylene diluted with argon using three different catalysts, namely, nickel formate, cobalt formate and ferrocene. The synthesis was carried out at 700 deg. C in a quartz reactor for 30 minutes. Thermal analysis was carried out in order to determine the yield of the nanotube. It was found that the deposit contains 86% nanotube, with nickel-based catalyst, which was the maximum. The yield of nanotube was 71 times that of the nickel loading. The TEM images reveal helical type of nanotubes with iron catalyst while cobalt and nickel catalysts yielded straight nanotubes. This technique can be explored for the bulk production of carbon nanotube in an economic way

  12. Direct Fabrication of Carbon Nanotubes STM Tips by Liquid Catalyst-Assisted Microwave Plasma-Enhanced Chemical Vapor Deposition

    Directory of Open Access Journals (Sweden)

    Fa-Kuei Tung

    2009-01-01

    Full Text Available Direct and facile method to make carbon nanotube (CNT tips for scanning tunneling microscopy (STM is presented. Cobalt (Co particles, as catalysts, are electrochemically deposited on the apex of tungsten (W STM tip for CNT growth. It is found that the quantity of Co particles is well controlled by applied DC voltage, concentration of catalyst solution, and deposition time. Using optimum growth condition, CNTs are successfully synthesized on the tip apex by catalyst-assisted microwave-enhanced chemical vapor deposition (CA-MPECVD. A HOPG surface is clearly observed at an atomic scale using the present CNT-STM tip.

  13. Electro-catalysts for hydrogen production from ethanol for use in SOFC anodes

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Marcos Aurelio da; Paz Fiuza, Raigenis da; Guedes, Bruna C.; Pontes, Luiz A.; Boaventura, Jaime Soares [UFBA, Salvador, Bahia (Brazil). Energy and Materials Science Group

    2010-07-01

    Nickel and cobalt catalysts, supported on YSZ, were prepared by wet impregnation, with and without citric acid; the metal load was 10 and 35% by weight. The catalyst composition was studied by XRF, XPS and SEM-EDS. At low metal concentration, the results of these techniques presented comparables figures; at high concentration, SEM-EDS suggested a non-uniform distribution. The analysis showed that the solids were mixed oxides and formed an alloy after reduction. The surface passivation was possible under controlled conditions. The catalytic test with the steam reforming of ethanol indicated that the metal load had almost no effect on the catalytic activity, but decreased its selectivity. Afterwards, a unitary SOFC was prepared with deposition of the cathode layer. AFM and EIS were used for the characterization of SOFC components. They showed that the electro-catalyst surface was almost all covered with the metal phase, including the large pore walls of the anode. The YSZ phase dominates the material conductance of the complete SOFC assembly (anode/electrolyte/cathode). The unitary SOFC was tested with hydrogen, gaseous ethanol or natural gas; the SOFC operating with ethanol and hydrogen fuel presented virtually no over-potential. (orig.)

  14. MAGNETO-CHEMICAL CHARACTER STUDIES OF NOVEL Fe CATALYSTS FOR COAL LIQUEFACTION

    Energy Technology Data Exchange (ETDEWEB)

    Murty A. Akundi; Jian H. Zhang; A.N. Murty; S.V. Naidu

    2002-04-01

    The objectives of the present study are: (1) To synthesize iron catalysts: Fe/MoO{sub 3}, and Fe/Co/MoO{sub 3} employing two distinct techniques: Pyrolysis with organic precursors and Co-precipitation of metal nitrates; (2) To investigate the magnetic character of the catalysts before and after exposure to CO and CO+H{sub 2} by (a) Mossbauer study of Iron (b) Zerofield Nuclear Magnetic Resonance study of Cobalt, and (c) Magnetic character of the catalyst composite; (3) To study the IR active surface species of the catalyst while stimulating (CO--Metal, (CO+H{sub 2})--Metal) interactions, by FTIR Spectroscopy; and (4) To analyze the catalytic character (conversion efficiency and product distribution) in both direct and indirect liquefaction Process and (5) To examine the correlations between the magnetic and chemical characteristics. This report presents the results of our investigation on (a) the effect of metal loading (b) the effect of intermetallic ratio and (c) the effect of catalyst preparation procedure on (i) the magnetic character of the catalyst composite (ii) the IR active surface species of the catalyst and (iii) the catalytic yields for three different metal loadings: 5%, 15%, and 25% (nominal) for three distinct intermetallic ratios (Fe/Co = 0.3, 1.5, 3.0).

  15. Phase composition and catalytic properties of oxide multicomponent molybdenum-containing catalysts for partial oxidation of propylene

    International Nuclear Information System (INIS)

    Malakhov, V.V.; Vlasov, A.A.; Boldyreva, N.N.; Dovlitova, L.S.; Plyasova, L.M.; Andrushkevich, T.V.; Kuznetsova, T.G.

    1996-01-01

    The catalytic properties and phase composition of multicomponent molybdenum-containing catalyst treated under various redox conditions have been studied. The phase composition has been considered by the methods of X-ray phase analysis and noncalibrated methods of differentiating dissolution (DD). Using the DD method the data on element composition, stoichiometry and quantitative content of phases of complex molybdates have been obtained for the first time. Data on modification of basic phases of the catalyst-cobalt and iron molybdates - by other cations from its composition suggest that the mechanism of action of the multicomponent catalyst is defined by the properties of one or several formed modified phases combining all the functions of an effective catalyst. 18 refs., 7 figs., 2 tabs

  16. Cobalt reduction of NSSS valve hardfacings for ALARA

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Joo Hak; Lee, Sang Sub [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1994-07-01

    This report informs NSSS designer that replacement of materials is one of the major means of ALARA implementation, and describes that NSSS valves with high-cobalt hardfacing are significant contributors to post-shutdown radiation fields caused by activation of cobalt-59 to cobalt-60. Generic procedures for implementing cobalt reduction programs for valves are presented. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. The nuclear safety issues involved with changing valve hardfacing materials are discussed. The common methods used to deposit hardfacing materials are described together with an explanation of the wear measurements. Wear resistance, corrosion resistance, friction coefficient, and mechanical properties of candidate hardfacing alloys are given. World-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The use of low-cobalt or cobalt-free alloys in other nuclear plant components is described. 17 figs., 38 tabs., 18 refs. (Author).

  17. Cobalt reduction of NSSS valve hardfacings for ALARA

    International Nuclear Information System (INIS)

    Kim, Joo Hak; Lee, Sang Sub

    1994-07-01

    This report informs NSSS designer that replacement of materials is one of the major means of ALARA implementation, and describes that NSSS valves with high-cobalt hardfacing are significant contributors to post-shutdown radiation fields caused by activation of cobalt-59 to cobalt-60. Generic procedures for implementing cobalt reduction programs for valves are presented. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. The nuclear safety issues involved with changing valve hardfacing materials are discussed. The common methods used to deposit hardfacing materials are described together with an explanation of the wear measurements. Wear resistance, corrosion resistance, friction coefficient, and mechanical properties of candidate hardfacing alloys are given. World-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The use of low-cobalt or cobalt-free alloys in other nuclear plant components is described. 17 figs., 38 tabs., 18 refs. (Author)

  18. High throughput experimentation for the discovery of new catalysts

    International Nuclear Information System (INIS)

    Thomson, S.; Hoffmann, C.; Johann, T.; Wolf, A.; Schmidt, H.-W.; Farrusseng, D.; Schueth, F.

    2002-01-01

    Full text: The use of combinatorial chemistry to obtain new materials has been developed extensively by the pharmaceutical and biochemical industries, but such approaches have been slow to impact on the field of heterogeneous catalysis. The reasons for this lie in with difficulties associated in the synthesis, characterisation and determination of catalytic properties of such materials. In many synthetic and catalytic reactions, the conditions used are difficult to emulate using High Throughput Experimentation (HTE). Furthermore, the ability to screen these catalysts simultaneously in real time, requires the development and/or modification of characterisation methods. Clearly, there is a need for both high throughput synthesis and screening of new and novel reactions, and we describe several new concepts that help to achieve these goals. Although such problems have impeded the development of combinatorial catalysis, the fact remains that many highly attractive processes still exist for which no suitable catalysts have been developed. The ability to decrease the tiFme needed to evaluate catalyst is therefore essential and this makes the use of high throughput techniques highly desirable. In this presentation we will describe the synthesis, catalytic testing, and novel screening methods developed at the Max Planck Institute. Automated synthesis procedures, performed by the use of a modified Gilson pipette robot, will be described, as will the development of two 16 and 49 sample fixed bed reactors and two 25 and 29 sample three phase reactors for catalytic testing. We will also present new techniques for the characterisation of catalysts and catalytic products using standard IR microscopy and infrared focal plane array detection, respectively

  19. High performance liquid chromatographic determination of vanadium in crude oils and cobalt and iron in pharmaceutical preparations

    International Nuclear Information System (INIS)

    Khuhawar, M.Y.; Lanjwani, S.N.; Khaskhely, G.Q.

    1993-01-01

    High performance liquid Chromatographic (HPLC) method has ben developed for the determination of vanadium in crude oils, based on acid decomposition of oils, followed by complexation with bis (salicylaldehyde) tetramethyl ethylenediamine (H2SA2Ten). The complex is extracted in organic phase and is separated from copper and nickel using normal phase HPLC column. Detection is achieved using spectrophtmetric detector. The vanadium in oil is obtained at sub microgram/g level. Similarly cobalt(II), cobalt(III) and iron(II) are separated on reversed phase HPLC column. Pre column derivatization is used to develop HPLC method for the determination of cobalt and iron in pharmaceutical preparations. Finally results are compared using atomic absorption spectrometer. (author)

  20. 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

  1. Cobalt-60 production in CANDU reactors

    International Nuclear Information System (INIS)

    Ross, Michel; Lemire, Christian

    2002-01-01

    CANDU reactors can produce cobalt-60 very efficiently and with an interesting return on investment. This paper discusses what is needed to convert a CANDU reactor into a cobalt-60 producer: what are the different phases, the safety studies required, the physical modifications needed, and what is the minimum involvement of the utility owning the plant. The past ten years of experience of Hydro-Quebec as a cobalt-60 producer will be reviewed, including the management of the risk of both incident and electricity generation loss, and including the benefits for the utility and its personnel. Originally a simple metal used for centuries as a pigment, cobalt-59 today is transformed into cobalt-60, a radioactive element of unprecedented value. Well known in medicine for cancer treatment, cobalt-60 is also used to sterilize a wide range of disposable medical products used in hospitals and to sanitize pharmaceutical and cosmetic products. Cobalt-60 is proving to be a new and effective solution, in the food sector, for preserving harvests and controlling food-borne diseases, or to advantageously replace certain gases and chemical products which are suspected of being harmful or carcinogenic. There are also other applications, such as: hardening of some plastics, treatment of sewage sludge and elimination of harmful insect populations. With a half-life of 5,3 years, cobalt-60 is a metal not found in nature. It is a radioactive isotope produced by exposing stable nuclei of cobalt-59 to neutrons. One of the best places to find such an important neutron source is a nuclear reactor. High energy gamma rays are then emitted during the process of radioactive decay, where cobalt-60 seeks again its stable state

  2. Catalysts for the production of hydrocarbons from carbon monoxide and water

    Science.gov (United States)

    Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

    1985-11-06

    A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

  3. Cobalt release from inexpensive jewellery

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten Stendahl; Menné, Torkil

    2010-01-01

    . Conclusions: This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future......Objectives: The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. Methods: The cobalt spot test was used to assess cobalt release from all items...

  4. Process optimization and properties of magnetically hard cobalt carbide nanoparticles via modified polyol method

    International Nuclear Information System (INIS)

    Zamanpour, Mehdi; Bennett, Steven P.; Majidi, Leily; Chen, Yajie; Harris, Vincent G.

    2015-01-01

    Highlights: • High-coercivity cobalt carbides were synthesized by polyol method. • No rare earth elements were used during synthesis process. • Process parameters (reaction temperature, precursors’ concentrations, surfactants and reaction duration) were studied/optimized. • Process was scaled-up to synthesis more than 5 g powders per batch. - Abstract: Cobalt carbide magnetic nanoparticles were successfully synthesized via a modified polyol process without using a rare-earth catalyst during the synthesis process. The present results show admixtures of Co 2 C and Co 3 C phases possessing magnetization values exceeding 47 emu/g and coercivity values exceeding 2.3 kOe at room temperature. Moreover, these experiments have illuminated the important role of the reaction temperature, hydroxyl ion concentrations and the reaction duration on the crystallographic structure and magnetic properties of the nanoparticles. The crystallographic structure and particle size of the Co x C nanoparticles were characterized by X-ray diffractometry and scanning electron microscopy. Vibrating sample magnetometry was used to determine magnetic properties. Scale-up of synthesis to more than 5 g per batch was demonstrated with no significant degradation of magnetic properties

  5. Process optimization and properties of magnetically hard cobalt carbide nanoparticles via modified polyol method

    Energy Technology Data Exchange (ETDEWEB)

    Zamanpour, Mehdi; Bennett, Steven P. [Center for Microwave Magnetic Materials and Integrated Circuits (CM3IC), Northeastern University, Boston, MA 02115 (United States); Majidi, Leily [Department of Mechanical and Industrial Engineering, Northeastern University, Boston, MA 02115 (United States); Chen, Yajie [Center for Microwave Magnetic Materials and Integrated Circuits (CM3IC), Northeastern University, Boston, MA 02115 (United States); Harris, Vincent G. [Center for Microwave Magnetic Materials and Integrated Circuits (CM3IC), Northeastern University, Boston, MA 02115 (United States); Department of Electrical and Computer Engineering, Northeastern University, Boston, MA 02115 (United States)

    2015-03-15

    Highlights: • High-coercivity cobalt carbides were synthesized by polyol method. • No rare earth elements were used during synthesis process. • Process parameters (reaction temperature, precursors’ concentrations, surfactants and reaction duration) were studied/optimized. • Process was scaled-up to synthesis more than 5 g powders per batch. - Abstract: Cobalt carbide magnetic nanoparticles were successfully synthesized via a modified polyol process without using a rare-earth catalyst during the synthesis process. The present results show admixtures of Co{sub 2}C and Co{sub 3}C phases possessing magnetization values exceeding 47 emu/g and coercivity values exceeding 2.3 kOe at room temperature. Moreover, these experiments have illuminated the important role of the reaction temperature, hydroxyl ion concentrations and the reaction duration on the crystallographic structure and magnetic properties of the nanoparticles. The crystallographic structure and particle size of the Co{sub x}C nanoparticles were characterized by X-ray diffractometry and scanning electron microscopy. Vibrating sample magnetometry was used to determine magnetic properties. Scale-up of synthesis to more than 5 g per batch was demonstrated with no significant degradation of magnetic properties.

  6. Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

    Science.gov (United States)

    Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

    2015-02-01

    Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression. Copyright © 2014. Published by Elsevier B.V.

  7. Production of perovskite catalysts on ceramic monoliths with nanoparticles for dual fuel system automobiles

    International Nuclear Information System (INIS)

    Khanfekr, A.; Arzani, K.; Nemati, A.; Hosseini, M.

    2009-01-01

    (Lanthanum, Cerium)(Iron, Manganese, Cobalt, Palladium)(Oxygen) 3 ,-Perovskite catalyst was prepared by the citrate route and deposited on ceramic monoliths via dip coating procedure. The catalyst was applied on a car with X U 7 motors and the amount of emission was monitored with vehicle emission test systems in Sapco company. The results were compared with the imported catalyst with noble metals such as Palladium, Platinum and Rhodium by Iran Khodro company based on the Euro III standards. The catalysts were characterized by specific surface area measurements, scanning electron microscopy, X-ray diffraction, line scan and map. In the results, obtained in the home made sample, the amount of carbon monoxide, nitrogen oxides and hydrocarbons were lower than imported catalyst with Iran Khodro company with nobel metals. The illustration shows nano particles size on coat. The microstructure evaluation showed that the improved properties can be related to the existence of nano particles on coating

  8. Immobilised carbon nanotubes as carrier for Co-Fischer-Tropsch synthesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Thiessen, J.; Rose, A.; Kiendl, I.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering; Curulla-Ferre, D. [Total S.A., Gas and Power, Paris La Defense (France)

    2011-07-01

    A possibility to immobilise carbon nanotubes (CNT) to make them applicable in a technical scale fixed bed reactor is studied. The approach to fabricate millimetre scale composites containing CNT presented in this work is to confine the nano-carbon in macro porous ceramic particles. Thus CNT were grown on the inner surface of silica and alumina pellets and spheres, respectively. Cobalt nano particles were successfully deposited on the carbon surface inside the two types of ceramic carriers and the systems were tested in Fischer - Tropsch synthesis (FTS). The cobalt mass related activity of these novel catalysts is similar to a conventional system. The selectivities of the Co/CNT/ceramic composites were compared with non supported CNT and carbon nanofibres (CNF). (orig.)

  9. Cobalt-60 production in CANDU power reactors

    International Nuclear Information System (INIS)

    Malkoske, G.R.; Norton, J.L.; Slack, J.

    2002-01-01

    elements in the core. For cobalt-60 production, the reactor's full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel bum-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. (author)

  10. High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane.

    Directory of Open Access Journals (Sweden)

    Faris A J Al-Doghachi

    Full Text Available A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.

  11. Production of High-Hydrogen Content Coal-Derived Liquids [Part 2 of 3

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Bergin

    2011-03-30

    The primary goal of this project has been to evaluate and compare the effect of the intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (FT) synthesis using coal-derived syngas. Crude oil, especially heavy, high-sulfur crude, is no longer the appropriate source for the additional, or marginal, amounts of middle-distillate fuels needed to meet growing US and world demand for diesel and jet fuels. Only about 1/3 of the marginal crude oil barrel can be made into diesel and jet fuels. The remaining 2/3 contributes further to global surpluses of by-products. FT can produce these needed marginal, low-sulfur middle-distillate fuels more efficiently, with less environmental impact, and from abundant US domestic resources. Cobalt FT catalyst is more efficient, and less expensive overall, than iron FT catalyst. Mechanisms of cobalt FT catalyst functioning, and poisoning, have been elucidated. Each of these primary findings is amplified by several secondary findings, and these are presented, and verified in detail. The most effective step the United States can take to begin building toward improved long-term national energy security, and to reduce dependence, over time, on imported crude oil from unfriendly and increasingly unstable areas of the world, is to begin producing additional, or marginal amounts of, middle-distillate-type fuels, such as ultralow sulfur diesel (ULSD) and jet fuel (not gasoline) from US domestic resources other than petroleum. FT synthesis of these middle distillate fuels offers the advantage of being able to use abundant and affordable US coal and biomass as the primary feedstocks. Use of the cobalt FT catalyst system has been shown conclusively to be more effective and less expensive than the use of iron FT catalyst with syngas derived from coal, or from coal and biomass combined. This finding is demonstrated in detail for the initial case of a relatively small FT plant of about 2000 barrels per day based upon coal

  12. Production of High-Hydrogen Content Coal-Derived Liquids [Part 3 of 3

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Bergin

    2011-03-30

    The primary goal of this project has been to evaluate and compare the effect of the intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (FT) synthesis using coal-derived syngas. Crude oil, especially heavy, high-sulfur crude, is no longer the appropriate source for the additional, or marginal, amounts of middle-distillate fuels needed to meet growing US and world demand for diesel and jet fuels. Only about 1/3 of the marginal crude oil barrel can be made into diesel and jet fuels. The remaining 2/3 contributes further to global surpluses of by-products. FT can produce these needed marginal, low-sulfur middle-distillate fuels more efficiently, with less environmental impact, and from abundant US domestic resources. Cobalt FT catalyst is more efficient, and less expensive overall, than iron FT catalyst. Mechanisms of cobalt FT catalyst functioning, and poisoning, have been elucidated. Each of these primary findings is amplified by several secondary findings, and these are presented, and verified in detail. The most effective step the United States can take to begin building toward improved long-term national energy security, and to reduce dependence, over time, on imported crude oil from unfriendly and increasingly unstable areas of the world, is to begin producing additional, or marginal amounts of, middle-distillate-type fuels, such as ultralow sulfur diesel (ULSD) and jet fuel (not gasoline) from US domestic resources other than petroleum. FT synthesis of these middle distillate fuels offers the advantage of being able to use abundant and affordable US coal and biomass as the primary feedstocks. Use of the cobalt FT catalyst system has been shown conclusively to be more effective and less expensive than the use of iron FT catalyst with syngas derived from coal, or from coal and biomass combined. This finding is demonstrated in detail for the initial case of a relatively small FT plant of about 2000 barrels per day based upon coal

  13. Production of High-Hydrogen Content Coal-Derived Liquids [Part 1 of 3

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Bergin

    2011-03-30

    The primary goal of this project has been to evaluate and compare the effect of the intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (FT) synthesis using coal-derived syngas. Crude oil, especially heavy, high-sulfur crude, is no longer the appropriate source for the additional, or marginal, amounts of middle-distillate fuels needed to meet growing US and world demand for diesel and jet fuels. Only about 1/3 of the marginal crude oil barrel can be made into diesel and jet fuels. The remaining 2/3 contributes further to global surpluses of by-products. FT can produce these needed marginal, low-sulfur middle-distillate fuels more efficiently, with less environmental impact, and from abundant US domestic resources. Cobalt FT catalyst is more efficient, and less expensive overall, than iron FT catalyst. Mechanisms of cobalt FT catalyst functioning, and poisoning, have been elucidated. Each of these primary findings is amplified by several secondary findings, and these are presented, and verified in detail. The most effective step the United States can take to begin building toward improved long-term national energy security, and to reduce dependence, over time, on imported crude oil from unfriendly and increasingly unstable areas of the world, is to begin producing additional, or marginal amounts of, middle-distillate-type fuels, such as ultralow sulfur diesel (ULSD) and jet fuel (not gasoline) from US domestic resources other than petroleum. FT synthesis of these middle distillate fuels offers the advantage of being able to use abundant and affordable US coal and biomass as the primary feedstocks. Use of the cobalt FT catalyst system has been shown conclusively to be more effective and less expensive than the use of iron FT catalyst with syngas derived from coal, or from coal and biomass combined. This finding is demonstrated in detail for the initial case of a relatively small FT plant of about 2000 barrels per day based upon coal

  14. Efeito do teor metálico em catalisadores Co/Al2O3 aplicados à reação de reforma a vapor de etanol Effect of metal load in Co/Al2o3 catalysts for ethanol steam reforming

    Directory of Open Access Journals (Sweden)

    Rudye K. S. Santos

    2005-08-01

    Full Text Available The development of cobalt catalysts to produce hydrogen from ethanol is the goal of this investigation. Co/Al2O3 catalysts were prepared by impregnation and characterized by atomic absorption, nitrogen adsorption, X-ray diffraction, Raman spectroscopy, temperature programmed reduction and carbon analysis. The catalysts contained Co3O4 oxide and Co3+ and Co2+ species interacting with alumina. The cobalt load affects the crystal size and the crystalline structure and higher Co loads influence the reaction mechanism, changing the selectivity of the catalysts, decreasing the amount of CO produced and avoiding the formation of products catalyzed by the support. The ethanol conversion was 50-70% with 10-<1% of CO in the hydrogen.

  15. Fischer-Tropsch synthesis: study of the promotion of Pt on the reduction property of Co/Al2O3 catalysts by in situ EXAFS of Co K and Pt LIII edges and XPS

    International Nuclear Information System (INIS)

    Jacobs, G.; Chaney, J.A.; Patterson, P.M.; Das, T.K.; Maillot, J.C.; Davis, B.H.

    2004-01-01

    The addition of platinum metal to cobalt/alumina-based Fischer-Tropsch synthesis (FTS) catalysts increases both the reduction rate and, consequently, the density of active cobalt sites. Platinum also lowers the temperature of the two-step conversion of cobalt oxide to cobalt metal observed in temperature programmed reduction (TPR) as Co 3 O 4 to CoO and CoO to Co 0 . The interaction of the alumina support with cobalt oxide ultimately determines the active site density of the catalyst surface. This interaction can be controlled by varying the cobalt loading and dispersion, selecting supports with differing surface areas or pore sizes, or changing the noble metal promoter. However, the active site density is observed to depend primarily on the cluster size and extent of reduction, and there is a direct relationship between site density and FTS rate. In this work, in situ extended X-ray absorption fine structure (EXAFS) at the L III edge of Pt was used to show that isolated Pt atoms interact with supported cobalt clusters without forming observable Pt-Pt bonds. K-edge EXAFS was also used to verify that the cobalt cluster size increases slightly for those systems with Pt promotion. X-ray absorption near-edge spectroscopy (XANES) was used to examine the remaining cobalt clusters after the first stage of TPR, and it revealed that the species were almost entirely cobalt (II) oxide. After the second stage of TPR to form cobalt metal, a residual oxide persists in the sample, and this oxide has been identified as cobalt (II) aluminate using X-ray photoelectron spectroscopy (XPS). Sequential in situ reduction of promoted and unpromoted systems was also monitored through XPS, and Pt was seen to increase the extent of cobalt reduction by a factor of two. (orig.)

  16. Cobalt: for strength and color

    Science.gov (United States)

    Boland, Maeve A.; Kropschot, S.J.

    2011-01-01

    Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

  17. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    Science.gov (United States)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil; Lidén, Carola; Julander, Anneli; Møller, Per; Johansen, Jeanne Duus

    2010-08-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure. The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. The cobalt spot test was used to assess cobalt release from all items. Microstructural characterization was made using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). Cobalt release was found in 4 (1.1%) of 354 items. All these had a dark appearance. SEM/EDS was performed on the four dark appearing items which showed tin-cobalt plating on these. This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future. Industries may not be fully aware of the potential cobalt allergy problem.

  18. Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene.

    Science.gov (United States)

    Petis, Stephen M; Vasarhelyi, Edward M; Lanting, Brent A; Howard, James L; Naudie, Douglas D R; Somerville, Lyndsay E; McCalden, Richard W

    2016-02-01

    The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan-Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0-10.6) years for cobalt-chrome and 7.8 (range 2.1-10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%-97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%-99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%-98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%-99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up.

  19. Silica nanoparticles as a highly efficient catalyst for the one-pot ...

    African Journals Online (AJOL)

    Silica nanoparticles as a highly efficient catalyst for the one-pot synthesis of sterically congested ... Bulletin of the Chemical Society of Ethiopia ... 42 nm) as a catalyst under solvent free conditions at room temperature is described. The ease of ...

  20. Cobalt

    International Nuclear Information System (INIS)

    Stolyarova, I.A.; Bunakova, N.Yu.

    1983-01-01

    The neutron-activation method for determining cobalt in rocks, polymetallic and iron ores and rockforming minerals at 2x10 -6 -5x10 -3 % content is developed. Cobalt determination is based on the formation under the effect of thermal neutrons of nuclear reactor of the 60 Co radioactive isotope by the 59 Co (n, γ) 60 Co reaction with radiation energy of the most intensive line of 1333 keV. Cobalt can be determined by the scheme of the multicomponent analysis from the sample with other elements. Co is determined in the solution after separation of all determinable by the scheme elements. The 60 Co intensity is measured by the mUltichannel gamma-spectrometer with Ge(Li)-detector

  1. Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions

    DEFF Research Database (Denmark)

    Kim, Jiwhan; Roh, Chi-Woo; Sahoo, Suman Kalyan

    2018-01-01

    Single atomic Pt catalyst can offer efficient utilization of the expensive platinum and provide unique selectivity because it lacks ensemble sites. However, designing such a catalyst with high Pt loading and good durability is very challenging. Here, single atomic Pt catalyst supported on antimony...... functional theory calculations show that replacing Sb sites with Pt atoms in the bulk phase or at the surface of SbSn or ATO is energetically favorable. The Pt1/ATO shows superior activity and durability for formic acid oxidation reaction, compared to a commercial Pt/C catalyst. The single atomic Pt...... structure is retained even after a harsh durability test, which is performed by repeating cyclic voltammetry in the range of 0.05–1.4 V for 1800 cycles. A full cell is fabricated for direct formic acid fuel cell using the Pt1/ATO as an anode catalyst, and an order of magnitude higher cell power is obtained...

  2. Piezoelectric properties and thermal stabilities of cobalt-modified potassium bismuth titanate

    International Nuclear Information System (INIS)

    Guo, Zhen-Lei; Wang, Chun-Ming; Zhao, Tian-Long; Yu, Si-Long; Cao, Zhao-Peng

    2013-01-01

    The cobalt-modified potassium bismuth titanate (K 0.5 Bi 4.5 Ti 4 O 15 , KBT) piezoelectric ceramics have been prepared using conventional solid–state reaction. X-ray diffraction analysis revealed that the cobalt-modified KBT ceramics have a pure four-layer (m = 4) Aurivillius-type structure. The dielectric, ferroelectric, and piezoelectric properties of cobalt-modified KBT ceramics were investigated in detail. The piezoelectric activities of KBT ceramics were significantly improved by the cobalt modification. The reasons for piezoelectric activities enhancement with cobalt modification were given. The piezoelectric coefficient d 33 and Curie temperature T c for the 5 mol% cobalt-modified KBT ceramics (KBT-Co5) were found to be 28 pC/N and 575 °C, respectively. The DC resistivity, frequency constants (N p and N t ), and electromechanical properties at elevated temperature were investigated, indicating the cobalt-modified KBT piezoelectric ceramics possess stable piezoelectric properties up to 500 °C. The results show the cobalt-modified KBT ceramics are potential materials for high temperature piezoelectric applications. - Highlights: • We examine the piezoelectric properties of the cobalt-modified K 0.5 Bi 4.5 Ti 4 O 15 . • A high level of piezoelectric activities (d 33 = 28 pC/N) are obtained. • High Curie temperature (T c = 575 °C) is acquired for the optimal composition. • The Co-modified K 0.5 Bi 4.5 Ti 4 O 15 is promising as high temperature materials

  3. Cobalt release from implants and consumer items and characteristics of cobalt sensitized patients with dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Menne, Torkil; Liden, Carola

    2012-01-01

    -containing dental alloys and revised hip implant components.Results. Six of eight dental alloys and 10 of 98 revised hip implant components released cobalt in the cobalt spot test, whereas none of 50 mobile phones gave positive reactions. The clinical relevance of positive cobalt test reactions was difficult......-tested dermatitis patients in an attempt to better understand cobalt allergy.Materials and methods. 19 780 dermatitis patients aged 4-99 years were patch tested with nickel, chromium or cobalt between 1985 and 2010. The cobalt spot test was used to test for cobalt ion release from mobile phones as well as cobalt...

  4. Multi-component titanium–copper–cobalt- and niobium nanostructured oxides as catalysts for ethyl acetate oxidation

    Czech Academy of Sciences Publication Activity Database

    Tsoncheva, T.; Henych, Jiří; Ivanova, R.; Kovacheva, D.; Štengl, Václav

    2015-01-01

    Roč. 116, č. 2 (2015), s. 397-408 ISSN 1878-5190 Institutional support: RVO:61388980 Keywords : Copper and cobalt oxides * Effect of support * Ethyl acetate combustion * Multicomponent oxides * Titania doped with niobium Subject RIV: CA - Inorganic Chemistry Impact factor: 1.265, year: 2015

  5. Synthesis Characterization and Photocatalytic Studies of Cobalt Ferrite-Silica-Titania Nanocomposites

    Directory of Open Access Journals (Sweden)

    David Greene

    2014-04-01

    Full Text Available In this work, CoFe2O4@SiO2@TiO2 core-shell magnetic nanostructures have been prepared by coating of cobalt ferrite nanoparticles with the double SiO2/TiO2 layer using metallorganic precursors. The Transmission Electron Microscopy (TEM, Energy Dispersive X-Ray Analysis (EDX, Vibrational Sample Magnetometer (VSM measurements and Raman spectroscopy results confirm the presence both of the silica and very thin TiO2 layers. The core-shell nanoparticles have been sintered at 600 °C and used as a catalyst in photo-oxidation reactions of methylene blue under UV light. Despite the additional non-magnetic coatings result in a lower value of the magnetic moment, the particles can still easily be retrieved from reaction mixtures by magnetic separation. This retention of magnetism was of particular importance allowing magnetic recovery and re-use of the catalyst.

  6. Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

    Directory of Open Access Journals (Sweden)

    Véronique Pitchon

    2012-02-01

    Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    Highly active nanoparticle SCR deNO(x) catalysts composed of amorphous vanadia on crystalline anatase have been prepared by a sol-gel, co-precipitation method using decomposable crystallization seeds. The catalysts were characterized by means of XRPD, TEM/SEM, FT-IR, nitrogen physisorption and NH(3......) catalysts reported in the literature in the examined temperature range of 200-400 degrees C. The catalysts showed very high resistivity towards potassium poisoning maintaining a 15-30 times higher activity than the equally poisoned industrial reference catalyst, upon impregnation by 280 mu mole potassium....../g of catalyst. (C) 2011 Elsevier Inc. All rights reserved....

  8. Immobilization of CoCl2 (cobalt chloride) on PAN (polyacrylonitrile) composite nanofiber mesh filled with carbon nanotubes for hydrogen production from hydrolysis of NaBH4 (sodium borohydride)

    International Nuclear Information System (INIS)

    Li, Fang; Arthur, Ernest Evans; La, Dahye; Li, Qiming; Kim, Hern

    2014-01-01

    Composite nanofiber sheets containing multiwalled carbon nanotubes and cobalt chloride dispersed in PAN (polyacrylonitrile) were produced by an electrospinning technique. The synthesized PAN/CoCl 2 /CNTs composite nanofiber was used as the catalyst for hydrogen production from the hydrolysis of sodium borohydride. FT-IR characterization showed that the pretreated CNTs possess different organic functional groups which help improve the compatibility between CNTs and PAN organic polymer. SEM (scanning electron microscopy), TEM (transmission electron microscopy) and EDX (energy-dispersive X-ray technique) were used to characterize the composite nanofiber and it was found that CNTs can be coaxially dispersed into the PAN nanofiber. During the hydrolysis of NaBH 4 , this PAN/CoCl 2 /CNTs composite nanofiber exhibited higher catalytic activity compared to the composite without CNTs doping. Kinetic analysis of NaBH 4 hydrolysis shows that the reaction of NaBH 4 hydrolysis based on this catalyst can be ascribed to the first-order reaction and the activation energy of the catalyst was approximately 52.857 kJ/mol. Meanwhile, the composite nanofiber catalyst shows excellent stability and reusability in the recycling experiment. - Highlights: • Composite nanofiber sheets were prepared via electrospinning. • PAN (polyacrylonitrile)/CoCl 2 (cobalt chloride)/CNTs (carbon nanotubes) nanofiber was used as the catalyst for hydrogen production. • CNTs can be coaxially dispersed into the PAN nanofiber. • PAN/CoCl 2 /CNTs composite nanofiber exhibited higher catalytic activity. • The composite nanofiber catalyst shows excellent stability and reusability

  9. Co-Zn-Al based hydrotalcites as catalysts for Fischer-Tropsch process

    Energy Technology Data Exchange (ETDEWEB)

    Bianchi, C.L.; Pirola, C.; Boffito, D.C.; Di Fronzo, A. [Univ. degli Studi di Milano (Italy). Dipt. di Chimica Fisica ed Elettrochimica; Di Michele, A. [Univ. degli Studi di Perugia (Italy). Dipt. di Fisica; Vivani, R.; Nocchetti, M.; Bastianini, M.; Gatto, S. [Univ. degli Studi di Perugia (Italy). Dipt. di Chimica

    2011-07-01

    Co-Zn-Al based hydrotalcites have been investigated as catalysts for the well-known Fischer- Tropsch synthesis. A series of ternary hydrotalcites in nitrate form was prepared with the urea method in order to obtain active catalysts for the above mentioned process. The thermal activation at 350 C gives raise to finely dispersed metallic Co on the mixed oxides, so resulting in retaining the metal distribution of the parent compounds. An optimization study concerning the amount of cobalt of the prepared catalysts (range 15-70% mol, metal based) and the reaction temperature (220-260 C) is reported. All the samples have been fully characterized (BET, ICP-OES, XRPD, TG-DTA, FT-IR, SEM and TEM) and tested in a laboratory pilot plant. Tests to evaluate the stability of these materials were carried out in stressed conditions concerning both the activation and the operating temperatures and pressures (up to 350 C and 2.0 MPa). The obtained results suggest the possibility of using synthetic hydrotalcites as suitable Co-based catalysts for the Fischer-Tropsch synthesis. (orig.)

  10. Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials.

    Science.gov (United States)

    Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan

    2011-12-23

    Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Cobalt metabolism and toxicology—A brief update

    International Nuclear Information System (INIS)

    Simonsen, Lars Ole; Harbak, Henrik; Bennekou, Poul

    2012-01-01

    with a significant long-term retention in tissues for several years. In serum cobalt (Co 2+ ) binds to albumin, and the concentration of free, ionized Co 2+ is estimated at 5–12% of the total cobalt concentration. In human red cells the membrane transport pathway for cobalt (Co 2+ ) uptake appears to be shared with calcium (Ca 2+ ), but with the uptake being essentially irreversible as cobalt is effectively bound in the cytosol and is not itself extruded by the Ca-pump. It is tempting to speculate that this could perhaps also be the case in other animal cells. If this were actually the case, the tissue partitioning and biokinetics of cobalt in cells and tissues would be closely related to the uptake of calcium, with cobalt partitioning primarily into tissues with a high calcium turn-over, and with cobalt accumulation and retention in tissues with a slow turn-over of the cells. The occupational cobalt exposure, e.g. in cobalt processing plants and hard-metal industry is well known and has probably been somewhat reduced in more recent years due to improved work place hygiene. Of note, however, adverse reactions to heart and lung have recently been demonstrated following cobalt exposure near or slightly under the current occupational exposure limit. Over the last decades the use of cobalt–chromium hard-metal alloys in orthopedic joint replacements, in particular in metal-on-metal bearings in hip joint arthroplasty, has created an entirely new source of internal cobalt exposure. Corrosion and wear produce soluble metal ions and metal debris in the form of huge numbers of wear particles in nanometric size, with systemic dissemination through lymph and systemic vascular system. This may cause adverse local reactions in peri-prosthetic soft-tissues, and in addition systemic toxicity. Of note, the metal nanoparticles have been demonstrated to be clearly more toxic than larger, micrometer-sized particles, and this has made the concept of nanotoxicology a crucial, new

  12. Plasma sprayed samarium--cobalt permanent magnets

    International Nuclear Information System (INIS)

    Willson, M.C.; Janowiecki, R.J.

    1975-01-01

    Samarium--cobalt permanent magnets were fabricated by arc plasma spraying. This process involves the injection of relatively coarse powder particles into a high-temperature gas for melting and spraying onto a substrate. The technique is being investigated as an economical method for fabricating cobalt--rare earth magnets for advanced traveling wave tubes and cross-field amplifiers. Plasma spraying permits deposition of material at high rates over large areas with optional direct bonding to the substrate, and offers the ability to fabricate magnets in a variety of shapes and sizes. Isotropic magnets were produced with high coercivity and good reproducibility in magnetic properties. Post-spray thermal treatments were used to enhance the magnetic properties of sprayed deposits. Samarium--cobalt magnets, sprayed from samarium-rich powder and subjected to post-spray heat treatment, displayed energy products in excess of 9 million gauss-oersteds and coercive forces of approximately 6000 oersteds. Bar magnet arrays were constructed by depositing magnets on ceramic substrates. (auth)

  13. Atomistic structure of cobalt-phosphate nanoparticles for catalytic water oxidation.

    Science.gov (United States)

    Hu, Xiao Liang; Piccinin, Simone; Laio, Alessandro; Fabris, Stefano

    2012-12-21

    Solar-driven water splitting is a key photochemical reaction that underpins the feasible and sustainable production of solar fuels. An amorphous cobalt-phosphate catalyst (Co-Pi) based on earth-abundant elements has been recently reported to efficiently promote water oxidation to protons and dioxygen, a main bottleneck for the overall process. The structure of this material remains largely unknown. We here exploit ab initio and classical atomistic simulations combined with metadynamics to build a realistic and statistically meaningful model of Co-Pi nanoparticles. We demonstrate the emergence and stability of molecular-size ordered crystallites in nanoparticles initially formed by a disordered Co-O network and phosphate groups. The stable crystallites consist of bis-oxo-bridged Co centers that assemble into layered structures (edge-sharing CoO(6) octahedra) as well as in corner- and face-sharing cubane units. These layered and cubane motifs coexist in the crystallites, which always incorporate disordered phosphate groups at the edges. Our computational nanoparticles, although limited in size to ~1 nm, can contain more than one crystallite and incorporate up to 18 Co centers in the cubane/layered structures. The crystallites are structurally stable up to high temperatures. We simulate the extended X-ray absorption fine structure (EXAFS) of our nanoparticles. Those containing several complete and incomplete cubane motifs-which are believed to be essential for the catalytic activity-display a very good agreement with the experimental EXAFS spectra of Co-Pi grains. We propose that the crystallites in our nanoparticles are reliable structural models of the Co-Pi catalyst surface. They will be useful to reveal the origin of the catalytic efficiency of these novel water-oxidation catalysts.

  14. Copper nanofiber-networked cobalt oxide composites for high performance Li-ion batteries

    Directory of Open Access Journals (Sweden)

    Shim Hee-Sang

    2011-01-01

    Full Text Available Abstract We prepared a composite electrode structure consisting of copper nanofiber-networked cobalt oxide (CuNFs@CoO x . The copper nanofibers (CuNFs were fabricated on a substrate with formation of a network structure, which may have potential for improving electron percolation and retarding film deformation during the discharging/charging process over the electroactive cobalt oxide. Compared to bare CoO x thin-film (CoO x TF electrodes, the CuNFs@CoO x electrodes exhibited a significant enhancement of rate performance by at least six-fold at an input current density of 3C-rate. Such enhanced Li-ion storage performance may be associated with modified electrode structure at the nanoscale, improved charge transfer, and facile stress relaxation from the embedded CuNF network. Consequently, the CuNFs@CoO x composite structure demonstrated here can be used as a promising high-performance electrode for Li-ion batteries.

  15. The Effect of Catalyst Type on The Microstructure and Magnetic Properties of Synthesized Hard Cobalt Ferrite Nanoparticles.

    Directory of Open Access Journals (Sweden)

    Shaima'a Jaber Kareem

    2018-02-01

    Full Text Available A sol-gel process prepared the nanoparticles of hard cobalt ferrite (CoFe2O4. Cobalt nitrate hexahydrate (Co (NO32⋅6H2O, iron nitrate nonahydrate (Fe (NO33⋅9H2O with using two catalysis acid (citric acid and alkaline (hydroxide ammonium were used as precursor materials. Crystallization behavior of the CoFe2O4 nanoparticles were studied by X-ray diffraction (XRD. Nanoparticles phases can change from amorphous to spinel ferrite crystalline depending on the calcinated temperature at 600°C, with using citric acid as a catalysis without finding forgone phase, while using hydroxide ammonium was shown second phase (α-Fe2O3 with CoFe2O4. Crystallite size was measured by Scherrer’s formula about (25.327 nm and (27.119 nm respectively. Structural properties were investigated by FTIR, which was appeared main bond of (Fe-O, (Co-O, (C-O, and (H-O. Scanning electron microscopy (FE- SEM was shown the microstructure observation of cobalt ferrite and the particle size at the range about (28.77-42.97 nm. Magnetization measurements were carried out on a vibrating sample magenometer (VSM that exhibited hard spinel ferrite.

  16. In situ electrochemical creation of cobalt oxide nanosheets with favorable performance as a high tap density anode material for lithium-ion batteries

    International Nuclear Information System (INIS)

    Lin, Qian; Sha, Yujing; Zhao, Bote; Chen, Yubo; Tadé, Moses O.; Shao, Zongping

    2015-01-01

    Highlights: • Cobalt oxide nanosheets in situ electrochemical generated from commercial LiCoO_2. • TEM indicates creation of cobalt oxide nanosheets from coarse layered LiCoO_2_. • Coarse-type LiCoO_2 with high tap density shows promising anode performance. • Optimizing weight ratio of LiCoO_2 in electrode, a high capacity was achieved. - Abstract: Cobalt oxides are attractive alternative anode materials for next-generation lithium-ion batteries (LIBs). To improve the performance of conversion-type anode materials such as cobalt oxides, well dispersed and nanosized particulate morphology is typically required. In this study, we describe the in situ electrochemical generation of cobalt oxide nanosheets from commercial micrometer-sized LiCoO_2 oxide as an anode material for LIBs. The electrode material as prepared was analyzed by XRD, FE-SEM and TEM. The electrochemical properties were investigated by cyclic voltammetry and by a constant current galvanostatic discharge–charge test. The material shows a high tap density and promising anode performance in terms of capacity, rate performance and cycling stability. A capacity of 560 mA h g"−"1 is still achieved at a current density of 1000 mA g"−"1 by increasing the amount of additives in the electrode to 40 wt%. This paper provides a new technique for developing a high-performance conversion-type anode for LIBs.

  17. Cobalt-free nickel-base superalloys

    International Nuclear Information System (INIS)

    Koizumi, Yutaka; Yamazaki, Michio; Harada, Hiroshi

    1979-01-01

    Cobalt-free nickel-base cast superalloys have been developed. Cobalt is considered to be a beneficial element to strengthen the alloys but should be eliminated in alloys to be used for direct cycle helium turbine driven by helium gas from HTGR (high temp. gas reactor). The elimination of cobalt is required to avoid the formation of radioactive 60 Co from the debris or scales of the alloys. Cobalt-free alloys are also desirable from another viewpoint, i.e. recently the shortage of the element has become a serious problem in industry. Cobalt-free Mar-M200 type alloys modified by the additions of 0.15 - 0.2 wt% B and 1 - 1.5 wt% Hf were found to have a creep rupture strength superior or comparable to that of the original Mar-M200 alloy bearing cobalt. The ductility in tensile test at 800 0 C, as cast or after prolonged heating at 900 0 C (the tensile test was done without removing the surface layer affected by the heating), was also improved by the additions of 0.15 - 0.2% B and 1 - 1.5% Hf. The morphology of grain boundaries became intricated by the additions of 0.15 - 0.2% B and 1 - 1.5% Hf, to such a degree that one can hardly distinguish grain boundaries by microscopes. The change in the grain boundary morphology was considered, as suggested previously by one of the authors (M.Y.), to be the reason for the improvements in the creep rupture strength and tensile ductility. (author)

  18. The cobalt-60 container scanner

    International Nuclear Information System (INIS)

    Jigang, A.; Liye, Z.; Yisi, L.; Haifeng, W.; Zhifang, W.; Liqiang, W.; Yuanshi, Z.; Xincheng, X.; Furong, L.; Baozeng, G.; Chunfa, S.

    1997-01-01

    The Institute of Nuclear Energy Technology (INET) has successfully designed and constructed a container (cargo) scanner, which uses cobalt-60 of 100-300 Ci as radiation source. The following performances of the Cobalt-60 container scanner have been achieved at INET: a) IQI (Image Quality Indicator) - 2.5% behind 100 mm of steel; b) CI (Contrast Indicator) - 0.7% behind 100 mm of steel; c) SP (Steel Penetration) - 240 mm of steel; d) Maximum Dose per Scanning - 0.02mGy; e) Throughput - twenty 40-foot containers per hour. These performances are equal or similar to those of the accelerator scanners. Besides these nice enough inspection properties, the Cobalt-60 scanner possesses many other special features which are better than accelerator scanners: a) cheap price - it will be only or two tenths of the accelerator scanner's; b) low radiation intensity - the radiation protection problem is much easier to solve and a lot of money can be saved on the radiation shielding building; c) much smaller area for installation and operation; d) simple operation and convenient maintenance; e) high reliability and stability. The Cobalt-60 container (or cargo) scanner is satisfied for boundary customs, seaports, airports and railway stations etc. Because of the nice special features said above, it is more suitable to be applied widely. Its high properties and low price will make it have much better application prospects

  19. Cobalt metabolism and toxicology-A brief update

    Energy Technology Data Exchange (ETDEWEB)

    Simonsen, Lars Ole, E-mail: LOSimonsen@dadlnet.dk; Harbak, Henrik; Bennekou, Poul

    2012-08-15

    phase lasting several weeks, and with a significant long-term retention in tissues for several years. In serum cobalt (Co{sup 2+}) binds to albumin, and the concentration of free, ionized Co{sup 2+} is estimated at 5-12% of the total cobalt concentration. In human red cells the membrane transport pathway for cobalt (Co{sup 2+}) uptake appears to be shared with calcium (Ca{sup 2+}), but with the uptake being essentially irreversible as cobalt is effectively bound in the cytosol and is not itself extruded by the Ca-pump. It is tempting to speculate that this could perhaps also be the case in other animal cells. If this were actually the case, the tissue partitioning and biokinetics of cobalt in cells and tissues would be closely related to the uptake of calcium, with cobalt partitioning primarily into tissues with a high calcium turn-over, and with cobalt accumulation and retention in tissues with a slow turn-over of the cells. The occupational cobalt exposure, e.g. in cobalt processing plants and hard-metal industry is well known and has probably been somewhat reduced in more recent years due to improved work place hygiene. Of note, however, adverse reactions to heart and lung have recently been demonstrated following cobalt exposure near or slightly under the current occupational exposure limit. Over the last decades the use of cobalt-chromium hard-metal alloys in orthopedic joint replacements, in particular in metal-on-metal bearings in hip joint arthroplasty, has created an entirely new source of internal cobalt exposure. Corrosion and wear produce soluble metal ions and metal debris in the form of huge numbers of wear particles in nanometric size, with systemic dissemination through lymph and systemic vascular system. This may cause adverse local reactions in peri-prosthetic soft-tissues, and in addition systemic toxicity. Of note, the metal nanoparticles have been demonstrated to be clearly more toxic than larger, micrometer-sized particles, and this has made the

  20. X-ray physico-chemical imaging during activation of cobalt-based Fischer-Tropsch synthesis catalysts

    Science.gov (United States)

    Beale, Andrew M.; Jacques, Simon D. M.; Di Michiel, Marco; Mosselmans, J. Frederick W.; Price, Stephen W. T.; Senecal, Pierre; Vamvakeros, Antonios; Paterson, James

    2017-11-01

    The imaging of catalysts and other functional materials under reaction conditions has advanced significantly in recent years. The combination of the computed tomography (CT) approach with methods such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) now enables local chemical and physical state information to be extracted from within the interiors of intact materials which are, by accident or design, inhomogeneous. In this work, we follow the phase evolution during the initial reduction step(s) to form Co metal, for Co-containing particles employed as Fischer-Tropsch synthesis (FTS) catalysts; firstly, working at small length scales (approx. micrometre spatial resolution), a combination of sample size and density allows for transmission of comparatively low energy signals enabling the recording of `multimodal' tomography, i.e. simultaneous XRF-CT, XANES-CT and XRD-CT. Subsequently, we show high-energy XRD-CT can be employed to reveal extent of reduction and uniformity of crystallite size on millimetre-sized TiO2 trilobes. In both studies, the CoO phase is seen to persist or else evolve under particular operating conditions and we speculate as to why this is observed. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

  1. High density tungsten-nickel-iron-cobalt alloys having improved hardness and method for making same

    International Nuclear Information System (INIS)

    Penrice, T.W.; Bost, J.

    1988-01-01

    This patent describes the process of making high density alloy containing about 85 to 98 weight percent tungsten and the balance of the alloy being essentially a binder of nickel, iron and cobalt, and wherein the cobalt is present in an amount within the range of about 5 to 47.5 weight percent of the binder, comprising: blending powders of the tungsten, nickel, iron and cobalt into a homogeneous composition, compacting the homogeneous composition into a shaped article, heating the shaped article to a temperature and for a time sufficient to sinter the article, subjecting the sintered article to a temperature sufficient to enable the intermetallic phase formed at the matrix to tungsten interface to diffuse into the gamma austenitic phase whereby the alpha tungsten/gamma austenite boundaries are essentially free of such intermetallic phase, quenching the article, and swaging the article to a reduction in area of about 5 to 40 percent, the article having improved mechanical properties, including improved tensile strength and hardness while maintaining suitable ductility for subsequent working thereof

  2. Studies on recycling and utilization of spent catalysts. Preparation of active hydrodemetallization catalyst compositions from spent residue hydroprocessing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Marafi, Meena; Stanislaus, Antony [Petroleum Refining Department, Petroleum Research and Studies Center, Kuwait Institute for Scientific Research, P.O. Box 24885, Safat (Kuwait)

    2007-02-15

    Spent catalysts form a major source of solid wastes in the petroleum refining industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al{sub 2}O{sub 3} with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure fixed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst. (author)

  3. Fluorinated cobalt for catalyzing hydrogen generation from sodium borohydride

    Energy Technology Data Exchange (ETDEWEB)

    Akdim, O.; Demirci, U.B.; Brioude, A.; Miele, P. [Laboratoire des Multimateriaux et Interfaces, UMR 5615 CNRS Universite Lyon 1, Universite de Lyon, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France)

    2009-07-15

    The present paper reports preliminary results relating to a search for durable cobalt-based catalyst intended to catalyze the hydrolysis of sodium borohydride (NaBH{sub 4}). Fluorination of Co [Suda S, Sun YM, Liu BH, Zhou Y, Morimitsu S, Arai K, et al. Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts. Appl Phys A 2001; 72: 209-12.] has attracted our attention whereas the fluorination of Co boride has never been envisaged so far. Our first objective was to compare the reactivity of fluorinated Co with that of Co boride. We focused our attention on the formation of Co boride from fluorinated Co. Our second objective was to show the fluorination effect on the reactivity of Co. Our third objective was to find an efficient, durable Co catalyst. It was observed a limited stabilization of the Co surface by virtue of the fluorination, which made the formation of surface Co boride more difficult while the catalytic activity was unaltered. The fluorination did not affect the number of surface active sites. Nevertheless, it did not prevent the formation of Co boride. The fluorination of Co boride was inefficient. Hence, fluorination is a way to gain in stabilization of the catalytic surface but it is quite inefficient to hinder the boride formation. Accordingly, it did not permit to compare the reactivity of Co boride with that of Co. (author)

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

    Science.gov (United States)

    Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.; Chater, Philip A.; Carter, James H.; Morgan, David J.; Fiordaliso, Elisabetta M.; Wagner, Jakob B.; Davies, Thomas E.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.; Rosseinsky, Matthew J.; Hutchings, Graham J.

    2016-03-01

    Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored—georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

  5. Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

    Science.gov (United States)

    Nguyen, Luan; Tao, Franklin Feng

    2018-02-01

    Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

  6. Passivation and corrosion behaviours of cobalt and cobalt-chromium-molybdenum alloy

    International Nuclear Information System (INIS)

    Metikos-Hukovic, M.; Babic, R.

    2007-01-01

    Passivation and corrosion behaviour of the cobalt and cobalt-base alloy Co30Cr6Mo was studied in a simulated physiological solution containing chloride and bicarbonate ions and with pH of 6.8. The oxido-reduction processes included solid state transformations occurring at the cobalt/electrolyte interface are interpreted using theories of surface electrochemistry. The dissolution of cobalt is significantly suppressed by alloying it with chromium and molybdenum, since the alloy exhibited 'chromium like' passivity. The structural and protective properties of passive oxide films formed spontaneously at the open circuit potential or during the anodic polarization were studied using electrochemical impedance spectroscopy in the wide frequency range

  7. Carbon nanocages: a new support material for Pt catalyst with remarkably high durability.

    Science.gov (United States)

    Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

    2014-03-24

    Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for "real world" application.

  8. Development of transition metal oxide catalysts for treatment of off-gases released during pyrolysis of organic ion exchange resins

    International Nuclear Information System (INIS)

    Sathi Sasidharan, N.; Deshingkar, D.S.; Wattal, P.K.

    2005-08-01

    The spent IX resin wastes arising from nuclear power plants have high radiation level due to fission product 137 Cesium and activation product 60 Cobalt. The pyrolysis and oxidative pyrolysis processes have potential to minimize final waste form volumes of these wastes. The major difficulty in deploying these processes for treatment of spent IX resins is release of off-gases containing large quantities of aromatic hydrocarbons, amines, sulphur dioxide, hydrogen sulphide, carbonyl sulphide etc. As an alternative to high temperature incineration of the pyrolysis off gases, feasibility of using catalytic combustion at moderate temperatures was investigated in the laboratory. Copper chromite, copper oxide-ceric oxide and vanadium pentaoxide catalysts supported on alumina were prepared and tested for oxidation of styrene monomer, toluene, ethyl benzene and trimethyl amine at 22500 hr -1 space velocity and temperature range of 300 to 500 degC. At temperatures over 475 degC, all three catatyst gave oxidation efficiency of over 97% for these compounds over concentration range of few tens of ppm to few thousands ppm. A composite catalyst bed of three catalysts comprising principally of copper chromite is proposed for treatment of IX resin pyrolysis off-gases. (author)

  9. Solid state synthesis, characterization, surface and catalytic properties of Pr2CoO4 and Pr2NiO4 catalyst

    International Nuclear Information System (INIS)

    Sinha, K.K.; Indu, N.K.; Sinha, S.K.; Pankaj, A.K.

    2008-01-01

    Full text: The most interesting non-stoichiometric oxides are found in transition metal and rare earth oxides at higher temperatures. The role of Solid State properties in the catalysis using mixed metal oxide as catalyst have wide applications in fertilizer, Petro-chemical, Pharmaceutical, cosmetic, paint detergents, plastics and food-stuff industries and these are also resistive towards acids and alkalies. The use of catalyst has opened up new process routes or revolutioned the existing process in terms of economics and efficiency and has radically changed the industrial scenario. The use of catalyst is so pervasive today that nearly 70 % of modern chemical processes are based on it at some stage or other and 90% new processes developed are catalytic nature. A series of non-stoichiometric spinel type of oxide catalyst of Praseodymium with cobalt and nickel were synthesized by their oxalates through Solid State reaction technique at different activation temperatures i.e. 600, 700, 800 and 900 deg C. The characterization of catalyst was done by XRD, FTIR and ESR methods. X-ray powder diffraction study shows that catalysts are made up of well grown crystallinities mostly in single phase crystal and system is of orthorhombic structure. FTIR is related to inadequate decomposition of oxalate ion from the Catalyst. The kinetic decomposition of Urea was employed as a model reaction to study the catalytic potentiality of different catalysts. Surface and Catalytic Properties of catalysts were measured. A relation between activation temperature and surface properties like excess surface oxygen (E.S.O.), surface acidity and surface area was observed. A linear relationship between the surface area of the catalyst and the amount of ammonia gas evolved per gm of the sample was observed also. Nickel containing catalysts were found a bit more catalytic active in comparison to cobalt oxide catalysts. Transition metal ions (i.e. Ni 2+ and Co 2+ ions) are mainly responsible for

  10. Metal-polypyridyl catalysts for electro- and photochemical reduction of water to hydrogen.

    Science.gov (United States)

    Zee, David Z; Chantarojsiri, Teera; Long, Jeffrey R; Chang, Christopher J

    2015-07-21

    Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an

  11. Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

    Science.gov (United States)

    Duan, Haohong; Dong, Juncai; Gu, Xianrui; Peng, Yung-Kang; Chen, Wenxing; Issariyakul, Titipong; Myers, William K; Li, Meng-Jung; Yi, Ni; Kilpatrick, Alexander F R; Wang, Yu; Zheng, Xusheng; Ji, Shufang; Wang, Qian; Feng, Junting; Chen, Dongliang; Li, Yadong; Buffet, Jean-Charles; Liu, Haichao; Tsang, Shik Chi Edman; O'Hare, Dermot

    2017-09-19

    Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

  12. Nickel-cobalt hydroxide nanosheets: Synthesis, morphology and electrochemical properties.

    Science.gov (United States)

    Schneiderová, Barbora; Demel, Jan; Zhigunov, Alexander; Bohuslav, Jan; Tarábková, Hana; Janda, Pavel; Lang, Kamil

    2017-08-01

    This paper reports the synthesis, characterization, and electrochemical performance of nickel-cobalt hydroxide nanosheets. The hydroxide nanosheets of approximately 0.7nm thickness were prepared by delamination of layered nickel-cobalt hydroxide lactate in water and formed transparent colloids that were stable for months. The nanosheets were deposited on highly oriented pyrolytic graphite by spin coating, and their electrochemical behavior was investigated by cyclic voltammetry in potassium hydroxide electrolyte. Our method of electrode preparation allows for studying the electrochemistry of nanosheets where the majority of the active centers can participate in the charge transfer reaction. The observed electrochemical response was ascribed to mutual compensation of the cobalt and nickel response via electron sharing between these metals in the hydroxide nanosheets, a process that differentiates the behavior of nickel-cobalt hydroxide nanosheets from single nickel hydroxide or cobalt hydroxide nanosheets or their physical mixture. The presence of cobalt in the nickel-cobalt hydroxide nanosheets apparently decreases the time of electrochemical activation of the nanosheet layer, which for the nickel hydroxide nanosheets alone requires more potential sweeps. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Study of the productivity of MWCNT over Fe and Fe–Co catalysts supported on SiO2, Al2O3 and MgO

    Directory of Open Access Journals (Sweden)

    S.A. Shokry

    2014-06-01

    Full Text Available In the present study, multi-walled carbon nanotubes (MWCNT were prepared in good quality and quantity, MWCNT were produced using the catalytic chemical vapor deposition (CCVD technique and the carbon source was acetylene. Different catalysts were synthesized based on iron and a mixture of iron and cobalt metal supported on SiO2, Al2O3 or MgO. The effect of parameters such as iron concentration, support type, bimetallic catalyst and the method of catalyst preparation has been investigated in the production of MWCNT. The quality of as-made nanotubes was investigated by the high-resolution transmission electron microscopy (HRTEM and thermogravimetric analysis (TGA. The best yield of MWCNT was 30 times of the amount of the used catalyst. The high yield of MWCNT was gained by 40 wt.% Fe on alumina support which was prepared by the sol–gel method. TEM analysis was done for the carbon deposit, which revealed that the walls of the MWCNT were graphitized, with regular inner channel and uniform diameter. It reflected a reasonable degree of purity. The TGA showed that MWCNT was decomposed at 635 °C by a small rate indicating a high thermal stability and well crystalline formation of the produced MWCNT.

  14. Development of high performance catalyst for off-gas treatment system in BWR

    International Nuclear Information System (INIS)

    Kawasaki, Toru; Kawabe, Kenichi; Maeda, Kiyomitsu; Matsubara, Hirofumi; Aizawa, Motohiro; Iizuka, Hidehiro; Kumagai, Naoki

    2011-01-01

    A high performance catalyst for off-gas treatment system in boiling water reactor (BWR) has been developed. The hydrogen concentration in the outlets of off-gas recombiners increased at several BWR plants in Japan. These phenomena were caused by deactivation of catalysts for the recombiners, and we assumed two types of deactivation mechanisms. The first cause was an increase of the amount of boehmite in the catalyst support due to alternation of the manufacturing process. The other cause was catalysts being poisoned by cyclic siloxanes that were introduced from the silicone sealant used in the upstream of the off-gas recombiners. The catalysts were manufactured by Pt adhering on alumina support. The conventional catalyst (CAT-A) used the aqueous solution of the chloroplatinic acid for adhesion of Pt. A dechlorination process by autoclave was applied to prevent the equipment at the downstream of the recombiners from stress corrosion cracking, but this process caused the support material to transform into boehmite. The boehmite-rich catalysts were deactivated more easily by organic silicon than gamma alumina-rich catalysts. Therefore, the CAT-A was replaced at many Japanese BWR plants by the improved catalyst (CAT-B), and their support was transformed into more stable gamma alumina by heating at 500degC. However, the siloxanes keep being detected in the off-gas though the source of siloxane had been removed and there still remain possibilities to deactivate the catalysts. Therefore, we have been developing high performance catalyst (CAT-C) that has higher activity and durability against poisoning. We investigated the properties of CAT-C by performance tests and instrumental analyses. The dependency of thermal output of nuclear reactor, and durability against siloxane poisoning were investigated. We found that CAT-C showed higher performance and better properties than CAT-B did. Moreover, we have been developing a modeling method to evaluate the hydrogen recombination

  15. High Performance Fe- and N- Doped Carbon Catalyst with Graphene Structure for Oxygen Reduction

    Science.gov (United States)

    Peng, Hongliang; Mo, Zaiyong; Liao, Shijun; Liang, Huagen; Yang, Lijun; Luo, Fan; Song, Huiyu; Zhong, Yiliang; Zhang, Bingqing

    2013-05-01

    Proton exchange membrane fuel cells are promising candidates for a clean and efficient energy conversion in the future, the development of carbon based inexpensive non-precious metal ORR catalyst has becoming one of the most attractive topics in fuel cell field. Herein we report a Fe- and N- doped carbon catalyst Fe-PANI/C-Mela with graphene structure and the surface area up to 702 m2 g-1. In 0.1 M HClO4 electrolyte, the ORR onset potential for the catalyst is high up to 0.98 V, and the half-wave potential is only 60 mV less than that of the Pt/C catalyst (Loadings: 51 μg Pt cm-2). The catalyst shows high stability after 10,000 cyclic voltammetry cycles. A membrane electrode assembly made with the catalyst as a cathode is tested in a H2-air single cell, the maximum power density reached ~0.33 W cm2 at 0.47 V.

  16. Effect study of the support in nickel and cobalt catalysts for obtaining hydrogen from ethanol steam reforming; Estudo do efeito do suporte em catalisadores de cobalto e niquel para obtencao de hidrogenio a partir da reforma a vapor do etanol

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Sirlane Gomes da

    2013-09-01

    A range of oxide-supported metal catalysts have been investigated for the steam reforming of ethanol for the production of hydrogen and subsequent application in fuel cells. The catalysts were synthesized by the co-precipitation and internal gelification methods using cobalt and nickel as active metals supported on aluminum, zirconium, lanthanum and cerium oxides. After prepared and calcined at 550 C Masculine-Ordinal-Indicator the solids were fully characterized by different techniques such as X-rays diffraction(DRX), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy, nitrogen adsorption (B.E.T), temperature-programmed reduction in H2 (TPR-H2) and thermogravimetric analysis. The catalytic tests were performed in a monolithic quartz reactor and submitted to different thermodynamic conditions of steam reforming of ethanol at temperatures varying from 500 Masculine-Ordinal-Indicator C to 800 Masculine-Ordinal-Indicator C. The product gas streams from the reactor were analyzed by an on-line gas chromatograph. The cobalt/nickel catalyst supported on a ceria-lanthania mixture (Co{sub 10%} / Ni{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3}) showed good catalytic performance in hydrogen selectivity reaching a concentration greater than 65%, when compared to other catalytic systems such as: Co{sub 10%} / Ni5% - CeO{sub 2}; Co{sub 10%} / Ni{sub 5%} - CeO{sub 2}ZrO{sub 2}; Co{sub 10%} / Ni{sub 5%} - ZrO{sub 2}; Co{sub 10%} / Ni{sub 5%} - La{sub 2}O{sub 3}; Co{sub 10%} / Ni{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3}/K{sub 2%}; Co{sub 10}% / Ni{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3} / Na{sub 2%}; Ni{sub 10%} / Co{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3}; Co-Al{sub 2}O{sub 3} e Co-Al{sub 2}O{sub 3}CeO{sub 2}. (author)

  17. Ternary cobalt-molybdenum-zirconium coatings for alternative energies

    Science.gov (United States)

    Yar-Mukhamedova, Gulmira; Ved', Maryna; Sakhnenko, Nikolay; Koziar, Maryna

    2017-11-01

    Consistent patterns for electrodeposition of Co-Mo-Zr coatings from polyligand citrate-pyrophosphate bath were investigated. The effect of both current density amplitude and pulse on/off time on the quality, composition and surface morphology of the galvanic alloys were determined. It was established the coating Co-Mo-Zr enrichment by molybdenum with current density increasing up to 8 A dm-2 as well as the rising of pulse time and pause duration promotes the content of molybdenum because of subsequent chemical reduction of its intermediate oxides by hydrogen ad-atoms. It was found that the content of the alloying metals in the coating Co-Mo-Zr depends on the current density and on/off times extremely and maximum Mo and Zr content corresponds to the current density interval 4-6 A dm-2, on-/off-time 2-10 ms. Chemical resistance of binary and ternary coatings based on cobalt is caused by the increased tendency to passivity and high resistance to pitting corrosion in the presence of molybdenum and zirconium, as well as the acid nature of their oxides. Binary coating with molybdenum content not less than 20 at.% and ternary ones with zirconium content in terms of corrosion deep index are in a group ;very proof;. It was shown that Co-Mo-Zr alloys exhibits the greatest level of catalytic properties as cathode material for hydrogen electrolytic production from acidic media which is not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2-4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for red-ox processes activating by oxygen as well as electrode materials for red-ox batteries.

  18. Elicitation threshold of cobalt chloride

    DEFF Research Database (Denmark)

    Fischer, Louise A; Johansen, Jeanne D; Voelund, Aage

    2016-01-01

    : On the basis of five included studies, the ED10 values of aqueous cobalt chloride ranged between 0.0663 and 1.95 µg cobalt/cm(2), corresponding to 30.8-259 ppm. CONCLUSIONS: Our analysis provides an overview of the doses of cobalt that are required to elicit allergic cobalt contactdermatitis in sensitized...

  19. thesis of high-purity carbon nanotubes over alumina and silica supported bimetallic catalysts

    Directory of Open Access Journals (Sweden)

    Sanja Ratković

    2009-10-01

    Full Text Available Carbon nanotubes (CNTs were synthesized by a catalytic chemical vapor deposition method (CCVD of ethylene over alumina and silica supported bimetallic catalysts based on Fe, Co and Ni. The catalysts were prepared by a precipitation method, calcined at 600 °C and in situ reduced in hydrogen flow at 700 °C. The CNTs growth was carried out by a flow the mixture of C2H4 and nitrogen over the catalyst powder in a horizontal oven. The structure and morphology of as-synthesized CNTs were characterized using SEM. The as-synthesized nanotubes were purified by acid and basic treatments in order to remove impurities such as amorphous carbon, graphite nanoparticles and metal catalysts. XRD and DTA/TG analyses showed that the amounts of by-products in the purified CNTs samples were reduced significantly. According to the observed results, ethylene is an active carbon source for growing high-density CNTs with high yield but more on alumina-supported catalysts than on their silica- supported counterparts. The last might be explained by SMSI formed in the case of alumina-supported catalysts, resulting in higher active phase dispersion.

  20. Grotrian diagrams for highly ionized cobalt Co VIII through Co XXVII

    Energy Technology Data Exchange (ETDEWEB)

    Shirai, Toshizo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Sugar, J.; Wiese, W.L.

    1997-07-01

    Grotrian diagrams are presented to provide graphical overviews for 1,247 spectral lines of highly ionized cobalt, Co VIII through Co XXVII. In the usual diagram display such as that by Bashkin and Stoner (North-Holland, Amsterdam, 1975), the density of transitions is often too high to allow each transition to be drawn separately. Here in our modified diagrams, the transitions are also represented by lines connecting the upper and lower energy levels, but the lower energy levels are extended and repeated for successive configurations as needed. As a sequence, dense packing is avoided and all lines in a multiplet can be accommodated. (author)

  1. Preparation of high purity cobalt

    International Nuclear Information System (INIS)

    Isshiki, M.; Fukuda, Y.; Igaki, K.

    1985-01-01

    A combination of anion exchange separation, electrolytic extraction, floating zone refining and dry hydrogen treatment was used to purify cobalt. The effectiveness of each purification process was confirmed by measurements of the residual resistivity ratio (RRR) and activation analyses. Proton activation analysis revealed that all the main metallic impurities except iron were effectively removed by a combination of these processes. The effective removal of oxygen, nitrogen and carbon by dry hydrogen treatment was confirmed by activation analyses using 3 He ion beams, proton beams and γ rays. It was found that the rate-controlling step in the decarburization process was a surface reaction. The maximum RRR obtained for the purified specimen was 334, which is higher than previously reported values. (Auth.)

  2. Synthesis of cobalt boride nanoparticles using radio frequency thermal plasma

    International Nuclear Information System (INIS)

    Lapitan, Jr. Lorico DS.; Ying Ying Chen; Seesoek Choe; Watanabe, Takayuki

    2012-01-01

    Nano size cobalt boride particles were synthesized from vapor phase using a 30 kw-4 MHz radio frequency (RF) thermal plasma. Cobalt and boron powder mixtures used as precursors in different composition and feed rate were evaporated immediately in the high temperature plasma and cobalt boride nanoparticles were produced through the quenching process. The x-ray diffractometry (XRD) patterns of cobalt boride nanoparticles prepared from the feed powder ratio of 1:2 and 1:3 for Co: B showed peaks that are associated with the Co 2 B and CoB crystal phases of cobalt boride. The XRD analysis revealed that increasing the powder feed rate results in a higher mass fraction and a larger crystalline diameter of cobalt boride nanoparticles. The images obtained by field emission scanning electron microscopy (FE-SEM) revealed that cobalt boride nanoparticles have a spherical morphology. The crystallite size of the particles estimated with XRD was found to be 18-22 nm. (author)

  3. The role of cobalt ferrite magnetic nanoparticles in medical science

    International Nuclear Information System (INIS)

    Amiri, S.; Shokrollahi, H.

    2013-01-01

    The nanotechnology industry is rapidly growing and promises that the substantial changes that will have significant economic and scientific impacts be applicable to a wide range of areas, such as aerospace engineering, nano-electronics, environmental remediation and medical healthcare. In this area, cobalt ferrite nanoparticles have been regarded as one of the competitive candidates because of their suitable physical, chemical and magnetic properties like the high anisotropy constant, high coercivity and high Curie temperature, moderate saturation magnetization and ease of synthesis. This paper introduces the magnetic properties, synthesis methods and some medical applications, including the hyperthermia, magnetic resonance imaging (MRI), magnetic separation and drug delivery of cobalt ferrite nanoparticles. Highlights: ► Cobalt ferrite nanoparticles are one of the most important materials for nanomedicine. ► They have high coercivity and moderate saturation magnetization. ► Cobalt ferrite nanoparticles are synthesized easily. ► They are a good candidate for hyperthermia and magnetic resonance imaging.

  4. The role of cobalt ferrite magnetic nanoparticles in medical science

    Energy Technology Data Exchange (ETDEWEB)

    Amiri, S.; Shokrollahi, H., E-mail: Shokrollahi@sutech.ac.ir

    2013-01-01

    The nanotechnology industry is rapidly growing and promises that the substantial changes that will have significant economic and scientific impacts be applicable to a wide range of areas, such as aerospace engineering, nano-electronics, environmental remediation and medical healthcare. In this area, cobalt ferrite nanoparticles have been regarded as one of the competitive candidates because of their suitable physical, chemical and magnetic properties like the high anisotropy constant, high coercivity and high Curie temperature, moderate saturation magnetization and ease of synthesis. This paper introduces the magnetic properties, synthesis methods and some medical applications, including the hyperthermia, magnetic resonance imaging (MRI), magnetic separation and drug delivery of cobalt ferrite nanoparticles. Highlights: Black-Right-Pointing-Pointer Cobalt ferrite nanoparticles are one of the most important materials for nanomedicine. Black-Right-Pointing-Pointer They have high coercivity and moderate saturation magnetization. Black-Right-Pointing-Pointer Cobalt ferrite nanoparticles are synthesized easily. Black-Right-Pointing-Pointer They are a good candidate for hyperthermia and magnetic resonance imaging.

  5. Flame spray synthesis of CoMo/Al2O3 hydrotreating catalysts

    DEFF Research Database (Denmark)

    Høj, Martin; Linde, Kasper; Hansen, Thomas Klint

    2011-01-01

    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...... obtained consisted mostly of γ-Al2O3 with some CoAl2O4, as evidenced by X-ray diffraction (XRD) and UV–vis spectroscopy. Bulk MoO3 was not detected by XRD, except at the highest molybdenum content (32wt.%) and in the unsupported sample, indicating that molybdenum is well dispersed on the surface.......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...

  6. Mild Hydroprocessing with Dispersed Catalyst of Highly Asphaltenic Pitch

    Science.gov (United States)

    Isquierdo, Fernanda

    Asphaltene are known to have diverse negative impacts on heavy oil extraction and hydroprocessing. This research then, explores the optimal conditions to convert asphaltenes into lighter material using mild conditions of pressure and temperature, and investigates changes in asphaltene structure during hydroprocessing. Feedstock and products were characterized by Simulated Distillation, Microdeasphalting, Sulfur content, X-ray diffraction, X-ray photoelectron spectroscopy, and Nuclear magnetic resonance spectroscopy. Solid catalysts were analyzed by Themogravimetric analysis, X-ray diffraction, and Dynamic light scattering. Based on the results obtained from X-ray diffraction and Nuclear magnetic resonance spectroscopy analysis a mechanism for the asphaltene hydroprocessing at mild conditions is proposed in which the alky peripheric portion from the original asphaltenes is partially removed during the reaction. The consequence of that process being an increase in the stacking of the aromatics sheets in the remaining asphaltenes. Also, this study investigates different for ultradispersed catalyst compositions, where CoWS, CoMoS, NiWS, FeWS, NiMo/NaHFeSi 2O6 and NaHFeSi2O6 showed a high asphaltene conversion as determined by asphaltene microdeasphalting, FeMoS and NaHFeSi 2O6 presented a high Vacuum Residue as determined by distillation (SIMDIST) analysis conversion, and in terms of sulfur removal CoMoS gave the higher conversion. In addition, all the catalyst tested showed a coke production lower than 1%. Finally, a kinetic study for the pitch hydroprocessing using CoMoS as catalysts gave a global activation energy of 97.3 kJ/mol.

  7. Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

    International Nuclear Information System (INIS)

    Alanis O, R.; Jimenez B, J.

    2010-01-01

    In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO 2 , which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO 2 synthesized by the Degussa company (TiO 2 Degussa P25) with and oxide of mixed cobalt valence (Co 3 O 4 ) synthesized using the sol-gel method. The synthesized photo catalyst TiO 2 /Co 3 O 4 was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

  8. Highly selective oxidative dehydrogenation of ethane with supported molten chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.A.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    Ethene production is one of the most important transformations in chemical industry, given that C{sub 2}H{sub 4} serves as building block for many mass-market products. Besides conventional thermal processes like steam cracking of ethane, ethane can be produced selectively by catalytic processes. One of the classes of catalysts that have been reported in literature as active and highly selective for the oxidative dehydrogenation of ethane is that of supported molten chloride catalysts, containing an alkali chloride overlayer on a solid support. This work deals with fundamental aspects of the catalytic action in latter class of catalysts. Results from kinetic reaction studies are related to observations in detailed characterization and lead to a comprehensive mechanistic understanding. Of fundamental importance towards mechanistic insights is the oxygen storage capacity of the catalysts that has been determined by transient step experiments. (orig.)

  9. Improved catalytic activity of cobalt core–platinum shell nanoparticles supported on surface functionalized graphene for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Zhang, Mingmei; Li, Yuan; Yan, Zaoxue; Jing, Junjie; Xie, Jimin; Chen, Min

    2015-01-01

    Poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene supported bimetallic catalysts of shell platinum on core cobalt (Co@Pt/PDDA-G) are synthesized using a two-step procedure involving the microwave synthesis method and replacement method. TEM indicate that a uniform dispersion of Co@Pt nanoparticles on PDDA functionalized graphene have the average particle size of 1.9 nm. The composite is applied to electrocatalysis for methanol oxidation. And the electrochemical surface areas of the as-prepared Co@Pt/PDDA-G, Pt supported on PDDA-graphene (Pt/PDDA-G), Co@Pt supported on graphene (Co@Pt/G) are evaluated by cyclic voltammetry, which are calculated to be 105.6 m 2 g −1 Pt , 92.8 m 2 g −1 Pt , and 83.4 m 2 g −1 Pt , with respect to 37.8 m 2 g −1 Pt of commercial Pt/C (TKK) catalyst. The current being examined by chronoamperometry reach a constant at 23 mA mg −1 for Co@Pt/PDDA–G catalyst, which is roughly 3.3-fold higher than that of commercial Pt/C catalyst. The electrochemical tests show that the activity and stability of Co@Pt supported on PDDA-G is highly better than the widely used Pt supported on PDDA-graphene sheets, also better than that of Co@Pt on unfunctional graphene with the same Pt content on the electrode. This improved activity could be attributed to not only the PDDA playing a crucial role in the dispersion and stabilization of Co@Pt on graphene, but also the high use ratio of Pt for its shell structure and the electronic effect of the underlying metal and Pt surface layer

  10. Catalytic Combustion of Low Concentration Methane over Catalysts Prepared from Co/Mg-Mn Layered Double Hydroxides

    Directory of Open Access Journals (Sweden)

    Hongfeng Liu

    2014-01-01

    Full Text Available A series of Co/Mg-Mn mixed oxides were synthesized through thermal decomposition of layered double hydroxides (LDHs precursors. The resulted catalysts were then subjected for catalytic combustion of methane. Experimental results revealed that the Co4.5Mg1.5Mn2LDO catalyst possessed the best performance with the T90=485°C. After being analyzed via XRD, BET-BJH, SEM, H2-TPR, and XPS techniques, it was observed that the addition of cobalt had significantly improved the redox ability of the catalysts whilst certain amount of magnesium was essential to guarantee the catalytic activity. The presence of Mg was helpful to enhance the oxygen mobility and, meanwhile, improved the dispersion of Co and Mn oxides, preventing the surface area loss after calcination.

  11. Highly sensitive silicon microreactor for catalyst testing

    DEFF Research Database (Denmark)

    Henriksen, Toke Riishøj; Olsen, Jakob Lind; Vesborg, Peter Christian Kjærgaard

    2009-01-01

    by directing the entire gas flow through the catalyst bed to a mass spectrometer, thus ensuring that nearly all reaction products are present in the analyzed gas flow. Although the device can be employed for testing a wide range of catalysts, the primary aim of the design is to allow characterization of model...... catalysts which can only be obtained in small quantities. Such measurements are of significant fundamental interest but are challenging because of the low surface areas involved. The relationship between the reaction zone gas flow and the pressure in the reaction zone is investigated experimentally......, it is found that platinum catalysts with areas as small as 15 mu m(2) are conveniently characterized with the device. (C) 2009 American Institute of Physics. [doi:10.1063/1.3270191]...

  12. Potential for cobalt recovery from lateritic ores in Europe

    Science.gov (United States)

    Herrington, R.

    2012-04-01

    Cobalt is one of the 'critical metals' identified under the EU Raw Materials Initiative. Annually the global mine production of cobalt is around 55,000 tonnes,with Europe's industries consuming around 30% of that figure. Currently Europe produces around 27 tonnes of cobalt from mines in Finland although new capacity is planned. Co-bearing nickel laterite ores being mined in Greece, Macedonia and Kosovo where the cobalt is currently not being recovered (ores have typical analyses of 0.055% Co and >1% Ni,). These ores are currently treated directly in pyrometallurgical plants to recover the contained nickel and this process means there is no separate cobalt product produced. Hydrometallurgical treatment of mineralogically suitable laterite ores can recover the cobalt; for example Cuba recovers 3,500 tonnes of cobalt from its laterite mining operations, which are of a similar scale to the current European operations. Implementation of hydrometallurgical techniques is in its infancy in Europe with one deposit in Turkey planning to use atmospheric heap leaching to recover nickel and copper from oxide-dominated ores. More widespread implementation of these methods to mineralogically suitable ore types could unlock the highly significant undeveloped resources (with metal contents >0.04% Co and >1% Ni), which have been defined throughout the Balkans eastwards into Turkey. At a conservative estimate, this region has the potential to supply up to 30% of the EU cobalt requirements.

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

    Science.gov (United States)

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

    2018-03-01

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

  14. In-situ reduction of promoted cobalt oxide supported on alumina by environmental transmission electron microscopy

    DEFF Research Database (Denmark)

    Dehghan, Roya; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    2011-01-01

    the reactivity of the nanoparticles and the importance of controlling the gas composition and specimen temperature during this type of experiment. Similar behaviour was observed for a non-promoted catalyst. Imaging and analysis of the promoted sample before and after reduction indicated a uniform distribution...... resolution transmission electron microscopy and scanning transmission electron microscopy imaging. The cobalt particles were mainly face centred cubic while some hexagonal close packed particles were also found. Reoxidation of the sample upon cooling to room temperature, still under flowing H2, underlines...

  15. Partial hydrogenation of alkynes on highly selective nano-structured mesoporous silica MCM-41 composite catalyst

    International Nuclear Information System (INIS)

    Kojoori, R.K.

    2016-01-01

    In this research, we have developed a silica MCM-41/Metformin/Pd (II) nano composite catalyst for the selective hydrogenation of alkynes to the corresponding (Z)-alkenes under a mild condition of atmospheric pressure and room temperature. Firstly, functionalized Si-MCM-41 metformin catalyst with the optimum performance was prepared. Then, the synthesized catalyst was elucidated by X-ray powder diffraction, BET surface area, FT-IR spectrophotometer, Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) and applied in partial hydrogenation of different alkynes, with high selectivity and high yield. The products were characterized by 1H-NMR, 13C-NMR, FT-IR, and Mass Spectrometry (MS) that strongly approved the (Z)-double bond configuration of produced alkenes. This prepared catalyst is competitive with the best palladium catalysts known for the selective liquid phase hydrogenation of alkynes and can be easily recovered and regenerated with keeping high activity and selectivity over at least three cycles with a simple regeneration procedure. (author)

  16. 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.

  17. Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Mikolajczuk-Zychora, A., E-mail: amikolajczuk@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Mazurkiewicz-Pawlicka, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Ciecierska, E. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Zimoch, A.; Opałło, M. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)

    2016-12-01

    Highlights: • Palladium catalyst used on the cathode DFAFC is comparable to commercial platinum catalyst. • The treatment of carbon supports in nitric acid(V) increases the electrochemically available metal surface area and the catalytic activity in oxygen reduction reaction of catalysts. - Abstract: One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

  18. Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

    Science.gov (United States)

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

    2018-01-31

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

  19. The development of isomerization catalysts for production of high-octane products

    Energy Technology Data Exchange (ETDEWEB)

    Pedrosa, A.M. Garrido; Melo, D.M.A.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Quimica; Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Engenharia Quimica

    2004-07-01

    In current petroleum industry, paraffins larger than C5 are used for catalytic reform. The catalytic reform is one of the most important processes for petroleum refine in reason of all reactions they drive to production of high-octane products. Reformate has high-octane products, but they contain 60% aromatics. Isomerization of C5- C7 can improve the octane number. The octane number of n-heptane is zero and increases after isomerization. For tri branched C7, the octane number reaches 113, which is higher than that of benzene. So, isomerization of C5-C7 is suggested to be a reasonable way to replace or partly replace the catalytic reforming process. It can decrease aromatics content with enhancement of octane number. Liquid acid catalysts were widely used in chemical industry in past decades. However, they face strong environmental challenges. The heavy corrosion of the reactor system is one of the main problems. Thus, solid acid catalysts are investigated for the isomerization reactions. The aim of this work is to develop a catalysts for the production of reformate products. Isomerization is catalyzed by metal-acid bifunctional catalysts. The metal components aid in hydrogenation, while the support, such as, zirconium, clays or zeolites, is the acidic component. (author)

  20. Magnetic properties of mosaic nanocomposites composed of nickel and cobalt nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Castillo-Sepúlveda, S.; Corona, R.M. [Departamento de Física, Universidad de Santiago de Chile (USACH), Av. Ecuador 3493, 9170124 Santiago (Chile); Altbir, D. [Departamento de Física, Universidad de Santiago de Chile (USACH), Av. Ecuador 3493, 9170124 Santiago (Chile); Center for the Development of Nanoscience and Nanotechnology (CEDENNA), 9170124 Santiago (Chile); Escrig, J., E-mail: juan.escrig@usach.cl [Departamento de Física, Universidad de Santiago de Chile (USACH), Av. Ecuador 3493, 9170124 Santiago (Chile); Center for the Development of Nanoscience and Nanotechnology (CEDENNA), 9170124 Santiago (Chile)

    2016-10-15

    Mosaic nanocomposites composed of nickel and cobalt nanowires arranged in different configurations were investigated using Monte Carlo simulations and a simple model that considers single-domain structures including length corrections due to the shape anisotropy. Our results showed that for an ordered array both the coercivity and the remanence decrease linearly as a function of the concentration of nickel nanowires. Besides, we obtained that the magnetic properties of an array of a certain hard magnetic material (cobalt) will not change, unless we have more than 50% of nanowires of other soft magnetic material (nickel) in the array. In principle the second material could be other soft magnetic material, but could also be a nonmagnetic material or could even be a situation in which some of the pore arrays were not filled by electrodeposition. Therefore, our results allow us to predict the behavior of magnetic mosaic nanocomposites that are promising candidates for functional electrodes, sensors, and model catalysts. - Highlights: • Mosaic nanocomposites composed of magnetic nanowires were investigated. • Magnetic properties can be adjusted by varying the concentration of nanowires. • Our results allow us to predict the behavior of magnetic mosaic nanocomposites.

  1. Antiferromagnetic coupling in a six-coordinate high spin cobalt(II)-semiquinonato complex.

    Science.gov (United States)

    Caneschi, Andrea; Dei, Andrea; Gatteschi, Dante; Tangoulis, Vassilis

    2002-07-01

    The 3,5-di-tert-butyl-catecholato and 9,10-phenanthrenecatecholato adducts of the cobalt-tetraazamacrocycle complex Co(Me(4)cyclam)(2+) (Me(4)cyclam = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) were synthesized and oxidized. The oxidation reaction products were isolated in the solid state as hexafluorophosphate derivatives. Both these complexes can be formulated as 1:1 cobalt(II)-semiquinonato complexes, that is, Co(Me(4)cyclam)(DBSQ)PF(6) (1) and Co(Me(4)cyclam)(PhSQ)PF(6) (2), in the temperature range 4-300 K, in striking contrast with the charge distribution found in similar adducts formed by related tetraazamacrocycles. The synthesis strategy and the structural, spectroscopic, and magnetic properties are reported and discussed. The crystallographic data for 2 are as follows: monoclinic, space group P2(1)/a, nomicron. 14, a = 14.087(4) A, b = 15.873(4) A, c = 14.263 (7) A, alpha = 89.91(3) degrees, beta = 107.34(2) degrees, gamma = 90.08(2) degrees, Z = 4. Both these complexes are characterized by triplet electronic ground states arising from the antiferromagnetic coupling between the high-spin d(7) metal ion and the radical ligand.

  2. Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

    Science.gov (United States)

    Akatay, Mehmed Cem

    Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

  3. Ammonia synthesis over multi-promoted iron catalysts obtained by high-energy ball-milling

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Jiang, Jianzhong; Mørup, Steen

    1999-01-01

    The feasibility of producing ammonia synthesis catalysts from high-energy ball-milling of a simple mixture of the constituent oxides has been investigated. The effect of ball-milling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show...

  4. Highly active and durable Ca-doped Ce-SBA-15 catalyst for biodiesel production

    International Nuclear Information System (INIS)

    Thitsartarn, Warintorn; Maneerung, Thawatchai; Kawi, Sibudjing

    2015-01-01

    In this work, Ca-doped Ce-incorporated SBA-15 (Ca/CeS) catalyst was successfully synthesized by using direct synthesis of Ce-incorporated SBA-15 followed by impregnation of CaO (calcium oxide). The maximum Si/Ce molar ratio that Ce atoms can be incorporated successfully into the mesoporous framework was found to be 5 (CeS-5). After the impregnation of 30 wt. % Ca, the obtained 30Ca/CeS-5 catalysts showed the superior catalytic performance for transesterification reaction of palm oil with methanol and also the higher catalytic activity as compared to other supported catalysts, i.e. CaO/CeO 2 and CaO–CeO 2 /SBA-15. This can be attributed to the well-dispersion of CaO on the CeS-5 support surface. Furthermore, it was found that the leaching of Si, Ce and Ca from the catalyst into biodiesel produced was negligible (i.e. <1 ppm after 7 cycles), indicating the strong interaction between CaO and CeS-5 support. As a result, the 30Ca/CeS-5 catalyst can be reused at least 15 cycles with insignificant decrease in catalytic activity, offering the efficient CaO-based catalyst for biodiesel production. - Highlights: • Mesoporous Ca-based catalyst was successfully developed for biodiesel production. • Catalyst exhibited high activity towards transesterification (FAME yield > 98%). • Catalyst can be effectively re-used at least 15 cycles. • Extremely low catalyst contaminant (<1 ppm) was presented

  5. Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

    Science.gov (United States)

    Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

    2016-12-01

    One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

  6. High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

    2009-01-01

    A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

  7. Biodiesel production from Silybum marianum L. seed oil with high FFA content using sulfonated carbon catalyst for esterification and base catalyst for transesterification

    International Nuclear Information System (INIS)

    Fadhil, Abdelrahman B.; Aziz, Akram M.; Al-Tamer, Marwa H.

    2016-01-01

    Highlights: • PET was converted to activated carbon and then sulfonated to prepare carbon acid catalyst. • Carbon acid catalyst was used for esterification of high acid value Silybum marianum L. seed oil. • Biodiesel was obtained with 96.98% efficiency. - Abstract: In this research work, waste of polyethylene terephthalate (PET) was converted into activated carbon and the latter was used in the preparation of a carbon acid catalyst. Waste of PET was converted into activated carbon via carbonization and steam activation, then the activated carbon was sulfonated using fuming sulfuric acid in order to produce the carbon acid catalyst. The prepared carbon acid catalyst was tested for esterification of high acid value non-edible oil, Silybum marianum L. seed oil (SMSO) via optimized protocol. Amount of the carbon acid catalyst, methanol to oil molar ratio, temperature and time were the experimental variables optimized. Esterification of SMSO with methanol using the prepared carbon acid catalyst reduced its parent acid value (20.0 mg KOH/g) to the acceptable limits for base-catalyzed transesterification (<2.0 mg KOH/g) using 6.0% w/w of the catalyst, 15:1 methanol to oil molar ratio, 68 °C reaction temperature and 180 min of reaction. The performance of the catalyst was reduced gradually during its recycling and reached to 60.0% at the 5th cycle. Kinetics of esterification of SMSO using the prepared carbon acid catalyst followed pseudo first order kinetics, and the activation energy was found to be 70.98 kJ/mol. The esterified oil was converted to biodiesel through optimized base-catalyzed transesterification with methanol. Biodiesel with (96.98% yield and purity of 96.69% w/w) yield was obtained using 0.80% KOH w/w, 6:1 methanol to oil molar ratio, 60 °C reaction temperature, 75 min of reaction and 600 rpm rate of stirring. The biodiesel properties were within the recommended biodiesel standards as prescribed by ASTM D 6751 and EN 14214. Transesterification of

  8. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October--December 1993

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, E.; Kirby, S.; Song, Chunshan; Schobert, H.H.

    1994-04-01

    Development of new catalysts is a promising approach to more, efficient coal liquefaction. It has been recognized that dispersed catalysts can be superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires infinite contact between the catalyst and coal. The primary objective of this research is to explore the potential of bimetallic dispersed catalysts from heterometallic molecular precursors in their use in model compound liquefaction reactions. This quarterly report describes the use of three precursors in model compound reactions. The first catalyst is a heterometallic complex consisting of two transition metals, Mo and Ni, and sulfur in a single molecule. The second is a thiocubane type complex consisting of cobalt, molybdenum and sulfur. The third is a thiocubane type cluster consisting of iron and sulfur and the fourth, the pure inorganic salt ammonium tetrathiomolybdate (ATM). It was found that the structure and the ligands in the model complexes affect the activity of the resulting catalyst significantly. The optimum reaction at a pressure of 6.9 MPa hydrogen gas varied for different catalysts. The bimetallic catalysts generated in situ from the organometallic precursor are more active than monometallic catalysts like ATTM and the thiocubane type cluster Fe{sub 4}. Main products are hydrogenated phenanthrene derivatives, like DBP, THP, sym-OHP, cis- and trans-unsym-OHP with minor isomerization products such as sym-OHA. Our results indicate that other transition metal and ligand combinations in the organometallic precursors and the use of another model compound could result in substantially higher conversion activity.

  9. Application of Co and Mn for a Co-Mn-Br or Co-Mn-C2H3O2 Petroleum Liquid Catalyst from the Cathode Material of Spent Lithium Ion Batteries by a Hydrometallurgical Route

    Directory of Open Access Journals (Sweden)

    Sung-Ho Joo

    2017-10-01

    Full Text Available We investigated the preparation of CMB (cobalt-manganese-bromide and CMA (cobalt-manganese-acetate liquid catalysts as petroleum liquid catalysts by simultaneously recovering Co and Mn from spent Li-ion battery cathode material. To prepare the liquid catalysts, the total preparation process for the liquid catalysts consisted of physical pre-treatments, such as grinding and sieving, and chemical processes, such as leaching, solvent extraction, and stripping. In the physical pre-treatment process, over 99% of Al was removed from material with a size of less than 0.42 mm. In the chemical process, the leaching solution as obtained under the following conditions: 2 mol/L sulfuric acid, 10 vol % H2O2, 0.1 of solid/liquid ratio, and 60 °C. In the solvent extraction process, the optimum concentration of bis (2,4,4-trimethylpentyl phosphinic acid (Cyanex 272, the equilibrium pH, the degree of saponification, the organic phase/aqueous phase ratio isotherm, and the stripping study for the extraction of Co and Mn were investigated. As a result, Co and Mn were recovered by 0.85 M Cyanex 272 with 50% saponification in counter current two extraction stages. Finally, a CMB and CMA liquid catalyst containing 33.1 g/L Co, 29.8 g/L Mn, and 168 g/L Br and 12.67 g/L Co, 12.0 g/L Mn, and 511 g/L C2H3O2, respectively, was produced by 2 M hydrogen bromide and 50 vol % acetic acid; it was also found that a shortage in the concentration can be compensated with cobalt and manganese salts.

  10. Characterization of a Cobalt-Tungsten Interconnect

    DEFF Research Database (Denmark)

    Harthøj, Anders; Holt, Tobias; Caspersen, Michael

    2012-01-01

    is to act both as a diffusion barrier for chromium and provide better protection against high temperature oxidation than a pure cobalt coating. This work presents a characterization of a cobalt-tungsten alloy coating electrodeposited on the ferritic steel Crofer 22 H which subsequently was oxidized in air......A ferritic steel interconnect for a solid oxide fuel cell must be coated in order to prevent chromium evaporation from the steel substrate. The Technical University of Denmark and Topsoe Fuel Cell have developed an interconnect coating based on a cobalt-tungsten alloy. The purpose of the coating...... for 300 h at 800 °C. The coating was characterized with Glow Discharge Optical Spectroscopy (GDOES), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The oxidation properties were evaluated by measuring weight change of coated samples of Crofer 22 H and Crofer 22 APU as a function...

  11. High Throughput In Situ XAFS Screening of Catalysts

    International Nuclear Information System (INIS)

    Tsapatsaris, Nikolaos; Beesley, Angela M.; Weiher, Norbert; Tatton, Helen; Schroeder, Sven L. M.; Dent, Andy J.; Mosselmans, Frederick J. W.; Tromp, Moniek; Russu, Sergio; Evans, John; Harvey, Ian; Hayama, Shu

    2007-01-01

    We outline and demonstrate the feasibility of high-throughput (HT) in situ XAFS for synchrotron radiation studies. An XAS data acquisition and control system for the analysis of dynamic materials libraries under control of temperature and gaseous environments has been developed. The system is compatible with the 96-well industry standard and coupled to multi-stream quadrupole mass spectrometry (QMS) analysis of reactor effluents. An automated analytical workflow generates data quickly compared to traditional individual spectrum acquisition and analyses them in quasi-real time using an HT data analysis tool based on IFFEFIT. The system was used for the automated characterization of a library of 91 catalyst precursors containing ternary combinations of Cu, Pt, and Au on γ-Al2O3, and for the in situ characterization of Au catalysts supported on Al2O3 and TiO2

  12. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

    KAUST Repository

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi Zhang

    2016-01-01

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  13. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

    Science.gov (United States)

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang

    2016-12-14

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  14. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

    KAUST Repository

    Zheng, Yao

    2016-11-28

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  15. Cobalt accumulation and circulation by blackgum trees

    International Nuclear Information System (INIS)

    Thomas, W.A.

    1975-01-01

    Blackgum (Nyssa sylvatica Marsh.) trees accumulate far greater concentrations of cobalt in mature foliage than do other species on the same site (363 ppM in ash of blackgum, compared with about 3 ppM by mockernut hickory and about 1 ppM by red maple, tulip tree, and white oak). Cobalt concentrations in dormant woody tissues of blackgum also significantly exceed those in the other four species. Inoculation of six blackgums with 60 Co revealed that cobalt remains mobile in the trees for at least 3 years. Foliar concentrations of stable cobalt increase uniformly until senescence. In late August, foliage accounts for only 9 percent of total tree weight but 57 percent of total tree cobalt. Losses of cobalt from trees occur almost entirely by leaf abscission, and the loss rates of weight and cobalt from decomposing litter are similar. Retention of cobalt in the biologically active soil layers perpetuates zones of cobalt concentration created by this species in woodlands

  16. Cobalt-60 production in CANDU power reactors

    International Nuclear Information System (INIS)

    Slack, J.; Norton, J.L.; Malkoske, G.R.

    2003-01-01

    MDS Nordion has been supplying cobalt-60 sources to industry for industrial and medical purposes since 1946. These cobalt-60 sources are used in many market and product segments. The major application is in the health care industry where irradiators are used to sterilize single use medical products. These irradiators are designed and built by MDS Nordion and are used by manufacturers of surgical kits, gloves, gowns, drapes and other medical products. The irradiator is a large shielded room with a storage pool for the cobalt-60 sources. The medical products are circulated through the shielded room and exposed to the cobalt-60 sources. This treatment sterilizes the medical products which can then be shipped to hospitals for immediate use. Other applications for this irradiation technology include sanitisation of cosmetics, microbial reduction of pharmaceutical raw materials and food irradiation. The cobalt-60 sources are manufactured by MDS Nordion in their Cobalt Operations Facility in Kanata. More than 75,000 cobalt-60 sources for use in irradiators have been manufactured by MDS Nordion. The cobalt-60 sources are double encapsulated in stainless steel capsules, seal welded and helium leak tested. Each source may contain up to 14,000 curies. These sources are shipped to over 170 industrial irradiators around the world. This paper will focus on the MDS Nordion proprietary technology used to produce the cobalt-60 isotope in CANDU reactors. Almost 55 years ago MDS Nordion and Atomic Energy of Canada developed the process for manufacturing cobalt-60 at the Chalk River Labs, in Ontario, Canada. A cobalt-59 target was introduced into a research reactor where the cobalt-59 atom absorbed one neutron to become cobalt-60. Once the cobalt-60 material was removed from the research reactor it was encapsulated in stainless steel and seal welded using a Tungsten Inert Gas weld. The first cobalt-60 sources manufactured using material from the Chalk River Labs were used in cancer

  17. Atomic-Level Co3O4 Layer Stabilized by Metallic Cobalt Nanoparticles: A Highly Active and Stable Electrocatalyst for Oxygen Reduction.

    Science.gov (United States)

    Liu, Min; Liu, Jingjun; Li, Zhilin; Wang, Feng

    2018-02-28

    Developing atomic-level transition oxides may be one of the most promising ways for providing ultrahigh electrocatalytic performance for oxygen reduction reaction (ORR), compared with their bulk counterparts. In this article, we developed a set of atomically thick Co 3 O 4 layers covered on Co nanoparticles through partial reduction of Co 3 O 4 nanoparticles using melamine as a reductive additive at an elevated temperature. Compared with the original Co 3 O 4 nanoparticles, the synthesized Co 3 O 4 with a thickness of 1.1 nm exhibits remarkably enhanced ORR activity and durability, which are even higher than those obtained by a commercial Pt/C in an alkaline environment. The superior activity can be attributed to the unique physical and chemical structures of the atomic-level oxide featuring the narrowed band gap and decreased work function, caused by the escaped lattice oxygen and the enriched coordination-unsaturated Co 2+ in this atomic layer. Besides, the outstanding durability of the catalyst can result from the chemically epitaxial deposition of the Co 3 O 4 on the cobalt surface. Therefore, the proposed synthetic strategy may offer a smart way to develop other atomic-level transition metals with high electrocatalytic activity and stability for energy conversion and storage devices.

  18. Catalysts of Cu(II) and Co(II) ions adsorbed in chitosan used in transesterification of soy bean and babassu oils - a new route for biodiesel syntheses.

    Science.gov (United States)

    da Silva, Rondinelly Brandão; Lima Neto, Alcides Fernandes; Soares Dos Santos, Lucas Samuel; de Oliveira Lima, José Renato; Chaves, Mariana Helena; Dos Santos, José Ribeiro; de Lima, Geraldo Magela; de Moura, Edmilson Miranda; de Moura, Carla Verônica Rodarte

    2008-10-01

    Catalysts of Cu(II) and Co(II) adsorbed in chitosan was used in transesterification of soy bean and babassu oils. The catalysts were characterized by infrared, atomic absorption and TG, and biodiesels was characterized by infrared, NMR, CG, TG, physic chemistry analysis. The maximum adsorption values found for copper and cobalt cations were 1.584 and 1.260mgg(-1), respectively, in 180min. However, conversion of oils in biodiesel was better when used Co(II) adsorbed in chitosan.

  19. Cobalt allergy in hard metal workers

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, T; Rystedt, I

    1983-03-01

    Hard metal contains about 10% cobalt. 853 hard metal workers were examined and patch tested with substances from their environment. Initial patch tests with 1% cobalt chloride showed 62 positive reactions. By means of secondary serial dilution tests, allergic reactions to cobalt were reproduced in 9 men and 30 women. Weak reactions could not normally be reproduced. A history of hand eczema was found in 36 of the 39 individuals with reproducible positive test reactions to cobalt, while 21 of 23 with a positive initial patch test but negative serial dilution test had never had any skin problems. Hand etching and hand grinding, mainly female activities and traumatic to the hands, were found to involve the greatest risk of cobalt sensitization. 24 individuals had an isolated cobalt allergy. They had probably been sensitized by hard metal work, while the individuals, all women, who had simultaneous nickel allergy had probably been sensitized to nickel before their employment and then became sensitized to cobalt by hard metal work. A traumatic occupation, which causes irritant contact dermatitis and/or a previous contact allergy or atopy is probably a prerequisite for the development of cobalt allergy.

  20. Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Alanis O, R.; Jimenez B, J., E-mail: jaime.jimenez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2010-07-01

    In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO{sub 2}, which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO{sub 2} synthesized by the Degussa company (TiO{sub 2} Degussa P25) with and oxide of mixed cobalt valence (Co{sub 3}O{sub 4}) synthesized using the sol-gel method. The synthesized photo catalyst TiO{sub 2}/Co{sub 3}O{sub 4} was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

  1. Nanocrystalline Iron-Cobalt Alloys for High Saturation Indutance

    Science.gov (United States)

    2016-02-24

    film deposited just like the pick-up of a turn-table music player. The contact pads provide the electrical contacts to the starting and end point of...anisotropy using the geometry of the thin toroid. We have shown experimentally that the thin film toroid calculations may be applicable to up to millimeter...thin film as well as bulk devices. 15. SUBJECT TERMS Micromagnetic Calculations, Nanocrystalline cobalt-iron, Thin Film Toroids 16. SECURITY

  2. Nitrogen and Fluorine co-doped carbon catalyst with high oxygen reduction performance, prepared by pyrolyzing a mixture of melamine and PTFE

    International Nuclear Information System (INIS)

    Peng, Hongliang; Liu, Fangfang; Qiao, Xiaochang; Xiong, Ziang; Li, Xiuhua; Shu, Ting; Liao, Shijun

    2015-01-01

    Graphical abstract: A novel N and F co-doped metal-free doped carbon catalyst with three dimensional vesicles structures and ultra thin walls are prepared by pyrolyzing the mixture of melamine and PTFE. The catalyst has high N and F contents (13 and 6 at.%), and exhibits high ORR activity, high stability, and high limitation current density in both alkaline and acid medium. - Highlights: • N and F co-doped carbon catalyst was derived from the mixture of PTFE and melamine. • The N and F contents of the catalyst are up to 13 and 6 at.%, respectively. • The catalyst has three dimensional vesicles structure with ultra thin walls. • ORR activity of the catalyst is superior to that of Pt/C catalyst in alkaline medium. - Abstract: A novel nitrogen and fluorine co-doped carbon catalyst (C-Mela-PTFE) is prepared by pyrolyzing a mixture of melamine and polytetrafluoroethylene (PTFE), the catalyst has a three-dimensional vesicular structure with ultrathin wall, and exhibits excellent ORR performance in both alkaline and acidic mediums. In an alkaline medium, the catalyst exhibits superior ORR activity to that of commercial Pt/C catalyst. Notably, the ORR activity of the catalyst is just slightly lower than that of Pt/C catalyst in acidic medium. It is interesting that the ORR limiting current density of our C-Mela-PTFE catalyst is much higher than that of Pt/C catalyst. The effects of the melamine/PTFE ratio and the pyrolysis temperature on the catalyst's ORR performance are investigated. The optimal melamine/PTFE ratio by weight is 1:1.5, and the optimal pyrolysis temperature is 950 °C. The catalyst samples are characterized by XRD, SEM/TEM, Raman analysis, and XPS, the results reveal the ultra-thin-walled vesicular structure, high surface area and porosity, and high doping amounts of N and F of the catalyst. For the optimal sample, the N and F contents are up to 13 and 6 at.%, respectively, the proportion of pyridinic N is up to 45 at.% according to the

  3. COBALT SALTS PRODUCTION BY USING SOLVENT EXTRACTION

    Directory of Open Access Journals (Sweden)

    Liudmila V. Dyakova

    2010-06-01

    Full Text Available The paper deals with the extracting cobalt salts by using mixtures on the basis of tertiary amine from multicomponent solutions from the process of hydrochloride leaching of cobalt concentrate. The optimal composition for the extraction mixture, the relationship between the cobalt distribution coefficients and modifier’s nature and concentration, and the saltingout agent type have been determined. A hydrochloride extraction technology of cobalt concentrate yielding a purified concentrated cobalt solution for the production of pure cobalt salts has been developed and introduced at Severonikel combine.

  4. Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun, E-mail: 1044208419@qq.com; Mao, Hui, E-mail: rejoice222@163.com [Sichuan Normal University, College of Chemistry and Materials Science (China)

    2016-10-15

    Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al{sub 2}O{sub 3} catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

  5. Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

    International Nuclear Information System (INIS)

    Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun; Mao, Hui

    2016-01-01

    Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al 2 O 3 catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

  6. Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Su, Hui [Iowa State Univ., Ames, IA (United States)

    2001-01-01

    Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection.

  7. Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

    International Nuclear Information System (INIS)

    Hui Su

    2001-01-01

    Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm(sub 2) for 40-(micro)m wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection

  8. Cobalt production in RAPS-1

    International Nuclear Information System (INIS)

    Krishnan, P.D.; Purandare, H.D.

    1978-01-01

    At present in RAPS-1 radioisotope Co 60 is produced by irradiating Co 59 in the adjusters which perform the function of regulation of reactivity, power and xenon override. But the manrem expenditure of the crew handling the charge and discharge of the adjusters is going to be prohibitively high. It is therefore proposed to irradiate Co 59 in the fuel channel positions. The physics optimisation study for such irradiation is presented. The burnup penalty and loss of power are estimated to produce the required quantity of Co 60 after optimising the number of cobalt pencils in a bundle and the positions of the cobalt producing channels in the reactor core. (author)

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

    CSIR Research Space (South Africa)

    Heveling, J

    1998-10-11

    Full Text Available The oligomerisation of ethylene into products in the C-4-C-20 range over heterogeneous nickel catalysts in a fixed-bed reactor at low temperature and high pressure (LT-HP) is reported. The catalysts were obtained by Ni (II) exchange or impregnation...

  10. A synthesis method for cobalt doped carbon aerogels with high surface area and their hydrogen storage properties

    Energy Technology Data Exchange (ETDEWEB)

    Tian, H.Y.; Buckley, C.E. [Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U 1987, Perth 6845, WA (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Sheppard, D.A.; Paskevicius, M. [Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U 1987, Perth 6845, WA (Australia); Hanna, N. [CSIRO Process Science and Engineering, Waterford, WA (Australia)

    2010-12-15

    Carbon aerogels doped with nanoscaled Co particles were prepared by first coating activated carbon aerogels using a wet-thin layer coating process. The resulting metal-doped carbon aerogels had a higher surface area ({proportional_to}1667 m{sup 2} g{sup -1}) and larger micropore volume ({proportional_to}0.6 cm{sup 3} g{sup -1}) than metal-doped carbon aerogels synthesised using other methods suggesting their usefulness in catalytic applications. The hydrogen adsorption behaviour of cobalt doped carbon aerogel was evaluated, displaying a high {proportional_to}4.38 wt.% H{sub 2} uptake under 4.6 MPa at -196 C. The hydrogen uptake capacity with respect to unit surface area was greater than for pure carbon aerogel and resulted in {proportional_to}1.3 H{sub 2} (wt. %) per 500 m{sup 2} g{sup -1}. However, the total hydrogen uptake was slightly reduced as compared to pure carbon aerogel due to a small reduction in surface area associated with cobalt doping. The improved adsorption per unit surface area suggests that there is a stronger interaction between the hydrogen molecules and the cobalt doped carbon aerogel than for pure carbon aerogel. (author)

  11. Development of Ultra-Low Platinum Alloy Cathode Catalysts for PEM Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Popov, Branko N. [Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering; Weidner, John [Univ. of South Carolina, Columbia, SC (United States)

    2016-01-07

    The goal of this project is to synthesize a low cost PEM fuel cell cathode catalyst and support with optimized average mass activity, stability of mass activity, initial high current density performance under H2/air (power density), and catalyst and support stability able to meet 2017 DOE targets for electrocatalysts for transportation applications. Pt*/ACCS-2 catalyst was synthesized according to a novel methodology developed at USC through: (i) surface modification, (ii) metal catalyzed pyrolysis and (iii) chemical leaching to remove excess meal used to dope the support. Pt* stands for suppressed platinum catalyst synthesized with Co doped platinum. The procedure results in increasing carbon graphitization, inclusion of cobalt in the bulk and formation of non-metallic active sites on the carbon surface. Catalytic activity of the support shows an onset potential of 0.86 V for the oxygen reduction reaction (ORR) with well-defined kinetic and mass transfer regions and 2.5% H2O2 production. Pt*/ACCS-2 catalyst durability under 0.6-1.0 V potential cycling and support stability under 1.0-1.5 V potential cycling was evaluated. The results indicated excellent catalyst and support performance under simulated start-up/shut down operating conditions (1.0 – 1.5 V, 5000 cycles) which satisfy DOE 2017 catalyst and support durability and activity. The 30% Pt*/ACCS-2 catalyst showed high initial mass activity of 0.34 A/mgPGM at 0.9 ViR-free and loss of mass activity of 45% after 30,000 cycles (0.6-1.0 V). The catalyst performance under H2-air fuel cell operating conditions showed only 24 mV (iR-free) loss at 0.8 A/cm2 with an ECSA loss of 42% after 30,000 cycles (0.6-1.0 V). The support stability under 1.0-1.5 V potential cycling showed mass activity loss of 50% and potential loss of 8 mV (iR-free) at 1.5 A/cm2. The ECSA loss was 22% after 5,000 cycles. Furthermore, the Pt*/ACCS-2 catalyst showed an

  12. Nickel acts as an adjuvant during cobalt sensitization

    DEFF Research Database (Denmark)

    Bonefeld, Charlotte Menne; Nielsen, Morten Milek; Vennegaard, Marie T.

    2015-01-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We...... investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found...... that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses...

  13. Simultaneous Reduction of CO 2 and Splitting of H 2 O by a Single Immobilized Cobalt Phthalocyanine Electrocatalyst

    KAUST Repository

    Morlanés, Natalia

    2016-04-12

    Perfluorinated cobalt phthalocyanine (CoFPc) immobilized on carbon electrodes was found to electrocatalyze the reduction of CO2 selectively to CO in an aqueous solution. The conversion of CO2 became apparent at -0.5 V vs RHE, and the Faradaic efficiency for the CO production reached as high as 93% at -0.8 V vs RHE. Highly stable electrolysis of CO2/H2O into CO/O2 was achieved for 12 h by applying the same catalyst as the cathode for CO2 reduction and the anode for water oxidation. This result indicates the highly robust nature of the CoFPc at wide range of potentials from -0.9 V to +2.2 V vs RHE, demonstrating the potential bipolar electrolytic system for CO2/H2O electrolysis, using the single-site molecular CoFPc-based electrocatalyst, which is simple, inexpensive, robust, and efficient. © 2016 American Chemical Society.

  14. A laboratory and field evaluation of the mobility of cobalt-60/EDTA

    International Nuclear Information System (INIS)

    Jones, T.L.; Gee, G.W.; Kirkham, R.R.; Swanson, J.L.

    1983-01-01

    We have observed a time and soil type dependence in the ability of the organic complexant EDTA to keep cobalt-60 in solution. Test results indicate that short-term adsorption tests lasting 5 days or less can be misleading. In short-term tests using cobalt-60/EDTA and soil from the Hanford site, low sorption in batch tests and high mobility in column tests were observed. During long-term batch test using cobalt-60/EDTA, the percentage of cobalt remaining in solution decreased from 90% after 7 days to less than 10% after 500 days. In laboratory and field column tests where low water flow rates allowed long contact time, virtually no cobalt movement was observed even though in the field test tritium was transported over 4 meters. Long-term batch tests using cobalt-60/EDTA and soil from Savannah River burial grounds showed that cobalt remainin in solution dropped to 30% of the total cobalt added after 5 days and to less than 1% after 15 days. Batch tests using soil from Oak Ridge burial grounds were less dramatic showing cobalt in solution decreasing from 90% after 5 days to 70% after 35 days. The cobalt-60/EDTA complex appears to be dissociating and leaving uncomplexed cobalt which is readily sorbed. The dissociation seems to be rather complete in Hanford and Savannah River soil but limited in the Oak Ridge soil. The implication to waste management is that the potential for transport of cobalt by EDTA may not be as serious at all burial sites as once thought

  15. Manganese substituted cobalt ferrite magnetostrictive materials for magnetic stress sensor applications

    OpenAIRE

    Paulsen, J. A.; Ring, A. P.; Lo, C. C. H.; Snyder, John Evan; Jiles, David

    2005-01-01

    Metal bonded cobalt ferrite composites have been shown to be promising candidate materials for use in magnetoelastic stress sensors, due to their large magnetostriction and high sensitivity of magnetization to stress. However previous results have shown that below 60 °C the cobalt ferrite material exhibits substantial magnetomechanical hysteresis. In the current study, measurements indicate that substituting Mn for some of the Fe in the cobalt ferrite can lower the Curie temperature of the ma...

  16. When Al-Doped Cobalt Sulfide Nanosheets Meet Nickel Nanotube Arrays: A Highly Efficient and Stable Cathode for Asymmetric Supercapacitors.

    Science.gov (United States)

    Huang, Jun; Wei, Junchao; Xiao, Yingbo; Xu, Yazhou; Xiao, Yujuan; Wang, Ying; Tan, Licheng; Yuan, Kai; Chen, Yiwang

    2018-03-27

    Although cobalt sulfide is a promising electrode material for supercapacitors, its wide application is limited by relative poor electrochemical performance, low electrical conductivity, and inefficient nanostructure. Here, we demonstrated that the electrochemical activity of cobalt sulfide could be significantly improved by Al doping. We designed and fabricated hierarchical core-branch Al-doped cobalt sulfide nanosheets anchored on Ni nanotube arrays combined with carbon cloth (denoted as CC/H-Ni@Al-Co-S) as an excellent self-standing cathode for asymmetric supercapacitors (ASCs). The combination of structural and compositional advantages endows the CC/H-Ni@Al-Co-S electrode with superior electrochemical performance with high specific capacitance (1830 F g -1 /2434 F g -1 at 5 mV s -1 /1 A g -1 ) and excellent rate capability (57.2%/72.3% retention at 1000 mV s -1 /100 A g -1 ). The corresponding all-solid-state ASCs with CC/H-Ni@Al-Co-S and multilayer graphene/CNT film as cathode and anode, respectively, achieve a high energy density up to 65.7 W h kg -1 as well as superb cycling stability (90.6% retention after 10 000 cycles). Moreover, the ASCs also exhibit good flexibility and stability under different bending conditions. This work provides a general, effective route to prepare high-performance electrode materials for flexible all-solid-state energy storage devices.

  17. Non-PGM cell catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

    2017-09-27

    A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

  18. Self-Assembled Hierarchical Formation of Conjugated 3D Cobalt Oxide Nanobead-CNT-Graphene Nanostructure Using Microwaves for High-Performance Supercapacitor Electrode.

    Science.gov (United States)

    Kumar, Rajesh; Singh, Rajesh Kumar; Dubey, Pawan Kumar; Singh, Dinesh Pratap; Yadav, Ram Manohar

    2015-07-15

    Here we report the electrochemical performance of a interesting three-dimensional (3D) structures comprised of zero-dimensional (0D) cobalt oxide nanobeads, one-dimensional (1D) carbon nanotubes and two-dimensional (2D) graphene, stacked hierarchically. We have synthesized 3D self-assembled hierarchical nanostructure comprised of cobalt oxide nanobeads (Co-nb), carbon nanotubes (CNTs), and graphene nanosheets (GNSs) for high-performance supercapacitor electrode application. This 3D self-assembled hierarchical nanostructure Co3O4 nanobeads-CNTs-GNSs (3D:Co-nb@CG) is grown at a large scale (gram) through simple, facile, and ultrafast microwave irradiation (MWI). In 3D:Co-nb@CG nanostructure, Co3O4 nanobeads are attached to the CNT surfaces grown on GNSs. Our ultrafast, one-step approach not only renders simultaneous growth of cobalt oxide and CNTs on graphene nanosheets but also institutes the intrinsic dispersion of carbon nanotubes and cobalt oxide within a highly conductive scaffold. The 3D:Co-nb@CG electrode shows better electrochemical performance with a maximum specific capacitance of 600 F/g at the charge/discharge current density of 0.7A/g in KOH electrolyte, which is 1.56 times higher than that of Co3O4-decorated graphene (Co-np@G) nanostructure. This electrode also shows a long cyclic life, excellent rate capability, and high specific capacitance. It also shows high stability after few cycles (550 cycles) and exhibits high capacitance retention behavior. It was observed that the supercapacitor retained 94.5% of its initial capacitance even after 5000 cycles, indicating its excellent cyclic stability. The synergistic effect of the 3D:Co-nb@CG appears to contribute to the enhanced electrochemical performances.

  19. Kinetic Control of Intralayer Cobalt Coordination in Layered Hydroxides: CoxoctCoxtet(OH)2(Cl)x(H2O)n

    International Nuclear Information System (INIS)

    Neilson, James R.; Schwenzer, Birgit; Seshadri, Ram; Morse, Daniel E.

    2009-01-01

    We report the synthesis and characterization of new structural variants of the isotypic compound with the generic chemical formula, Co 1-0.5x oct Co x tet (OH) 2 (Cl) x (H 2 O) n , all modifications of an α-Co(OH) 2 lattice. We show that the occupancy of tetrahedrally coordinated cobalt sites and associated chloride ligands, x, is modulated by the rate of formation of the respective layered hydroxide salts from kinetically controlled aqueous hydrolysis at an air-water interface. This new level of structural control is uniquely enabled by the slow diffusion of a hydrolytic catalyst, a simple technique. Independent structural characterizations of the compounds separately describe various attributes of the materials on different length scales, revealing details hidden by the disordered average structures. The precise control over the population of distinct octahedrally and tetrahedrally coordinated cobalt ions in the lattice provides a gentle, generic method for modulating the coordination geometry of cobalt in the material without disturbing the lattice or using additional reagents. A mechanism is proposed to reconcile the observation of the kinetic control of the structure with competing interactions during the initial stages of hydrolysis and condensation.

  20. Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

    Science.gov (United States)

    Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

    2018-04-01

    In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.

  1. The challenges of treating high strength wastewaters: CWAO using MWNT supported ruthenium catalysts

    International Nuclear Information System (INIS)

    GarcIa, J.; Gomes, H.T.; Figueiredo, J.L.; Faria, J.L.; Garcia, J.; Serp, P.; Kalck, P.

    2005-01-01

    High strength wastewaters containing aromatic compounds are normally not efficiently treated by conventional methods, including the common biological treatment. In these cases a more sophisticated approach is necessary to attain the desired levels of purification. Catalytic wet air oxidation (CWAO) using carbon based catalysts is employed worldwide as effective pre-treatment of effluents with these characteristics. Carbon materials are preferred as active catalysts or support for preparing them due to their morphological and structural characteristics. In the last 10 years, due to a tremendous development in materials production and processing, carbon nano-structures are becoming more accessible and common widening their range of applications [1]. In this context, the scope of the present work is to illustrate a potential use of multi-walled carbon nano-tubes (MWNT) supported ruthenium catalysts for catalytic wet air oxidation of aniline polluted wastewaters. The metal was supported by incipient wetness and excess impregnation, starting from liquid solutions of three different Ru precursors. Impregnation was carried out on modified MWNT, namely on MWNT-COOH (HNO 3 modified) and MWNT-COONa (HNO 3 /Na 2 CO 3 modified). For the 1% weight Ru/MWNT catalysts, the order of activities decreased in the sequence Ru(COD)(COT)≥RuCl 3 ≥Ru(C 5 H 5 ) 2 . The conversion of aniline after 45 min of reaction was 100% for the catalyst prepared with Ru(COD)(COT). The influence of the Ru precursor, preparation method and the support surface modification was studied comparing the conversion of aniline obtained for the different prepared Ru/MWNT catalysts (Figure 1). MWNT as support material, provide a significant metal dispersion with very small Ru nanoparticles (Figure 2) being observed. This will induce an efficient surface contact between the aniline molecule and the active sites [2]. The excellent catalytic performances of Ru/MWNT are explained in terms of the high dispersion of

  2. Microstructure and Properties of Cobalt-and Zinc-Containing Magnetic Magnesium Alloys Processed by High-Pressure Die Casting

    Science.gov (United States)

    Klose, Christian; Demminger, Christian; Maier, Hans Jürgen

    The inherent magnetic properties of lightweight alloys based on magnesium and cobalt offer a novel way in order to measure mechanical loads throughout the entire structural component using the magnetoelastic effect. Because the solubility of cobalt in the magnesium matrix is negligible, the magnetic properties mainly originate from Co-rich precipitates. Thus, the size and distribution of Co-containing phases within the alloy's microstructure wields a major influence on the amplitude of the load-sensitive properties which can be measured by employing the harmonic analysis of eddy-current signals. In this study, Mg-Co-based alloys are produced by several casting methods which allow the application of different cooling rates, e.g. gravity die casting and high-pressure die casting. The differences between the manufactured alloys' micro- and phase structures are compared depending on the applied cooling rate and the superior magnetic and mechanical properties of the high-pressure die cast material are demonstrated.

  3. A combination of CoO and Co nanoparticles supported on electrospun carbon nanofibers as highly stable air electrodes

    Science.gov (United States)

    Alegre, Cinthia; Busacca, Concetta; Di Blasi, Orazio; Antonucci, Vincenzo; Aricò, Antonino Salvatore; Di Blasi, Alessandra; Baglio, Vincenzo

    2017-10-01

    Bifunctional materials able to catalyze both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions in alkaline media are still a challenge for the progress of energy conversion and storage devices such as metal-air batteries or unitized regenerative fuel cells. In this work, carbon nanofibers synthesized by electrospinning are modified with a combination of cobalt oxide and metallic cobalt (CoO-Co/CNF) and studied as a bifunctional air electrode for metal-air batteries. The performance of CoO-Co/CNF for both reactions is compared with state-of-the-art catalysts such as Pt/C and IrO2. The combination of cobalt oxide and metallic cobalt, finely distributed on the surface of graphitic carbon nanofibers, leads to a bifunctional catalyst with a half-wave potential for the ORR slightly better than Pt/C and a reversibility (ΔEOER-ORR) of 809 mV. The stability of CoO-Co/CNF is assessed by means of different stress tests: polarizations at high electrochemical potentials (2 V vs. RHE), rapid charge-discharge cycles at ±80 mA cm-2 and long durability tests by charging for 12 h at 60 mA cm-2 and discharging for 8 h at -80 mA cm-2. CoO-Co/CNF shows a remarkable stability, maintaining, at least, an 82% of its performance for the ORR after the stress tests, even when cycled for more than 100 h.

  4. hermo-Physical and Mechanical Properties of Unsaturated Polyester /Cobalt Ferrite Composites

    Directory of Open Access Journals (Sweden)

    Lamees Salam Faiq

    2017-04-01

    Full Text Available Unsaturated polyester was used as a matrix which was filled with different percentages of cobalt ferrite using hand lay-up method. Cobalt ferrite was synthesized using solid state ceramic method with reagent of CoO and Fe2O3. Mechanical properties such tensile strength, Young's modulus and shore D hardness of the composite have been studied. All these properties have increased by 10% with increasing cobalt ferrite contents. Also the thermal properties such thermal conductivity and specific heat capacity are highly increased as the ferrite content increased, while the thermal diffusivity increased by 22 %. On the other hand dielectric strength of composite has been measured which increased by 50% by increasing the cobalt ferrite content.

  5. Highly active self-immobilized FI-Zr catalysts in a PCP framework for ethylene polymerization.

    Science.gov (United States)

    Li, He; Xu, Bo; He, Jianghao; Liu, Xiaoming; Gao, Wei; Mu, Ying

    2015-12-04

    A series of zirconium-based porous coordination polymers (PCPs) containing FI catalysts in the frameworks have been developed and studied as catalysts for ethylene polymerization. These PCPs exhibit good catalytic activities and long life times, producing polyethylenes with high molecular weights and bimodal molecular weight distribution in the form of particles.

  6. Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

    Science.gov (United States)

    Yin, Peiqun; Yao, Tao; Wu, Yuen; Zheng, Lirong; Lin, Yue; Liu, Wei; Ju, Huanxin; Zhu, Junfa; Hong, Xun; Deng, Zhaoxiang; Zhou, Gang; Wei, Shiqiang; Li, Yadong

    2016-08-26

    A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

    Science.gov (United States)

    Kapoor, S; Sharma, P D; Gupta, Y K

    1975-09-01

    Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

  8. Homogeneous and heterogeneous catalysts of Fe3+, Co2+ and Cu2+ for the degradation of methyl parathion in diluted aqueous medium

    Directory of Open Access Journals (Sweden)

    Cindy A. Vela-Monroy

    2016-07-01

    Full Text Available Degradation of pesticides (plaguicides, herbicides, fungicides, among others in aqueous media is a subject of great importance for ensuring the water quality into numerous hydric sources. This work reports the assessment of homogeneous (metal ion solutions and heterogeneous (oxides supported on alumina systems that are based on Fe3+, Co2+ y Cu2+, which were used as catalysts for oxidation (degradation of methyl parathion (a plaguicide in aqueous solution. Hydrogen peroxide was herein used as oxidizing molecule under mild condition of reaction (25 ºC and atmospheric pressure. The solids were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Fe3+/H2O2 (Fenton system was the most active homogeneous catalyst compared to Co2+/H2O2 and Cu2+/H2O2 systems. Solids catalysts such as cobalt, copper or iron oxides as well as mixed oxides supported on alumina were active at pH close to neutrality. Fe-Co-Cu/Al2O3, Co-Cu/Al2O3 and FeCo/Al2O3 mixed systems were solids with the highest catalytic activity. In addition, an important effect of the support (-Al2O3 on the reaction pH was observed, allowing to reach values close to that of the neutrality, and thus increasing the catalytic activity of both cobalt oxide and copper oxide species. These results allow advancing on a new pathway for searching catalysts to remove organophosphorous pesticides from residual waters.

  9. JAEA thermodynamic database for performance assessment of geological disposal of high-level and TRU wastes. Selection of thermodynamic data of cobalt and nickel

    International Nuclear Information System (INIS)

    Kitamura, Akira; Yui, Mikazu; Kirishima, Akira; Saito, Takumi; Shibutani, Sanae; Tochiyama, Osamu

    2009-11-01

    Within the scope of the JAEA thermodynamic database project for performance assessment of geological disposal of high-level and TRU wastes, the selection of the thermodynamic data on the inorganic compounds and complexes of cobalt and nickel have been carried out. For cobalt, extensive literature survey has been performed and all the obtained literatures have been carefully reviewed to select the thermodynamic data. Selection of thermodynamic data of nickel has been based on a thermodynamic database published by the Nuclear Energy Agency in the Organisation for Economic Co-operation and Development (OECD/NEA), which has been carefully reviewed by the authors, and then thermodynamic data have been selected after surveying latest literatures. Based on the similarity of chemical properties between cobalt and nickel, complementary thermodynamic data of nickel and cobalt species expected under the geological disposal condition have been selected to complete the thermodynamic data set for the performance assessment of geological disposal of radioactive wastes. (author)

  10. Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

    Science.gov (United States)

    Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

    2016-05-04

    The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

  11. Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

    Science.gov (United States)

    Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

    2015-07-21

    The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

  12. Thermal effects in highly dispersed iron catalysts

    International Nuclear Information System (INIS)

    Alvarez, A.M.; Cagnoli, M.V.; Gallegos, N.G.; Marchetti, S.G.; Yeramian, A.A.; Mercader, R.C.

    1994-01-01

    The Moessbauer spectra of three Fe/SiO 2 catalysts with 5 wt% iron content show the presence of several Fe species and display different magnetic behaviours when the precursors are subjected to various thermal treatments. Based on the Moessbauer parameters and CO chemisorption measurements, the average crystal sizes of the catalysts are estimated and discussed in connection with the thermal pretreatment severity and magnetic properties of the samples. (orig.)

  13. Preliminary feasibility study on production of cobalt-60 source for industrial irradiation

    International Nuclear Information System (INIS)

    Joo, Po Kook; Park, Kyung Bae; Ahn, Yun Soo; Lee, Jong Tai; Kim, Hark Rho

    1999-05-01

    As there is a high possible demand of industrial Co-60 source in the world market, feasibility study of a project was performed to produce and to export Co-60 sources, utilizing KEPCO's Wolsung NPP for irradiation of cobalt and KAERI's hot-cells for fabrication of cobalt sources. Main concerns of the study were to understand irradiation and fabrication (encapsulation) processes and to examine related technologies, required facilities and equipment. In particular, it was examined intensively if it would be possible to modify facilities around the reactor vessel of Wolsung NPP tp substantiate the related licensing in order to irradiate cobalt in the reactor. It is expected that once, if cooperation scheme with MDS Nordion of Canada is established, main issues such as modification of facilities, related licensing, raw material procurement and technology transfer for high quality product will be solved. In order to review overall feasibility of the project, present status and prospect of the world market was surveyed and various usages of cobalt sources were reviewed with emphasis on possible demand increase per usage. Food poisoning accidents are prevailing worldwide and food irradiation with cobalt sources is considered as a promising measure to prevent them and may bring forth high increase of cobalt sources demand in the world market. Preliminary economic feasibility was studied in conservation, evaluating roughly the investment and the operating cost based on materials from various information sources. (author)

  14. Cobalt sensitization and dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob P

    2012-01-01

    : This clinical review article presents clinical and scientific data on cobalt sensitization and dermatitis. It is concluded that cobalt despite being a strong sensitizer and a prevalent contact allergen to come up on patch testing should be regarded as a very complex metal to test with. Exposure...

  15. High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

    Science.gov (United States)

    Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

    2018-02-26

    The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

  16. Cobalt 60 availability for radiation processing

    International Nuclear Information System (INIS)

    Fraser, F.M.

    1986-01-01

    In the last 20 years, the steady and significant growth in the application of radiation processing to industrial sterilization has been seen. The principal application of this technology is the sterilization of disposable medical products, food irradiation, the irradiation of personal care goods and so on. At present, more than 70 million curies of cobalt-60 supplied by Atomic Energy of Canada Ltd. have been used for gamma processing in these applications. This is estimated to be more than 80 % of the total cobalt-60 in service in the world. Commercial food irradiation has an exciting future, and as to the impact of food irradiation on the availability of cobalt-60 over the next ten years, two principal factors must be examined, namely, the anticipated demand for cobalt-60 in all radiation processing applications, and the supply of cobalt-60 to reliably meet the expected demand. As for the cobalt-60 in service today, 90 % is used for the sterilization of disposable medical products, 5 % for food irradiation, and 5 % for other application. The demand for up to 30 million curies of cobalt-60 is expected over the next 10 years. Today, it is estimated that over 150,000 tons of spices, fruit and fish are irradiated. The potential cobalt-60 production could exceed 110 million curies per year. Gamma processing application will demand nearly 50 million curies in 1990. (Kako, I.)

  17. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    Science.gov (United States)

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  18. Cobalt uptake and binding in human red blood cells

    DEFF Research Database (Denmark)

    Simonsen, Lars Ole; Brown, Anthony M; Harbak, Henrik

    2011-01-01

    of cobalt, and also from the initial slope of the cobalt buffering curve. The cobalt accumulation is similar in fed and ATP-depleted cells. The buffering curve for [Co(T)](c) can be fitted by a Michaelis type function with B(max)=24 mmol (l cells)(-1) and half-saturation at 240 µM [Co(2+)](c). The tracer...... reversibly bound, being releasable by excess extracellular EGTA in the presence of A23187, and partly tightly bound, remaining in the cells even at high ionophore concentrations. The tightly bound fraction builds up over time, and is larger and develops earlier in fed cells compared to ATP-depleted cells......-migrate with hemoglobin in Sephadex column chromatography of a lysate of (57)Co-loaded cells. (57)Co also co-migrates with hemoglobin when added to a lysate of unlabeled cells or to a solution of purified hemoglobin, in both cases with a time-dependent development of tight binding. Cobalt is known to bind to the globin...

  19. Rice husk-derived sodium silicate as a highly efficient and low-cost basic heterogeneous catalyst for biodiesel production

    International Nuclear Information System (INIS)

    Roschat, Wuttichai; Siritanon, Theeranun; Yoosuk, Boonyawan; Promarak, Vinich

    2016-01-01

    Graphical abstract: Rice husk-derived sodium silicate exhibits high potential as a low-cost solid catalyst for industrial biodiesel production. - Highlights: • Rice husk-derived sodium silicate was employed as a high performance catalyst for biodiesel production. • 97% yield of FAME was achieved in 30 min at 65 °C. • The room-temperature transesterification gave 94% yield of FAME after only 150 min. - Abstract: In the present work, rice husk-derived sodium silicate was prepared and employed as a solid catalyst for simple conversion of oils to biodiesel via the transesterification reaction. The catalyst was characterized by TG–DTA, XRD, XRF, FT-IR, SEM, BET and Hammett indicator method. Under the optimal reaction conditions of catalyst loading amount of 2.5 wt.%, methanol/oil molar ratio of 12:1, the prepared catalysts gave 97% FAME yield in 30 min at 65 °C, and 94% FAME yield in 150 min at room temperature. The transesterification was proved to be pseudo-first order reaction with the activation energy (Ea) and the frequency factor (A) of 48.30 kJ/mol and 2.775 × 10"6 min"−"1 respectively. Purification with a cation-exchange resin efficiently removed all soluble ions providing high-quality biodiesel product that meets all the ASTM and EN standard specifications. Rice husk-derived sodium silicate showed high potential to be used as a low-cost, easy to prepare and high performance solid catalyst for biodiesel synthesis.

  20. Hot corrosion of low cobalt alloys

    Science.gov (United States)

    Stearns, C. A.

    1982-01-01

    The hot corrosion attack susceptibility of various alloys as a function of strategic materials content are investigated. Preliminary results were obtained for two commercial alloys, UDIMET 700 and Mar-M 247, that were modified by varying the cobalt content. For both alloys the cobalt content was reduced in steps to zero. Nickel content was increased accordingly to make up for the reduced cobalt but all other constituents were held constant. Wedge bar test samples were produced by casting. The hot corrosion test consisted of cyclically exposing samples to the high velocity flow of combustion products from an air-fuel burner fueled with jet A-1 and seeded with a sodium chloride aqueous solution. The flow velocity was Mach 0.5 and the sodium level was maintained at 0.5 ppm in terms of fuel plus air. The test cycle consisted of holding the test samples at 900 C for 1 hour followed by 3 minutes in which the sample could cool to room temperature in an ambient temperature air stream.

  1. Cobalt(II Complexes with N,N,N-Scorpionates and Bidentate Ligands: Comparison of Hydrotris(3,5-dimethylpyrazol-1-ylborate Tp* vs. Phenyltris(4,4-dimethyloxazolin-2-ylborate ToM to Control the Structural Properties and Reactivities of Cobalt Centers

    Directory of Open Access Journals (Sweden)

    Toshiki Nishiura

    2018-06-01

    Full Text Available Scorpionate ligands Tp* (hydrotris(3,5-dimethylpyrazol-1-ylborate and ToM (tris(4,4-dimethyloxazolin-2-ylphenylborate complexes of cobalt(II with bidentate ligands were synthesized. Both Tp* and ToM coordinate to cobalt(II in a tridentate fashion when the bidentate ligand is the less hindered acetylacetonate. In crystal structures, the geometry of cobalt(II supported by the N3O2 donor set in the Tp* complex is a square-pyramid, whereas that in the ToM complex is close to a trigonal-bipyramid. Both Tp*- and ToM-acac complexes exhibit solvatochromic behavior, although the changing structural equilibria of these complexes in MeCN are quite different. In the bis(1-methylimidazol-2-ylmethylphenylborate (LPh complexes, Tp* retains the tridentate (к3 mode, whereas ToM functions as the bidentate (к2 ligand, giving the tetrahedral cobalt(II complex. The bowl-shaped cavity derived from the six methyl groups on ToM lead to susceptibility to the bulkiness of the opposite bidentate ligand. The entitled scorpionate compounds mediate hydrocarbon oxidation with organic peroxides. Allylic oxidation of cyclohexene occurs mainly on the reaction with tert-butyl hydroperoxide (TBHP, although the catalytic efficiency of the scorpionate ligand complexes is lower than that of Co(OAc2 and Co(acac2. On cyclohexane oxidation with meta-chloroperbenzoic acid (mCPBA, both ToM and Tp* complexes function as catalysts for hydroxylation. The higher electron-donating ToM complexes show faster initial reaction rates compared to the corresponding Tp* complexes.

  2. Facile synthesis of a platinum-lead oxide nanocomposite catalyst with high activity and durability for ethanol electrooxidation.

    Science.gov (United States)

    Yang, Wei-Hua; Wang, Hong-Hui; Chen, De-Hao; Zhou, Zhi-You; Sun, Shi-Gang

    2012-12-21

    Aimed at searching for highly active and stable nano-scale Pt-based catalysts that can improve significantly the energy conversion efficiency of direct ethanol fuel cells (DEFCs), a novel Pt-PbO(x) nanocomposite (Pt-PbO(x) NC) catalyst with a mean size of 3.23 nm was synthesized through a simple wet chemistry method without using a surfactant, organometallic precursors and high temperature. Electrocatalytic tests demonstrated that the as-prepared Pt-PbO(x) NC catalyst possesses a much higher catalytic activity and a longer durability than Pt nanoparticles (nm-Pt) and commercial Pt black catalysts for ethanol electrooxidation. For instance, Pt-PbO(x) NC showed an onset potential that was 30 mV and 44 mV less positive, together with a peak current density 1.7 and 2.6 times higher than those observed for nm-Pt and Pt black catalysts in the cyclic voltammogram tests. The ratio of current densities per unit Pt mass on Pt-PbO(x) NC, nm-Pt and Pt black catalysts is 27.3 : 3.4 : 1 for the long-term (2 hours) chronoamperometric experiments measured at -0.4 V (vs. SCE). In situ FTIR spectroscopic studies revealed that the activity of breaking C-C bonds of ethanol of the Pt-PbO(x) NC is as high as 5.17 times that of the nm-Pt, which illustrates a high efficiency of ethanol oxidation to CO(2) on the as-prepared Pt-PbO(x) NC catalyst.

  3. The challenges of treating high strength wastewaters: CWAO using MWNT supported ruthenium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    GarcIa, J.; Gomes, H.T.; Figueiredo, J.L.; Faria, J.L. [Porto Univ., Lab. de Catalise e Materiais, Dept. de Engenharia Quimica, Faculdade de Engenharia (Portugal); Garcia, J. [Madrid Univ. Complutense, Grupo de Catalisis y Operaciones de Separacion, Dept. de Ingenieria Quimica, Facultad de Ciencias (Spain); Serp, P.; Kalck, P. [Ecole Nationale Superieure des Ingenieurs en Arts Chimiques et Technologiques, Lab. de Catalyse, Chimie Fine et Polymeres, 31 - Toulouse (France)

    2005-07-01

    High strength wastewaters containing aromatic compounds are normally not efficiently treated by conventional methods, including the common biological treatment. In these cases a more sophisticated approach is necessary to attain the desired levels of purification. Catalytic wet air oxidation (CWAO) using carbon based catalysts is employed worldwide as effective pre-treatment of effluents with these characteristics. Carbon materials are preferred as active catalysts or support for preparing them due to their morphological and structural characteristics. In the last 10 years, due to a tremendous development in materials production and processing, carbon nano-structures are becoming more accessible and common widening their range of applications [1]. In this context, the scope of the present work is to illustrate a potential use of multi-walled carbon nano-tubes (MWNT) supported ruthenium catalysts for catalytic wet air oxidation of aniline polluted wastewaters. The metal was supported by incipient wetness and excess impregnation, starting from liquid solutions of three different Ru precursors. Impregnation was carried out on modified MWNT, namely on MWNT-COOH (HNO{sub 3} modified) and MWNT-COONa (HNO{sub 3}/Na{sub 2}CO{sub 3} modified). For the 1% weight Ru/MWNT catalysts, the order of activities decreased in the sequence Ru(COD)(COT){>=}RuCl{sub 3}{>=}Ru(C{sub 5}H{sub 5}){sub 2}. The conversion of aniline after 45 min of reaction was 100% for the catalyst prepared with Ru(COD)(COT). The influence of the Ru precursor, preparation method and the support surface modification was studied comparing the conversion of aniline obtained for the different prepared Ru/MWNT catalysts (Figure 1). MWNT as support material, provide a significant metal dispersion with very small Ru nanoparticles (Figure 2) being observed. This will induce an efficient surface contact between the aniline molecule and the active sites [2]. The excellent catalytic performances of Ru/MWNT are explained

  4. Concentration of radioactive cobalt by seaweeds in the food chain

    International Nuclear Information System (INIS)

    Nakahara, Motokazu; Koyanagi, Taku; Saiki, Masamichi

    1976-01-01

    On the pathway of radioactive substances in marine environments, seaweeds play an important role because of their higher concentration factors for many radionuclides and because they constitute a link of food chain in the sea. In the present work, uptake, distribution and excretion of radioactive cobalt were studied on several kinds of seaweeds by radioisotope tracer experiments under laboratory conditions and concentration factors were calculated. The concentration factors were also estimated from the results of stable cobalt determination by activation analysis or atomic absorption spectrometry on seaweeds and seawater, and compared with the results of tracer expts. The seaweeds showed the species specificity for the concentration of stable and radioactive cobalt with diverse values of concentration factors and biological half-lives. The transfer of radioactive cobalt in the food chain from contaminated seaweeds to mollusca was examined by feeding abalones, Haliotis discus, with four kinds of seaweed labelled with 60 Co and observing retention. Absorption rate for radioactive cobalt by abalones calculated at two days after feeding showed diverse values depending upon the species of seaweed, as follows: 47% through Laminaria japonica and Ulva pertusa, 31% through Undaria pinnatifida and 26 through Eisenia bicyclis, respectively. From the results, it was assumed that the accumulation of radioactive cobalt by mollusca is affected by the species of seaweeds as food. A very high concentration of ingested radioactive cobalt in the midgut gland was seen on the autoradiograph of abalone samples. (auth.)

  5. Concentration of radioactive cobalt by seaweeds in the food chain

    International Nuclear Information System (INIS)

    Nakahara, M.; Koyanagi, T.; Saiki, M.

    1975-01-01

    On the pathway of radioactive substances in marine environments, seaweeds play an important role because of their higher concentration factors for many radionuclides and because they constitute a link in the food chain. In the present work, uptake, distribution and excretion of radioactive cobalt were studied on several kinds of seaweeds by radioisotope tracer experiments under laboratory conditions and concentration factors were calculated. The concentration factors were also estimated from the results of stable cobalt determination by activation analysis or atomic absorption spectrometry on seaweeds and seawater, and compared with the results of tracer experiments. The seaweeds showed the species specificity for the concentration of stable and radioactive cobalt with diverse values of concentration factors and biological half-lives. The transfer of radioactive cobalt in the food chain from contaminated seaweeds to mollusca was examined by feeding abalones, Haliotis discus, with four kinds of seaweed labelled with 60 Co and observing retention. Absorption rate for radioactive cobalt by abalones calculated at two days after feeding showed diverse values depending upon the species of seaweed, as follows: 47% through Laminaria japonica and Ulva pertusa, 31% through Undaria pinnatifida and 26% through Eisenia bicyclis, respectively. From the results, it was assumed that the accumulation of radioactive cobalt by mollusca is affected by the species of seaweeds as food. A very high concentration of ingested radioactive cobalt in the midgut gland was seen on the autoradiograph of abalone samples. (author)

  6. Effect of Lanthanum as a Promoter on Fe-Co/SiO2 Catalyst for Fischer-Tropsch Synthesis

    Directory of Open Access Journals (Sweden)

    Ali Abbasi

    2014-03-01

    Full Text Available Iron-Cobalt catalyst is well known from both operational and economical aspects for Fischer-Tropsch synthesis. Effort to increase the efficiency of this kind of catalyst is an important research topic. In this work, the effect of lanthanum on characteristic behavior, conversion and selectivity of a Fe-Co/SiO2 Fischer-Tropsch catalyst was studied. The Fe-Co-La/SiO2 Catalysts were prepared using an incipient wetness impregnation method. These catalysts were then characterized by XRF-EDAX, BET and TPR techniques, and their performance were evaluated in a lab-scale reactor at 250ºC, H2/CO = 1.8 of molar ratio, 16 barg pressure and GHSV=600 h-1. TPR analysis showed that the addition of La lowered the reduction temperature of Fe-Co catalyst, and due to a lower temperature, the sintering of the catalyst can be mitigated. Furthermore, from the micro reactor tests (about 4 days, it was found that lanthanum promoted catalyst had higher selectivity toward hydrocarbons, and lower selectivity toward CO2.Received: 8th July 2013; Revised: 18th November 2013; Accepted: 1st December 2013[How to Cite: Abbasi, A., Ghasemi, M., Sadighi, S. (2014. Effect of Lanthanum as a Promoter on Fe-Co/SiO2 Catalyst for Fischer-Tropsch Synthesis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 23-27. (doi:10.9767/bcrec.9.1.5142.23-27][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5142.23-27

  7. Nitrogen-doped carbonaceous catalysts for gas-diffusion cathodes for alkaline aluminum-air batteries

    Science.gov (United States)

    Davydova, E. S.; Atamanyuk, I. N.; Ilyukhin, A. S.; Shkolnikov, E. I.; Zhuk, A. Z.

    2016-02-01

    Cobalt tetramethoxyphenyl porphyrin and polyacrylonitrile - based catalysts for oxygen reduction reaction were synthesized and characterized by means of SEM, TEM, XPS, BET, limited evaporation method, rotating disc and rotating ring-disc electrode methods. Half-cell and Al-air cell tests were carried out to determine the characteristics of gas-diffusion cathodes. Effect of active layer thickness and its composition on the characteristics of the gas-diffusion cathodes was investigated. Power density of 300 mW cm-2 was achieved for alkaline Al-air cell with an air-breathing polyacrylonitrile-based cathode.

  8. N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

    Science.gov (United States)

    Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

    2017-08-01

    It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

  9. High temperature H2/CO2 separation using cobalt oxide silica membranes

    Energy Technology Data Exchange (ETDEWEB)

    Smart, S.; Diniz da Costa, J.C. [The University of Queensland, FIMLab - Films and Inorganic Membrane Laboratory, School of Chemical Engineering, Brisbane, Qld 4072 (Australia); Vente, J.F. [Energy research Centre of the Netherlands ECN, P.O. Box 1, 1755 ZG Petten (Netherlands)

    2012-09-15

    In this work high quality cobalt oxide silica membranes were synthesized on alumina supports using a sol-gel, dip coating method. The membranes were subsequently connected into a steel module using a graphite based proprietary sealing method. The sealed membranes were tested for single gas permeance of He, H2, N2 and CO2 at temperatures up to 600C and feed pressures up to 600 kPa. Pressure tests confirmed that the sealing system was effective as no gas leaks were observed during testing. A H2 permeance of 1.9 x 10{sup -7} mol m{sup -2} s{sup -1} Pa-1 was measured in conjunction with a H2/CO2 permselectivity of more than 1500, suggesting that the membranes had a very narrow pore size distribution and an average pore diameter of approximately 3 Angstrom. The high temperature testing demonstrated that the incorporation of cobalt oxide into the silica matrix produced a structure with a higher thermal stability, able to resist thermally induced densification up to at least 600C. Furthermore, the membranes were tested for H2/CO2 binary feed mixtures between 400 and 600C. At these conditions, the reverse of the water gas shift reaction occurred, inadvertently generating CO and water which increased as a function of CO2 feed concentration. The purity of H2 in the permeate stream significantly decreased for CO2 feed concentrations in excess of 50 vol%. However, the gas mixtures (H2, CO2, CO and water) had a more profound effect on the H2 permeate flow rates which significantly decreased, almost exponentially as the CO2 feed concentration increased.

  10. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.

    1987-01-01

    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  11. High power passive μDMFC with low catalyst loading for small power generation

    International Nuclear Information System (INIS)

    Ahmad, M.M.; Kamarudin, S.K.; Daud, W.R.W.; Yaakub, Z.

    2010-01-01

    The main constraint for commercialization of micro direct methanol fuel cell (μDMFC) for small power generation is the performance of the fuel cell. In this study, a high power μDMFC with a power output of 56 mW and an active area of 4 cm 2 was successfully developed. The cell required low catalyst loading of 5 mg cm -2 and 0.5 mg cm -2 at the anode and cathode, respectively. Optimal design parameters for methanol concentration and catalyst loading were examined. Finally, long-term performance testing was performed and OCV curves are reported. The results obtained for this gives the highest power density at low catalyst loading as compare to other researchers in this area.

  12. Dose-dependent cytotoxicity of clinically relevant cobalt nanoparticles and ions on macrophages in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Young-Min; Xia Zhidao; Glyn-Jones, Sion; Beard, David; Gill, Harinderjit S; Murray, David W, E-mail: young-min.kwon@ndos.ox.ac.u [Nuffield Department of Orthopaedic Surgery, University of Oxford, Oxford OX3 7LD (United Kingdom)

    2009-04-15

    Despite the satisfactory short-term implant survivorship of metal-on-metal hip resurfacing arthroplasty, periprosthetic soft-tissue masses such as pseudotumours are being increasingly reported. Cytotoxic effects of cobalt or chromium have been suggested to play a role in its aetiology. The aim of this study was to investigate the effects of clinically relevant metal nanoparticles and ions on the viability of macrophages in vitro. A RAW 264.7 murine macrophage cell line was cultured in the presence of either: (1) cobalt, chromium and titanium nanoparticles sized 30-35 nm; or (2) cobalt sulphate and chromium chloride. Two methods were used to quantify cell viability: Alamar Blue assay and Live/Dead assay. The cytotoxicity was observed only with cobalt. Cobalt nanoparticles and ions demonstrated dose-dependent cytotoxic effects on macrophages in vitro: the cytotoxic concentrations of nanoparticles and ions were 1 x 10{sup 12} particles ml{sup -1} and 1000 {mu}M, respectively. The high concentration of cobalt nanoparticles required for cytotoxicity of macrophages in vitro suggests that increased production of cobalt nanoparticles in vivo, due to excessive MoM implant wear, may lead to local adverse biological effects. Therefore, cytotoxicity of high concentrations of metal nanoparticles phagocytosed by macrophages located in the periprosthetic tissues may be an important factor in pathogenesis of pseudotumours.

  13. Influence of Cobalt Doping on the Physical Properties of Zn0.9Cd0.1S Nanoparticles

    Directory of Open Access Journals (Sweden)

    Gupta Hari Om

    2009-01-01

    Full Text Available Abstract Zn0.9Cd0.1S nanoparticles doped with 0.005–0.24 M cobalt have been prepared by co-precipitation technique in ice bath at 280 K. For the cobalt concentration >0.18 M, XRD pattern shows unidentified phases along with Zn0.9Cd0.1S sphalerite phase. For low cobalt concentration (≤0.05 M particle size, d XRDis ~3.5 nm, while for high cobalt concentration (>0.05 M particle size decreases abruptly (~2 nm as detected by XRD. However, TEM analysis shows the similar particle size (~3.5 nm irrespective of the cobalt concentration. Local strain in the alloyed nanoparticles with cobalt concentration of 0.18 M increases ~46% in comparison to that of 0.05 M. Direct to indirect energy band-gap transition is obtained when cobalt concentration goes beyond 0.05 M. A red shift in energy band gap is also observed for both the cases. Nanoparticles with low cobalt concentrations were found to have paramagnetic nature with no antiferromagnetic coupling. A negative Curie–Weiss temperature of −75 K with antiferromagnetic coupling was obtained for the high cobalt concentration.

  14. HLA -A, -B, -C and -DR antigens in individuals with sensitivity to cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, T; Rystedt, I; Saefwenberg, J; Egle, I

    1984-01-01

    In a skin investigation of 853 individuals working with hard metal manufacturing 39 cases of cobalt allergy were found. Thirty-five of the individuals with cobalt sensitivity and 102 matched controls were HLA-A, -B, -C and -DR typed. No significantly deviating HLA antigen frequencies were observed when the two groups were compared. Thus, there are no signs that a certain HLA antigen would dispose to cobalt allergy. In the cobalt sensitive group the B7 positive individuals showed particularly often simultaneous reactions to other contact allergens. The B12 positive individuals had low reactivity while the A28 positive showed high reactivity.

  15. Microwave-activated Ni/carbon catalysts for highly selective hydrogenation of nitrobenzene to cyclohexylamine.

    Science.gov (United States)

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

    2017-06-01

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

  16. Non-Fermi Liquids as Highly Active Oxygen Evolution Reaction Catalysts.

    Science.gov (United States)

    Hirai, Shigeto; Yagi, Shunsuke; Chen, Wei-Tin; Chou, Fang-Cheng; Okazaki, Noriyasu; Ohno, Tomoya; Suzuki, Hisao; Matsuda, Takeshi

    2017-10-01

    The oxygen evolution reaction (OER) plays a key role in emerging energy conversion technologies such as rechargeable metal-air batteries, and direct solar water splitting. Herein, a remarkably low overpotential of ≈150 mV at 10 mA cm -2 disk in alkaline solutions using one of the non-Fermi liquids, Hg 2 Ru 2 O 7 , is reported. Hg 2 Ru 2 O 7 displays a rapid increase in current density and excellent durability as an OER catalyst. This outstanding catalytic performance is realized through the coexistence of localized d-bands with the metallic state that is unique to non-Fermi liquids. The findings indicate that non-Fermi liquids could greatly improve the design of highly active OER catalysts.

  17. Synthesis of new cobalt aluminophosphate framework by opening a cobalt methylphosphonate layered material

    Czech Academy of Sciences Publication Activity Database

    Zaarour, M.; Pérez, O.; Boullay, P.; Martens, J.; Mihailova, B.; Karaghiosoff, K.; Palatinus, Lukáš; Mintova, S.

    2017-01-01

    Roč. 19, č. 34 (2017), s. 5100-5105 ISSN 1466-8033 Institutional support: RVO:68378271 Keywords : cobalt aluminophosphate * cobalt methylphosphonate * layered materials * crystallic structure * X-ray diffraction Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.474, year: 2016

  18. Radio cobalt in French rivers

    International Nuclear Information System (INIS)

    Lambrechts, A.; Baudin-Jaulent, Y.

    1996-01-01

    The isotopes 58 and 60 of cobalt present in liquid wastes from nuclear plants or from fuel reprocessing plant of Marcoule are fixed in the different compartments of French rivers. The activity levels of radio-cobalt vary according to the sampled compartments nature (bryophyta > immersed plants > sediment > fish). Elsewhere, laboratory experimentations show that the contamination of fish occurs essentially from the water way rather than from food. Cobalt is mainly fixed by kidneys; muscles is no more than 30 % of the total fish activity. (author)

  19. Development of Highly Nano-Dispersed NiO/GDC Catalysts from Ion Exchange Resin Templates

    Directory of Open Access Journals (Sweden)

    Angel Caravaca

    2017-11-01

    Full Text Available Novel NiO/GDC (Gadolinium-doped Ceria cermet catalysts were developed by the Weak Acid Resin (WAR method using an ion exchange resin template. In addition, the specific surface area of these tunable materials was enhanced by NiO partial dissolution in aqueous acid solution. The whole procedure highly improved the micro-structural properties of these materials compared to previous studies. Catalysts with high metal loadings (≥10%, small Ni nanoparticles (<10 nm, and high specific surface areas (>70 m2/g were achieved. These properties are promising for catalytic applications such as methane steam reforming for H2 production.

  20. Cobalt doped ZrO2 decorated multiwalled carbon nanotube: A promising nanocatalyst for photodegradation of indigo carmine and eosin Y dyes

    Directory of Open Access Journals (Sweden)

    William Wilson Anku

    2016-08-01

    Full Text Available This paper reports the degradation of indigo carmine and eosin Y dyes in water, catalyzed by cobalt and multiwalled carbon nanotube modified zirconium oxide nanocomposite (Co-ZrO2-MWCNTs under simulated visible light. The bare ZrO2, ZrO2-MWCNTs, Co-ZrO2 and Co-ZrO2-MWCNTs with different percentage compositions of cobalt were synthesized by homogeneous co-precipitation method. Characterization of the prepared nanocomposites was carried out using X-Ray powder Diffraction (XRD, Fourier Transformer Infrared (FTIR Spectroscopy, Transmission Electron Microscopy (TEM, Raman Spectroscopy, (UV–Vis-Spectroscopy and Energy Dispersive Spectroscopy (EDS for their structure, formation, morphology, size and elemental analysis. The experimental results indicated that all the cobalt and MWCNTs modified nanocomposites demonstrated higher photocatalytic activities compared to the bare ZrO2. The most efficient catalyst (0.5% Co-ZrO2-MWCNTs with the band gap and Ka values of 5.21 eV and 16.86×10−3 min−1 respectively exhibited 98% degradation efficiency toward indigo carmine and 87% toward eosin Y in 180 min.

  1. KF-loaded mesoporous Mg-Fe bi-metal oxides: high performance transesterification catalysts for biodiesel production.

    Science.gov (United States)

    Tao, Guiju; Hua, Zile; Gao, Zhe; Zhu, Yan; Zhu, Yan; Chen, Yu; Shu, Zhu; Zhang, Lingxia; Shi, Jianlin

    2013-09-21

    Using newly developed mesoporous Mg-Fe bi-metal oxides as supports, a novel kind of high performance transesterification catalysts for biodiesel production has been synthesized. More importantly, the impregnation solvent was for the first time found to substantially affect the structures and catalytic performances of the resultant transesterification catalysts.

  2. Design of high-activity single-atom catalysts via n-p codoping

    Science.gov (United States)

    Wang, Xiaonan; Zhou, Haiyan; Zhang, Xiaoyang; Jia, Jianfeng; Wu, Haishun

    2018-03-01

    The large-scale synthesis of stable single-atom catalysts (SACs) in experiments remains a significant challenge due to high surface free energy of metal atom. Here, we propose a concise n-p codoping approach, and find it can not only disperse the relatively inexpensive metal, copper (Cu), onto boron (B)-doped graphene, but also result in high-activity SACs. We use CO oxidation on B/Cu codoped graphene as a prototype example, and demonstrate that: (1) a stable SAC can be formed by stronger electrostatic attraction between the metal atom (n-type Cu) and support (p-type B-doped graphene). (2) the energy barrier of the prototype CO oxidation on B/Cu codoped graphene is 0.536 eV by the Eley-Rideal mechanism. Further analysis shows that the spin selection rule can provide well theoretical insight into high activity of our suggested SAC. The concept of n-p codoping may lead to new strategy in large-scale synthesis of stable single-atom catalysts.

  3. Molecular mechanics calculations on cobalt phthalocyanine dimers

    NARCIS (Netherlands)

    Heuts, J.P.A.; Schipper, E.T.W.M.; Piet, P.; German, A.L.

    1995-01-01

    In order to obtain insight into the structure of cobalt phthalocyanine dimers, molecular mechanics calculations were performed on dimeric cobalt phthalocyanine species. Molecular mechanics calculations are first presented on monomeric cobalt(II) phthalocyanine. Using the Tripos force field for the

  4. Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

    Science.gov (United States)

    Jiang, Rongzhong; Tran, Dat T; McClure, Joshua P; Chu, Deryn

    2015-08-26

    In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.

  5. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

  6. Facile fabrication of cobalt oxalate nanostructures with superior specific capacitance and super-long cycling stability

    Science.gov (United States)

    Cheng, Guanhua; Si, Conghui; Zhang, Jie; Wang, Ying; Yang, Wanfeng; Dong, Chaoqun; Zhang, Zhonghua

    2016-04-01

    Transition metal oxalate materials have shown huge competitive advantages for applications in supercapacitors. Herein, nanostructured cobalt oxalate supported on cobalt foils has been facilely fabricated by anodization, and could directly serve as additive/binder-free electrodes for supercapacitors. The as-prepared cobalt oxalate electrodes present superior specific capacitance of 1269 F g-1 at the current density of 6 A g-1 in the galvanostatic charge/discharge test. Moreover, the retained capacitance is as high as 87.2% as the current density increases from 6 A g-1 to 30 A g-1. More importantly, the specific capacitance of cobalt oxalate retains 91.9% even after super-long cycling of 100,000 cycles. In addition, an asymmetric supercapacitor assembled with cobalt oxalate (positive electrode) and activated carbon (negative electrode) demonstrates excellent capacitive performance with high energy density and power density.

  7. AN ELECTROPLATING METHOD OF FORMING PLATINGS OF NICKEL, COBALT, NICKEL ALLOYS OR COBALT ALLOYS

    DEFF Research Database (Denmark)

    1997-01-01

    An electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys with reduced stresses in an electrodepositing bath of the type: Watt's bath, chloride bath or a combination thereof, by employing pulse plating with periodic reverse pulse and a sulfonated naphthalene...

  8. Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport.

    Science.gov (United States)

    Zalitis, Christopher M; Kramer, Denis; Kucernak, Anthony R

    2013-03-28

    An alternative approach to the rotating disk electrode (RDE) for characterising fuel cell electrocatalysts is presented. The approach combines high mass transport with a flat, uniform, and homogeneous catalyst deposition process, well suited for studying intrinsic catalyst properties at realistic operating conditions of a polymer electrolyte fuel cell (PEFC). Uniform catalyst layers were produced with loadings as low as 0.16 μgPt cm(-2) and thicknesses as low as 200 nm. Such ultra thin catalyst layers are considered advantageous to minimize internal resistances and mass transport limitations. Geometric current densities as high as 5.7 A cm(-2)Geo were experimentally achieved at a loading of 10.15 μgPt cm(-2) for the hydrogen oxidation reaction (HOR) at room temperature, which is three orders of magnitude higher than current densities achievable with the RDE. Modelling of the associated diffusion field suggests that such high performance is enabled by fast lateral diffusion within the electrode. The electrodes operate over a wide potential range with insignificant mass transport losses, allowing the study of the ORR at high overpotentials. Electrodes produced a specific current density of 31 ± 9 mA cm(-2)Spec at a potential of 0.65 V vs. RHE for the oxygen reduction reaction (ORR) and 600 ± 60 mA cm(-2)Spec for the peak potential of the HOR. The mass activity of a commercial 60 wt% Pt/C catalyst towards the ORR was found to exceed a range of literature PEFC mass activities across the entire potential range. The HOR also revealed fine structure in the limiting current range and an asymptotic current decay for potentials above 0.36 V. These characteristics are not visible with techniques limited by mass transport in aqueous media such as the RDE.

  9. Tailoring the magnetic properties of cobalt-ferrite nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Vega, A. Estrada de la; Garza-Navarro, M. A., E-mail: marco.garzanr@uanl.edu.mx; Durán-Guerrero, J. G.; Moreno Cortez, I. E.; Lucio-Porto, R.; González-González, V. [Universidad Autónoma de Nuevo León, Facultad de Ingeniería Mecánica y Eléctrica (Mexico)

    2016-01-15

    In this contribution, we report on the tuning of magnetic properties of cobalt-ferrite nanoclusters. The cobalt-ferrite nanoclusters were synthesized from a two-step approach that consists of the synthesis of cobalt-ferrite nanoparticles in organic media, followed by their dispersion into aqueous dissolution to form an oil-in-water emulsion. These emulsions were prepared at three different concentrations of the cationic surfactant cetyltrimethylammonium bromide (CTAB), in order to control the size and clustering density of the nanoparticles in the nanoclusters. The synthesized samples were characterized by transmission electron microscopy and their related techniques, such as bright-field and Z-contrast imaging, electron diffraction and energy-dispersive X-ray spectrometry; as well as static magnetic measures. The experimental evidence indicates that the size, morphology, and nanoparticles clustering density in the nanoclusters is highly dependent of the cobalt-ferrite:CTAB molar ratio that is used in their synthesis. In addition, due to the clustering of the nanoparticles into the nanoclusters, their magnetic moments are blocked to relax cooperatively. Hence, the magnetic response of the nanoclusters can be tailored by controlling the size and nanoparticles clustering density.

  10. Modified solvothermal synthesis of cobalt ferrite (CoFe2O4 magnetic nanoparticles photocatalysts for degradation of methylene blue with H2O2/visible light

    Directory of Open Access Journals (Sweden)

    Abul Kalam

    2018-03-01

    Full Text Available Different grads of magnetic nano-scaled cobalt ferrites (CoFe2O4 photocatalysts were synthesized by modified Solvothermal (MST process with and without polysaccharide. The indigenously synthesized photocatalysts were characterized by means of X-ray diffraction (XRD, scanning electron microscopy (SEM, transmission electron microscopy (TEM, high-resolution transmission electron microscopy (HRTEM, thermo gravimetric analysis (TGA, Fourier transform infrared (FT-IR, UV–visible (UV–vis spectroscopy and N2 adsorption–desorption isotherm method. The Fourier transform infrared spectroscopy study showed the Fe-O stretching vibration 590–619 cm−1, confirming the formation of metal oxide. The crystallite size of the synthesized photocatalysts was found in the range between 20.0 and 30.0 nm. The surface area of obtained magnetic nanoparticles is found to be reasonably high in the range of 63.0–76.0 m2/g. The results shown that only MST-2 is the most active catalyst for photo-Fenton like scheme for fast photodegradation action of methylene blue dye, this is possible due to optical band gap estimated of 2.65 eV. Captivatingly the percentage of degradation efficiency increases up to 80% after 140 min by using MST-2 photocatalyst. Photocatalytic degradation of methylene blue (MB dye under visible light irradiation with cobalt ferrite magnetic nanoparticles followed first order kinetic constant and rate constant of MST-2 is almost 2.0 times greater than MST-1 photocatalyst. Keywords: Cobalt ferrite, Photocatalysis, Kinetics, Optical properties, Surface area studies

  11. Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

    Science.gov (United States)

    Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di-Jia

    2015-01-01

    Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A⋅cm−3 at 0.9 V or 450 A⋅cm−3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed. PMID:26261338

  12. Pyrolysis-catalysis of waste plastic using a nickel-stainless-steel mesh catalyst for high-value carbon products.

    Science.gov (United States)

    Zhang, Yeshui; Nahil, Mohamad A; Wu, Chunfei; Williams, Paul T

    2017-11-01

    A stainless-steel mesh loaded with nickel catalyst was produced and used for the pyrolysis-catalysis of waste high-density polyethylene with the aim of producing high-value carbon products, including carbon nanotubes (CNTs). The catalysis temperature and plastic-to-catalyst ratio were investigated to determine the influence on the formation of different types of carbon deposited on the nickel-stainless-steel mesh catalyst. Increasing temperature from 700 to 900°C resulted in an increase in the carbon deposited on the nickel-loaded stainless-steel mesh catalyst from 32.5 to 38.0 wt%. The increase in sample-to-catalyst ratio reduced the amount of carbon deposited on the mesh catalyst in terms of g carbon g -1 plastic. The carbons were found to be largely composed of filamentous carbons, with negligible disordered (amorphous) carbons. Transmission electron microscopy analysis of the filamentous carbons revealed them to be composed of a large proportion (estimated at ∼40%) multi-walled carbon nanotubes (MWCNTs). The optimum process conditions for CNT production, in terms of yield and graphitic nature, determined by Raman spectroscopy, was catalysis temperature of 800°C and plastic-to-catalyst ratio of 1:2, where a mass of 334 mg of filamentous/MWCNTs g -1 plastic was produced.

  13. Hydroprocessing catalysts utilization and regeneration schemes

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E.

    The catalyst reactor inventory represents an important part of the cost of hydroprocessing operation. The selection of a suitable catalyst and reactor is influenced by feedstock properties. Processes ensuring an uninterrupted operation during catalyst addition and withdrawal are preferred for processing high asphaltene and metal content feedstocks. The spent catalyst can be regenerated and returned to the operation if the extent of its deactivation is not high. The regeneration may be performed either in-situ or off-site. The former is suitable for fixed bed reactors whereas the catalyst from ebullated bed reactors must be regenerated off-site. The regeneration of spent catalysts heavily loaded with metals such as V, Ni and Fe may not be economic. Such catalysts may be suitable for metal reclamation. An environmentally safe method for catalyst disposal must be found if neither regeneration nor metal reclamation from spent catalysts can be performed.

  14. Study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel

    International Nuclear Information System (INIS)

    Ismailova, M.M.; Egorova, L.A.; Khamidov, B.O.

    1993-01-01

    Present article is devoted to study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel. The condition of cobalt in various rate of oxidation in acrylamide aqueous solutions was studied. The concentration conditions of stability of system Co(II)-Co(III) were defined. The composition of coordination compounds of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel was determined.

  15. Nannochloropsis algae pyrolysis with ceria-based catalysts for production of high-quality bio-oils.

    Science.gov (United States)

    Aysu, Tevfik; Sanna, Aimaro

    2015-10-01

    Pyrolysis of Nannochloropsis was carried out in a fixed-bed reactor with newly prepared ceria based catalysts. The effects of pyrolysis parameters such as temperature and catalysts on product yields were investigated. The amount of bio-char, bio-oil and gas products, as well as the compositions of the resulting bio-oils was determined. The results showed that both temperature and catalyst had significant effects on conversion of Nannochloropsis into solid, liquid and gas products. The highest bio-oil yield (23.28 wt%) and deoxygenation effect was obtained in the presence of Ni-Ce/Al2O3 as catalyst at 500°C. Ni-Ce/Al2O3 was able to retain 59% of the alga starting energy in the bio-oil, compared to only 41% in absence of catalyst. Lower content of acids and oxygen in the bio-oil, higher aliphatics (62%), combined with HHV show promise for production of high-quality bio-oil from Nannochloropsis via Ni-Ce/Al2O3 catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Natural phosphate-supported palladium: A highly efficient and recyclable catalyst for the suzuki-miyaura coupling under microwave irradiation

    KAUST Repository

    Hassine, Ayoub; Bouhrara, Mohamed; Sebti, Said; Solhy, Abderrahim; Mahfouz, Remi; Luart, Denis; Lene, Christophe; Fihri, Aziz

    2015-01-01

    This report explores Suzuki-Miyaura coupling under microwave irradiation, using a new generation of catalyst that is based on natural phosphate (NP) impregnated by palladium. This catalyst was prepared by the treatment of natural phosphate with bis(benzonitrile)palladium(II) chloride in acetone at room temperature. The catalyst displayed high catalytic activity for the Suzuki-Miyaura coupling of aryl bromides and chlorides with aryl boronic acids in pure water and with the use of microwave irradiation. The low-cost and availability of the solid support, mild reaction conditions, high yields of desired products, recyclability of the catalyst and short reaction times are the notable features of these methods.

  17. Natural phosphate-supported palladium: A highly efficient and recyclable catalyst for the suzuki-miyaura coupling under microwave irradiation

    KAUST Repository

    Hassine, Ayoub

    2015-01-19

    This report explores Suzuki-Miyaura coupling under microwave irradiation, using a new generation of catalyst that is based on natural phosphate (NP) impregnated by palladium. This catalyst was prepared by the treatment of natural phosphate with bis(benzonitrile)palladium(II) chloride in acetone at room temperature. The catalyst displayed high catalytic activity for the Suzuki-Miyaura coupling of aryl bromides and chlorides with aryl boronic acids in pure water and with the use of microwave irradiation. The low-cost and availability of the solid support, mild reaction conditions, high yields of desired products, recyclability of the catalyst and short reaction times are the notable features of these methods.

  18. Enzyme-like catalysis via ternary complex mechanism: alkoxy-bridged dinuclear cobalt complex mediates chemoselective O-esterification over N-amidation.

    Science.gov (United States)

    Hayashi, Yukiko; Santoro, Stefano; Azuma, Yuki; Himo, Fahmi; Ohshima, Takashi; Mashima, Kazushi

    2013-04-24

    Hydroxy group-selective acylation in the presence of more nucleophilic amines was achieved using acetates of first-row late transition metals, such as Mn, Fe, Co, Cu, and Zn. Among them, cobalt(II) acetate was the best catalyst in terms of reactivity and selectivity. The combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (2a: R = CF3, 2b: R = CH3, 2c: R = (t)Bu) with nitrogen-containing ligands, such as 2,2'-bipyridine, provided an efficient catalytic system for transesterification, in which an alkoxide-bridged dinuclear complex, Co2(OCO(t)Bu)2(bpy)2(μ2-OCH2-C6H4-4-CH3)2 (10), was successfully isolated as a key intermediate. Kinetic studies and density functional theory calculations revealed Michaelis-Menten behavior of the complex 10 through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting the formation of alkoxides followed by coordination of the ester.

  19. Rational Design of Cobalt-Iron Selenides for Highly Efficient Electrochemical Water Oxidation.

    Science.gov (United States)

    Zhang, Jun-Ye; Lv, Lin; Tian, Yifan; Li, Zhishan; Ao, Xiang; Lan, Yucheng; Jiang, Jianjun; Wang, Chundong

    2017-10-04

    Exploring active, stable, earth-abundant, low-cost, and high-efficiency electrocatalysts is highly desired for large-scale industrial applications toward the low-carbon economy. In this study, we apply a versatile selenizing technology to synthesize Se-enriched Co 1-x Fe x Se 2 catalysts on nickel foams for oxygen evolution reactions (OERs) and disclose the relationship between the electronic structures of Co 1-x Fe x Se 2 (via regulating the atom ratio of Co/Fe) and their OER performance. Owing to the fact that the electron configuration of the Co 1-x Fe x Se 2 compounds can be tuned by the incorporated Fe species (electron transfer and lattice distortion), the catalytic activity can be adjusted according to the Co/Fe ratios in the catalyst. Moreover, the morphology of Co 1-x Fe x Se 2 is also verified to strongly depend on the Co/Fe ratios, and the thinner Co 0.4 Fe 0.6 Se 2 nanosheets are obtained upon selenization treatment, in which it allows more active sites to be exposed to the electrolyte, in turn promoting the OER performance. The Co 0.4 Fe 0.6 Se 2 nanosheets not only exhibit superior OER performance with a low overpotential of 217 mV at 10 mA cm -2 and a small Tafel slope of 41 mV dec -1 but also possess ultrahigh durability with a dinky degeneration of 4.4% even after 72 h fierce water oxidation test in alkaline solution, which outperforms the commercial RuO 2 catalyst. As expected, the Co 0.4 Fe 0.6 Se 2 nanosheets have shown great prospects for practical applications toward water oxidation.

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

    Directory of Open Access Journals (Sweden)

    Khalid Khazzal Hummadi

    2009-06-01

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