WorldWideScience

Sample records for single metal catalyst

  1. Single-layer transition metal sulfide catalysts

    Science.gov (United States)

    Thoma, Steven G [Albuquerque, NM

    2011-05-31

    Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

  2. Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

    Science.gov (United States)

    Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

    2018-01-10

    Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    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.

  4. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang

    2018-04-04

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  5. 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.

  6. CO oxidation studies over supported noble metal catalysts and single crystals: A review

    Science.gov (United States)

    Boecker, Dirk; Gonzalez, Richard D.

    1987-01-01

    The catalytic oxidation of CO over noble metal catalysts is reviewed. Results obtained on supported noble metal catalysts and single crystals both at high pressures and under UHV conditions are compared. The underlying causes which result in surface instabilities and multiple steady-state oscillations are considered, in particular, the occurrence of hot spots. CO islands of reactivity, surface oxide formation and phase transformations under oscillatory conditions are discussed.

  7. Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra.

    Science.gov (United States)

    Hoffman, Adam S; Fang, Chia-Yu; Gates, Bruce C

    2016-10-06

    Determining and controlling the uniformity of isolated metal sites on surfaces of supports are central goals in investigations of single-site catalysts because well-defined species provide opportunities for fundamental understanding of the surface sites. CO is a useful probe of surface metal sites, often reacting with them to form metal carbonyls, the infrared spectra of which provide insights into the nature of the sites and the metal-support interface. Metals bonded to various support surface sites give broad bands in the spectra, and when narrow bands are observed, they indicate a high degree of uniformity of the metal sites. Much recent work on single-site catalysts has been done with supports that are inherently nonuniform, giving supported metal species that are therefore nonuniform. Herein we summarize values of ν CO data characterizing supported iridium gem-dicarbonyls, showing that the most nearly uniform of them are those supported on zeolites and the least uniform are those supported on metal oxides. Guided by ν CO data of supported iridium gem-dicarbonyls, we have determined new, general synthesis methods to maximize the degree of uniformity of iridium species on zeolites and on MgO. We report results for a zeolite HY-supported iridium gem-dicarbonyl with full width at half-maximum values of only 4.6 and 5.2 cm -1 characterizing the symmetric and asymmetric CO stretches and implying that this is the most nearly uniform supported single-site metal catalyst.

  8. 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.

  9. Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

    Science.gov (United States)

    Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

    2017-08-09

    Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

  10. Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework.

    Science.gov (United States)

    Li, Zhanyong; Schweitzer, Neil M; League, Aaron B; Bernales, Varinia; Peters, Aaron W; Getsoian, Andrew Bean; Wang, Timothy C; Miller, Jeffrey T; Vjunov, Aleksei; Fulton, John L; Lercher, Johannes A; Cramer, Christopher J; Gagliardi, Laura; Hupp, Joseph T; Farha, Omar K

    2016-02-17

    Developing supported single-site catalysts is an important goal in heterogeneous catalysis since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based metal-organic framework (MOF), NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a MOF (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.

  11. Electrochemical reduction of CO2on graphene supported transition metals - towards single atom catalysts.

    Science.gov (United States)

    He, Haiying; Jagvaral, Yesukhei

    2017-05-10

    In this study, we have investigated the use of single metal atoms supported on defective graphene as catalysts for the electrochemical reduction of CO 2 using the first-principles approach and the computational hydrogen electrode model. Reaction pathways to produce a variety of C 1 products CO, HCOOH, HCHO, CH 3 OH and CH 4 have been studied in detail for five representative transition metals Ag, Cu, Pd, Pt, and Co. Different pathways were revealed in contrast to those found for metallic crystalline surfaces and nanoparticles. These single atom catalysts have demonstrated a general improvement in rate limiting potentials to generate C 1 hydrocarbons. They also show distinct differences in terms of their efficiency and selectivity in CO 2 reduction, which can be correlated with their elemental properties as a function of their group number in the periodic table. Six best candidates for CH 4 production are identified by conducting computational screening of 28 d-block transition metals. Ag has the lowest overpotential (0.73 V), and is followed by Zn, Ni, Pd, Pt and Ru with overpotentials all below 1 V. Cu in the supported single atom form shows a strong preference towards producing CH 3 OH with an overpotential of 0.68 V well below the value of 1.04 V for producing CH 4 .

  12. 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.

  13. Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

    Science.gov (United States)

    Liu, Lichen; Corma, Avelino

    2018-04-16

    Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

  14. Noble metal ionic catalysts.

    Science.gov (United States)

    Hegde, M S; Madras, Giridhar; Patil, K C

    2009-06-16

    Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the

  15. Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

    KAUST Repository

    Li, Shu-Long

    2017-10-27

    We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

  16. Metal-Catalyst-Free Synthesis and Characterization of Single-Crystalline Silicon Oxynitride Nanowires

    Directory of Open Access Journals (Sweden)

    Shuang Xi

    2012-01-01

    Full Text Available Large quantities of single-crystal silicon oxynitride nanowires with high N concentration have been synthesized directly on silicon substrate at 1200°C without using any metal catalyst. The diameter of these ternary nanowires is ranging from 10 to 180 nm with log-normal distribution, and the length of these nanowires varies from a few hundreds of micrometers to several millimeters. A vapor-solid mechanism was proposed to explain the growth of the nanowires. These nanowires are grown to form a disordered mat with an ultrabright white nonspecular appearance. The mat demonstrates highly diffusive reflectivity with the optical reflectivity of around 80% over the whole visible wavelength, which is comparable to the most brilliant white beetle scales found in nature. The whiteness might be resulted from the strong multiscattering of a large fraction of incident light on the disordered nanowire mat. These ultra-bright white nanowires could form as reflecting surface to meet the stringent requirements of bright-white light-emitting-diode lighting for higher optical efficiency. They can also find applications in diverse fields such as sensors, cosmetics, paints, and tooth whitening.

  17. Sintering-resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhanyong; Schweitzer, Neil; League, Aaron; Bernales Candia, Sandra Varinia; Peters, Aaron; Getsoian, Andrew G.; Wang, Timothy; Miller, Jeffrey T.; Vjunov, Aleksei; Fulton, John L.; Lercher, Johannes A.; Cramer, Christopher J.; Gagliardi, Laura; Hupp, Joseph; Farha, Omar

    2016-02-17

    Developing supported single-site catalysts is an important goal in heterogeneous catalysis, since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based MOF, NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a metal–organic framework (MOF) (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.

  18. Single transition metal atom embedded into a MoS2nanosheet as a promising catalyst for electrochemical ammonia synthesis.

    Science.gov (United States)

    Zhao, Jia; Zhao, Jingxiang; Cai, Qinghai

    2018-03-21

    The electrochemical reduction of N2 to NH3 (NRR) under ambient conditions is significant for sustainable agriculture. Here, by means of density functional theory (DFT) computations, the potential of a series of single transition metal (TM) atoms embedded into a MoS2 monolayer with an S-vacancy (TM/MoS2) as electrocatalysts for NRR was systematically investigated. Our DFT results revealed that among all these considered candidate catalysts, the single Mo atom embedded into the MoS2 nanosheet was found to be the most active catalyst for NRR with an onset potential of -0.53 V, in which the hydrogenation of the adsorbed N2* to N2H* is the potential-determining step. The high stabilization of the N2H* species is responsible for the superior performance of the embedded Mo atom for the NRR, which is well consistent with its d-band center. Our findings may facilitate the further design of single-atom electrocatalysts with high efficiency for NH3 synthesis at room temperature.

  19. Supported molten-metal catalysts

    Science.gov (United States)

    Datta, Ravindra; Singh, Ajeet; Halasz, Istvan; Serban, Manuela

    2001-01-01

    An entirely new class of catalysts called supported molten-metal catalysts, SMMC, which can replace some of the existing precious metal catalysts used in the production of fuels, commodity chemicals, and fine chemicals, as well as in combating pollution. SMMC are based on supporting ultra-thin films or micro-droplets of the relatively low-melting (metals and semimetals from groups 1, 12, 13, 14, 15 and 16, of the periodic table, or their alloys and intermetallic compounds, on porous refractory supports, much like supported microcrystallites of the traditional solid metal catalysts. It thus provides orders of magnitude higher surface area than is obtainable in conventional reactors containing molten metals in pool form and also avoids corrosion. These have so far been the chief stumbling blocks in the application of molten metal catalysts.

  20. Dispersion enhanced metal/zeolite catalysts

    Science.gov (United States)

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  1. Germanium nanowires grown using different catalyst metals

    Energy Technology Data Exchange (ETDEWEB)

    Gouveia, R.C., E-mail: riama@ifsp.edu.br [Departamento de Física – NanO Lab, Universidade Federal de São Carlos, Rod. Washington Luís, Km 235 – SP 310, São Carlos, CEP 13565-905 (Brazil); Área de Ciências, Instituto Federal de Educação Ciência e Tecnologia de São Paulo, Rua Américo Ambrósio, 269, Jd. Canaã, Sertãozinho, CEP 14169-263 (Brazil); Kamimura, H.; Munhoz, R.; Rodrigues, A.D. [Departamento de Física – NanO Lab, Universidade Federal de São Carlos, Rod. Washington Luís, Km 235 – SP 310, São Carlos, CEP 13565-905 (Brazil); Leite, E.R. [Departamento de Química – LIEC, Universidade Federal de São Carlos, São Carlos, CEP 13565-905 (Brazil); Chiquito, A.J. [Departamento de Física – NanO Lab, Universidade Federal de São Carlos, Rod. Washington Luís, Km 235 – SP 310, São Carlos, CEP 13565-905 (Brazil)

    2016-11-01

    Germanium nanowires have been synthesized by the well known vapor-liquid-solid growth mechanism using gold, silver, cooper, indium and nickel as catalyst metals. The influence of metal seeds on nanowires structural and electronic transport properties was also investigated. Electron microscopy images demonstrated that, despite differences in diameters, all nanowires obtained presented single crystalline structures. X-ray patterns showed that all nanowires were composed by germanium with a small amount of germanium oxide, and the catalyst metal was restricted at the nanowires' tips. Raman spectroscopy evidenced the long range order in the crystalline structure of each sample. Electrical measurements indicated that variable range hopping was the dominant mechanism in carrier transport for all devices, with similar hopping distance, regardless the material used as catalyst. Then, in spite of the differences in synthesis temperatures and nanowires diameters, the catalyst metals have not affected the composition and crystalline quality of the germanium nanowires nor the carrier transport in the germanium nanowire network devices. - Highlights: • Ge nanowires were grown by VLS method using Au, Ag, Cu, In and Ni as catalysts. • All nanowires presented high single crystalline quality and long range order. • Devices showed semiconducting behavior having VRH as dominant transport mechanism. • The metal catalyst did not influence structural properties or the transport mechanism.

  2. Rare earth metals for automotive exhaust catalysts

    International Nuclear Information System (INIS)

    Shinjoh, Hirohumi

    2006-01-01

    The usage of rare earth metals for automotive exhaust catalysts is demonstrated in this paper. Rare earth metals have been widely used in automotive catalysts. In particular, three-way catalysts require the use of ceria compounds as oxygen storage materials, and lanthana as both a stabilizer of alumina and a promoter. The application for diesel catalysts is also illustrated. Effects of inclusion of rare earth metals in automotive catalysts are discussed

  3. Metal phthalocyanine catalysts

    Science.gov (United States)

    Ellis, Jr., Paul E.; Lyons, James E.

    1994-01-01

    As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.

  4. Supported metal alloy catalysts

    Science.gov (United States)

    Barrera, Joseph; Smith, David C.

    2000-01-01

    A process of preparing a Group IV, V, or VI metal carbonitride including reacting a Group IV, V, or VI metal amide complex with ammonia to obtain an intermediate product; and, heating the intermediate product to temperatures and for times sufficient to form a Group IV, V, or VI metal carbonitride is provided together with the product of the process and a process of reforming an n-alkane by use of the product.

  5. Novel non-platinum metal catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel non-platinum metal catalyst material for use in low temperature fuel cells and electrolysers and to fuel cells and electrolysers comprising the novel non-platinum metal catalyst material. The present invention also relates to a novel method for synthesizing...... the novel non-platinum metal catalyst material....

  6. Thin film hydrous metal oxide catalysts

    Science.gov (United States)

    Dosch, Robert G.; Stephens, Howard P.

    1995-01-01

    Thin film (metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

  7. Biorecovered precious metals from industrial wastes: single-step conversion of a mixed metal liquid waste to a bioinorganic catalyst with environmental application.

    Science.gov (United States)

    Mabbett, Amanda N; Sanyahumbi, Douglas; Yong, Ping; Macaskie, Lynne E

    2006-02-01

    The complete and continuous reduction of 1 mM Cr(VI) to Cr(III) was achieved in a flow-through reactor using a novel bioinorganic catalyst ("MM-bio-Pd(0)"), which was produced by single-step reduction of platinum group metals (PGM) from industrial waste solution onto biomass of Desulfovibrio desulfuricans ATCC 29577. Two flow-through reactor systems were compared using both "MM-bioPd(0)" and chemically reduced Pd(0). Reactors containing the latter removed Cr(VI) for 1 week only at the expense of formate as the electron donor, whereas the former gave complete Cr(VI) removal for 3 months of continuous operation. Mass balance analysis showed 100% reduction of Cr(VI) to soluble Cr(III) in the bioreactor exit solution. With the use of electron paramagnetic resonance (EPR) no intermediate Cr(V) species could be detected. Pd(0) was biodeposited similarly using Escherichia coliMC4100 and "bio-Pd(0)". The latter was used to recover Pd(II) from two acidic industrial waste leachates to generate two types of "MM-bio-Pd(0)": "SI-bio-Pd(0)" and "SII-bio-Pd(0)", respectively. The biomaterial composition was comparable in both cases, and the catalytic activity was related inversely to the amount of chloride in the waste leachate from which it was derived.

  8. A Polymer Encapsulation Strategy to Synthesize Porous Nitrogen-Doped Carbon-Nanosphere-Supported Metal Isolated-Single-Atomic-Site Catalysts.

    Science.gov (United States)

    Han, Aijuan; Chen, Wenxing; Zhang, Shaolong; Zhang, Maolin; Han, Yunhu; Zhang, Jian; Ji, Shufang; Zheng, Lirong; Wang, Yu; Gu, Lin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

    2018-03-06

    A novel polymer encapsulation strategy to synthesize metal isolated-single-atomic-site (ISAS) catalysts supported by porous nitrogen-doped carbon nanospheres is reported. First, metal precursors are encapsulated in situ by polymers through polymerization; then, metal ISASs are created within the polymer-derived p-CN nanospheres by controlled pyrolysis at high temperature (200-900 °C). Transmission electron microscopy and N 2 sorption results reveal this material to exhibit a nanospheric morphology, a high surface area (≈380 m 2 g -1 ), and a porous structure (with micropores and mesopores). Characterization by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure confirms the metal to be present as metal ISASs. This methodology is applicable to both noble and nonprecious metals (M-ISAS/p-CN, M = Co, Ni, Cu, Mn, Pd, etc.). In particular, the Co-ISAS/p-CN nanospheres obtained using this method show comparable (E 1/2 = 0.838 V) electrochemical oxygen reduction activity to commercial Pt/C with 20 wt% Pt loading (E 1/2 = 0.834 V) in alkaline media, superior methanol tolerance, and outstanding stability, even after 5000 cycles. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Mesoporous metal catalysts formed by ultrasound

    Energy Technology Data Exchange (ETDEWEB)

    Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Universitaet Bayreuth (Germany)

    2010-07-01

    We study the ultrasound-driven formation of mesoporous metal sponges. The collapse of acoustic cavitations leads to very high temperatures and pressures on very short scales. Therefore, structures may be formed and quenched far from equilibrium. Mechanism of metal modification by ultrasound is complex and involves a variety of aspects. We propose that modification of metal particles and formation of mesoporous inner structures can be achieved due to thermal etching of metals by ultrasound stimulated high speed jets of liquid. Simultaneously, oxidation of metal surfaces by free radicals produced in water during cavitation stabilizes developed metal structures. Duration and intensity of the ultrasonication treatment is able to control the structure and morphology of metal sponges. We expect that this approach to the formation of nanoscale composite sponges is universal and opens perspective for a whole new class of catalytic materials that can be prepared in a one-step process. The developed method makes it possible to control the sponge morphology and can be used for formation of modern types of catalysts. For example, the sonication technique allows to combine the fabrication of mesoporous support and distribution of metal (Cu, Pd, Au, Pt etc.) nanoparticles in its pores into a single step.

  10. Nanoparticular metal oxide/anatase catalysts

    DEFF Research Database (Denmark)

    2010-01-01

    the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

  11. Metal Nanoparticle Catalysts for Carbon Nanotube Growth

    Science.gov (United States)

    Pierce, Benjamin F.

    2003-01-01

    Work this summer involved and new and unique process for producing the metal nanoparticle catalysts needed for carbon nanotube (CNT) growth. There are many applications attributed to CNT's, and their properties have deemed them to be a hot spot in research today. Many groups have demonstrated the versatility in CNT's by exploring a wide spectrum of roles that these nanotubes are able to fill. A short list of such promising applications are: nanoscaled electronic circuitry, storage media, chemical sensors, microscope enhancement, and coating reinforcement. Different methods have been used to grow these CNT's. Some examples are laser ablation, flame synthesis, or furnace synthesis. Every single approach requires the presence of a metal catalyst (Fe, Co, and Ni are among the best) that is small enough to produce a CNT. Herein lies the uniqueness of this work. Microemulsions (containing inverse micelles) were used to generate these metal particles for subsequent CNT growth. The goal of this summer work was basically to accomplish as much preliminary work as possible. I strived to pinpoint which variable (experimental process, metal product, substrate, method of application, CVD conditions, etc.) was the determining factor in the results. The resulting SEM images were sufficient for the appropriate comparisons to be made. The future work of this project consists of the optimization of the more promising experimental procedures and further exploration onto what exactly dictated the results.

  12. Stereogenic-Only-at-Metal Asymmetric Catalysts.

    Science.gov (United States)

    Zhang, Lilu; Meggers, Eric

    2017-09-19

    Chirality is an essential feature of asymmetric catalysts. This review summarizes asymmetric catalysts that derive their chirality exclusively from stereogenic metal centers. Reported chiral-at-metal catalysts can be divided into two classes, namely, inert metal complexes, in which the metal fulfills a purely structural role, so catalysis is mediated entirely through the ligand sphere, and reactive metal complexes. The latter are particularly appealing because structural simplicity (only achiral ligands) is combined with the prospect of particularly effective asymmetric induction (direct contact of the substrate with the chiral metal center). Challenges and solutions for the design of such reactive stereogenic-only-at-metal asymmetric catalysts are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Metal nanoparticles as a conductive catalyst

    Science.gov (United States)

    Coker, Eric N [Albuquerque, NM

    2010-08-03

    A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

  14. Making A Noble-Metal-On-Metal-Oxide Catalyst

    Science.gov (United States)

    Miller, Irvin M.; Davis, Patricia P.; Upchurch, Billy T.

    1989-01-01

    Catalyst exhibits superior performance in oxidation of CO in CO2 lasers. Two-step process developed for preparing platinum- or palladium-on-tin-oxide catalyst for recombination of CO and O2, decomposition products that occur in high-voltage discharge region of closed-cycle CO2 laser. Process also applicable to other noble-metal/metal-oxide combinations.

  15. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  16. Hyperfine interactions in metallic catalysts

    International Nuclear Information System (INIS)

    Saitovitch, Henrique; Silva, Paulo R.J.; Passos, Fabio B.

    2005-01-01

    Heterogeneous catalysts are of fundamental importance in several modern chemical processes. The characterization of catalysts is an issue of very present interest as it can provide a better understanding of the fundamental aspects of the catalytic phenomena, thus helping in the development of more efficient catalysts. In order to extend and improve the characterization of catalysts, new and less conventional methods are being applied, such as nuclear spectroscopies. In this paper we focus on the application of angular correlation, with can be used to resolve different local environments of probe atoms in solids and can be applied, as shown here, in the characterization of heterogeneous catalysts. A brief theoretical introduction is given and experimental results related to catalytic systems of alumina and niobia-supported Pt-In and Pd-In catalysts are presented. (author)

  17. Bi-metallic catalysts, methods of making, and uses thereof

    KAUST Repository

    Basset, Jean-Marie

    2017-01-19

    Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

  18. Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

    Science.gov (United States)

    DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

    2017-10-11

    Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

  19. 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.

  20. XRLINE, a program to evaluate the crystallite size of supported metal catalysts by single X-ray profile Fourier analysis

    International Nuclear Information System (INIS)

    Aldea, N.; Indrea, E.

    1990-01-01

    The computer program presented is based on the Fourier analysis of a singel X-ray diffraction profile. An X-ray diffraction method is presented which is capable of determining the average particle size, microstrain, stacking fault probability as well as the particle size distribution function in crystalline materials. The main numerical methods used are: (i) Smoothing and interpolation by 3rd-order piecewise polynomial functions or by cubic splines with the least squares method; (ii) numerical integration by successive five points formulae and numerical derivative by cubic splines with the least squares method; (iii) estimation of parameters by the weighted least squares method. The results for supported platinum catalysts used in the H/D isotopic exchange reaction are illustrated. (orig.)

  1. Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

    Science.gov (United States)

    Gangwal, Santosh; Jothimurugesan, Kandaswamy

    1999-01-01

    A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption processes, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gasses from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or "passivating" the heavy metals on the spent FCC catalyst as an intermediate step.

  2. Computational Study on M1/POM Single-Atom Catalysts (M = Cu, Zn, Ag, and Au; POM = [PW12O40]3-): Metal-Support Interactions and Catalytic Cycle for Alkene Epoxidation.

    Science.gov (United States)

    Liu, Chun-Guang; Jiang, Meng-Xu; Su, Zhong-Min

    2017-09-05

    Geometrical structures, metal-support interactions, and infrared (IR) spectroscopy of a series of M 1 /POM (M = Cu, Zn, Ag, and Au; POM = [PW 12 O 40 ] 3- ) single-atom catalysts (SACs), and catalytic cycle for alkene epoxidation catalyzed by M 1 /POM SACs were studied using density functional theory (DFT) calculations. The calculations demonstrate that the most probable anchoring sties for the isolated single atoms studied here in the M 1 /POM SACs are the fourfold hollow sites on the surface of POM support. The bonding interaction between single metal atom and surface of POM support comes from the molecular orbitals with a mixture of d atomic orbital of metal and 2p group orbital of surface oxygen atoms of POM cage. The calculated adsorption energy of isolated metal atoms in these M 1 /POM SACs indicates that the early transition metals (Cu and Zn) have high thermal stability. The DFT-derived IR spectra show that the four characteristic peaks of free Keggin-type POM structure split into six because of introduction of isolated metal atom. Compared with other metal atoms, the Zn 1 /POM SAC has the high reactivity for activity of dioxygen molecule, because the dioxygen moiety in Zn 1 /POM SAC displays O 2 - · radical feature with [POM 4- ·Zn 2+ O 2 - ·] 3- configuration. Finally, a catalytic cycle for ethylene epoxidation by O 2 catalyzed by Zn 1 /POM SAC was proposed based on our DFT calculations. Supported noble-metal SACs are among the most important catalysts currently. However, noble metals are expensive and of limited supply. Development of non-noble-metal SACs is of essential importance. Therefore, the reported Zn 1 /POM SAC would be very useful to guide the search for SACs into non-noble metals.

  3. Mechanistic studies aimed at the development of single site metal alkoxide catalysts for the production of polyoxygenates from renewable resources.

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, Malcolm H. [The Ohio State Univ., Columbus, OH (United States)

    2015-12-15

    The work proposed herein follows on directly from the existing 3 year grant and the request for funding is for 12 months to allow completion of this work and graduation of current students supported by DOE. The three primary projects are as follows. 1.) A comparative study of the reactivity of LMg(OR) (solvent), where L= a β-diiminate or pyrromethene ligand, in the ring-opening of cyclic esters. 2.) The homopolymerization of expoxides, particularly propylene oxide and styrene oxide, and their copolymerizations with carbon dioxide or organic anhydrides to yield polycarbonates or polyesters, respectively. 3.) The development of well-defined bismuth (III) complexes for ring-opening polymerizations that are tolerant of both air and water. In each of these topics special emphasis is placed on developing a detailed mechanistic understanding of the ring-opening event and how this is modified by the employment of specific metal and ligand combinations. This document also provides a report on findings of the past grant period that are not yet in the public domain/published and shows how the proposed work will bring the original project to conclusion.

  4. The effect of metal ions as co-catalysts on acidic ionic liquid catalyzed single-step saccharification of corn stover in water.

    Science.gov (United States)

    Wiredu, Bernard; Amarasekara, Ananda S

    2015-01-01

    The effects of adding Cr(3+), Mn(2+), Fe(3+), Co(2+) Ni(2+), Cu(2+), Zn(2+) and La(3+) chlorides as co-catalysts to 1-(1-propylsulfonic)-3-methylimidazolium chloride acidic ionic liquid catalyzed saccharification of corn stover in aqueous medium was studied at 140-170 °C, by measuring the total reducing sugar (TRS) and glucose yields. The samples with Mn(2+), Fe(3+), Co(2+) as co-catalysts produced higher TRS yields compared to the sample without the metal ions. The Mn(2+) produced the highest catalytic effect enhancements and produced TRS yields of 68.0%, 72.9%, 90.2% and 87.9% at 140, 150, 160 and 170 °C respectively; whereas the corn stover samples without the Mn(2+) produced TRS yields of 42.9%, 52.3%, 54.4% and 53.5% at the same four temperatures. At higher temperatures of 160 and 170 °C, all metal ions studied produced significant enhancements in glucose yields, except Cr(3+). The addition of La(3+) as a co-catalyst produced the highest glucose yield improvement. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Current advances in precious metal core–shell catalyst design

    Science.gov (United States)

    Wang, Xiaohong; He, Beibei; Hu, Zhiyu; Zeng, Zhigang; Han, Sheng

    2014-01-01

    Precious metal nanoparticles are commonly used as the main active components of various catalysts. Given their high cost, limited quantity, and easy loss of catalytic activity under severe conditions, precious metals should be used in catalysts at low volumes and be protected from damaging environments. Accordingly, reducing the amount of precious metals without compromising their catalytic performance is difficult, particularly under challenging conditions. As multifunctional materials, core–shell nanoparticles are highly important owing to their wide range of applications in chemistry, physics, biology, and environmental areas. Compared with their single-component counterparts and other composites, core–shell nanoparticles offer a new active interface and a potential synergistic effect between the core and shell, making these materials highly attractive in catalytic application. On one hand, when a precious metal is used as the shell material, the catalytic activity can be greatly improved because of the increased surface area and the closed interfacial interaction between the core and the shell. On the other hand, when a precious metal is applied as the core material, the catalytic stability can be remarkably improved because of the protection conferred by the shell material. Therefore, a reasonable design of the core–shell catalyst for target applications must be developed. We summarize the latest advances in the fabrications, properties, and applications of core–shell nanoparticles in this paper. The current research trends of these core–shell catalysts are also highlighted. PMID:27877695

  6. Alkaline earth metal catalysts for asymmetric reactions.

    Science.gov (United States)

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

    The group 2 alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) are among the most common elements on Earth, abundant in both the sea and the Earth's crust. Although they are familiar in our daily lives, their application to organic synthesis has, so far, been limited. Some particularly useful properties of these elements include (i) low electronegativity, (ii) a stable oxidation state of +2, meaning that they can potentially form two covalent bonds with anions, and (iii) the ability to occupy a variety of coordination sites due to their large ionic radius. Furthermore, the alkaline earth metals, found between the group 1 and group 3 elements, show mild but significant Lewis acidity, which can be harnessed to control coordinative molecules via a Lewis acid-base interaction. Taken together, these characteristics make the metals Ca, Sr, and Ba very promising components of highly functionalized acid-base catalysts. In this Account, we describe the development of chiral alkaline earth metal catalysts for asymmetric carbon-carbon bond-forming reactions. Recently prepared chiral alkaline earth metal complexes have shown high diastereo- and enantioselectivities in fundamental and important chemical transformations. We chose chiral bisoxazoline (Box) derivatives bearing a methylene tether as a ligand for chiral modification. These molecules are very useful because they can covalently coordinate to alkaline earth metals in a bidentate fashion through deprotonation of the tether portion. It was found that chiral calcium-Box complexes could successfully promote catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions with high diastereo- and enantioselectivities. Both the calcium-Box complexes and chiral strontium-bis-sulfonamide and chiral barium-BINOLate complexes could catalyze asymmetric 1,4-addition reactions with high enantioselectivities. Furthermore, we designed a calcium-neutral coordinative ligand complex as a new type of chiral alkaline

  7. Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

    Science.gov (United States)

    Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

    2015-06-28

    Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

  8. Non-noble metal fuel cell catalysts

    CERN Document Server

    Chen, Zhongwei; Zhang, Jiujun

    2014-01-01

    Written and edited by a group of top scientists and engineers in the field of fuel cell catalysts from both industry and academia, this book provides a complete overview of this hot topic. It covers the synthesis, characterization, activity validation and modeling of different non-noble metal and metalfree electrocatalysts for the reduction of oxygen, as well as their integration into acid or alkaline polymer exchange membrane (PEM) fuel cells and their performance validation, while also discussing those factors that will drive fuel cell commercialization. With its well-structured app

  9. Development of radioactive platinum group metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H.S.; Kim, Y.S.; Kim, Y.E. [and others

    1999-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m{sup 2}/g.The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs.

  10. Development of radioactive platinum group metal catalysts

    International Nuclear Information System (INIS)

    Chung, H.S.; Kim, Y.S.; Kim, Y.E.

    1999-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m 2 /g. The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs

  11. Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems.

    Science.gov (United States)

    Gewirth, Andrew A; Varnell, Jason A; DiAscro, Angela M

    2018-01-31

    A comprehensive review of recent advances in the field of oxygen reduction electrocatalysis utilizing nonprecious metal (NPM) catalysts is presented. Progress in the synthesis and characterization of pyrolyzed catalysts, based primarily on the transition metals Fe and Co with sources of N and C, is summarized. Several synthetic strategies to improve the catalytic activity for the oxygen reduction reaction (ORR) are highlighted. Recent work to explain the active-site structures and the ORR mechanism on pyrolyzed NPM catalysts is discussed. Additionally, the recent application of Cu-based catalysts for the ORR is reviewed. Suggestions and direction for future research to develop and understand NPM catalysts with enhanced ORR activity are provided.

  12. Peptide-templated noble metal catalysts: syntheses and applications.

    Science.gov (United States)

    Wang, Wei; Anderson, Caleb F; Wang, Zongyuan; Wu, Wei; Cui, Honggang; Liu, Chang-Jun

    2017-05-01

    Noble metal catalysts have been widely used in many applications because of their high activity and selectivity. However, a controllable preparation of noble metal catalysts still remains as a significant challenge. To overcome this challenge, peptide templates can play a critical role in the controllable syntheses of catalysts owing to their flexible binding with specific metallic surfaces and self-assembly characteristics. By employing peptide templates, the size, shape, facet, structure, and composition of obtained catalysts can all be specifically controlled under the mild synthesis conditions. In addition, catalysts with spherical, nanofiber, and nanofilm structures can all be produced by associating with the self-assembly characteristics of peptide templates. Furthermore, the peptide-templated noble metal catalysts also reveal significantly enhanced catalytic behaviours compared with conventional catalysts because the electron conductivity, metal dispersion, and reactive site exposure can all be improved. In this review, we summarize the research progresses in the syntheses of peptide-templated noble metal catalysts. The applications of the peptide-templated catalysts in organic reactions, photocatalysis, and electrocatalysis are discussed, and the relationship between structure and activity of these catalysts are addressed. Future opportunities, including new catalytic materials designed by using biological principles, are indicated to achieve selective, eco-friendly, and energy neutral synthesis approaches.

  13. Interaction between Nafion ionomer and noble metal catalyst for PEMFCs

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma

    The implement of polymer impregnation in electrode structure (catalyst layer) decreasing the noble metal catalyst loading by a factor of ten , , is one of the essential mile stones in the evolution of Proton Exchange Membrane Fuel Cells’ development among the application of catalyst support...... and electrode deposition etc. In fuel cell reactions, both electrons and protons are involved. Impregnation of Nafion ionomer in catalyst layer effectively increases the proton-electron contact, enlarge the reaction zone, extend the reaction from the surface to the entire electrode. Therefore, the entire...... catalyst layer conducts both electrons and protons so that catalyst utilization in the layer is improved dramatically. The catalyst layer will in turn generate and sustain a higher current density. One of the generally adapted methods to impregnate Nafion into the catalyst layer is to mix the catalysts...

  14. First-row transition metal hydrogenation and hydrosilylation catalysts

    Science.gov (United States)

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  15. An improved method of preparation of nanoparticular metal oxide catalysts

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step....

  16. Application of a mixed metal oxide catalyst to a metallic substrate

    Science.gov (United States)

    Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

    2009-01-01

    A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

  17. A stable rhodium single-site catalyst encapsulated within dendritic mesoporous nanochannels.

    Science.gov (United States)

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

    2018-01-18

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

  18. Method of making metal-polymer composite catalysts

    Science.gov (United States)

    Zelena, Piotr [Los Alamos, NM; Bashyam, Rajesh [Los Alamos, NM

    2009-06-23

    A metal-polymer-carbon composite catalyst for use as a cathode electrocatalyst in fuel cells. The catalyst includes a heteroatomic polymer; a transition metal linked to the heteroatomic polymer by one of nitrogen, sulfur, and phosphorus, and a recast ionomer dispersed throughout the heteroatomic polymer-carbon composite. The method includes forming a heteroatomic polymer-carbon composite and loading the transition metal onto the composite. The invention also provides a method of making a membrane electrode assembly for a fuel cell that includes the metal-polymer-carbon composite catalyst.

  19. Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis.

    Science.gov (United States)

    Afewerki, Samson; Córdova, Armando

    2016-11-23

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

  20. Olefin polymerization from single site catalysts confined within porous media

    Science.gov (United States)

    Kasi, Rajeswari M.

    Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

  1. Subnanometer to nanometer transition metal CO oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Vajda, Stefan; Fortunelli, Alessandro; Yasumatsu, Hisato

    2017-12-26

    The present invention provides a catalyst defined in part by a conductive substrate; a film overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises between 8 and 11 atoms. Further provided is a catalyst defined in part by a conductive substrate; a layer overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises at least two metals.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-08

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

  3. Metal-Free Boron-Containing Heterogeneous Catalysts.

    Science.gov (United States)

    Fang, Yuanxing; Wang, Xinchen

    2017-12-04

    Metal-free catalysts have distinct advantages over metal and metal oxide catalysts, such as lower cost as well as higher reliability and sustainability. Among the nonmetal compounds used in catalysis, boron-containing compounds with a few unique properties have been developed. In this Minireview, the recent advances in the field of boron-containing metal-free catalysts are presented, including binary and ternary boron-containing catalytic materials. Additionally, the three main applications in catalysis are considered, namely, electrocatalysis, thermal catalysis, and photocatalysis, with the role of boron discussed in depth for each specific catalytic application. Boron-containing compounds could have a substantial impact on the field of metal-free catalysts in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Metal Catalysts Recycling and Heterogeneous/Homogeneous Catalysis

    Directory of Open Access Journals (Sweden)

    Masahiko Arai

    2015-05-01

    Full Text Available Heterogeneous metal catalysts rather than homogeneous ones are recommended for industrial applications after considering their performance in activity, separation, and recycling [1]. The recycling of metal catalysts is important from economic and environmental points of view. When supported and bulk metal catalysts are used in liquid-phase organic reactions, there is a possibility that active metal species are leaching away into the liquid phases [2,3]. The metal leaching would make it difficult for the catalysts to maintain their desired initial performance for repeated batch reactions and during continuous ones. The metal leaching would also cause some undesired contamination of products by the metal species dissolved in the reaction mixture, and the separation of the metal contaminants would be required to purify the products. Therefore, various novel methods have been proposed so far to immobilize/stabilize the active metal species and to separate/collect/reuse the dissolved metal species [4]. In addition, knowledge on the heterogeneous and homogeneous natures of organic reactions using heterogeneous catalysts is important to discuss their reaction mechanisms and catalytically working active species. [...

  5. Dissolution of Metal Supported Spent Auto Catalysts in Acids

    Directory of Open Access Journals (Sweden)

    Fornalczyk A.

    2016-03-01

    Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

  6. 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

  7. Synthesis, Characterizations, and Applications of Metal-Ions Incorporated High Quality MCM-41 Catalysts

    International Nuclear Information System (INIS)

    Lim, Steven S.; Haller, Gary L.

    2013-01-01

    Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically V 5+ , Co 2+ , and Ni 2+ -incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated

  8. Metal-free phenanthrenequinone cyclotrimer as an effective heterogeneous catalyst.

    Science.gov (United States)

    Zhang, Jian; Wang, Xuan; Su, Qi; Zhi, Linjie; Thomas, Arne; Feng, Xinliang; Su, Dang Sheng; Schlögl, Robert; Müllen, Klaus

    2009-08-19

    A phenanthrenequinone macrocyclic trimer was synthesized and used as a heterogeneous catalyst for oxidative dehydrogenation of ethylbenzene. This model molecule under comparable kinetic conditions is up to 47 times more active than extended solid catalysts including nanocarbons, metal phosphates, and oxides, confirming the hypothesis that diketone-like groups can serve as active sites.

  9. Nitrogen-doped carbon nanotubes as a metal catalyst support

    CSIR Research Space (South Africa)

    Mabena, LF

    2011-05-01

    Full Text Available The science and technology of catalysis is of fundamental importance to a national economy. Today about 90% of all technical chemicals are manufactured by the use of catalysts. Nanoparticles of noble metals are extremely important materials...

  10. Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

    Science.gov (United States)

    Marks, Tobin J [Evanston, IL; Rodriguez, Brandon A [Evanston, IL; Delferro, Massimiliano [Chicago, IL

    2012-08-07

    A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ravindra Datta; Ajeet Singh; Manuela Serban; Istvan Halasz

    2006-06-02

    We describe a new class of heterogeneous catalysts called supported molten metal catalysis (SMMC), in which molten metal catalysts are dispersed as nanodroplets on the surface of porous supports, allowing much larger active surface area than is possible in conventional contacting techniques for catalytic metals that are molten under reaction conditions, thus greatly enhancing their activity and potential utility. Specific examples of different types of reactions are provided to demonstrate the broad applicability of the technique in designing active, selective, and stable new catalysts. It is shown that dispersing the molten metal on a support in the suggested manner can enhance the rate of a reaction by three to four orders of magnitude as a result of the concomitant increase in the active surface area. New reaction examples include {gamma}-Al{sub 2}O{sub 3} supported molten Te (melting point 450 C) and Ga (MP 30 C) catalysts for bifunctional methylcyclohexane dehydrogenation. These catalysts provide activity similar to conventional Pt-based catalysts for this with better resistance to coking. In addition, results are described for a controlled pore glass supported molten In (MP 157 C) catalyst for the selective catalytic reduction of NO with ethanol in the presence of water, demonstrating activities superior to conventional catalysts for this reaction. A discussion is also provided on the characterization of the active surface area and dispersion of these novel supported catalysts. It is clear based on the results described that the development of new active and selective supported molten metal catalysts for practical applications is entirely plausible.

  12. Surface Structures of Model Metal Catalysts in Reactant Gases.

    Science.gov (United States)

    Tao, Franklin Feng; Ralston, Walter T; Liu, Huimin; Somorjai, Gabor A

    2018-01-18

    Atomic scale knowledge of the surface structure of a metal catalyst is essential for fundamentally understanding the catalytic reactions performed on it. A correlation between the true atomic surface structure of a metal catalyst under reaction conditions and the corresponding catalytic performance is the key in pursuing mechanistic insight at a molecular level. Here the surface structures of model, metal catalysts in both ultrahigh vacuum (UHV) and gaseous environments of CO at a wide range of pressures are discussed. The complexity of observed surface structures in CO is illustrated, driving the necessity for visualization of the catalytic metals under realistic reaction conditions. Technical barriers for visualization of metal surfaces in situ at high temperature and high pressure are discussed.

  13. Single-atom catalysts for CO2electroreduction with significant activity and selectivity improvements.

    Science.gov (United States)

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

    2017-02-01

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

  14. Reactivity of metal catalysts in glucose-fructose conversion.

    Science.gov (United States)

    Loerbroks, Claudia; van Rijn, Jeaphianne; Ruby, Marc-Philipp; Tong, Qiong; Schüth, Ferdi; Thiel, Walter

    2014-09-15

    A joint experimental and computational study on the glucose-fructose conversion in water is reported. The reactivity of different metal catalysts (CrCl3, AlCl3, CuCl2, FeCl3, and MgCl2) was analyzed. Experimentally, CrCl3 and AlCl3 achieved the best glucose conversion rates, CuCl2 and FeCl3 were only mediocre catalysts, and MgCl2 was inactive. To explain these differences in reactivity, DFT calculations were performed for various metal complexes. The computed mechanism consists of two proton transfers and a hydrogen-atom transfer; the latter was the rate-determining step for all catalysts. The computational results were consistent with the experimental findings and rationalized the observed differences in the behavior of the metal catalysts. To be an efficient catalyst, a metal complex should satisfy the following criteria: moderate Brønsted and Lewis acidity (pKa = 4-6), coordination with either water or weaker σ donors, energetically low-lying unoccupied orbitals, compact transition-state structures, and the ability for complexation of glucose. Thus, the reactivity of the metal catalysts in water is governed by many factors, not just the Lewis acidity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Hydrous metal oxide catalysts for oxidation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.E.; Dosch, R.G.; McLaughlin, L.I. [Sandia National Labs., Albuquerque, NM (United States). Process Research Dept.

    1993-07-01

    This report describes work performed at Sandia under a CRADA with Shell Development of Houston, Texas aimed at developing hydrous metal oxide (HMO) catalysts for oxidation of hydrocarbons. Autoxidation as well as selective oxidation of 1-octene was studied in the presence of HMO catalysts based on known oxidation catalysts. The desired reactions were the conversion of olefin to epoxides, alcohols, and ketones, HMOs seem to inhibit autoxidation reactions, perhaps by reacting with peroxides or radicals. Attempts to use HMOs and metal loaded HMOs as epoxidation catalysts were unsuccessful, although their utility for this reaction was not entirely ruled out. Likewise, alcohol formation from olefins in the presence of HMO catalysts was not achieved. However, this work led to the discovery that acidified HMOs can lead to carbocation reactions of hydrocarbons such as cracking. An HMO catalyst containing Rh and Cu that promotes the reaction of {alpha}-olefins with oxygen to form methyl ketones was identified. Although the activity of the catalyst is relatively low and isomerization reactions of the olefin simultaneously occur, results indicate that these problems may be addressed by eliminating mass transfer limitations. Other suggestions for improving the catalyst are also made. 57 refs.

  16. Precious metal compounds and recovery. Fischer-Tropsch catalysts and catalysts for hydroformylation and oxo processes

    Energy Technology Data Exchange (ETDEWEB)

    Schapp, J.; Arndt, M. [W.C. Heraeus GmbH, Hanau (Germany); Meyer, H. [Heraeus Metal Processing Inc., Santa Fe Springs, CA (United States)

    2006-07-01

    Solid-phase Fischer-Tropsch catalysts, which are used in the emerging field of interest known as ''Gas-to-Liquid'' (GTL), consist to a high percentage of cobalt. In addition, they contain on a value basis, a considerable amount of platinum group metals or rhenium as promoters. Therefore, there is an imperative need for economically feasible recycling processes triggered not only by the value of the metals in spent Fischer-Tropsch catalysts, but also by the potentially limited availability of promoters like rhenium. Heraeus, as a precious metal expert, is supporting this important technology with its profound know-how in developing tailor-made hydrometallurgical recycling processes for all kinds of catalyst systems. Besides giving an overview of state-of-the-art recovery processes, this paper will clarify the economic and environmental aspects involved. Hydroformylation and oxo processes are technologies which consume a major percentage of homogeneous catalysts worldwide. The focus lies on organometallic compounds with rhodium as the catalytic center. With significant rises of the rhodium price, many companies are being pushed to look more closely at the involved recycling terms. Accordingly, Heraeus is proud to offer its HeraCYCLE {sup registered} recovery process recently developed for homogeneous catalysts in particular. Furthermore, Heraeus manufactures the required quantities of fresh homogeneous catalysts ensuring highest quality standards. Key economic, technical, and environmental aspects of the precious metal loops will be covered by this paper. (orig.)

  17. Metal-Support Cooperative Catalysts for Environmentally Benign Molecular Transformations.

    Science.gov (United States)

    Kaneda, Kiyotomi; Mitsudome, Takato

    2017-01-01

    Metal-support cooperative catalysts have been developed for sustainable and environmentally benign molecular transformations. The active metal centers and supports in these catalysts could cooperatively activate substrates, resulting in high catalytic performance for liquid-phase reactions under mild conditions. These catalysts involved hydrotalcite-supported gold and silver nanoparticles with high catalytic activity for organic reactions such as aerobic oxidation, oxidative carbonylation, and chemoselective reduction of epoxides to alkenes and nitrostyrenes to aminostyrenes using alcohols and CO/H 2 O as reducing reagents. This high catalytic performance was due to cooperative catalysis between the metal nanoparticles and basic sites of the hydrotalcite support. To increase the metal-support cooperative effect, core-shell nanostructured catalysts consisting of gold or silver nanoparticles in the core and ceria supports in the shell were designed. These core-shell nanocomposite catalysts were effective for the chemoselective hydrogenation of nitrostyrenes to aminostyrenes, unsaturated aldehydes to allyl alcohols, and alkynes to alkenes using H 2 as a clean reductant. In addition, these solid catalysts could be recovered easily from the reaction mixture by simple filtration, and were reusable with high catalytic activity. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  19. Studies on PEM fuel cell noble metal catalyst dissolution

    DEFF Research Database (Denmark)

    Andersen, S. M.; Grahl-Madsen, L.; Skou, E. M.

    2011-01-01

    A combination of electrochemical, spectroscopic and gravimetric methods was carried out on Proton Exchange Membrane (PEM) fuel cell electrodes with the focus on platinum and ruthenium catalysts dissolution, and the membrane degradation. In cyclic voltammetry (CV) experiments, the noble metals were...... found to dissolve in 1 M sulfuric acid solution and the dissolution increased exponentially with the upper potential limit (UPL) between 0.6 and 1.6 vs. RHE. 2-20% of the Pt (depending on the catalyst type) was found to be dissolved during the experiments. Under the same conditions, 30-100% of the Ru...... (depending on the catalyst type) was found to be dissolved. The faster dissolution of ruthenium compared to platinum in the alloy type catalysts was also confirmed by X-ray diffraction measurements. The dissolution of the carbon supported catalyst was found one order of magnitude higher than the unsupported...

  20. Aerobic Oxidations of Light Alkanes over Solid Metal Oxide Catalysts.

    Science.gov (United States)

    Grant, Joseph T; Venegas, Juan M; McDermott, William P; Hermans, Ive

    2017-11-07

    Heterogeneous metal oxide catalysts are widely studied for the aerobic oxidations of C 1 -C 4 alkanes to form olefins and oxygenates. In this review, we outline the properties of supported metal oxides, mixed-metal oxides, and zeolites and detail their most common applications as catalysts for partial oxidations of light alkanes. By doing this we establish similarities between different classes of metal oxides and identify common themes in reaction mechanisms and research strategies for catalyst improvement. For example, almost all partial alkane oxidations, regardless of the metal oxide, follow Mars-van Krevelen reaction kinetics, which utilize lattice oxygen atoms to reoxidize the reduced metal centers while the gaseous O 2 reactant replenishes these lattice oxygen vacancies. Many of the most-promising metal oxide catalysts include V 5+ surface species as a necessary constituent to convert the alkane. Transformations involving sequential oxidation steps (i.e., propane to acrylic acid) require specific reaction sites for each oxidation step and benefit from site isolation provided by spectator species. These themes, and others, are discussed in the text.

  1. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation.

    Science.gov (United States)

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

    2018-03-05

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

  2. Metal salt catalysts for enhancing hydrogen spillover

    Science.gov (United States)

    Yang, Ralph T; Wang, Yuhe

    2013-04-23

    A composition for hydrogen storage includes a receptor, a hydrogen dissociating metal doped on the receptor, and a metal salt doped on the receptor. The hydrogen dissociating metal is configured to spill over hydrogen to the receptor, and the metal salt is configured to increase a rate of the spill over of the hydrogen to the receptor.

  3. Hydrogenation of coal liquid utilizing a metal carbonyl catalyst

    Science.gov (United States)

    Feder, Harold M.; Rathke, Jerome W.

    1979-01-01

    Coal liquid having a dissolved transition metal, catalyst as a carbonyl complex such as Co.sub.2 (CO.sub.8) is hydrogenated with hydrogen gas or a hydrogen donor. A dissociating solvent contacts the coal liquid during hydrogenation to form an immiscible liquid mixture at a high carbon monoxide pressure. The dissociating solvent, e.g. ethylene glycol, is of moderate coordinating ability, while sufficiently polar to solvate the transition metal as a complex cation along with a transition metal, carbonyl anion in solution at a decreased carbon monoxide pressure. The carbon monoxide pressure is reduced and the liquids are separated to recover the hydrogenated coal liquid as product. The dissociating solvent with the catalyst in ionized form is recycled to the hydrogenation step at the elevated carbon monoxide pressure for reforming the catalyst complex within fresh coal liquid.

  4. Towards ALD thin film stabilized single-atom Pd1 catalysts.

    Science.gov (United States)

    Piernavieja-Hermida, Mar; Lu, Zheng; White, Anderson; Low, Ke-Bin; Wu, Tianpin; Elam, Jeffrey W; Wu, Zili; Lei, Yu

    2016-08-18

    Supported precious metal single-atom catalysts have shown interesting activity and selectivity in recent studies. However, agglomeration of these highly mobile mononuclear surface species can eliminate their unique catalytic properties. Here we study a strategy for synthesizing thin film stabilized single-atom Pd1 catalysts using atomic layer deposition (ALD). The thermal stability of the Pd1 catalysts is significantly enhanced by creating a nanocavity thin film structure. In situ infrared spectroscopy and Pd K-edge X-ray absorption spectroscopy (XAS) revealed that the Pd1 was anchored on the surface through chlorine sites. The thin film stabilized Pd1 catalysts were thermally stable under both oxidation and reduction conditions. The catalytic performance in the methanol decomposition reaction is found to depend on the thickness of protecting layers. While Pd1 catalysts showed promising activity at low temperature in a methanol decomposition reaction, 14 cycle TiO2 protected Pd1 was less active at high temperature. Pd L3 edge XAS indicated that the low reactivity compared with Pd nanoparticles is due to the strong adsorption of carbon monoxide even at 250 °C. These results clearly show that the ALD nanocavities provide a basis for future design of single-atom catalysts that are highly efficient and stable.

  5. New catalysts for coal processing: Metal carbides and nitrides

    Energy Technology Data Exchange (ETDEWEB)

    S. Ted Oyama; David F. Cox

    1999-12-03

    The subject of this research project was to investigate the catalytic properties of a new class of materials, transition metal carbides and nitrides, for treatment of coal liquid and petroleum feedstocks. The main objectives were: (1) preparation of catalysts in unsupported and supported form; (2) characterization of the materials; (3) evaluation of their catalytic properties in HDS and HDN; (4) measurement of the surface properties; and (5) observation of adsorbed species. All of the objectives were substantially carried out and the results will be described in detail below. The catalysts were transition metal carbides and nitrides spanning Groups 4--6 in the Periodic Table. They were chosen for study because initial work had shown they were promising materials for hydrotreating. The basic strategy was first to prepare the materials in unsupported form to identify the most promising catalyst, and then to synthesize a supported form of the material. Already work had been carried out on the synthesis of the Group VI compounds Mo{sub 2}C, Mo{sub 2}N, and WC, and new methods were developed for the Group V compounds VC and NbC. All the catalysts were then evaluated in a hydrotreating test at realistic conditions. It was found that the most active catalyst was Mo{sub 2}C, and further investigations of the material were carried out in supported form. A new technique was employed for the study of the bulk and surface properties of the catalysts, near edge x-ray absorption spectroscopy (NEXAFS), that fingerprinted the electronic structure of the materials. Finally, two new research direction were explored. Bimetallic alloys formed between two transition metals were prepared, resulting in catalysts having even higher activity than Mo{sub 2}C. The performance of the catalysts in hydrodechloration was also investigated.

  6. EXAFS characterization of supported metal catalysts in chemically dynamic environments

    International Nuclear Information System (INIS)

    Robota, H.J.

    1991-01-01

    Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

  7. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    Science.gov (United States)

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

  8. Propane Dehydrogenation on Metal and Metal Oxide Catalysts

    NARCIS (Netherlands)

    Sattler, Jesper

    2014-01-01

    In this PhD thesis, the catalytic performance and deactivation of various propane dehydrogenation catalysts is studied. First of all, a literature study is performed, where the three most commonly used formulations, namely Pt-, CrOx- and GaOx-based catalysts are compared in terms of yield relative

  9. Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts.

    Science.gov (United States)

    Ye, Rong; Zhukhovitskiy, Aleksandr V; Deraedt, Christophe V; Toste, F Dean; Somorjai, Gabor A

    2017-08-15

    Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles-some without homogeneous analogues-for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have

  10. Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

    Science.gov (United States)

    2010-11-01

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

  11. Process for Making a Noble Metal on Tin Oxide Catalyst

    Science.gov (United States)

    Davis, Patricia; Miller, Irvin; Upchurch, Billy

    2010-01-01

    To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

  12. Metal content determination in polymerization catalysts by direct methods

    International Nuclear Information System (INIS)

    Bichinho, K.M.; Pires, Gilvan P.; Stedile, F.C.; Santos, J.H.Z. dos

    2002-01-01

    Metal contents in polymerization catalysts were comparatively determined by Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF) spectroscopy. Catalysts were prepared by grafting metallocene onto bare silica or onto silica chemically modified with methylaluminoxane (MAO). Catalysts were compressed as self-supporting pellets (RBS and XRF), or mounted on adhesive copper tape (XPS). The proximity of the mass of the atomic nuclei did not allow resolution by RBS of the signals corresponding to Zr and Nb, nor Si and Al in catalyst systems such as (nBuCp) 2 ZrCl 2 /Cp 2 NbCl 2 /MAO/SiO 2 . On the other hand, Zr, Nb, Si and Al lines were completely resolved in an XRF spectrum. For supported metallocenes on bare silica, XPS measurement was ca. 40% higher than that obtained by RBS. Silica-supported zirconocene showed good agreement in Zr content determination by XRF and RBS

  13. Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

    Science.gov (United States)

    Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

    2018-03-07

    The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

  14. PHENOL OXIDATION USING NATURAL ZEOLITE SUPPORTED METAL ION CATALYST

    Directory of Open Access Journals (Sweden)

    Sri Wardhani

    2010-06-01

    Full Text Available Phenol which contained in waste water has to be reduced and it could be done by oxygen oxidation.  In order to increase the rate of reaction it was needed a catalyst. In this research the capability of various catalysts, namely zeolite-Zn(II, zeolite-Cu(II and zeolite-Co(IIin oxidation of phenol has been investigated. The aim of this research was to study the type of metal ion catalyst towards the percentage of oxidated phenol. The oxidation process were carried out in an aqueous phenol of 100 ppm with oxygen flow rate of 200 mL/min. in the presence of catalysts with 0.2M of initial impregnation concentration. The capabilities of catalysts were performed by calculating the activation energy and it was done at two different temperatures, i.e. 70 and 90 oC. The percentage of oxidated phenol was determinated by measuring its concentration using UV-VIS spectrophotometer. In addition, the impregnated metal was calculated by measuring the ion concentration remains in the filtrate solution and it was determined using Atomic Absorption Spectrophotometer. The results showed that metal ion types affected the catalytic activity. The order of phenol oxidationactivity decreased as Co(II > Cu(II > Zn(II. The surface characteristics of catalysts were supported by pore volume and pore diameter i.e 0.009 cm3/g and 16.59 Å for Zn(II whereas specific surface area was 10.32 m2/g for Zn(II, 0.004 cm3/g and 24.37 Å for Cu(II whereas specific surface area was 3.57 m2/g for Cu(II, 0.001 cm3/g and 19.63 Å for Co(II whereas specific surface area was 10.26m2/g for Co(II.   Keywords: phenol,natural zeolite, catalyst, oxidation

  15. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    Science.gov (United States)

    Lyons, James E.; Ellis, Jr., Paul E.; Wagner, Richard W.

    1996-01-01

    Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  16. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Science.gov (United States)

    Qian, Xiaoshuang; Qin, Hongmei; Meng, Tao; Lin, Yi; Ma, Zhen

    2014-01-01

    Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2) have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO4)6(OH)2, denoted as Ca-P-O here) also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La) catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP) atomic emission spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), CO2 temperature-programmed desorption (CO2-TPD), X-ray photoelectron spectroscopy (XPS), and H2 temperature-programmed reduction (H2-TPR). This work furnishes a new catalyst system for CO oxidation and other possible reactions. PMID:28788293

  17. Synthesis-Structure-Performance Relationships for Supported Metal Catalysts

    NARCIS (Netherlands)

    Munnik, Peter|info:eu-repo/dai/nl/328228524

    2014-01-01

    Heterogeneous catalysts, which consist of many metal nanoparticles supported on highly porous, mechanically strong and chemically inert supports, are at the center of many existing as well as new and more sustainable processes, such as energy conversion and storage, nanoelectronics and the catalytic

  18. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  19. Catalysts, methods of making catalysts, and methods of use

    KAUST Repository

    Renard, Laetitia

    2014-03-06

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  20. Recovering platinum-group metals from auto catalysts

    International Nuclear Information System (INIS)

    Hoffmann, J.E.

    1988-01-01

    A variety of technical challenges confront the prospective processor of spent automotive catalysts, including a frequently high (1-10%) lead content; the presence of alumina in both soluble, γ, and insoluble, α, forms; the need for recovery of greater than 90% to assure an economical process; the disposition and control of process effluents, refractory residues, and lead metal salts from catalyst processing; and the highly aggressive and corrosive reagents required. Six different processes for recovery of platinum, palladium and rhodium are described and compared on the basis of their utility and how well they meet these technical challenges

  1. Studies on PEM Fuel Cell Noble Metal Catalyst Dissolution

    DEFF Research Database (Denmark)

    Ma, Shuang; Skou, Eivind Morten

    Incredibly vast advance has been achieved in fuel cell technology regarding to catalyst efficiency, improvement of electrolyte conductivity and optimization of cell system. With breathtakingly accelerating progress, Proton Exchange Membrane Fuel Cells (PEMFC) is the most promising and most widely....... Membrane Electrode Assembly (MEA) is commonly considered as the heart of cell system [2]. Degradation of the noble metal catalysts in MEAs especially Three-Phase-Boundary (TPB) is a key factor directly influencing fuel cell durability. In this work, electrochemical degradation of Pt and Pt/Ru alloy were...

  2. Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.

    Science.gov (United States)

    Wang, Xiao Xia; Cullen, David A; Pan, Yung-Tin; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Wang, Jingyun; Engelhard, Mark H; Zhang, Hanguang; He, Yanghua; Shao, Yuyan; Su, Dong; More, Karren L; Spendelow, Jacob S; Wu, Gang

    2018-03-01

    Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  4. An environmentally friendly process for the recovery of valuable metals from spent refinery catalysts.

    Science.gov (United States)

    Rocchetti, Laura; Fonti, Viviana; Vegliò, Francesco; Beolchini, Francesca

    2013-06-01

    The present study dealt with the whole valorization process of exhaust refinery catalysts, including metal extraction by ferric iron leaching and metal recovery by precipitation with sodium hydroxide. In the leaching operation the effects on metal recovery of the concentration and kind of acid, the concentration of catalyst and iron (III) were determined. The best operating conditions were 0.05 mol L(-1) sulfuric acid, 40 g L(-1) iron (III), 10% catalyst concentration; almost complete extraction of nickel and vanadium, and 50%extraction efficiency of aluminium and less than 20% for molybdenum. Sequential precipitation on the leach liquor showed that it was not possible to separate metals through such an approach and a recovery operation by means of a single-stage precipitation at pH 6.5 would simplify the procedures and give a product with an average content of iron (68%), aluminium (13%), vanadium (11%), nickel (6%) and molybdenum (1%) which would be potentially of interest in the iron alloy market. The environmental sustainability of the process was also assessed by means of life cycle assessment and yielded an estimate that the highest impact was in the category of global warming potential with 0.42 kg carbon dioxide per kg recovered metal.

  5. High performance, high durability non-precious metal fuel cell catalysts

    Science.gov (United States)

    Wood, Thomas E.; Atanasoski, Radoslav; Schmoeckel, Alison K.

    2016-03-15

    This invention relates to non-precious metal fuel cell cathode catalysts, fuel cells that contain these catalysts, and methods of making the same. The fuel cell cathode catalysts are highly nitrogenated carbon materials that can contain a transition metal. The highly nitrogenated carbon materials can be supported on a nanoparticle substrate.

  6. COATING OF POLYMERIC SUBSTRATE CATALYSTS ON METALLIC SURFACES

    Directory of Open Access Journals (Sweden)

    H. HOSSEINI

    2010-12-01

    Full Text Available This article presents results of a study on coating of a polymeric substrate ca-talyst on metallic surface. Stability of coating on metallic surfaces is a proper specification. Sol-gel technology was used to synthesize adhesion promoters of polysilane compounds that act as a mediator. The intermediate layer was coated by synthesized sulfonated polystyrene-divinylbenzene as a catalyst for production of MTBE in catalytic distillation process. Swelling of catalyst and its separation from the metal surface was improved by i increasing the quantity of divinylbenzene in the resin’s production process and ii applying adhesion pro¬moters based on the sol-gel process. The rate of ethyl silicate hydrolysis was intensified by increasing the concentration of utilized acid while the conden¬sation polymerization was enhanced in the presence of OH–. Sol was formed at pH 2, while the pH should be 8 for the formation of gel. By setting the ratio of the initial concentrations of water to ethyl silicate to 8, the gel formation time was minimized.

  7. Noble metal catalysts in the production of biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, A.

    2013-11-01

    The energy demand is increasing in the world together with the need to ensure energy security and the desire to decrease greenhouse gas emissions. While several renewable alternatives are available for the production of electricity, e.g. solar energy, wind power, and hydrogen, biomass is the only renewable source that can meet the demand for carbon-based liquid fuels and chemicals. The technology applied in the conversion of biomass depends on the type and complexity of the biomass, and the desired fuel. Hydrogen and hydrogen-rich mixtures (synthesis gas) are promising energy sources as they are more efficient and cleaner than existing fuels, especially when they are used in fuel cells. Hydrotreatment is a catalytic process that can be used in the conversion of biomass or biomass-derived liquids into fuels. In autothermal reforming (ATR), catalysts are used in the production of hydrogen-rich mixtures from conventional fuels or bio-fuels. The different nature of biomass and biomass-derived liquids and mineral oil makes the use of catalysts developed for the petroleum industry challenging. This requires the improvement of available catalysts and the development of new ones. To overcome the limitations of conventional hydrotreatment and ATR catalysts, zirconia-supported mono- and bimetallic rhodium, palladium, and platinum catalysts were developed and tested in the upgrading of model compounds for wood-based pyrolysis oil and in the production of hydrogen, using model compounds for gasoline and diesel. Catalysts were also tested in the ATR of ethanol. For comparative purposes commercial catalysts were tested and the results obtained with model compounds were compared with those obtained with real feedstocks (hydrotreatmet tests with wood-based pyrolysis oil and ATR tests with NExBTL renewable diesel). Noble metal catalysts were active and selective in the hydrotreatment of guaiacol used as the model compound for the lignin fraction of wood-based pyrolysis oil and wood

  8. Catalytic Metallodrugs: Substrate-Selective Metal Catalysts as Therapeutics.

    Science.gov (United States)

    Yu, Zhen; Cowan, James A

    2017-10-12

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

  9. Merging Metallic Catalysts and Sonication: A Periodic Table Overview

    Directory of Open Access Journals (Sweden)

    Claudia E. Domini

    2017-04-01

    Full Text Available This account summarizes and discusses recent examples in which the combination of ultrasonic waves and metal-based reagents, including metal nanoparticles, has proven to be a useful choice in synthetic planning. Not only does sonication often enhance the activity of the metal catalyst/reagent, but it also greatly enhances the synthetic transformation that can be conducted under milder conditions relative to conventional protocols. For the sake of clarity, we have adopted a structure according to the periodic-table elements or families, distinguishing between bulk metal reagents and nanoparticles, as well as the supported variations, thus illustrating the characteristics of the method under consideration in target synthesis. The coverage focuses essentially on the last decade, although the discussion also strikes a comparative balance between the more recent advancements and past literature.

  10. Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells

    Science.gov (United States)

    Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

    2015-03-01

    Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells.

  11. Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

    Science.gov (United States)

    Lennon, David; Winfield, John M

    2017-01-28

    Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

  12. Pyrometallurgical Recovery of Platinum Group Metals from Spent Catalysts

    Science.gov (United States)

    Peng, Zhiwei; Li, Zhizhong; Lin, Xiaolong; Tang, Huimin; Ye, Lei; Ma, Yutian; Rao, Mingjun; Zhang, Yuanbo; Li, Guanghui; Jiang, Tao

    2017-09-01

    As an important secondary resource with abundant platinum group metals (PGMs), spent catalysts demand recycling for both economic and environmental benefits. This article reviews the main pyrometallurgical processes for PGM recovery from spent catalysts. Existing processes, including smelting, vaporization, and sintering processes, are discussed based in part on a review of the physiochemical characteristics of PGMs in spent catalysts. The smelting technology, which produces a PGM-containing alloy, is significantly influenced by the addition of various collectors, such as lead, copper, iron, matte, or printed circuit board (PCB), considering their chemical affinities for PGMs. The vaporization process can recover PGMs in vapor form at low temperatures (250-700°C), but it suffers high corrosion and potential environmental and health risks as a result of involvement of the hazardous gases, mainly Cl2 and CO. The sintering process serves as a reforming means for recycling of the spent catalysts by in situ reduction of their oxidized PGMs components. Among these processes, the smelting process seems more promising although its overall performance can be further improved by seeking a suitable target-oriented collector and flux, together with proper pretreatment and process intensification using an external field.

  13. Noble metal-free hydrogen evolution catalysts for water splitting.

    Science.gov (United States)

    Zou, Xiaoxin; Zhang, Yu

    2015-08-07

    Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

  14. Nanostructured nonprecious metal catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Wu, Gang; Zelenay, Piotr

    2013-08-20

    Platinum-based catalysts represent a state of the art in the electrocatalysis of oxygen reduction reaction (ORR) from the point of view of their activity and durability in harnessing the chemical energy via direct electrochemical conversion. However, because platinum is both expensive and scarce, its widespread implementation in such clean energy applications is limited. Recent breakthroughs in the synthesis of high-performance nonprecious metal catalysts (NPMCs) make replacement of Pt in ORR electrocatalysts with earth-abundant elements, such as Fe, Co, N, and C, a realistic possibility. In this Account, we discuss how we can obtain highly promising M-N-C (M: Fe and/or Co) catalysts by simultaneously heat-treating precursors of nitrogen, carbon, and transition metals at 800-1000 °C. The activity and durability of resulting catalysts depend greatly on the selection of precursors and synthesis chemistry. In addition, they correlate quite well with the catalyst nanostructure. While chemists have presented no conclusive description of the active catalytic site for this class of NPMCs, they have developed a designed approach to making active and durable materials, focusing on the catalyst nanostructure. The approach consists of nitrogen doping, in situ carbon graphitization, and the usage of graphitic structures (possibly graphene and graphene oxides) as carbon precursors. Various forms of nitrogen, particularly pyridinic and quaternary, can act as n-type carbon dopants in the M-N-C catalysts, assisting in the formation of disordered carbon nanostructures and donating electrons to the carbon. The CNx structures are likely a crucial part of the ORR active site(s). Noteworthy, the ORR activity is not necessarily governed by the amount of nitrogen, but by how the nitrogen is incorporated into the nanostructures. Apart from the possibility of a direct participation in the active site, the transition metal often plays an important role in the in situ formation of various

  15. Noble metal nanoparticle@metal oxide core/yolk-shell nanostructures as catalysts: recent progress and perspective.

    Science.gov (United States)

    Li, Guodong; Tang, Zhiyong

    2014-04-21

    Controllable integration of noble metals (e.g., Au, Ag, Pt, and Pd) and metal oxides (e.g., TiO₂, CeO₂, and ZrO₂) into single nanostructures has attracted immense research interest in heterogeneous catalysis, because they not only combine the properties of both noble metals and metal oxides, but also bring unique collective and synergetic functions in comparison with single-component materials. Among many strategies recently developed, one of the most efficient ways is to encapsulate and protect individual noble metal nanoparticles by a metal oxide shell of a certain thickness to generate the core-shell or yolk-shell structure, which exhibits enhanced catalytic performance compared with conventional supported catalysts. In this review article, we summarize the state-of-the art progress in synthesis and catalytic application of noble metal nanoparticle@metal oxide core/yolk-shell nanostructures. We hope that this review will help the readers to obtain better insight into the design and application of well-defined nanocomposites in both the energy and environmental fields.

  16. Non-precious metal catalysts prepared from precursor comprising cyanamide

    Science.gov (United States)

    Chung, Hoon Taek; Zelenay, Piotr

    2015-10-27

    Catalyst comprising graphitic carbon and methods of making thereof; said graphitic carbon comprising a metal species, a nitrogen-containing species and a sulfur containing species. A catalyst for oxygen reduction reaction for an alkaline fuel cell was prepared by heating a mixture of cyanamide, carbon black, and a salt selected from an iron sulfate salt and an iron acetate salt at a temperature of from about 700.degree. C. to about 1100.degree. C. under an inert atmosphere. Afterward, the mixture was treated with sulfuric acid at elevated temperature to remove acid soluble components, and the resultant mixture was heated again under an inert atmosphere at the same temperature as the first heat treatment step.

  17. Oxide-supported metal clusters: models for heterogeneous catalysts

    International Nuclear Information System (INIS)

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  18. High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Wang, J.J.; Yin, G.P.; Zhang, J.; Wang, Z.B.; Gao, Y.Z.

    2007-01-01

    This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method

  19. Effects of preparation method and active metal content on of Ni/kieselguhr catalyst activity

    International Nuclear Information System (INIS)

    Galuh Widiyarti; Wuryaningsih Sri Rahayu

    2010-01-01

    The preparation and the active metal content influence the activity of catalyst. Study has been conducted to see the activity of Ni/kieselguhr based on preparation method and Nickel (Ni) contents in the catalyst in the laboratory scale. The Ni/kieselguhr catalyst were prepared by impregnation and precipitation methods, with Ni active contents of 10, 20, and 30 % by weight. The catalysts characterization was analyzed using X-Ray Diffraction (XRD). Catalysts activities were analyzed based on decreasing of iodine number from hydrogenation of crude palm oil for 2 hours. The activity tests results show that precipitation catalysts are more active than impregnation catalysts. The decreasing in iodine number of fatty acid after 2 hours of hydrogenation process using precipitation catalysts and impregnation catalysts are 51.53 and 21.85 %, respectively. In addition, the catalysts are more active with increasing Ni contents. (author)

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

    Science.gov (United States)

    Gardner, Todd H.

    2015-09-15

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

  1. Preparation and Characterization of Double Metal Cyanide Complex Catalysts

    Directory of Open Access Journals (Sweden)

    Weilin Guo

    2003-01-01

    Full Text Available A series of double metal cyanide (DMC complex catalysts were prepared in two different methods by using ß-cyclodextrin, PEG-1000 and Tween-60 as an additional complex ligands respectively. It was showed that a mixture of crystalline and amorphous DMC was synthesized by using traditional method in which the additional complex ligand was added after the precipitation of DMC. Amorphous and dispersed DMC with higher activity could be obtained when the additional complex ligand was added in the reactant solution before reaction. The effect of additional complex ligand and preparation method on the crystalline state and catalytic property of DMC were also investigated.

  2. Metallic bionanocatalysts: potential applications as green catalysts and energy materials.

    Science.gov (United States)

    Macaskie, Lynne E; Mikheenko, Iryna P; Omajai, Jacob B; Stephen, Alan J; Wood, Joseph

    2017-09-01

    Microbially generated or supported nanocatalysts have potential applications in green chemistry and environmental application. However, precious (and base) metals biorefined from wastes may be useful for making cheap, low-grade catalysts for clean energy production. The concept of bionanomaterials for energy applications is reviewed with respect to potential fuel cell applications, bio-catalytic upgrading of oils and manufacturing 'drop-in fuel' precursors. Cheap, effective biomaterials would facilitate progress towards dual development goals of sustainable consumption and production patterns and help to ensure access to affordable, reliable, sustainable and modern energy. © 2017 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

  3. Ambiphilic Molecules: From Organometallic Curiosity to Metal-Free Catalysts.

    Science.gov (United States)

    Fontaine, Frédéric-Georges; Rochette, Étienne

    2018-02-20

    Ambiphilic molecules were first used as functional ligands for transition elements, which could enable intriguing organometallic transformations. In the past decade, these intramolecular Lewis pairs, first considered organometallic curiosities, have become staples in organometallic chemistry and catalysis, acting as Z ligands, activating inert molecules using the concept of frustrated Lewis pair (FLP) chemistry, and acting as metal-free catalysts. In this Account, we detail our contribution to this blossoming field of research, focusing on the use of ambiphilic molecules as metal-free catalysts for CO 2 reduction and C-H borylation reactions. A major emphasis is put on the mechanistic investigations we carried out using reactivity studies and theoretical tools, which helped us steer our research from stoichiometric transformations to highly active catalytic processes. We first report the interaction of aluminum-phosphine ambiphilic molecules with carbon dioxide. Although these Lewis pairs can bind CO 2 , a study of the deactivation process in the presence of CO 2 and hydroboranes led us to discover that simple phosphinoborane molecules could act as active precatalysts for the hydroboration of carbon dioxide into methanol precursors. In these systems, the Lewis basic sites interact with the reducing agents rather than with the electrophilic carbon of CO 2 , increasing the nucleophilicity of hydroboranes. Simultaneously, the weak Lewis acids stabilize the oxygen of the gas molecule in the transition state, leading to high reaction rates. Replacing the phosphine by an amine leads to a system enabling CO 2 hydrogenation, albeit only in stoichiometric transformations. Investigation of the protodeborylation deactivation of aminoboranes led us to develop metal-free catalysts for the C-H borylation of heteroarenes. By protecting the Lewis acid sites of these catalysts using fluoride, we were able to synthesize practical, air-stable precatalysts allowing the convenient

  4. Metal-support bonds in supported metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gates, B.C.

    1990-01-01

    This research project, now in its third year, is an investigation of the synthesis, structure, and bonding of a family of metal complexes, clusters, and particles on the surfaces of high-area metal oxide supports. The focus is the structure of the metal-support interface. Surface species have been prepared by synthetic organometallic chemistry on the support surfaces. The organometallic precursors are complexes of W, Re, Os, Ir, and Pt, including W(CO){sub 6}, HRe(CO){sub 5}, Re{sub 2}(CO){sub 10}, H{sub 3}Re{sub 3}(CO){sub 12}, H{sub 2}Os(CO){sub 4}, Ir({eta}{sup 3}-C{sub 3}H{sub 5}){sub 3}, and Pt({eta}{sup 3}-C{sub 3}H{sub 5}){sub 2}. The supports are primarily MgO and {gamma}-Al{sub 2}O{sub 3}. The surface species have been characterized by infrared and EXAFS spectroscopies, among other techniques. 7 refs., 5 figs., 4 tabs.

  5. Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor

    Science.gov (United States)

    Dhooge, Patrick M.

    1987-10-13

    A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.

  6. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds

    Science.gov (United States)

    Allendorf, Mark D.; Stavila, Vitalie

    2017-08-01

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

  7. Platinum group metal recovery and catalyst manufacturing process

    International Nuclear Information System (INIS)

    Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.

    1998-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m 2 /g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs

  8. Platinum group metal recovery and catalyst manufacturing process

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.

    1998-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m{sup 2}/g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs.

  9. Controlled metal nitrate decomposition for the preparation of supported metal Catalysts

    NARCIS (Netherlands)

    Wolters, M.

    2010-01-01

    High surface area supported metal (oxide) catalysts are essential for the production of fuels, chemicals, pharmaceuticals and the abatement of environmental pollution. Impregnation of high surface area supports, often silica or alumina, followed by drying, calcination and reduction is one of the

  10. Graphene layer encapsulated metal nanoparticles as a new type of non-precious metal catalysts for oxygen reduction

    DEFF Research Database (Denmark)

    Hu, Yang; Zhong, Lijie; Jensen, Jens Oluf

    2016-01-01

    Cheap and efficient non-precious metal catalysts for oxygen reduction have been a focus of research in the field of low-temperature fuel cells. This review is devoted to a brief summary of the recent work on a new type of catalysts, i.e., the graphene layer encapsulated metal nanoparticles...

  11. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

    Stanger, Keith James [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-α-acetamidocinnamate (MAC), has the illustrated structure as established by 31P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]4, [Rh(COD)2]+BF4-, [Rh(COD)Cl]2, and RhCl3• 3H2O, adsorbed on SiO2 are optimally activated for toluene hydrogenation by pretreatment with H2 at 200 C. The same complexes on Pd-SiO2 are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH2)3s-]Re(O)(Me)(PPh3) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  12. Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

    KAUST Repository

    AlMana, Noor

    2016-06-19

    The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance

  13. Highly aligned vertical GaN nanowires using submonolayer metal catalysts

    Science.gov (United States)

    Wang, George T [Albuquerque, NM; Li, Qiming [Albuquerque, NM; Creighton, J Randall [Albuquerque, NM

    2010-06-29

    A method for forming vertically oriented, crystallographically aligned nanowires (nanocolumns) using monolayer or submonolayer quantities of metal atoms to form uniformly sized metal islands that serve as catalysts for MOCVD growth of Group III nitride nanowires.

  14. In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts.

    Science.gov (United States)

    van Oversteeg, Christina H M; Doan, Hoang Q; de Groot, Frank M F; Cuk, Tanja

    2017-01-03

    X-ray absorption studies of the geometric and electronic structure of primarily heterogeneous Co, Ni, and Mn based water oxidation catalysts are reviewed. The X-ray absorption near edge and extended X-ray absorption fine structure studies of the metal K-edge, characterize the metal oxidation state, metal-oxygen bond distance, metal-metal distance, and degree of disorder of the catalysts. These properties guide the coordination environment of the transition metal oxide radical that localizes surface holes and is required to oxidize water. The catalysts are investigated both as-prepared, in their native state, and under reaction conditions, while transition metal oxide radicals are generated. The findings of many experiments are summarized in tables. The advantages of future X-ray experiments on water oxidation catalysts, which include the limited data available of the oxygen K-edge, metal L-edge, and resonant inelastic X-ray scattering, are discussed.

  15. Metal (Hydr)oxides@Polymer Core-Shell Strategy to Metal Single-Atom Materials.

    Science.gov (United States)

    Zhang, Maolin; Wang, Yang-Gang; Chen, Wenxing; Dong, Juncai; Zheng, Lirong; Luo, Jun; Wan, Jiawei; Tian, Shubo; Cheong, Weng-Chon; Wang, Dingsheng; Li, Yadong

    2017-08-16

    Preparing metal single-atom materials is currently attracting tremendous attention and remains a significant challenge. Herein, we report a novel core-shell strategy to synthesize single-atom materials. In this strategy, metal hydroxides or oxides are coated with polymers, followed by high-temperature pyrolysis and acid leaching, metal single atoms are anchored on the inner wall of hollow nitrogen-doped carbon (CN) materials. By changing metal precursors or polymers, we demonstrate the successful synthesis of different metal single atoms dispersed on CN materials (SA-M/CN, M = Fe, Co, Ni, Mn, FeCo, FeNi, etc.). Interestingly, the obtained SA-Fe/CN exhibits much higher catalytic activity for hydroxylation of benzene to phenol than Fe nanoparticles/CN (45% vs 5% benzene conversion). First-principle calculations further reveal that the high reactivity originates from the easier formation of activated oxygen species at the single Fe site. Our methodology provides a convenient route to prepare a variety of metal single-atom materials representing a new class of catalysts.

  16. Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn

    Science.gov (United States)

    Wickham, David [Boulder, CO; Cook, Ronald [Lakewood, CO

    2008-10-28

    The present invention provides metal-exchanged hexaaluminate catalysts that exhibit good catalytic activity and/or stability at high temperatures for extended periods with retention of activity as combustion catalysts, and more generally as oxidation catalysts, that make them eminently suitable for use in methane combustion, particularly for use in natural gas fired gas turbines. The hexaaluminate catalysts of this invention are of particular interest for methane combustion processes for minimization of the generation of undesired levels (less than about 10 ppm) of NOx species. Metal exchanged hexaaluminate oxidation catalysts are also useful for oxidation of volatile organic compounds (VOC), particularly hydrocarbons. Metal exchanged hexaaluminate oxidation catalysts are further useful for partial oxidation, particularly at high temperatures, of reduced species, particularly hydrocarbons (alkanes and alkenes).

  17. Understanding the role of aluminum-based activators in single site iron catalysts for ethylene oligomerization.

    OpenAIRE

    Boudene , Zoubeyr; Boudier , Adrien; Breuil , Pierre-Alain; Olivier-Bourbigou , Hélène; Raybaud , Pascal; Toulhoat , Hervé; De Bruin , Theodorus

    2014-01-01

    International audience; In a combined experimental and theoretical study, the activation process of a single site ethylene oligomerization catalyst with aluminum-based activators has been studied. The results put forward a plausible deactivation reaction path of the catalyst for trimethylaluminum, while for methylaluminoxane and a novel phenoxyaluminum-based activator, the experimental catalyst's activity correlates with the energy barrier for the ethylene insertion.

  18. Metal catalysts for steam reforming of tar derived from the gasification of lignocellulosic biomass.

    Science.gov (United States)

    Li, Dalin; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

    2015-02-01

    Biomass gasification is one of the most important technologies for the conversion of biomass to electricity, fuels, and chemicals. The main obstacle preventing the commercial application of this technology is the presence of tar in the product gas. Catalytic reforming of tar appears a promising approach to remove tar and supported metal catalysts are among the most effective catalysts. Nevertheless, improvement of catalytic performances including activity, stability, resistance to coke deposition and aggregation of metal particles, as well as catalyst regenerability is greatly needed. This review focuses on the design and catalysis of supported metal catalysts for the removal of tar in the gasification of biomass. The recent development of metal catalysts including Rh, Ni, Co, and their alloys for steam reforming of biomass tar and tar model compounds is introduced. The role of metal species, support materials, promoters, and their interfaces is described. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Activation and discovery of earth-abundant metal catalysts using sodium tert-butoxide.

    Science.gov (United States)

    Docherty, Jamie H; Peng, Jingying; Dominey, Andrew P; Thomas, Stephen P

    2017-06-01

    First-row, earth-abundant metals offer an inexpensive and sustainable alternative to precious-metal catalysts. As such, iron and cobalt catalysts have garnered interest as replacements for alkene and alkyne hydrofunctionalization reactions. However, these have required the use of air- and moisture-sensitive catalysts and reagents, limiting both adoption by the non-expert as well as applicability, particularly in industrial settings. Here, we report a simple method for the use of earth-abundant metal catalysts by general activation with sodium tert-butoxide. Using only robust air- and moisture-stable reagents and pre-catalysts, both known and, significantly, novel catalytic activities have been successfully achieved, covering hydrosilylation, hydroboration, hydrovinylation, hydrogenation and [2π+2π] alkene cycloaddition. This activation method allows for the easy use of earth-abundant metals, including iron, cobalt, nickel and manganese, and represents a generic platform for the discovery and application of non-precious metal catalysis.

  20. Highly Stereoselective Heterogeneous Diene Polymerization by Co-MFU-4l: A Single-Site Catalyst Prepared by Cation Exchange.

    Science.gov (United States)

    Dubey, Romain J-C; Comito, Robert J; Wu, Zhenwei; Zhang, Guanghui; Rieth, Adam J; Hendon, Christopher H; Miller, Jeffrey T; Dincă, Mircea

    2017-09-13

    Molecular catalysts offer tremendous advantages for stereoselective polymerization because their activity and selectivity can be optimized and understood mechanistically using the familiar tools of organometallic chemistry. Yet, this exquisite control over selectivity comes at an operational price that is generally not justifiable for the large-scale manufacture of polyfolefins. In this report, we identify Co-MFU-4l, prepared by cation exchange in a metal-organic framework, as a solid catalyst for the polymerization of 1,3-butadiene with high stereoselectivity (>99% 1,4-cis). To our knowledge, this is the highest stereoselectivity achieved with a heterogeneous catalyst for this transformation. The polymer's low polydispersity (PDI ≈ 2) and the catalyst's ready recovery and low leaching indicate that our material is a structurally resilient single-site heterogeneous catalyst. Further characterization of Co-MFU-4l by X-ray absorption spectroscopy provided evidence for discrete, tris-pyrazolylborate-like coordination of Co(II). With this information, we identify a soluble cobalt complex that mimics the structure and reactivity of Co-MFU-4l, thus providing a well-defined platform for studying the catalytic mechanism in the solution phase. This work underscores the capacity for small molecule-like tunability and mechanistic tractability available to transition metal catalysis in metal-organic frameworks.

  1. Development of new transition metal oxide catalysts for the destruction of PCDD/Fs.

    Science.gov (United States)

    Yu, Ming-Feng; Li, Wen-Wei; Li, Xiao-Dong; Lin, Xiao-Qing; Chen, Tong; Yan, Jian-Hua

    2016-08-01

    Various transition metal oxide and vanadium-containing multi-metallic oxide catalysts were developed for the destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans). A stable PCDD/Fs generating system was installed to support the catalytic destruction tests in this study. Nano-titania supported vanadium catalyst (VOx/TiO2) showed the highest activity, followed by CeOx, MnOx, WOx and finally MoOx. Multi-metallic oxide catalysts, prepared by doping WOx, MoOx, MnOx and CeOx into VOx/TiO2 catalysts, showed different activities on the decomposition of PCDD/Fs. The highest destruction efficiency of 92.5% was observed from the destruction test over VOxCeOx/TiO2 catalyst. However, the addition of WOx and MoOx even played a negative role in multi-metallic VOx/TiO2 catalysts. Characterizations of transition metal oxides and multi-metallic VOx/TiO2 catalysts were also investigated with XRD and TPR. After the catalysts were used, the conversion from high valent metals to low valence states was observed by XPS. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Water oxidation using earth-abundant transition metal catalysts: opportunities and challenges.

    Science.gov (United States)

    Kärkäs, Markus D; Åkermark, Björn

    2016-10-07

    Catalysts for the oxidation of H2O are an integral component of solar energy to fuel conversion technologies. Although catalysts based on scarce and precious metals have been recognized as efficient catalysts for H2O oxidation, catalysts composed of inexpensive and earth-abundant element(s) are essential for realizing economically viable energy conversion technologies. This Perspective summarizes recent advances in the field of designing homogeneous water oxidation catalysts (WOCs) based on Mn, Fe, Co and Cu. It reviews the state of the art catalysts, provides insight into their catalytic mechanisms and discusses future challenges in designing bioinspired catalysts based on earth-abundant metals for the oxidation of H2O.

  3. Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

    Directory of Open Access Journals (Sweden)

    Hermenegildo Garcia

    2014-01-01

    Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

  4. CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

    Science.gov (United States)

    Herz, Richard K.

    1990-01-01

    Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

  5. Water Splitting by Thin Film Metal-Oxo Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nocera, Daniel [Harvard Univ., Cambridge, MA (United States)

    2013-03-15

    The dropping price of silicon photovoltaics in the United States is causing load defection to solar supply at an accelerated pace. This conversion to solar and, more generally, other renewable energy sources has accordingly turned the energy research focus from generation to one of storage. Truly disruptive improvements in energy storage technologies are limited by energy density. This limitation, however, does not apply to fuels, which possess the energy density needed for large-scale energy storage. The first step of the basic science needed to drive such historic restructuring of the U.S. energy infrastructure begins with the solar-driven generation of hydrogen and oxygen from water. The solar-produced hydrogen may then be combined with carbon dioxide to deliver any number of fuels. Obviously, light does not directly act on water to engender its splitting into its elemental components. Hence, catalysts are needed to drive the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Of these two reactions, the four-electron, four-proton oxidation of OER is the more kinetically challenging reaction, and therefore the development of energy efficient solar fuels processes demands that OER be accomplished at a minimal overpotential. The research completed in this program developed catalysts that drive OER and at the same time meet the important criteria of (1) using non-critical materials that (2) are easy to assemble and (3) accomplish OER under simple conditions. Research was designed to uncover the chemical principles that underlie the self-assembly of metal oxide oxygen evolving catalysts (M-OEC) from the metals of M = Mn, Co, and Ni. For example, a dogma of heterogeneous catalysis of any sort is that “edges” matter in promoting catalytic transformations. We provided a rationale for such dogma by showing that the OER in Co-OEC occurred at a dimensionally reduced dicobalt edge site. Edge site reactivity was clearly revealed analyzing 18O labeled

  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. Effect of catalyst properties and operating conditions on hydroprocessing high metals feeds

    Energy Technology Data Exchange (ETDEWEB)

    Pazos, J.M.; Gonzalez, J.C.; Saluzar-Gullen, A.J.

    1983-10-01

    Catalytic hydroprocessing of high metals heavy oils, containing over 480 ppm Ni + V, was carried out in trickle bed pilot units. The analyses of the used catalysts (coke, metals content, and vanadium distribution) were correlated with the deactivation runs. The deactivation by coke is very much dependent on the catalyst physical properties (mean pore diameter), rather than on the chemical properties, and on the nature of the feed. As metals removal is a diffusion-controlled reaction, catalysts and operating conditions that increase the Thiele modulus, e.g., high activity and small pore catalysts, high hydrogen pressures and temperatures, show a stronger deactivation by feed metals. In this case, most of the vanadium was deposited in the outer edge of the catalyst particle. Unconventional vanadium profiles along the reactor length were obtained under certain conditions. Based on these data, a kinetic model was proposed which considers that demetallization is a complex reaction that occurs through a series of consecutive and parallel reactions.

  8. A new generation of zirconia supported metal oxide catalysts for converting low grade renewable feedstocks to biodiesel.

    Science.gov (United States)

    Kim, Manhoe; DiMaggio, Craig; Salley, Steven O; Simon Ng, K Y

    2012-08-01

    A new class of zirconia supported mixed metal oxides (ZnO-TiO(2)-Nd(2)O(3)/ZrO(2) and ZnO-SiO(2)-Yb(2)O(3)/ZrO(2)) has demonstrated the ability to convert low quality, high free fatty acid (FFA) bio-oils into biodiesel. Pelletized catalysts of ZrO(2) supported metal oxides were prepared via a sol-gel process and tested in continuous flow packed bed reactors for up to 6 months. In a single pass, while operating at mild to moderate reaction conditions, 195 °C and 300 psi, these catalysts can perform simultaneous esterification and transesterification reactions on feedstock of 33% FFA and 67% soybean oil to achieve FAME yields higher than 90%. Catalytic activity of the ZrO(2) supported metal oxide catalysts was highly dependent on the metal oxide composition. These heterogeneous catalysts will enable biodiesel manufacturers to avoid problems inherent in homogeneous processes, such as separation and washing, corrosive conditions, and excessive methanol usage. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Kim, In Soo [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Nanophotonics Center, Korea Institute of Science and Technology, Seoul 02792 South Korea; Li, Zhanyong [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Zheng, Jian [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Platero-Prats, Ana E. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Mavrandonakis, Andreas [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Pellizzeri, Steven [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Lab, 9700 S. Cass Ave. Argonne IL 60439 USA; Vjunov, Aleksei [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Gallington, Leighanne C. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Webber, Thomas E. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Vermeulen, Nicolaas A. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Penn, R. Lee [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Getman, Rachel B. [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Cramer, Christopher J. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Chapman, Karena W. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Fulton, John L. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, Technische Universität München, Lichtenbergstrasse 4 85748 Garching Germany; Farha, Omar K. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Hupp, Joseph T. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Martinson, Alex B. F. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA

    2018-01-02

    Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

  10. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

    KAUST Repository

    Pelletier, Jeremie

    2016-03-09

    ConspectusHeterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the

  11. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts.

    Science.gov (United States)

    Pelletier, Jérémie D A; Basset, Jean-Marie

    2016-04-19

    Heterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity). Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the support taken

  12. Life Cycle Assessment of Biochar versus Metal Catalysts Used in Syngas Cleaning

    Directory of Open Access Journals (Sweden)

    Robert S. Frazier

    2015-01-01

    Full Text Available Biomass gasification has the potential to produce renewable fuels, chemicals and power at large utility scale facilities. In these plants catalysts would likely be used to reform and clean the generated biomass syngas. Traditional catalysts are made from transition metals, while catalysts made from biochar are being studied. A life cycle assessment (LCA study was performed to analyze the sustainability, via impact assessments, of producing a metal catalyst versus a dedicated biochar catalyst. The LCA results indicate that biochar has a 93% reduction in greenhouse gas (GHG emissions and requires 95.7% less energy than the metal catalyst to produce. The study also estimated that biochar production would also have fewer impacts on human health (e.g., carcinogens and respiratory impacts than the production of a metal catalyst. The possible disadvantage of biochar production in the ecosystem quality is due mostly to its impacts on agricultural land occupation. Sensitivity analysis was carried out to assess environmental impacts of variability in the two production systems. In the metal catalyst manufacture, the extraction and production of nickel (Ni had significant negative effects on the environmental impacts. For biochar production, low moisture content (MC, 9% and high yield type (8 tons/acre switchgrass appeared more sustainable.

  13. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts

    Science.gov (United States)

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

    2013-01-01

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

  14. Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation.

    Science.gov (United States)

    Jodłowski, Przemysław J; Jędrzejczyk, Roman J; Chlebda, Damian K; Dziedzicka, Anna; Kuterasiński, Łukasz; Gancarczyk, Anna; Sitarz, Maciej

    2017-07-07

    The aim of this study was to obtain nanocrystalline mixed metal-oxide-ZrO₂ catalysts via a sonochemically-induced preparation method. The effect of a stabiliser's addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature.

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

    Science.gov (United States)

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

    2013-01-01

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

  16. Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics.

    Science.gov (United States)

    Corma, Avelino; Serna, Pedro; Concepción, Patricia; Calvino, José Juan

    2008-07-09

    It is generally accepted that good hydrogenation noble and nonnoble metal catalysts such as Pt, Ru, or Ni are not chemoselective for hydrogenation of nitro groups in substituted aromatic molecules. We have found that it is possible to transform nonchemoselective into highly chemoselective metal catalysts by controlling the coordination of metal surface atoms while introducing a cooperative effect between the metal and a properly selected support. Thus, highly chemoselective and general hydrogenation Pt, Ru, and Ni catalysts can be prepared by generating nanosized crystals of the metals on the surface of a TiO 2 support and decorating the exposed (111) and (100) crystal faces by means of a simple catalyst activation procedure. By doing this, it has been possible to change the relative rate for hydrogenating competitive groups present in the molecule by almost 2 orders of magnitude, increasing the chemoselectivity from less than 1% to more than 95%.

  17. Chemical imaging of single catalyst particles with scanning μ-XANES-CT and μ-XRF-CT.

    Science.gov (United States)

    Price, S W T; Ignatyev, K; Geraki, K; Basham, M; Filik, J; Vo, N T; Witte, P T; Beale, A M; Mosselmans, J F W

    2015-01-07

    The physicochemical state of a catalyst is a key factor in determining both activity and selectivity; however these materials are often not structurally or compositionally homogeneous. Here we report on the 3-dimensional imaging of an industrial catalyst, Mo-promoted colloidal Pt supported on carbon. The distribution of both the active Pt species and Mo promoter have been mapped over a single particle of catalyst using microfocus X-ray fluorescence computed tomography. X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure revealed a mixed local coordination environment, including the presence of both metallic Pt clusters and Pt chloride species, but also no direct interaction between the catalyst and Mo promoter. We also report on the benefits of scanning μ-XANES computed tomography for chemical imaging, allowing for 2- and 3-dimensional mapping of the local electronic and geometric environment, in this instance for both the Pt catalyst and Mo promoter throughout the catalyst particle.

  18. Confined-interface-directed synthesis of Palladium single-atom catalysts on graphene/amorphous carbon

    DEFF Research Database (Denmark)

    Xi, Jiangbo; Sun, Hongyu; Zhang, Zheye

    2018-01-01

    The maximized atomic efficiency of supported catalysts is highly desired in heterogeneous catalysis. Therefore, the design and development of active, stable, and atomic metal-based catalysts remains a formidable challenge. To tackle these problems, it is necessary to investigate the interaction b...

  19. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    KAUST Repository

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

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

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  1. Analysis of noble metal on automotive exhaust catalysts by radioisotope-induce x-ray fluorescence

    International Nuclear Information System (INIS)

    Elgart, M.F.

    1976-01-01

    A technique was developed for the in-situ analysis of noble metals deposited on monolithic automotive exhaust catalysts. This technique is based on radioisotope-induced x-ray fluorescence, and provides a detailed picture of the distribution of palladium and platinum on catalyst samples. The experimental results for the cross section of a monolithic exhaust catalyst, analyzed in increments of 0.2 cm 3 , are compared with analyses for palladium and platinum obtained by instrumental neutron activation analysis

  2. Stability of noble metal catalysts for the hydrogen-oxygen reaction.

    Science.gov (United States)

    Armstrong, W. E.; Jennings, T. J.; Voge, H. H.

    1972-01-01

    Stability of various supported noble metal catalysts for initiation of the hydrogen-oxygen reaction was tested by means of steam-hydrogen treatment at 1000-1200 C followed by a simple activity test. Many catalysts were stable to 1100 C, but all lost some activity at 1200 C. The most active with very good stability was an iridium/alumina catalyst of high iridium content.

  3. Aqueous reductive amination using a dendritic metal catalyst in a dialysis bag

    OpenAIRE

    Willemsen, J.S.; Hest, J.C.M. van; Rutjes, F.P.J.T.

    2013-01-01

    Summary Water-soluble dendritic iridium catalysts were synthesized by attaching a reactive metal complex to DAB-Am dendrimers via an adapted asymmetric bipyridine ligand. These dendritic catalysts were applied in the aqueous reductive amination of valine while contained in a dialysis bag. Comparable conversions were observed as for the noncompartmentalized counterparts, albeit with somewhat longer reaction times. These results clearly show that the encapsulated catalyst system is suitable to ...

  4. Recent Progress on Transition Metal Catalyst Separation and Recycling in ATRP.

    Science.gov (United States)

    Ding, Mingqiang; Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2015-10-01

    Atom transfer radical polymerization (ATRP) is a versatile and robust tool to synthesize a wide spectrum of monomers with various designable structures. However, it usually needs large amounts of transition metal as the catalyst to mediate the equilibrium between the dormant and propagating species. Unfortunately, the catalyst residue may contaminate or color the resultant polymers, which limits its application, especially in biomedical and electronic materials. How to efficiently and economically remove or reduce the catalyst residue from its products is a challenging and encouraging task. Herein, recent advances in catalyst separation and recycling are highlighted with a focus on (1) highly active ppm level transition metal or metal free catalyzed ATRP; (2) post-purification method; (3) various soluble, insoluble, immobilized/soluble, and reversible supported catalyst systems; and (4) liquid-liquid biphasic catalyzed systems, especially thermo-regulated catalysis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Vladimiro Dal Santo

    2010-05-01

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

  6. Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation

    Science.gov (United States)

    Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo

    2013-11-01

    Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  8. Intracluster atomic and electronic structural heterogeneities in supported nanoscale metal catalysts

    NARCIS (Netherlands)

    Elsen, A.; Jung, U.; Vila, F.; Li, Y.; Safonova, O.V.; Thomas, R.; Tromp, M.; Rehr, J.J.; Nuzzo, R.G.; Frenkel, A.I.

    2015-01-01

    This work reveals and quantifies the inherent intracluster heterogeneity in the atomic structure and charge distribution present in supported metal catalysts. The results demonstrate that these distributions are pronounced and strongly coupled to both structural and dynamic perturbations. They also

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-06-30

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

  10. Studies on mixed metal oxides solid solutions as heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    H. R. Arandiyan

    2009-03-01

    Full Text Available In this work, a series of perovskite-type mixed oxide LaMo xV1-xO3+δ powder catalysts (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0, with 0.5 < δ < 1.5, prepared by the sol-gel process and calcined at 750ºC, provide an attractive and effective alternative means of synthesizing materials with better control of morphology. Structures of resins obtained during the gel formation process by FT-IR spectroscopy and XRD analysis showed that all the LaMo xV1-xO3+δ samples are single phase perovskite-type solid solutions. The surface area (BET between 2.5 - 5.0 m²/g (x = 0.1 and 1.0 respectively increases with increasing Mo ratio in the samples. They show high purity, good chemical homogeneity, and lower calcinations temperatures as compared with the solid-state chemistry route. SEM coupled to EDS and thermogravimetric analysis/differential thermal analyses (TGA/DTA have been carried out in order to evaluate the homogeneity of the catalyst. Finally, the experimental studies show that the calcination temperature and Mo content exhibited a significant influence on catalytic activity. Among the LaMo xV1-xO3+δ samples, LaMo0.7V0.3O4.2 showed the best catalytic activity for the topic reaction and the best activity and stability for ethane reforming at 850ºC under 8 bar.

  11. Synthesis and stabilization of supported metal catalysts by atomic layer deposition.

    Science.gov (United States)

    Lu, Junling; Elam, Jeffrey W; Stair, Peter C

    2013-08-20

    Supported metal nanoparticles are among the most important catalysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer-Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition-precipitation to control and tune these factors, to establish structure-performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leads to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe

  12. Carbon-Based Metal-Free Catalysts for Electrocatalysis beyond the ORR.

    Science.gov (United States)

    Hu, Chuangang; Dai, Liming

    2016-09-19

    Besides their use in fuel cells for energy conversion through the oxygen reduction reaction (ORR), carbon-based metal-free catalysts have also been demonstrated to be promising alternatives to noble-metal/metal oxide catalysts for the oxygen evolution reaction (OER) in metal-air batteries for energy storage and for the splitting of water to produce hydrogen fuels through the hydrogen evolution reaction (HER). This Review focuses on recent progress in the development of carbon-based metal-free catalysts for the OER and HER, along with challenges and perspectives in the emerging field of metal-free electrocatalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Molecular metal-Oxo catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  14. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    International Nuclear Information System (INIS)

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  15. Catalytic water oxidation by single-site ruthenium catalysts.

    Science.gov (United States)

    Concepcion, Javier J; Jurss, Jonah W; Norris, Michael R; Chen, Zuofeng; Templeton, Joseph L; Meyer, Thomas J

    2010-02-15

    A series of monomeric ruthenium polypyridyl complexes have been synthesized and characterized, and their performance as water oxidation catalysts has been evaluated. The diversity of ligand environments and how they influence rates and reaction thermodynamics create a platform for catalyst design with controllable reactivity based on ligand variations.

  16. Oxygen-assisted conversion of propane over metal and metal oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Laate, Leiv

    2002-07-01

    An experimental set-up has been build and applied in activity/selectivity studies of the oxygen-assisted conversion of propane over metals and metal oxide catalysts. The apparatus has been used in order to achieve an improved understanding of the reactions between alkanes/alkenes and oxygen. Processes that have been studied arc the oxidative dehydrogenation of propane over a VMgO catalyst and the selective combustion of hydrogen in the presence of hydrocarbons over Pt-based catalysts and metal oxide catalysts. From the experiments, the following conclusions are drawn: A study of the oxidative dehydrogenation of propane over a vanadium-magnesium-oxide catalyst confirmed that the main problem with this system is the lack of selectivity due to complete combustion. Selectivity to propene up to about 60% was obtained at 10% conversion at 500{sup o}C, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by- products were CO and CO{sub 2}. The selectivity to propene is a strong function of the conversion of propane. The reaction rate of propane was found to be 1.0 {+-} 0.1 order in propane and 0.07 {+-} 0.02 order in oxygen. The kinetic results are in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbons as the slow step. The rate of propene oxidation to CO{sub 2} was studied and found to be significantly higher than that of propane. Another possible process involves the simultaneous equilibrium dehydrogenation of alkanes to alkenes and combustion of the hydrogen formed to shift the equilibrium dehydrogenation reaction further to the product alkenes. A study of the selective combustion of hydrogen in the presence of propane/propene was found to be possible under certain reaction conditions over some metal oxide catalysts. In{sub 2}O{sub 3}/SiO{sub 2}, unsupported Bi{sub 2}O{sub 3} and ZSM-5 show the ability to combust hydrogen in a gas mixture with propane and oxygen with good selectivity. Bi{sub 2

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

    Science.gov (United States)

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

    2018-04-01

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

  18. Tackling CO Poisoning with Single Atom Alloy Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jilei; Lucci, Felicia R.; Yang, Ming; Lee, Sungsik; Marcinkowski, Matthew D.; Therrien, Andrew J.; Williams, Christopher T.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

    2016-05-01

    Platinum (Pt) catalysts are extensively used in the chemical industry and as electrocatalysts in fuel cells. Pt is notorious for its sensitivity to poisoning by strong CO adsorption. Here we demonstrate that the single atom alloy (SAA) strat-egy applied to Pt reduces the binding strength of CO while maintaining catalytic performance. By using surface sensi-tive studies, we accurately determined the binding strength of CO to different Pt ensembles, and this in turn guided the preparation of PtCu alloy nanoparticles. The atomic ratio Pt:Cu = 1:120 yielded a SAA which exhibited excellent CO tolerance in H2 activation, the key elementary step for hy-drogenation and hydrogen electro-oxidation. As a probe reaction, the selective hydrogenation of acetylene to ethene was performed under flow conditions on the SAA nanopar-ticles supported on alumina without activity loss in the pres-ence of CO. The ability to maintain reactivity in the presence of CO is vital to other industrial reactions including fuel reforming and methanol/ethanol fuel cells.

  19. Hydrogen production from bio-fuels using precious metal catalysts

    Directory of Open Access Journals (Sweden)

    Pasel Joachim

    2017-01-01

    Full Text Available Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3 and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

  20. Hydrogen production from bio-fuels using precious metal catalysts

    Science.gov (United States)

    Pasel, Joachim; Wohlrab, Sebastian; Rotov, Mikhail; Löhken, Katrin; Peters, Ralf; Stolten, Detlef

    2017-11-01

    Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3) and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

  1. Application of ASA supported noble metal catalysts in the deep hydrodesulphurisation of diesel fuel

    Energy Technology Data Exchange (ETDEWEB)

    Reinhoudt, H.R.; Troost, R.; Van Schalkwijk, S.; Van Langeveld, A.D.; Sie, S.T.; Moulijn, J.A. [Delft University of Technology, Delft (Netherlands); Schulz, H. [Universitaet Karlsruhe, Engler Bunte Institut, Karlsruhe (Germany); Chadwick, D. [Imperial College of Science, Technology and Medicine, London (United Kingdom); Cambra, J. [Escuela de Ingenierios, Bilbao (Spain); De Beer, V.H.J.; Van Veen, J.A.R. [Eindhoven University of Technology, Eindhoven (Netherlands); Fierro, J.L.G. [C.S.I.C., Madrid (Spain)

    1997-07-01

    The potential of Amorphous Silica Alumina (ASA) supported Pt and Pd catalysts for deep hydrodesulphurisation (HDS) of diesel fuels was investigated. It appeared that the ASA supported catalysts exhibit an excellent activity for the conversion of 4-Ethyl, 6-Methyl Dibenzothiophene (4-E,6-M DBT) under model conditions as compared to conventional HDS catalysts and {gamma}-Al{sub 2}O{sub 3} supported noble metal catalysts. Pt/ASA was also tested under practical conditions using a diesel fuel feed. The Pt/ASA catalyst showed a comparable activity to the NiW/{gamma}-Al{sub 2}O{sub 3} catalyst which was higher than that of the conventional CoMo/{gamma}-Al{sub 2}O{sub 3} catalyst. The main difference of the catalyst was the better hydroconversion of the 4,6 di-alkylated DBT's. The better performance of Pt/ASA in the testing under model conditions as compared to the diesel fuel HDS can be attributed to poisoning of part of the active phase by basic nitrogen compounds like quinoline. It is concluded that ASA supported noble metal catalysts have a promising potential for deep HDS processing. 5 refs.

  2. Staining of fluid-catalytic cracking catalysts: Localising Brønsted acidity within a single catalyst particle

    NARCIS (Netherlands)

    Buurmans, I.L.C.|info:eu-repo/dai/nl/31406592X; Ruiz Martinez, J.|info:eu-repo/dai/nl/341386405; van Leeuwen, S.L.; van der Beek, D.; Bergwerff, J.A.; Knowles, W.V.; Vogt, Eelco|info:eu-repo/dai/nl/073717398; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2012-01-01

    A time-resolved in situ micro-spectroscopic approach has been used to investigate the Brønsted acidic properties of fluid-catalytic-cracking (FCC) catalysts at the single particle level by applying the acid-catalysed styrene oligomerisation probe reaction. The reactivity of individual FCC components

  3. Recycling of spent noble metal catalysts with emphasis on pyrometallurgical processing

    Energy Technology Data Exchange (ETDEWEB)

    Hagelueken, C. [Degussa Huels AG, Hanau (Germany)

    1999-09-01

    Precious metal catalysts for catalytic Naphta Reforming, Isomerization, Hydrogenation and other chemical and petrochemical processes are valuable assets for oil refineries and chemical companies. At the end of the service life of a reactor load of catalyst, the efficient and reliable recovery of the precious metals contained in the catalyst is of paramount importance. More than 150 years of technological advances at Degussa-Huels have resulted in refining methods for all kinds of precious metal containing materials which guarantee an optimum technical yield of the precious metals included. The refining of catalysts today is one of the important activities in the precious metals business unit. In the state-of-the-art precious metal refinery at Hanau in the centre of Germany, a wide variety of processes for the recovery of all precious metals is offered. These processes include accurate preparation, sampling and analysis as well as both wet-chemical and pyrometallurgical recovery techniques. Special emphasis in this presentation is laid on the advantages of pyrometallurgical processes for certain kinds of catalysts. To avoid any risks during transport, sampling and treatment of the spent catalyst, all parties involved in the recycling chain strictly have to follow the relevant safety regulations. Under its commitment to 'Responsible Care' standard procedures have been developed which include pre-shipment samples, safety data sheets/questionnaires and inspection of spent catalysts. These measures not only support a safe and environmentally sound catalyst recycling but also enable to determine the most suitable and economic recovery process - for the benefit of the customer. (orig.)

  4. A review of dry (CO2) reforming of methane over noble metal catalysts.

    Science.gov (United States)

    Pakhare, Devendra; Spivey, James

    2014-11-21

    Dry (CO2) reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer-Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800-1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The most widely used catalysts for DRM are based on Ni. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. This review will cover DRM literature for catalysts based on Rh, Ru, Pt, and Pd metals. This includes the effect of these noble metals on the kinetics, mechanism and deactivation of these catalysts.

  5. Polymeric heterogeneous catalysts of transition-metal oxides: surface characterization, physicomechanical properties, and catalytic activity.

    Science.gov (United States)

    Nhi, Bui Dinh; Akhmadullin, Renat Maratovich; Akhmadullina, Alfiya Garipovna; Samuilov, Yakov Dmitrievich; Aghajanian, Svetlana Ivanova

    2013-12-16

    We investigate the physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, specifically, the specific surface area, elongation at break, breaking strength, specific electrical resistance, and volume resistivity. Digital microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. The experimental results show that polymeric heterogeneous catalysts of transition-metal oxides exhibit high stability and can maintain their catalytic activity under extreme reaction conditions for long-term use. The oxidation mechanism of sulfur-containing compounds in the presence of polymeric heterogeneous catalysts of transition-metal oxides is confirmed. Microstructural characterization of the catalysts is performed by using X-ray computed tomography. The activity of various catalysts in the oxidation of sulfur-containing compounds is determined. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Synthesis and Activity of A Single Active Site N-doped Electro-catalyst for Oxygen Reduction

    International Nuclear Information System (INIS)

    Bayati, Maryam; Scott, Keith

    2016-01-01

    Nitrogen doped carbon materials are promising oxygen reduction reaction (ORR) catalysts which could potentially replace platinum. However, despite extensive studies, their active sites are still controversial and their impact on overall ORR remains obscure. Herein, we present a method for preparation of a single active site catalyst based on cycling an iron-inserted N-doped carbon catalyst in a wide potential window firstly in sulfuric acid and later in alkaline solution to study the contribution of the remaining one active group in overall activity. Following preparation of the metal-inserted N-doped carbon catalyst (MINC), its morphology was characterized using X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and the electro-catalytic behavior was investigated by employing linear sweep voltammetry (LSV) using a rotating ring disk electrode (RRDE). XPS revealed that graphitic nitrogen was the only remaining active nitrogen-containing group after elimination the pyridinic and pyrrolic groups and also iron nano-materials removal confirmed from auger peak of Fe LMMa and poisoning reaction with cyanide. The C1 s XPS region data showed an increase in the oxygen reduction intermediate C-OH peak, after the reaction, which indicates electrocatalytic activity of the graphitic carbon. Electrochemical studies revealed no significant changes in limiting current, a small increase in H 2 O 2 production and 47 mV shift in half wave potential for degraded catalyst which is in line with previous theoretical calculations.

  7. A high performance catalyst for methane conversion to methanol: graphene supported single atom Co.

    Science.gov (United States)

    Yuan, Jinyun; Zhang, Wenhua; Li, Xingxing; Yang, Jinlong

    2018-02-27

    Employing first principles calculations, we show a two-step reaction mechanism for direct methane oxidation to methanol over a single atom Co-embedded graphene (Gr) catalyst, with N 2 O as the O-donor molecule. C-H activation is the rate-limiting step. The high reaction activity and selectivity under mild conditions were predicted for this catalyst.

  8. Bis(benzimidazole)amine vanadium catalysts for olefin polymerisation and co-polymerisation: thermally robust, single-site catalysts activated by simple alkylaluminium reagents.

    Science.gov (United States)

    Tomov, Atanas K; Gibson, Vernon C; Zaher, Damien; Elsegood, Mark R J; Dale, Sophie H

    2004-09-07

    Vanadium complexes containing bis(benzimidazole)amine ligands, upon activation by simple alkylaluminium reagents, give unusually robust, single-site, catalysts for olefin polymerisation/co-polymerisation.

  9. beads immobilized metal nanoparticle catalysts for the reduction of ...

    Indian Academy of Sciences (India)

    economic advantage. Further, the existing catalyst cannot be continuously packed into ... neous NP catalysts with higher efficiency, stability, economy, easy synthesis and reusability for potential degradation ... then the solution was refluxed in an oil bath at 80◦C. The reaction mixture has been protected from light to avoid the.

  10. Transition metal oxide loaded MCM catalysts for photocatalytic ...

    Indian Academy of Sciences (India)

    Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was ...

  11. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  12. Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts

    Science.gov (United States)

    Choi, Jae Soon; Armstrong, Beth L; Schwartz, Viviane

    2015-04-21

    A method for synthesizing catalyst beads of bulk transmission metal carbides, nitrides and phosphides is provided. The method includes providing an aqueous suspension of transition metal oxide particles in a gel forming base, dropping the suspension into an aqueous solution to form a gel bead matrix, heating the bead to remove the binder, and carburizing, nitriding or phosphiding the bead to form a transition metal carbide, nitride, or phosphide catalyst bead. The method can be tuned for control of porosity, mechanical strength, and dopant content of the beads. The produced catalyst beads are catalytically active, mechanically robust, and suitable for packed-bed reactor applications. The produced catalyst beads are suitable for biomass conversion, petrochemistry, petroleum refining, electrocatalysis, and other applications.

  13. Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction

    DEFF Research Database (Denmark)

    Bagger, Alexander; Ju, Wen; Varela, Ana Sofia

    2017-01-01

    the competing Hydrogen Evolution Reaction (HER). The single metal site in a porphyrine-like structure requires an ontop site binding of hydrogen, compared to the hollow site binding of hydrogen on a metal catalyst surface. The difference in binding site structure gives a fundamental energy-shift in the scaling......Currently, no catalysts are completely selective for the electrochemical CO2 Reduction Reaction (CO2RR). Based on trends in density functional theory calculations of reaction intermediates we find that the single metal site in a porphyrine-like structure has a simple advantage of limiting...

  14. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

    2009-07-14

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

  15. 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

  16. Development of Coke-tolerant Transition Metal Catalysts for Dry Reforming of Methane

    KAUST Repository

    Al-Sabban, Bedour E.

    2016-11-07

    Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-04

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

  18. Recent Advances in Supported Metal Catalysts for Syngas Production from Methane

    Directory of Open Access Journals (Sweden)

    Mohanned Mohamedali

    2018-03-01

    Full Text Available Over the past few years, great attention is paid to syngas production processes from different resources especially from abundant sources, such as methane. This review of the literature is intended for syngas production from methane through the dry reforming (DRM and the steam reforming of methane (SRM. The catalyst development for DRM and SRM represents the key factor to realize a commercial application through the utilization of more efficient catalytic systems. Due to the enormous amount of published literature in this field, the current work is mainly dedicated to the most recent achievements in the metal-oxide catalyst development for DRM and SRM in the past five years. Ni-based supported catalysts are considered the most widely used catalysts for DRM and SRM, which are commercially available; hence, this review has focused on the recent advancements achieved in Ni catalysts with special focus on the various attempts to address the catalyst deactivation challenge in both DRM and SRM applications. Furthermore, other catalytic systems, including Co-based catalysts, noble metals (Pt, Rh, Ru, and Ir, and bimetallic systems have been included in this literature review to understand the observed improvements in the catalytic activities and coke suppression property of these catalysts.

  19. 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

    -doped tin oxide (Pt1/ATO) is synthesized by conventional incipient wetness impregnation, with up to 8 wt% Pt. The single atomic Pt structure is confirmed by high-angle annular dark field scanning tunneling electron microscopy images and extended X-ray absorption fine structure analysis results. Density......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...

  20. Surface/structure functionalization of copper-based catalysts by metal-support and/or metal-metal interactions

    Science.gov (United States)

    Konsolakis, Michalis; Ioakeimidis, Zisis

    2014-11-01

    Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal-metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO2, La2O3, Sm2O3), or (ii) ceria-based mixed oxides (Ce1-xSmxOδ) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu-Co/CeO2). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal-metal interactions are provided, paving the way for real-life industrial applications.

  1. Biodiesel production using alkali earth metal oxides catalysts synthesized by sol-gel method

    Directory of Open Access Journals (Sweden)

    Majid Mohadesi

    2014-03-01

    Full Text Available Biodiesel fuel is considered as an alternative to diesel fuel. This fuel is produced through transesterification reactions of vegetable oils or animal fat by alcohols in the presence of different catalysts. Recent studies on this process have shown that, basic heterogeneous catalysts have a higher performance than other catalysts. In this study different alkali earth metal oxides (CaO, MgO and BaO doped SiO2 were used as catalyst for the biodiesel production process. These catalysts were synthesis by using the sol-gel method. A transesterification reaction was studied after 8h by mixing corn oil, methanol (methanol to oil molar ratio of 16:1, and 6 wt. % catalyst (based on oil at 60oC and 600rpm. Catalyst loading was studied for different catalysts ranging in amounts from 40, 60 to 80%. The purity and yield of the produced biodiesel for 60% CaO/SiO2 was higher than other catalysts and at 97.3% and 82.1%, respectively.

  2. In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts

    NARCIS (Netherlands)

    van Oversteeg, Christina H M|info:eu-repo/dai/nl/413490483; Doan, Hoang Q; de Groot, Frank M F|info:eu-repo/dai/nl/08747610X; Cuk, Tanja

    2016-01-01

    X-ray absorption studies of the geometric and electronic structure of primarily heterogeneous Co, Ni, and Mn based water oxidation catalysts are reviewed. The X-ray absorption near edge and extended X-ray absorption fine structure studies of the metal K-edge, characterize the metal oxidation state,

  3. Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve

    Science.gov (United States)

    Tang, Yadan; Roberts, Charles A.; Perkins, Ryan T.; Wachs, Israel E.

    2016-08-01

    This study revisits the classic volcano curve for HCOOH decomposition by metal catalysts by taking a modern catalysis approach. The metal catalysts (Au, Ag, Cu, Pt, Pd, Ni, Rh, Co and Fe) were prepared by H2 reduction of the corresponding metal oxides. The number of surface active sites (Ns) was determined by formic acid chemisorption. In situ IR indicated that both monodentate and bidentate/bridged surface HCOO* were present on the metals. Heats of adsorption (ΔHads) for surface HCOO* values on metals were taken from recently reported DFT calculations. Kinetics for surface HCOO* decomposition (krds) were determined with TPD spectroscopy. Steady-state specific activity (TOF = activity/Ns) for HCOOH decomposition over the metals was calculated from steady-state activity (μmol/g-s) and Ns (μmol/g). Steady-state TOFs for HCOOH decomposition weakly correlated with surface HCOO* decomposition kinetics (krds) and ΔHads of surface HCOO* intermediates. The plot of TOF vs. ΔHads for HCOOH decomposition on metal catalysts does not reproduce the classic volcano curve, but shows that TOF depends on both ΔHads and decomposition kinetics (krds) of surface HCOO* intermediates. This is the first time that the classic catalysis study of HCOOH decomposition on metallic powder catalysts has been repeated since its original publication.

  4. Chemoselective Oxidation of Bio-Glycerol with Nano-Sized Metal Catalysts

    DEFF Research Database (Denmark)

    Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

    2015-01-01

    to selectively oxidize glycerol and yield products with good selectivity is the use of nano-sized metal particles as heterogeneous catalysts. In this short review, recent developments in chemoselective oxidation of glycerol to specific products over nano-sized metal catalysts are described. Attention is drawn...... to various reaction parameters such as the type of the support, the size of the metal particles, and the acid/base properties of the reaction medium which were illustrated to largely influence the activity of the nanocatalyst and selectivity to the target product. - See more at: http...

  5. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    Science.gov (United States)

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  6. Structure, Mobility, and Composition of Transition Metal Catalyst Surfaces. High-Pressure Scanning Tunneling Microscopy and Ambient-Pressure X-ray Photoelectron Spectroscopy Studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zhongwei [Univ. of California, Berkeley, CA (United States)

    2013-12-06

    Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

  7. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    Directory of Open Access Journals (Sweden)

    Johanna K. Dombrovskis

    2014-12-01

    Full Text Available Transition metal ion-chelating ordered mesoporous carbon (TM-OMC materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  8. Accumulation of heavy metals from single and mixed metal solutions ...

    African Journals Online (AJOL)

    The usefulness of the intertidal gastropod Tympanotonus fuscatus L as a biomonitor of heavy metals in tropical estuaries was assessed. The periwinkles were collected from a site in the upper Bonny Estuary, Southern Nigeria and exposed in a series of experiments either singly or binary mixtures to copper, zinc and ...

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

    Science.gov (United States)

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

    2004-02-01

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

  10. Shape-Controlled Metal-Free Catalysts: Facet-Sensitive Catalytic Activity Induced by the Arrangement Pattern of Noncovalent Supramolecular Chains.

    Science.gov (United States)

    Geng, Guangwei; Chen, Penglei; Guan, Bo; Jiang, Lang; Xu, Zhongfei; Di, Dawei; Tu, Zeyi; Hao, Weichang; Yi, Yuanping; Chen, Chuncheng; Liu, Minghua; Hu, Wenping

    2017-05-23

    Metal-free catalytic materials have recently received broad attention as promising alternatives to metal-involved catalysts. This is owing to their inherent capability to overcome the inevitable limitations of metal-involved catalysts, such as high sensitivity to poisoning, the limited reserves, high cost and scarcity of metals (especially noble metals), etc. However, the lack of shape-controlled metal-free catalysts with well-defined facets is a formidable bottleneck limiting our understandings on the underlying structure-activity relationship at atomic/molecular level, which thereby restrains their rational design. Here, we report that catalytically active crystals of a porphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, could be shaped into well-defined cubes and sheet-like tetradecahedrons (TDHD), which are exclusively and predominantly enclosed by {101} and {001} facets, respectively. Fascinatingly, compared to the cubes, the TDHDs display substantially enhanced catalytic activity toward water decontamination under visible-light irradiation, although both the architectures have identical crystalline structure. We disclose that such interesting shape-sensitive catalytic activity is ascribed to the distinct spatial separation efficiency of photogenerated electrons and holes induced by single-channel and multichannel charge transport pathways along noncovalent supramolecular chains, which are arranged as parallel-aligned and 2D network patterns, respectively. Our findings provide an ideal scientific platform to guide the rational design of next-generation metal-free catalysts of desired catalytic performances.

  11. Gallium-rich Pd-Ga phases as supported liquid metal catalysts

    Science.gov (United States)

    Taccardi, N.; Grabau, M.; Debuschewitz, J.; Distaso, M.; Brandl, M.; Hock, R.; Maier, F.; Papp, C.; Erhard, J.; Neiss, C.; Peukert, W.; Görling, A.; Steinrück, H.-P.; Wasserscheid, P.

    2017-09-01

    A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

  12. Principles and Methods for the Rational Design of Core-Shell Nanoparticle Catalysts with Ultralow Noble Metal Loadings.

    Science.gov (United States)

    Hunt, Sean T; Román-Leshkov, Yuriy

    2018-03-06

    Conspecuts Commercial and emerging renewable energy technologies are underpinned by precious metal catalysts, which enable the transformation of reactants into useful products. However, the noble metals (NMs) comprise the least abundant elements in the lithosphere, making them prohibitively scarce and expensive for future global-scale technologies. As such, intense research efforts have been devoted to eliminating or substantially reducing the loadings of NMs in various catalytic applications. These efforts have resulted in a plethora of heterogeneous NM catalyst morphologies beyond the traditional supported spherical nanoparticle. In many of these new architectures, such as shaped, high index, and bimetallic particles, less than 20% of the loaded NMs are available to perform catalytic turnovers. The majority of NM atoms are subsurface, providing only a secondary catalytic role through geometric and ligand effects with the active surface NM atoms. A handful of architectures can approach 100% NM utilization, but severe drawbacks limit general applicability. For example, in addition to problems with stability and leaching, single atom and ultrasmall cluster catalysts have extreme metal-support interactions, discretized d-bands, and a lack of adjacent NM surface sites. While monolayer thin films do not possess these features, they exhibit such low surface areas that they are not commercially relevant, serving predominantly as model catalysts. This Account champions core-shell nanoparticles (CS NPs) as a vehicle to design highly active, stable, and low-cost materials with high NM utilization for both thermo- and electrocatalysis. The unique benefits of the many emerging NM architectures could be preserved while their fundamental limitations could be overcome through reformulation via a core-shell morphology. However, the commercial realization of CS NPs remains challenging, requiring concerted advances in theory and manufacturing. We begin by formulating seven

  13. Screening single-atom catalysts for methane activation: α -A l2O3(0001 ) -supported Ni

    Science.gov (United States)

    Gao, Fei; Gao, Shiwu; Meng, Sheng

    2017-08-01

    Methane activation is one of the biggest challenges for chemical conversion of hydrocarbons and fundamental science. We systematically screen d -block transition metal elements as potential candidates of single-atom catalysts (SACs) for methane dissociation. The adsorption of methane on free metal atoms strongly depends on the number of d electrons of SAC, where the maximum binding energy is formed with the Ni group (electronic configuration d8s2 or d9s1 ). Interestingly, the magnetic moment of the SACs decreases by 2 μB for strong interactions, suggesting that the methane-metal bond forms a spin singlet state involving two electrons of opposite spins. To examine the effect of substrates, the screened transition metals, Ni, Rh, and Pt are further put onto prototype metal oxide surfaces. The substrate dramatically modifies the discrete energy levels of a single metal and its catalytic properties. Single Ni atoms supported on an O-terminated α -A l2O3(0001 ) surface (N i1/A l2O3 ) show superior catalytic properties, with a low activation barrier of 0.4 eV (0.11 eV after zero-point energy correction) for the C-H bond dissociation and simultaneously an extreme stability with a high binding energy of ˜9.39 eV for the Ni anchor. This work identifies N i1/A l2O3 catalyst as an optimal SAC and offers new atomistic insights into the mechanism of methane activation on SACs.

  14. Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

    Science.gov (United States)

    Lü, Yinyun; Jiang, Yating; Zhou, Qi; Li, Yunmei; Chen, Luning; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

    2017-12-01

    The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.

  15. Removal Of Phenol From Wastewater By Using Low-Cost Catalyst From Metal Production

    Directory of Open Access Journals (Sweden)

    Galbičková Blanka

    2014-12-01

    Full Text Available Utilization of AOPs (Advanced oxidation processes as an emerging technology for removing of pollutants from wastewater is developed. In this paper, UV photodegradation was used for removing of phenol from wastewater. As a source of UV radiation medium pressure mercury lamp with output 400W was used. The influence of low-cost catalysts on this process was also monitored. Wastes from metal production, red mud and black nickel mud, were used as catalysts.

  16. Removal Of Phenol From Wastewater By Using Low-Cost Catalyst From Metal Production

    Science.gov (United States)

    Galbičková, Blanka; Soldán, Maroš; Belčík, Michal; Balog, Karol

    2014-12-01

    Utilization of AOPs (Advanced oxidation processes) as an emerging technology for removing of pollutants from wastewater is developed. In this paper, UV photodegradation was used for removing of phenol from wastewater. As a source of UV radiation medium pressure mercury lamp with output 400W was used. The influence of low-cost catalysts on this process was also monitored. Wastes from metal production, red mud and black nickel mud, were used as catalysts.

  17. Comparison of nickel molybdenum hydrous metal oxides with commercial catalysts for HDS/HDN of coal liquids

    Energy Technology Data Exchange (ETDEWEB)

    Lott, S.E.; Gardner, T.J.; McLaughlin, L.I.; Oelfke, J.B.

    1994-06-01

    Improved efficiency in direct coal liquefaction processes can be obtained by developing catalysts with better activity, selectivity, and life. In previous exploratory research at Sandia National Laboratories, catalysts prepared via hydrous metal oxide (HMO) ion exchangers have been shown to have potential for application to a number of reactions associated with the conversion of coal to liquid fuels. In the present effort, one member of this class of catalysts, hydrous titanium oxide (HTO), has been used to develop catalysts for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of coal liquids. For HYD of pyrone, unsupported NiMoHTO catalysts performed better than commercial benchmark catalysts on either a catalyst weight or active metals basis. In a side-by-side comparison of supported NiMoHTO catalysts with commercial counterparts, the supported NiMoHTO catalysts outperformed the Shell 324 and Amocat 1C catalysts for HYD of pyrene. For HDS/HDN of coal liquids, the supported and bulk forms of the NiMoHTO catalysts equaled the performance of the commercial catalysts at 500, 1000, and 1500 psig while containing less active metals. Possible reasons for the high activity of the NiMoHTO catalysts are a high dispersion of the active MoS{sub 2} phase and a high acidity of the bulk NiMoHTO.

  18. Hydrogen production by steam reforming of acetic acid: Comparison of conventional supported metal catalysts and metal-incorporated mesoporous smectite-like catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Iwasa, Nobuhiro; Yamane, Toshiyuki; Arai, Masahiko [Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Takei, Masaaki; Ozaki, Jun-ichi [Department of Chemical and Environmental Engineering, Graduate School of Engineering, Gunma University, Kiryu 376-8515 (Japan)

    2010-01-15

    The activities of various metal catalysts were tested in steam reforming of acetic acid for the production of H{sub 2}, using conventional metal oxides and transition metal-incorporated mesoporous smectite-like materials as supports. It has been found that Pt is superior to Ni, Co, and Fe among Al{sub 2}O{sub 3} supported catalysts, Al{sub 2}O{sub 3} is more effective than ZrO{sub 2} and SiO{sub 2} as support for Pt, Ni incorporated smectite (SM(Ni)) support is more effective than Fe and Co incorporated ones for Pt, and SM(Ni) is also active in the absence of Pt. The total activity for the conversion of acetic acid is in the order of Pt/Al{sub 2}O{sub 3} > Pt/SM(Ni) > SM(Ni) but the ability of H{sub 2} production is comparable among these catalysts. These catalysts (and the other ones) were observed to lose their activities during the reforming reactions. The activity of Pt/Al{sub 2}O{sub 3} decreased during the whole course of reaction up to 10 h. In contrast, the activity of SM(Ni) also decreased within 2 h but it showed a stable activity in the following stage of reaction. The initial activity of the used Pt/SM(Ni) and SM(Ni) was able to be almost completely restored by thermal treatment with H{sub 2} but less effectively for the used Pt/Al{sub 2}O{sub 3}. The catalyst deactivation was shown to occur by the formation and deposition of carbon materials on the catalysts (XRD, TEM, thermal analysis). The properties of carbon deposits formed on Pt/Al{sub 2}O{sub 3} and SM(Ni) catalysts should be different and this may be responsible for the differences in the extent of deactivation and in the regeneration behavior between the two catalysts. (author)

  19. Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

    International Nuclear Information System (INIS)

    Britton, M.D.

    1995-01-01

    This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

  20. Doped Graphene as Non-Metallic Catalyst for Fuel Cells

    Directory of Open Access Journals (Sweden)

    Adriana MARINOIU

    2017-08-01

    Full Text Available Aiming a commercial development of proton exchange membrane fuel cells (PEMFC, a low cost, sustainable and high performance electrocatalyst for oxygen reduction reaction (ORR with capability to replace/reduce rare metals, are high desirable. In this paper, we present a class of doped graphene, namely iodinated graphene with highly ORR electrochemical performances, synthesized by using the electrophilic substitution method. The prepared samples were characterized by different techniques, including Scanning Electron Microscopy SEM, X-ray photoelectron spectroscopy XPS, Raman spectroscopy, surface area measurement by BET method, that revealed the structure and morphology. The most highly iodinated graphene was tested in a single cell by measuring the cyclic voltammetry. The electrochemical performances were evaluated and compared with a typical PEMFC configuration, when a single cathodic peak at 0.2 V with a current density of – 3.67 mA cm-2 for the Pt/C electrode was obtained. The best electrochemical performances in terms of electrochemical active area, was obtained for a new concept of cathode composed from Pt/C – iodine doped graphene, when a well-defined peak centred at 0.23 V with a current density of approx. – 9.1 mA cm-2 was obtained, indicating a high catalytic activity for ORR.DOI: http://dx.doi.org/10.5755/j01.ms.23.2.16216

  1. Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

    Science.gov (United States)

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

    2016-02-05

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

  2. Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States); Frei, Heinz [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division; Univ. of California, Berkeley, CA (United States)

    2017-02-22

    Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. In conclusion, combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

  3. Esterification of phenyl acetic acid withp-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

    Science.gov (United States)

    Bhaskar, M; Surekha, M; Suma, N

    2018-02-01

    The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

  4. Study of Metal-Humic Catalysts before and After the Gas Desulphurization Process Using Thermal Analysis

    Science.gov (United States)

    Szyszka, Danuta; Wieckowska, Jadwiga

    2017-12-01

    The study of metal-humic catalysts before and after the SO2 conversion has been carried out using thermal analysis. The thermogravimetric analysis and differential thermal analysis has been carried out using Perkin-Elmer TGA 7 and DTA 7 equipment in an argonic atmosphere. The heating rate of samples in the DTA was 10 °C/min., and in the TGA 40 °C/min. The following catalysts have been chosen for analysis: H-Pb2+/450 °C, H-B/450 °C, H-Sn2+/450 °C, H-Ce 4+. The study of metal-humic catalysts using thermal analysis has shown that, in the DTA curves of studied catalysts before SO2 conversion, endothermic peaks related to decomposition of metal carbonates, melting of metals or decomposition of metal-humic bonding. In the DTA curves after the SO2 conversion process, there are additional endothermic peaks related to the presence of sulphur in the metal-humic compounds and to thermal decomposition of those bonds.

  5. Ceria doped mixed metal oxide nanoparticles as oxidation catalysts: Synthesis and their characterization

    Directory of Open Access Journals (Sweden)

    S.S.P. Sultana

    2015-11-01

    Full Text Available Mixed metal nanoparticles (NPs have attracted significant attention as catalysts for various organic transformations. In this study, we have demonstrated the preparation of nickel–manganese mixed metal oxide NPs doped with X% nano cerium oxide (X = 1, 3, 5 mol% by a facile co-precipitation technique using surfactant and surfactant free methodologies. The as-synthesized materials were calcined at different temperatures (300 °C, 400 °C, and 500 °C, and were characterized using various spectroscopic techniques, including, FTIR and XRD. SEM analysis, TEM analysis and TGA were employed to evaluate the structural properties of the as-prepared catalyst. These were evaluated for their catalytic behaviour towards the conversion of benzyl alcohol to benzaldehyde, which was used as a model reaction with molecular oxygen as oxidant. Furthermore, the effect of the variation of the percentage of nano ceria doping and the calcination temperature on the performance of as-prepared mixed metal catalysts was also evaluated. The kinetic studies of the reactions performed employing gas chromatographic technique have revealed that the mixed metal oxide catalyst doped with 5% nano ceria displayed excellent catalytc activity, among various catalysts synthesized.

  6. Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs

    Science.gov (United States)

    Santoro, Carlo; Kodali, Mounika; Herrera, Sergio; Serov, Alexey; Ieropoulos, Ioannis; Atanassov, Plamen

    2018-02-01

    Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e- transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm-2 and 10 mgcm-2. Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm-2 and 262 ± 4 μWcm-2 with catalyst loading of 0.1 mgcm-2 and 10 mgcm-2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

  7. Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs.

    Science.gov (United States)

    Santoro, Carlo; Kodali, Mounika; Herrera, Sergio; Serov, Alexey; Ieropoulos, Ioannis; Atanassov, Plamen

    2018-02-28

    Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e - transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm -2 and 10 mgcm -2 . Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm -2 and 262 ± 4 μWcm -2 with catalyst loading of 0.1 mgcm -2 and 10 mgcm -2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

  8. Enantioselection on Heterogeneous Noble Metal Catalyst: Proline-Induced Asymmetry in the Hydrogenation of Isophorone on Pd Catalyst.

    Science.gov (United States)

    Rodríguez-García, Laura; Hungerbühler, Konrad; Baiker, Alfons; Meemken, Fabian

    2015-09-23

    In the (S)-proline-mediated asymmetric hydrogenation of isophorone (IP) on supported Pd catalyst, excellent enantioselectivity is achieved, with an enantiomeric excess of up to 99%. The role of the heterogeneous catalyst has been the subject of a controversial debate, and the current mechanistic understanding cannot explain the observed enantioselectivity of this catalytic system. The lack of in situ information about the role of the heterogeneous catalyst has prompted us to investigate the surface processes occurring at the methanol-Pd catalyst interface using attenuated total reflection infrared spectroscopy. Time-resolved monitoring of the homogeneous solution and of the catalytic solid-liquid interface coupled with catalytic data provides crucial information on the catalytically relevant enantiodifferentiating processes. While the condensation of IP and the corresponding chiral product 3,3,5-trimethylcyclohexanone with the chiral amine is connected to the enantiodifferentiation, it was found that the crucial enantioselectivity-controlling steps take place on the metal surface, and the reaction has to be classified as heterogeneous asymmetric hydrogenation. The presented spectroscopic and catalytic results provide strong evidence for the existence of two competing enantioselective processes leading to opposing enantioselection. Depending on surface coverage of the Pd catalyst, the reaction is controlled either by kinetic resolution ((S)-pathway) or by chiral catalysis ((R)-pathway). Steering the hydrogenation on the (R)-reaction pathway requires sufficient concentration of IP-(S)-proline condensate, as this chiral reactive intermediate becomes the most abundant surface species, inhibiting the competing kinetic resolution. The unraveled (R)-reaction pathway emphasizes an intriguing strategy for inducing chirality in heterogeneous asymmetric catalysis.

  9. Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

    2015-09-30

    To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

  10. Particle size distribution and morphological changes in activated carbon-metal oxide hybrid catalysts prepared under different heating conditions.

    Science.gov (United States)

    Barroso-Bogeat, A; Alexandre-Franco, M; Fernández-González, C; Gómez-Serrano, V

    2016-03-01

    In catalysis processes, activated carbon (AC) and metal oxides (MOs) are widely used either as catalysts or as catalyst supports because of their unique properties. A combination of AC and a MO in a single hybrid material entails changes not only in the composition, microstructure and texture but also in the morphology, which may largely influence the catalytic behaviour of the resulting product. This work is aimed at investigating the modifications in the morphology and particle size distribution (PSD) for AC-MO hybrid catalysts as a result of their preparation under markedly different heating conditions. From a commercial AC and six MO (Al2O3, Fe2O3, ZnO, SnO2, TiO2 and WO3) precursors, two series of such catalysts are prepared by wet impregnation, oven-drying at 120 ºC, and subsequent heat treatment at 200 ºC or 850 ºC in inert atmosphere. The resulting samples are characterized in terms of their morphology and PSD by scanning electron microscopy and ImageJ processing program. Obtained results indicate that the morphology, PSD and degree of dispersion of the supported catalysts are strongly dependent both on the MO precursor and the heat treatment temperature. With the temperature rise, trends are towards the improvement of crystallinity, the broadening of the PSD and the increase in the average particle size, thus suggesting the involvement of sintering mechanisms. Such effects are more pronounced for the Fe, Sn and W catalysts due to the reduction of the corresponding MOs by AC during the heat treatment at 850 ºC. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

  11. Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts.

    Science.gov (United States)

    Matsubu, John C; Zhang, Shuyi; DeRita, Leo; Marinkovic, Nebojsa S; Chen, Jingguang G; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

    2017-02-01

    The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal-support interactions can be exploited to optimize metal active-site properties are lacking. Here we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCO x ) on reducible oxide supports (TiO 2 and Nb 2 O 5 ) that induce oxygen-vacancy formation in the support and cause HCO x -functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO 2 -reduction selectivity.

  12. Metal catalyst in CVD growth of carbon nanotubes: role of chemical composition

    Science.gov (United States)

    Yazyev, Oleg V.; Pasquarello, Alfredo

    2010-01-01

    Using first principles methods, we systematically study the crucial steps of CVD growth of CNTs, the binding and the diffusion of the carbon feedstock as well as the nucleation of CNTs. Late transition (Ni, Pd, Pt) and coinage (Cu, Ag, Au) metal catalysts were investigated. For all metals, we considered various diffusion mechanisms including both surface and subsurface channels, finding the lowest activation barriers for carbon adatoms on nanoparticles of coinage metals. For these metals, our calculations further show that the diffusion is restricted to the nanoparticle surface when diatomic carbon is initially obtained from the decomposition of the precursor gas. From the binding energies of armchair and zigzag edges of CNT fragments, we infer a high preference for the growth of armchair CNTs. These results indicate that coinage metal catalysts, in particular Cu, favor CVD growth of CNTs at low temperatures and with narrow chirality distributions.

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

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  14. Mesoporous zeolite single crystal catalysts: Diffusion and catalysis in hierarchical zeolites

    DEFF Research Database (Denmark)

    Christensen, Christina Hviid; Johannsen, Kim; Toernqvist, Eric

    2007-01-01

    in the zeolite micropores. Here, we briefly discuss the most important ways of introducing mesopores into zeolites and, for the first time, we show experimentally that the presence of mesopores dramatically increases the rate of diffusion in zeolite catalysts. This is done by studying the elution of iso-butane...... from packed beds of conventional and mesoporous zeolite catalysts. Moreover, we discuss in detail the recent observation of improved activity and selectivity in the alkylation of benzene with ethene using mesoporous zeolite single crystal catalysts. For this reaction, we show by calculation...

  15. Synthesis and characterization of metal oxide promoted alumina catalyst for biofuel production

    Science.gov (United States)

    Anisuzzaman, S. M.; Krishnaiah, D.; Bono, A.; Abang, S.; Sundang, M.; Suali, E.; Lahin, F. A.; Shaik Alawodeen, A.

    2016-06-01

    Alumina has been widely used as a support in catalysis process which owing to its extremely thermal and mechanical stability, high surface area, large pore size and pore volume. The aim of this study was to synthesize calcium oxide-supported basic alumina catalysts (CaO/Al2O3) by impregnation method and to characterize the properties of the catalyst based on its surface area and porosity, functional group, surface morphology and particle size. Impregnation method was chosen for the synthesization of catalyst which involved contacting the support with the impregnating solution for a particular period of time, drying the support to remove the imbibed liquid and calcination process. In the preparation of catalyst, catalytic performance of CaO/Al2O3 catalyst was measured at different calcined temperatures (650°C, 750°C and 800°C). Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Mercury intrusion porosimetry (MIP), and particle size analyzer (Zetasizer) was used to characterize the catalyst. The highest total specific area and the total porosity of the catalyst was obtained at 750oC. FTIR analysis basically studied on the functional groups present in each catalyst synthesized, while SEM analysis was observed to have pores on its surface. Moreover, CaO/Al2O3 catalysts at 650°C produced the smallest particle size (396.1 mn), while at 750°C produced the largest particle size (712.4 mn). Thus it can be concluded that CaO/Al2O3 catalysts has great potential coimnercialization since CaO has attracted many attentions compared to other alkali earth metal oxides especially on the transesterification reaction.

  16. Wire gauze and cordierite supported noble metal catalysts for passive autocatalytic recombiner

    International Nuclear Information System (INIS)

    Sanap, Kiran K.; Varma, S.; Waghmode, S.B.; Bharadwaj, S.R.

    2015-01-01

    Highlights: • Synthesis by electroless deposition method and chemical reduction route. • Particle size of 0.1–0.5 μm & 3.5–5 nm for Pt–Pd/Wg & Pt–Pd/Cord catalysts. • Active for H 2 and O 2 reaction with initial H 2 concentration of 1.5 to 7% in air. • Active in presence of different contaminants like CO 2 , CH 4 , CO & relative humidity. • Enhanced resistance of Pt–Pd/Cord catalyst towards the poisoning of CO. - Abstract: Hydrogen released in nuclear reactor containment under severe accident scenario poses a threat to containment and hence needs to be regulated by catalytic recombination. Mixed noble metal catalysts with platinum–palladium supported on stainless steel wire gauze and cordierite support have been developed for this purpose. The developed catalysts have been found to be highly efficient for removal of hydrogen concentration in the range of 1.5 to 7.0% v/v in air. Though both the catalysts exhibit similar kinetics for lower hydrogen concentration, cordierite supported catalysts exhibits better kinetic rate at higher hydrogen concentration. The performances of these catalysts in presence of various probable catalytic poison like carbon monoxide and catalytic inhibitors like moisture, carbon dioxide, and hydrocarbons provide data for use of these catalysts under the actual scenario. Compared to stainless steel wire gauze supported catalyst, the cordierite based catalyst are found to exhibit enhanced resistance towards carbon monoxide and limited temperature rise for safer application at higher hydrogen concentrations.

  17. Supported noble metal catalysts in the catalytic wet air oxidation of industrial wastewaters and sewage sludges.

    Science.gov (United States)

    Besson, M; Descorme, C; Bernardi, M; Gallezot, P; di Gregorio, F; Grosjean, N; Minh, D Pham; Pintar, A

    2010-12-01

    This paper reviews some catalytic wet air oxidation (CWAO) investigations of industrial wastewaters over platinum and ruthenium catalysts supported on TiO2 and ZrO2 formulated to be active and resistant to leaching, with particular focus on the stability of the catalyst. Catalyst recycling experiments were performed in batch reactors and long-term stability tests were conducted in trickle-bed reactors. The catalyst did not leach upon treatment of Kraft bleaching plant and olive oil mill effluents, and could be either recycled or used for long periods of time in continuous reactors. Conversely, these catalysts were rapidly leached when used to treat effluents from the production of polymeric membranes containing N,N-dimethylformamide. The intermediate formation of amines, such as dimethylamine and methylamine with a high complexing capacity for the metal, was shown to be responsible for the metal leaching. These heterogeneous catalysts also deactivated upon CWAO of sewage sludges due to the adsorption of the solid organic matter. Pre-sonication of the sludge to disintegrate the flocs and improve solubility was inefficient.

  18. Fabrication of vertical GaN/InGaN heterostructure nanowires using Ni-Au bi-metal catalysts

    OpenAIRE

    Ha, Ryong; Kim, Sung-Wook; Choi, Heon-Jin

    2013-01-01

    We have fabricated the vertically aligned coaxial or longitudinal heterostructure GaN/InGaN nanowires. The GaN nanowires are first vertically grown by vapor?liquid-solid mechanism using Au/Ni bi-metal catalysts. The GaN nanowires are single crystal grown in the [0001] direction, with a length and diameter of 1 to 10 ?m and 100 nm, respectively. The vertical GaN/InGaN coaxial heterostructure nanowires (COHN) are then fabricated by the subsequent deposition of 2 nm of InxGa1-xN shell on the sur...

  19. Fabrication of vertical GaN/InGaN heterostructure nanowires using Ni-Au bi-metal catalysts.

    Science.gov (United States)

    Ha, Ryong; Kim, Sung-Wook; Choi, Heon-Jin

    2013-06-26

    We have fabricated the vertically aligned coaxial or longitudinal heterostructure GaN/InGaN nanowires. The GaN nanowires are first vertically grown by vapor-liquid-solid mechanism using Au/Ni bi-metal catalysts. The GaN nanowires are single crystal grown in the [0001] direction, with a length and diameter of 1 to 10 μm and 100 nm, respectively. The vertical GaN/InGaN coaxial heterostructure nanowires (COHN) are then fabricated by the subsequent deposition of 2 nm of InxGa1-xN shell on the surface of GaN nanowires. The vertical GaN/InGaN longitudinal heterostructure nanowires (LOHN) are also fabricated by subsequent growth of an InGaN layer on the vertically aligned GaN nanowires using the catalyst. The photoluminescence from the COHN and LOHN indicates that the optical properties of GaN nanowires can be tuned by the formation of a coaxial or longitudinal InGaN layer. Our study demonstrates that the bi-metal catalysts are useful for growing vertical as well as heterostructure GaN nanowires. These vertically aligned GaN/InGaN heterostructure nanowires may be useful for the development of high-performance optoelectronic devices.

  20. Engineering catalyst microenvironments for metal-catalyzed hydrogenation of biologically derived platform chemicals.

    Science.gov (United States)

    Schwartz, Thomas J; Johnson, Robert L; Cardenas, Javier; Okerlund, Adam; Da Silva, Nancy A; Schmidt-Rohr, Klaus; Dumesic, James A

    2014-11-17

    It is shown that microenvironments formed around catalytically active sites mitigate catalyst deactivation by biogenic impurities that are present during the production of biorenewable chemicals from biologically derived species. Palladium and ruthenium catalysts are inhibited by the presence of sulfur-containing amino acids; however, these supported metal catalysts are stabilized by overcoating with poly(vinyl alcohol) (PVA), which creates a microenvironment unfavorable for biogenic impurities. Moreover, deactivation of Pd catalysts by carbon deposition from the decomposition of highly reactive species is suppressed by the formation of bimetallic PdAu nanoparticles. Thus, a PVA-overcoated PdAu catalyst was an order of magnitude more stable than a simple Pd catalyst in the hydrogenation of triacetic acid lactone, which is the first step in the production of biobased sorbic acid. A PVA-overcoated Ru catalyst showed a similar improvement in stability during lactic acid hydrogenation to propylene glycol in the presence of methionine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

    Science.gov (United States)

    Yuan, Heyang; He, Zhen

    2017-07-01

    Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. High quality syngas production from microwave pyrolysis of rice husk with char-supported metallic catalysts.

    Science.gov (United States)

    Zhang, Shuping; Dong, Qing; Zhang, Li; Xiong, Yuanquan

    2015-09-01

    This study aimed to obtain the maximum possible gas yield and the high quality syngas production from microwave pyrolysis of rice husk with rice husk char and rice husk char-supported metallic (Ni, Fe and Cu) catalysts. The rice husk char-supported metallic catalysts had developed pore structure and catalytic activity for gas productions and tar conversion. The temperature-rising characteristic, product yields, properties of gas products and tar conversion mechanisms were investigated. It was found that three rice husk char-supported metallic catalysts improved the microwave absorption capability and increased heating rate and final temperature. Rice husk char-supported Ni catalyst presented most effective effects on gas production, e.g. the gas yield is 53.9%, and the volume concentration of desired syngas is 69.96%. Rice husk char-supported Ni and Fe catalysts played pivotal roles in tar conversion that less heavy compounds can be detected along with the reduction of organic compound number. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Two-dimensional metallic tantalum disulfide as a hydrogen evolution catalyst.

    Science.gov (United States)

    Shi, Jianping; Wang, Xina; Zhang, Shuai; Xiao, Lingfeng; Huan, Yahuan; Gong, Yue; Zhang, Zhepeng; Li, Yuanchang; Zhou, Xiebo; Hong, Min; Fang, Qiyi; Zhang, Qing; Liu, Xinfeng; Gu, Lin; Liu, Zhongfan; Zhang, Yanfeng

    2017-10-16

    Two-dimensional metallic transition metal dichalcogenides are emerging as prototypes for uncovering fundamental physical phenomena, such as superconductivity and charge-density waves, as well as for engineering-related applications. However, the batch production of such envisioned transition metal dichalcogenides remains challenging, which has hindered the aforementioned explorations. Herein, we fabricate thickness-tunable tantalum disulfide flakes and centimetre-sized ultrathin films on an electrode material of gold foil via a facile chemical vapour deposition route. Through temperature-dependent Raman characterization, we observe the transition from nearly commensurate to commensurate charge-density wave phases with our ultrathin tantalum disulfide flakes. We have obtained high hydrogen evolution reaction efficiency with the as-grown tantalum disulfide flakes directly synthesized on gold foils comparable to traditional platinum catalysts. This work could promote further efforts for exploring new efficient catalysts in the large materials family of metallic transition metal dichalcogenides, as well as exploiting their applications towards more versatile applications.Metallic transition metal dichalcogenides are important materials for catalysis, but scalable and controllable preparation methods are scarce. Here, the authors synthesize 2H-TaS 2 as centimetre-scale films of tunable thickness and show they are an efficient catalyst for hydrogen evolution.

  4. Supported transition metal catalysts for para- to ortho-hydrogen conversion

    Science.gov (United States)

    Brooks, Christopher J.; Wang, Wei; Eyman, Darrell P.

    1994-01-01

    The main goal of this study was to develop and improve on existing catalysts for the conversion of ortho- to para-hydrogen. Starting with a commercially available Air Products nickel silicate, which had a beta value of 20, we were trying to synthesize catalysts that would be an improvement to AP. This was accomplished by preparing silicates with various metals as well as different preparation methods. We also prepared supported ruthenium catalysts by various techniques using several metal precursors to improve present technology. What was also found was that the activation conditions prior to catalytic testing was highly important for both the silicates and the supported ruthenium catalysts. While not the initial focus of the research, we made some interesting observations into the adsorption of H2 on ruthenium. This helped us to get a better understanding of how ortho- to para-H2 conversion takes place, and what features in a catalyst are important to optimize activity. Reactor design was the final area in which some interesting conclusions were drawn. As discussed earlier, the reactor catalyst bed must be constructed using straight 1/8 feet OD stainless steel tubing. It was determined that the use of 1/4 feet OD tubing caused two problems. First, the radius from the center of the bed to the wall was too great for thermal equilibrium. Since the reaction of ortho- to para-H2 is exothermic, the catalyst bed center was warmer than the edges. Second, the catalyst bed was too shallow using a 1/4 feet tube. This caused reactant blow-by which was thought to decrease the measured activity when the flow rate was increased. The 1/8 feet tube corrected both of these concerns.

  5. Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

    Science.gov (United States)

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

    2014-10-07

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

  6. Recycling of platinum group metals from the automotive catalysts; Reciclagem de metais do grupo da platina proveniente de catalisadores automotivos

    Energy Technology Data Exchange (ETDEWEB)

    Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo, E-mail: patymhp@yahoo.com.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Faculdade de Engenharia. Departamento de Materiais

    2014-07-01

    Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

  7. C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

    Science.gov (United States)

    Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

    2018-01-24

    Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

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

    NARCIS (Netherlands)

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

    2013-01-01

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

  9. Oxidative coupling of 1-naphthols over noble and base metal catalysts

    CSIR Research Space (South Africa)

    Maphoru, MV

    2014-01-01

    Full Text Available by the competitive cleavage of one of the two O[BOND]Me bonds at higher temperature. Unpromoted platinum and a range of other metallic catalysts, including gold and Raney nickel, were also found to be active. The products obtained are brightly colored solids...

  10. Comparison Of Different Noble Metal Catalysts For The Low Temperature Catalytic Partial Oxidation Of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, S.; Truong, T.-B.; Vogel, F.

    2005-03-01

    The generation of synthesis gas at low temperatures can contribute to a more economic production of clean transportation fuels (Fischer-Tropsch liquids) from natural gas. In this report, the performance of different noble metal catalysts in a low temperature catalytic partial oxidation process is presented. (author)

  11. Catalytic Ring Hydrogenation of Benzoic Acid with Supported Transition Metal Catalysts in scCO2

    Directory of Open Access Journals (Sweden)

    Fengyu Zhao

    2007-07-01

    Full Text Available The ring hydrogenation of benzoic acid to cyclohexanecarboxylic acid overcharcoal-supported transition metal catalysts in supercritical CO2 medium has been studiedin the present work. The cyclohexanecarboxylic acid can be produced efficiently insupercritical CO2 at the low reaction temperature of 323 K. The presence of CO2 increasesthe reaction rate and several parameters have been discussed.

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

    NARCIS (Netherlands)

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

    2005-01-01

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

  13. Neutral versus cationic Group 3 metal alkyl catalysts : performance in intramolecular hydroamination/cyclisation

    NARCIS (Netherlands)

    de Araujo Bambirra, Sergio; Tsurugi, H; van Leusen, D; Hessen, B

    2006-01-01

    The relative catalytic activity of neutral dialkyl versus cationic monoalkyl Group 3 metal catalysts in the intramolecular hydroamination/cyclisation of the 2,2-dimethyl-4-pentenylamine reference substrate was investigated. This was found to depend strongly on the nature of the monoanionic ancillary

  14. Direct observation of surface reconstruction and termination on a complex metal oxide catalyst by electron microscopy

    KAUST Repository

    Zhu, Yihan

    2012-03-19

    On the surface: The surface reconstruction of an MoVTeO complex metal oxide catalyst was observed directly by various electron microscopic techniques and the results explain the puzzling catalytic behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2016-07-01

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

  16. Preparation of supported vanadium and molybdenum oxide catalysts using metal acetylacetonate complexes

    NARCIS (Netherlands)

    van Hengstum, A.J.; van Ommen, J.G.; Bosch, H.; Gellings, P.J.

    1983-01-01

    Supported vanadium and molybdenum oxide catalysts were prepared by reaction of the corresponding acetylacetonate complex in a non-aqueous solution with the surface hydroxyl groups of the carrier. Continuous or batch adsorption of the metal acetylacetonate from toluene, as well as wet impregnation

  17. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Carla F. Pereira

    2016-10-01

    Full Text Available Porphyrin-based Metal-Organic Frameworks (Por-MOFs constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  18. High-pressure catalytic reactions over single-crystal metal surfaces

    Science.gov (United States)

    Rodriguez, JoséA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  19. PREPARATION AND CHARACTERIZATION THE NON-SULFIDED METAL CATALYST: Ni/USY and NiMo/USY

    Directory of Open Access Journals (Sweden)

    Khoirina Dwi Nugrahaningtyas

    2010-06-01

    Full Text Available The two-new catalysts had been prepared by using the impregnation method according to Nugrahaningtyas [6] and Li [4]. One catalyst is of Nickel (Ni, supported on Ultra Stable Zeolite Y (USY, whereas the other one is NiMo supported on same supporting agent. These new catalysts are expected to be more effective when applied on the hydrotreatment reaction in standpoint of its capabilities on removing the unwanted-heteroatom. Characterization those two types of catalysts then carried out by using the criteria of acidity, porosity and, metal content. The result shows that these non-sulfide catalysts have several good characters that supporting their usefulness in hydrotreatment-catalytic reaction. In addition, catalyst NiMo/USY - 1 performs many ideal criteria as the best functional catalyst.   Keywords: Non-sulfided Catalyst, hydro-treating, preparation, characterization

  20. Water Adsorption and Dissociation on Ceria-Supported Single-Atom Catalysts: A First-Principles DFT+U Investigation.

    Science.gov (United States)

    Han, Zhong-Kang; Gao, Yi

    2016-02-01

    Single-atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on-site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO 2 (111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO 2 (111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO 2 (111) surface and dissociative adsorption on STMA/CeO 2 (111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized Brønsted-Evans-Polanyi principle. By combining the oxygen spillovers, single-atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria-supported single-atom catalysts for reactions in which the dissociation of water plays an important role, such as the water-gas shift reaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Supported rhodium catalysts for ammonia-borane hydrolysis. Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Liangbing; Li, Hongliang; Zhang, Wenbo; Zhao, Xiao; Qiu, Jianxiang; Li, Aowen; Zheng, Xusheng; Zeng, Jie [Hefei National Lab. for Physical Sciences at the Microscale, Key Lab. of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, Hefei, Anhui(China); Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui (China); Hu, Zhenpeng [School of Physics, Nankai University, Tianjin (China); Si, Rui [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences (China)

    2017-04-18

    Supported metal nanocrystals have exhibited remarkable catalytic performance in hydrogen generation reactions, which is influenced and even determined by their supports. Accordingly, it is of fundamental importance to determine the direct relationship between catalytic performance and metal-support interactions. Herein, we provide a quantitative profile for exploring metal-support interactions by considering the highest occupied state in single-atom catalysts. The catalyst studied consisted of isolated Rh atoms dispersed on the surface of VO{sub 2} nanorods. It was observed that the activation energy of ammonia-borane hydrolysis changed when the substrate underwent a phase transition. Mechanistic studies indicate that the catalytic performance depended directly on the highest occupied state of the single Rh atoms, which was determined by the band structure of the substrates. Other metal catalysts, even with non-noble metals, that exhibited significant catalytic activity towards NH{sub 3}BH{sub 3} hydrolysis were rationally designed by adjusting their highest occupied states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Mesoporous diphosphine-transition metal complex catalyst for hydroformylation

    NARCIS (Netherlands)

    Reek, J.N.H.; Coppens, M.O.

    2012-01-01

    The invention pertains to a diphosphine-transition metal complex comprising a diphosphine-transition metal ligand that is covalently bonded to an insoluble mesoporous support having an average pore diameter of from 4.5 nm to 50 nm, characterized in that the ligand as attached to the support has the

  3. Single-Atom Pt as Co-Catalyst for Enhanced Photocatalytic H2 Evolution.

    Science.gov (United States)

    Li, Xiaogang; Bi, Wentuan; Zhang, Lei; Tao, Shi; Chu, Wangsheng; Zhang, Qun; Luo, Yi; Wu, Changzheng; Xie, Yi

    2016-03-23

    Isolated single-atom platinum (Pt) embedded in the sub-nanoporosity of 2D g-C3 N4 as a new form of co-catalyst is reported. The highly stable single-atom co-catalyst maximizes the atom efficiency and alters the surface trap states of g-C3 N4 , leading to significantly enhanced photocatalytic H2 evolution activity, 8.6 times higher than that of Pt nanoparticles and up to 50 times that for bare g-C3 N4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

    Energy Technology Data Exchange (ETDEWEB)

    Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

    2015-03-24

    Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

  5. Integrated Transmission Electron and Single-Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

    OpenAIRE

    Hendriks, Frank C.; Mohammadian, Sajjad; Ristanovic, Zoran; Kalirai, Samanbir; Meirer, Florian; Vogt, Eelco T. C.; Bruijnincx, Pieter C. A.; Gerritsen, Hans; Weckhuysen, Bert M.

    2018-01-01

    Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single-molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure–reactivity information was obtained for 100 nm thin, microtomed sections of a ...

  6. Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

    Science.gov (United States)

    Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

    2018-09-01

    The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

  7. Ultrahigh figure-of-merit for hydrogen generation from sodium borohydride using ternary metal catalysts

    Science.gov (United States)

    Hu, Lunghao; Ceccato, R.; Raj, R.

    We report further increase in the figure-of-merit (FOM) for hydrogen generation from NaBH 4 than reported in an earlier paper [1], where a sub-nanometer layer of metal catalysts are deposited on carbon nanotube paper (CNT paper) that has been functionalized with polymer-derived silicon carbonitride (SiCN) ceramic film. Ternary, Ru-Pd-Pt, instead of the binary Pd-Pt catalyst used earlier, together with a thinner CNT paper is shown to increase the figure-of-merit by up to a factor of six, putting is above any other known catalyst for hydrogen generation from NaBH 4. The catalysts are prepared by first impregnating the functionalized CNT-paper with solutions of the metal salts, followed by reduction in a sodium borohydride solution. The reaction mechanism and the catalyst efficiency are described in terms of an electric charge transfer, whereby the negative charge on the BH 4 - ion is exchanged with hydrogen via the electronically conducting SiCN/CNT substrate [1].

  8. A review of metal recovery from spent petroleum catalysts and ash.

    Science.gov (United States)

    Akcil, Ata; Vegliò, Francesco; Ferella, Francesco; Okudan, Mediha Demet; Tuncuk, Aysenur

    2015-11-01

    With the increase in environmental awareness, the disposal of any form of hazardous waste has become a great concern for the industrial sector. Spent catalysts contribute to a significant amount of the solid waste generated by the petrochemical and petroleum refining industry. Hydro-cracking and hydrodesulfurization (HDS) catalysts are extensively used in the petroleum refining and petrochemical industries. The catalysts used in the refining processes lose their effectiveness over time. When the activity of catalysts decline below the acceptable level, they are usually regenerated and reused but regeneration is not possible every time. Recycling of some industrial waste containing base metals (such as V, Ni, Co, Mo) is estimated as an economical opportunity in the exploitation of these wastes. Alkali roasted catalysts can be leached in water to get the Mo and V in solution (in which temperature plays an important role during leaching). Several techniques are possible to separate the different metals, among those selective precipitation and solvent extraction are the most used. Pyrometallurgical treatment and bio-hydrometallurgical leaching were also proposed in the scientific literature but up to now they did not have any industrial application. An overview on patented and commercial processes was also presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-02-20

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  10. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-03-03

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  11. Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

    Science.gov (United States)

    Zell, Thomas; Milstein, David

    2015-07-21

    The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in

  12. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts.

    Science.gov (United States)

    Varnell, Jason A; Tse, Edmund C M; Schulz, Charles E; Fister, Tim T; Haasch, Richard T; Timoshenko, Janis; Frenkel, Anatoly I; Gewirth, Andrew A

    2016-08-19

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

  13. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    Science.gov (United States)

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

    2017-06-01

    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

  14. Metal recovery from spent refinery catalysts by means of biotechnological strategies.

    Science.gov (United States)

    Beolchini, F; Fonti, V; Ferella, F; Vegliò, F

    2010-06-15

    A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts. Copyright 2010 Elsevier B.V. All rights reserved.

  15. Bimetallic platinum group metal-free catalysts for high power generating microbial fuel cells.

    Science.gov (United States)

    Kodali, Mounika; Santoro, Carlo; Herrera, Sergio; Serov, Alexey; Atanassov, Plamen

    2017-10-31

    M1-M2-N-C bimetallic catalysts with M1 as Fe and Co and M2 as Fe, Co, Ni and Mn were synthesized and investigated as cathode catalysts for oxygen reduction reaction (ORR). The catalysts were prepared by Sacrificial Support Method in which silica was the template and aminoantipyrine (AAPyr) was the organic precursor. The electro-catalytic properties of these catalysts were investigated by using rotating ring disk (RRDE) electrode setup in neutral electrolyte. Fe-Mn-AAPyr outperformed Fe-AAPyr that showed higher performances compared to Fe-Co-AAPyr and Fe-Ni-AAPyr in terms of half-wave potential. In parallel, Fe-Co-AAPyr, Co-Mn-AAPyr and Co-Ni-AAPyr outperformed Co-AAPyr. The presence of Co within the catalyst contributed to high peroxide production not desired for efficient ORR. The catalytic capability of the catalysts integrated in air-breathing cathode was also verified. It was found that Co-based catalysts showed an improvement in performance by the addition of second metal compared to simple Co- AAPyr. Fe-based bimetallic materials didn't show improvement compared to Fe-AAPyr with the exception of Fe-Mn-AAPyr catalyst that had the highest performance recorded in this study with maximum power density of 221.8 ± 6.6 μWcm -2 . Activated carbon (AC) was used as control and had the lowest performances in RRDE and achieved only 95.6 ± 5.8 μWcm -2 when tested in MFC.

  16. Extraction of metals from spent hydrotreating catalysts: physico-mechanical pre-treatments and leaching stage.

    Science.gov (United States)

    Ferella, Francesco; Ognyanova, Albena; De Michelis, Ida; Taglieri, Giuliana; Vegliò, Francesco

    2011-08-15

    The present paper is focused on physico-mechanical pre-treatments of spent hydrotreating catalysts aimed at concentration of at least one of the valuable metals contained in such secondary raw material. In particular, dry Ni-Mo and Co-Mo as well as wet Ni-Mo catalysts were used. Flotation, grain size separation and attrition processes were tested. After that, a rods vibrating mill and a ball mill were used to ground the catalysts in order to understand the best mechanical pre-treatment before leaching extraction. The results showed that flotation is not able to concentrate any metals due to the presence of coke or other depressant compounds. The particle size separation produces two fractions enriched in Mo and Co when dry Co-Mo catalyst is used, whereas attrition is not suitable as metals are uniformely distributed in rings' volume. Roasting at 550°C and vibrating grinding are the most suitable pre-treatments able to produce fractions easily leached by NaOH and H(2)SO(4) after grain size separation. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

    OpenAIRE

    Jyothi, Divya; Deshpande, Parag A; Venugopal, BR; Chandrasekaran, Srinivasan; Madras, Giridhar

    2012-01-01

    Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the...

  18. A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts

    OpenAIRE

    Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

    2012-01-01

    Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO3 and MnO2, were used as cathode catalysts, meanwhile CoO was us...

  19. Rational control of nano-scale metal-catalysts for biomass conversion.

    Science.gov (United States)

    Wang, Yunzhu; De, Sudipta; Yan, Ning

    2016-05-07

    Nano-scale metal particles have huge potential due to their wide range of diverse catalytic applications. Recently, they have found numerous applications in the field of biomass conversion. The proposed contribution is aimed at providing a brief account of remarkable recent findings and advances in the design of metal-based nanocatalysts for biomass valorization. We have discussed the rational control of the size, shape, composition and surface properties of nano-scale metal catalysts. Following that, the interplay between various structural parameters and the catalytic properties in the transformation of cellulose, chitin, lignin and lipids has been critically discussed.

  20. Preparation of chiral-at-metal catalysts and their use in asymmetric photoredox chemistry.

    Science.gov (United States)

    Ma, Jiajia; Zhang, Xiao; Huang, Xiaoqiang; Luo, Shipeng; Meggers, Eric

    2018-04-01

    Asymmetric catalysis is a powerful approach for the synthesis of optically active compounds, and visible light constitutes an abundant source of energy to enable chemical transformations, which are often triggered by photoinduced electron transfer (photoredox chemistry). Recently, bis-cyclometalated iridium(III) and rhodium(III) complexes were introduced as a novel class of catalysts for combining asymmetric catalysis with visible-light-induced photoredox chemistry. These catalysts are attractive because of their unusual feature of chirality originating exclusively from a stereogenic metal center, which offers the prospect of an especially effective asymmetric induction upon direct coordination of the substrate to the metal center. As these chiral catalysts contain only achiral ligands, special strategies are required for their synthesis. In this protocol, we describe strategies for preparing two types of chiral-at-metal catalysts, namely the Λ- and Δ-enantiomers (left- and right-handed propellers, respectively) of the iridium complex IrS and the rhodium complex RhS. Both contain two cyclometalating 5-tert-butyl-2-phenylbenzothiazoles in addition to two acetonitrile ligands and a hexafluorophosphate counterion. The two cyclometalated ligands set the propeller-shaped chiral geometry, but the acetonitriles are labile and can be replaced by substrate molecules. The synthesis protocol consists of three stages: first, preparation of the ligand 5-tert-butyl-2-phenylbenzothiazole; second, preparation of salicylthiazoline (used for iridium) and salicyloxazoline (used for rhodium) chiral auxiliaries; and third, the auxiliary-mediated synthesis of the individual enantiopure Λ- and Δ-configured catalysts. This class of stereogenic-only-at-metal complexes is of substantial value in the field of asymmetric catalysis, offering stereocontrolled radical reactions based on visible-light-activated photoredox chemistry. Representative examples of visible-light-induced asymmetric

  1. Sythesis of metal sulfide nanomaerials via thermal decomposition of single-source percursors

    Energy Technology Data Exchange (ETDEWEB)

    Jen-La Plante, Ilan; Zeid, Tahani W.; Yang, Peidong; Mokari, Taleb

    2010-06-03

    In this report, we present a synthetic method for the formation of cuprous sulfide (Cu2S) and lead sulfide (PbS) nanomaterials directly on substrates from the thermolysis of single-source precursors. We find that the final morphology and arrangement of the nanomaterials may be controlled through the concentration of the dissolved precursors and choice of solvent. One-dimensional (1-D) morphologies may also be grown onto substrates with the addition of a metal catalyst layer through solution-liquid-solid (SLS) growth. These synthetic techniques may be expanded to other metal sulfide materials.

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

    NARCIS (Netherlands)

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

    1993-01-01

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

  3. A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts.

    Science.gov (United States)

    Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

    2012-01-01

    Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO₃ and MnO₂, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW·cm⁻² has been achieved at 65°C, which increases by a factor of 1.7-3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC.

  4. A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts

    Science.gov (United States)

    Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

    2012-08-01

    Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO3 and MnO2, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW.cm-2 has been achieved at 65°C, which increases by a factor of 1.7-3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC.

  5. Metal oxides as heterogeneous catalysts for esterification of fatty acids obtained from soybean oil

    Energy Technology Data Exchange (ETDEWEB)

    Mello, Vinicius M.; Pousa, Gabriella P.A.G.; Pereira, Mirian S.C.; Dias, Ingrid M.; Suarez, Paulo A.Z. [Laboratorio de Materiais e Combustiveis, Instituto de Quimica, Universidade de Brasilia (Brazil)

    2011-01-15

    The growing demand for renewable energy sources stimulates the development of new technologies for biofuel production. Biodiesel synthesis by esterification of fatty acids is a favorable route, because, differently from transesterification, it does not produce glycerin and uses cheaper raw materials. In this work the study of metal oxides and their performance as Lewis acid catalysts in the esterification of fatty acids obtained from soybean oil presented promising results in heterogeneous catalysis, with reaction yields as high as 89%. The influence of variables such as temperature, reaction time and the amount of catalyst in the reaction yield was also evaluated. The possibility of recycling tin oxide was also studied, showing that it was possible to reuse the catalyst up to ten times without significant losses in its catalytic activity. (author)

  6. CO Hydrogenation over Transition Metals (Fe, Co, or Ni Modified K/Mo2C Catalysts

    Directory of Open Access Journals (Sweden)

    Minglin Xiang

    2013-01-01

    Full Text Available Transition metals (Fe, Co, or Ni modified K/Mo2C catalysts were prepared and investigated as catalysts for CO hydrogenation. The addition of Fe, Co, or Ni to K/Mo2C catalyst led to a sharp increase in both the activity and selectivity of C2+OH, but the promotion effects were quite different and followed the sequence: Ni > Co > Fe for the activity and Fe > Co > Ni for the alcohol selectivity. For the products distributions, it also displayed some differences; Co promoter showed much higher C5+ hydrocarbon selectivity than Fe or Ni promoter, but Fe or Co promoter gave lower methane selectivity than Ni promoter, and Fe promoter showed the highest C2=-C4= selectivity.

  7. A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts

    Science.gov (United States)

    Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

    2012-01-01

    Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO3 and MnO2, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW·cm−2 has been achieved at 65°C, which increases by a factor of 1.7–3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC. PMID:22880160

  8. Zeolites Modified Metal Cations as Catalysts in Hydrocarbon Oxidation and the Alkyl Alcohol

    Directory of Open Access Journals (Sweden)

    Agadadsh Makhmud Aliyev

    2014-09-01

    Full Text Available The results of studies on the creation of highly metalltceolitnyh systems and the study of their catalytic activities in the oxidation of lower olefin hydrocarbons (ethylene to acetaldehyde, acetone, propylene, butylene methyl ethyl ketone; aliphatic C1-C5 alcohols to their corresponding aldehydes, ketones, carboxylic acids and carboxylic acid esters; oxidative dehydrogenation of naphthenes in the alicyclic diene hydrocarbons and the oxidative dimerization of methane to acetylene. It has been established that the selectivity of these catalysts determined optimal combination of metal components with the acidity and the structure of the zeolite. Selected highly effective catalysts for the reactions studied. Based on the results of experimental studies of the kinetics of the reactions of oxidation of lower olefin hydrocarbons and aliphatic alcohols, the oxidative dehydrogenation of naphthenes and oxidative coupling of methane on the synthesized catalysts are represented by their probable stepwise mechanism and kinetic models developed reactions.

  9. Ni catalyst wash-coated on metal monolith with enhanced heat-transfer capability for steam reforming

    Science.gov (United States)

    Ryu, Jae-Hong; Lee, Kwan-Young; La, Howon; Kim, Hak-Joo; Yang, Jung-Il; Jung, Heon

    A commercial Ni-based catalyst is wash-coated on a monolith made of 50 μm-thick fecralloy plates. Compared with the same volume of coarsely powdered Ni catalysts, the monolith wash-coated Ni catalysts give higher methane conversion in the steam reforming reaction, especially at gas hourly space velocities (GHSV) higher than 28,000 h -1, and with no pressure drop. A higher conversion of the monolith catalyst is obtained, even though it contains a lower amount of active catalyst (3 g versus 17 g for a powdered catalyst), which indicates that the heat-transfer capability of the wash-coated Ni catalyst is significantly enhanced by the use of a metal monolith. The efficacy of the monolith catalyst is tested using a shell-and-tube type heat-exchanger reactor with 912 cm 3 of the monolith catalyst charged on to the tube side and hot combusted gas supplied to the shell side in a counter-current direction to the reactant flow. A methane conversion greater than 94% is obtained at a GHSV of 7300 h -1 and an average temperature of 640 °C. Nickel catalysts should first be reduced to become active for steam reforming. Doping a small amount (0.12 wt.%) of noble metal (Ru or Pt) in the commercial Ni catalyst renders the wash-coated catalyst as active as a pre-reduced Ni catalyst. Thus, noble metal-doped Ni appears useful for steam reforming without any pre-reduction procedure.

  10. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    Science.gov (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  11. Stability and Activity of Non-Noble-Metal-Based Catalysts Toward the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Ledendecker, Marc; Mondschein, Jared S; Kasian, Olga; Geiger, Simon; Göhl, Daniel; Schalenbach, Max; Zeradjanin, Aleksandar; Cherevko, Serhiy; Schaak, Raymond E; Mayrhofer, Karl

    2017-08-07

    A fundamental understanding of the behavior of non-noble based materials toward the hydrogen evolution reaction is crucial for the successful implementation into practical devices. Through the implementation of a highly sensitive inductively coupled plasma mass spectrometer coupled to a scanning flow cell, the activity and stability of non-noble electrocatalysts is presented. The studied catalysts comprise a range of compositions, including metal carbides (WC), sulfides (MoS 2 ), phosphides (Ni 5 P 4 , Co 2 P), and their base metals (W, Ni, Mo, Co); their activity, stability, and degradation behavior was elaborated and compared to the state-of-the-art catalyst platinum. The non-noble materials are stable at HER potentials but dissolve substantially when no current is flowing. Through pre- and post-characterization of the catalysts, explanations of their stability (thermodynamics and kinetics) are discussed, challenges for the application in real devices are analyzed, and strategies for circumventing dissolution are suggested. The precise correlation of metal dissolution with applied potential/current density allows for narrowing down suitable material choices as replacement for precious group metals as for example, platinum and opens up new ways in finding cost-efficient, active, and stable new-generation electrocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Molecular polypyridine-based metal complexes as catalysts for the reduction of CO2.

    Science.gov (United States)

    Elgrishi, Noémie; Chambers, Matthew B; Wang, Xia; Fontecave, Marc

    2017-02-06

    Polypyridyl transition metal complexes represent one of the more thoroughly studied classes of molecular catalysts towards CO 2 reduction to date. Initial reports in the 1980s began with an emphasis on 2nd and 3rd row late transition metals, but more recently the focus has shifted towards earlier metals and base metals. Polypyridyl platforms have proven quite versatile and amenable to studying various parameters that govern product distribution for CO 2 reduction. However, open questions remain regarding the key mechanistic steps that govern product selectivity and efficiency. Polypyridyl complexes have also been immobilized through a variety of methods to afford active catalytic materials for CO 2 reductions. While still an emerging field, materials incorporating molecular catalysts represent a promising strategy for electrochemical and photoelectrochemical devices capable of CO 2 reduction. In general, this class of compounds remains the most promising for the continued development of molecular systems for CO 2 reduction and an inspiration for the design of related non-polypyridyl catalysts.

  13. Hydrogenation of nitrocompounds with supported palladium catalysts: influence of metal dispersion and nitrocompound nature

    Energy Technology Data Exchange (ETDEWEB)

    Carturan, G.; Facchin, G.; Cocco, G.; Navazio, G.; Gubitosa, G.

    1983-07-01

    Nitrobenzene, Et-NO/sub 2/, and t-Bu-NO/sub 2/ are hydrogenated to corresponding amines using Pd catalysts in n-octane suspension at 90/sup 0/C and at constant H/sub 2/ pressure. Nitrobenzene reduction to aniline has been studied with several Pd catalysts having a different degree of metal dispersion determined by X-ray methods and chemisorption analysis. Results indicate that the process is a structure sensitive reaction; a peculiar lowering in catalytic activity as the degree of Pd dispersion increases is observed. This fact is discussed in terms of metallic surface oxidation due to the sorbed nitrocompound. Hydrogenation kinetic patterns change with the nature of the nitrocompound. Reduction of Et-NO/sub 2/ and t-Bu-NO/sub 2/ depends on substrate concentration, while nitrobenzene hydrogenation is independent of this parameter. The relevant kinetic experiments allow the formulation of a general reaction mechanism accounting for the different kinetic patterns observed on changing the substrate. The discussion illustrates the possibility that in nitrocompound reduction with metal catalysts the rate determining step may be hydrogenation of the metallic surface oxidized by the sorbed nitrocompound.

  14. Transition Metal Sulfide Hydrogen Evolution Catalysts for Hydrobromic Acid Electrolysis

    NARCIS (Netherlands)

    Ivanovskaya, Anna; Singh, Nirala; Liu, Ru-Fen; Kreutzer, Haley; Baltrusaitis, Jonas; Nguyen, Trung Van; Metiu, Horia; McFarland, Eric

    2013-01-01

    Mixed metal sulfides containing combinations of W, Fe, Mo, Ni, and Ru were synthesized and screened for activity and stability for the hydrogen evolution reaction (HER) in aqueous hydrobromic acid (HBr). Co- and Ni-substituted RuS2 were identified as potentially active HER electrocatalysts by

  15. Ultrasound-driven design of new mesoporous metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Univ. Bayreuth (Germany); Skorb, Ekaterina [Max-Planck-Institut fuer Kolloid- und Grenzflaechenforschung, Golm (Germany)

    2011-07-01

    Mesoporous metal nanocomposites were formed by a ''green chemistry'' method with ultrasound irradiation. The sonication technique combines the fabrication of a mesoporous support consisting of metallic particles (Al, Mg) several tens of micrometers in size and the subsequent incorporation of metal (Ag, Au, Pt etc.) nanoparticles into its pores. Next to filling the mesoporous support with particles we are also able to form mesoporous alloys e.g. AlNi or CoAlFe. The resulting material is analyzed by transmission electron microscopy, powder X-ray diffraction, small-angle neutron scattering and the Brunauer-Emmett-Teller and the Barrett-Joyner-Halenda method. Surface areas up to 200 m{sup 2}/g with a narrow pore size distribution around 3 nm can be achieved. The mesoporous structures are analyzed by confocal light microscopy after coloring the particles with dye. We explain the formation of the mesoporous inner structures by the following mechanism: Thermal etching and recrystallization of metals by ultrasound-stimulated high-speed jets of liquid form the porous structure that is stabilized by surface oxidation through free radicals generated during cavitation. We expect this approach to be universal and opening perspectives for a whole new class of catalytic materials that can be prepared in a fairly easy and cost effective way.

  16. Scattering cross section of metal catalyst atoms in silicon nanowires

    DEFF Research Database (Denmark)

    Markussen, Troels; Rurali, R.; Cartoixa, X.

    2010-01-01

    strength of the different metal atoms. We find that Au, Ag, and Cu impurities have very similar scattering cross sections, while Al differs from the rest. Impurities located in the center of the wires scatter significantly more than impurities close to or at the surface. The results for nanowires...

  17. Oxidatively Electrodeposited Thin-Film Transition Metal (Oxy)hydroxides as Oxygen Evolution Catalysts.

    Science.gov (United States)

    Morales-Guio, Carlos G; Liardet, Laurent; Hu, Xile

    2016-07-20

    The electrolysis of water to produce hydrogen and oxygen is a simple and attractive approach to store renewable energies in the form of chemical fuels. The oxygen evolution reaction (OER) is a complex four-electron process that constitutes the most energy-inefficient step in water electrolysis. Here we describe a novel electrochemical method for the deposition of a family of thin-film transition metal (oxy)hydroxides as OER catalysts. The thin films have nanodomains of crystallinity with lattice spacing similar to those of double-layered hydroxides. The loadings of these thin-film catalysts were accurately determined with a resolution of below 1 μg cm(-2) using an electrochemical quartz microcrystal balance. The loading-activity relations for various catalysts were established using voltammetry and impedance spectroscopy. The thin-film catalysts have up to four types of loading-activity dependence due to film nucleation and growth as well as the resistance of the films. A zone of intrinsic activity has been identified for all of the catalysts where the mass-averaged activity remains constant while the loading is increased. According to their intrinsic activities, the metal oxides can be classified into three categories: NiOx, MnOx, and FeOx belong to category I, which is the least active; CoOx and CoNiOx belong to category II, which has medium activity; and FeNiOx, CoFeOx, and CoFeNiOx belong to category III, which is the most active. The high turnover frequencies of CoFeOx and CoFeNiOx at low overpotentials and the simple deposition method allow the fabrication of high-performance anode electrodes coated with these catalysts. In 1 M KOH and with the most active electrode, overpotentials as low as 240 and 270 mV are required to reach 10 and 100 mA cm(-2), respectively.

  18. Hierarchical zeolites: progress on synthesis and characterization of mesoporous zeolite single crystal catalysts

    DEFF Research Database (Denmark)

    Kustova, Marina; Egeblad, Kresten; Christensen, Claus H.

    2007-01-01

    in a hierarchical pore size distribution. In this work, the preparation of mesoporous ZSM-12 single crystal catalysts using a new improved procedure for directly introducing carbon in the reaction mixture is reported. The microwave heating technique is also applied for the synthesis of mesoporous silicalite-1...... measurements. Additionally, the results of diffusion of n-hexadecane in conventional and mesoporous zeolites are presented. Isomerization and cracking of n-hexadecane was chosen as model test reaction for these materials. All results support that mesoporous zeolites are superior catalysts due to improved mass...

  19. A comparative study of metal oxide and sulfate catalysts for selective catalytic reduction of NO with NH3.

    Science.gov (United States)

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

    2017-05-01

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

  20. Stereospecific olefin polymerization with chiral metallocene catalysts

    OpenAIRE

    Brintzinger, Hans-Herbert; Fischer, David; Mülhaupt, Rolf; Rieger, Bernhard; Waymouth, Robert M.

    1995-01-01

    Current studies on novel, metallocenebased catalysts for the polymerization of α-olefins have far-reaching implications for the development of new materials as well as for the understanding of basic reaction mechanisms responsible for the growth of a polymer chain at a catalyst center and the control of its stereoregularity. In contrast to heterogeneous Ziegler–Natta catalysts, polymerization by a homogeneous, metallocene-based catalyst occurs principally at a single type of metal center with...

  1. Electro catalyst in the last 30 years - from precious metals to cheaper but sophisticated complex systems

    International Nuclear Information System (INIS)

    Hadzi Jordanov, Svetomir; Paunovic, Perica; Dimitrov, Aleksandar; Slavkov, Dragan; Popovski, Orce

    2004-01-01

    The paper is concerned with the advance and diversification of materials used as electrodes for evolution of chlorine, hydrogen and oxygen. In the first part a survey is given of our research in the field of electro catalysis 30 years ago, when Ru and other precious metals were the exclusive electro catalyst materials. A brief scope of the achievements of electro catalysis in that period is given as well. The second part deals with our recent research on formulation and characterization of a new class of electrocatalysts, based on a combination of non-precious metals, but still exhibiting an ability to promote hydrogen evolution reaction as successful as platinum and other precious metals are. Among the produced (non-platinum) catalysts the best performance for the hydrogen evolution reaction was measured at the electro catalyst containing Co or CoNi as hyper d phase and TiO 2 as hypo d phase. A typical formulation of the electrodes is, e.g.: 18% (TiO 2 ) alloyed with 10% Co and applied on a substrat of carbon powder (Vulcan XC-72). At this electro catalyst hydrogen evolution overpotential at 10 mA·cm -2 was 40 mV higher than that on a corresponding electrode containing platinum as hyper d phase. For both electro catalyst systems of interest analysis is made and aimed to recognize the sources that cause the electrocatalytic activity. This is the proper way how to use the acquired knowledge for further improvement of the existing materials or/and to discover new ones. (Author)

  2. Novel application of a Fe-Zn double-metal cyanide catalyst in the synthesis of biodegradable, hyperbranched polymers.

    Science.gov (United States)

    Sebastian, Joby; Srinivas, Darbha

    2011-10-07

    The use of Fe-Zn double-metal cyanide as a solid catalyst for synthesizing biodegradable, hyperbranched polymers from diacids and glycerol has been reported, for the first time, wherein acidity, micro-mesoporosity and hydrophobicity of the catalyst played an important role in controlling gelation. This journal is © The Royal Society of Chemistry 2011

  3. Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

    Science.gov (United States)

    A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

  4. 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.

  5. Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

    NARCIS (Netherlands)

    Yin, Wang; Venderbosch, Robbie H.; He, Songbo; Bykova, Maria V.; Khromova, Sofia A.; Yakovlev, Vadim A.; Heeres, Hero J.

    Catalytic hydrotreatment is a promising technology to convert pyrolysis liquids into intermediates with improved properties. Here, we report a catalyst screening study on the catalytic hydrotreatment of pyrolysis liquids using bi- and tri-metallic nickel-based catalysts in a batch autoclave (initial

  6. Rapid accurate analysis of metal (oxide)-on-silica catalysts by atomic absorption spectrometry

    NARCIS (Netherlands)

    Jütte, B.A.H.G.; Heikamp, A.; Agterdenbos, J.

    1979-01-01

    The catalysts, which contain 10–60% copper, chromium, nickel and silicon, are decomposed in sealed Teflon-lined vessels and analyzed by atomic absorption spectrometry. Matrix matching and bracketing standards are applied. The RSD of a single determination is about 1% for all components.

  7. Biogenic metallic nanoparticles as catalyst for bioelectricity production: A novel approach in microbial fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Saravanakumar, Kandasamy, E-mail: saravana732@gmail.com [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai (China); State Key Laboratory of Microbial Metabolism, Shanghai Jiao Tong University, Shanghai (China); Key Laboratory of Urban Agriculture (South), Ministry of Agriculture, Shanghai (China); MubarakAli, Davoodbasha [Microbial Genetic Engineering Laboratory, Division of Bioengineering, College of Life Science and Bioengineering, Incheon National University, Songdo 406772, Incheon (Korea, Republic of); Department of Microbiology, School of Lifesciences, Bharathidasan University, Tiruchirappalli 620024 (India); Kathiresan, Kandasamy [Centre of Advanced Study in Marine Biology, Faculty of Marine Sciences, Annamalai University, Parangipettai 608 502, Tamil Nadu (India); Thajuddin, Nooruddin [Department of Microbiology, School of Lifesciences, Bharathidasan University, Tiruchirappalli 620024 (India); Department of Botany and Microbiology, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Alharbi, Naiyf S. [Department of Botany and Microbiology, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Chen, Jie, E-mail: jiechen59@sjtu.edu.cn [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai (China); State Key Laboratory of Microbial Metabolism, Shanghai Jiao Tong University, Shanghai (China); Key Laboratory of Urban Agriculture (South), Ministry of Agriculture, Shanghai (China)

    2016-01-15

    Highlights: • Trichoderma sp., showed an abilities to synthesis of AgNPs and AuNPs with an excellent stability. • AuNPs significantly enhanced the bioelectricity production by MFC of anaerobic fermentation as catalyst. • Maximum bioelectricity production was optimized and obtained the voltage of 432.80 mA using RSM. - Abstract: The present work aimed to use the biogenic metallic nanoparticles as catalyst for bioelectricity production in microbial fuel cell (MFC) approach under anaerobic condition. Silver and gold nanoparticles (AuNPs) were synthesized using Trichoderma sp. Particle size and cystallinity were measured by X-ray diffraction revealed the crystalline structure with average size of 36.17 nm. Electron microscopic studies showed spherical shaped silver nanoparticles (AgNPs) and cubical shaped AuNPs with size ranges from 50 to 150 nm. The concentration of biogenic metallic nanoparticles as catalyst for enhanced bioelectricity generations and estimated by response surface methodology (RSM) and found at the greatest of 342.80 mA under optimized conditions are time interval, temperature, nanoparticles used as 63 h, 28 ± 2.0 °C, 22.54 mg l{sup −1} (AgNPs) and 25.62 mg l{sup −1} (AuNPs) in a batch reactor. AuNPs acted as an excellent catalyst to enhance the bioelectricity production. This novel technique could be used for eco-friendly, economically feasible and facile electricity production.

  8. Nitrogen-Doped Activated Carbon as Metal-Free Catalysts Having Various Functions

    Directory of Open Access Journals (Sweden)

    Shin-Ichiro Fujita

    2017-10-01

    Full Text Available Nitrogen-doped carbon materials have been gaining increasing interest as metal-free catalysts. In this article, the authors have briefly introduced their recent studies on the utilization of nitrogen-doped activated carbon (N-AC for several organic synthesis reactions, which include base catalyzed reactions of Knoevenagel condensation and transesterification, aerobic oxidation of xanthene and alcohols, and transfer hydrogenation of nitrobenzene, 3-nitrostyrene, styrene, and phenylacetylene with hydrazine. Doped-nitrogen species existed on the AC surface in different structures. For example, pyridine-type nitrogen species appear to be involved in the active sites for Knoevenagel condensation and for the oxidation of xanthene, while graphite-type nitrogen species appear to be involved for the oxidation of alcohols. Being different from these reactions, both surface nitrogen and oxygen species are involved in the active sites for the hydrogenation of nitrobenzene. N-AC was practically inactive for the transfer hydrogenation of vinyl and ethynyl groups, but it can catalyze those hydrogenation reactions assisted by co-existing nitrobenzene. Comparison of N-AC with conventional catalysts shows that N-AC can alternate with conventional solid base catalysts and supported metal catalysts for the Knoevenagel condensation and oxidation reactions.

  9. Single-Site Heterogeneous Catalysts: Innovations, Advantages, and Future Potential in Green Chemistry and Sustainable Technology

    Science.gov (United States)

    Raja, Robert; Thomas, John Meurig

    The advantages that flow from the availability of single-site heterogeneous catalysts are many. They facilitate the determination of the kinetics and mechanism of catalytic turnover and render accessible the energetics of various intermediates. More importantly, it is possible to prepare soluble molecular fragments that circumscribe the single site, thus enabling a direct comparison to be made between the catalytic performance of the same active site when functioning as a heterogeneous or a homogeneous catalyst. Our approach adopts the principles and practices of solid-state chemistry, augmented by lessons derived from enzymology, as well as computational chemistry. We have succeeded in designing a range of new catalysts to effect, inter alia, shape-selective, regioselective, bifunctional, and enantioselective catalytic conversions. In particular, large fractions of these catalysts are ideally suited for the era of clean technology in which single-step and/or solvent-free processes abound, and in which benign oxidants such as air or oxygen and inexpensive nanoporous materials are employed.

  10. Single-Atom Pd₁/Graphene Catalyst Achieved by Atomic Layer Deposition: Remarkable Performance in Selective Hydrogenation of 1,3-Butadiene.

    Science.gov (United States)

    Yan, Huan; Cheng, Hao; Yi, Hong; Lin, Yue; Yao, Tao; Wang, Chunlei; Li, Junjie; Wei, Shiqiang; Lu, Junling

    2015-08-26

    We reported that atomically dispersed Pd on graphene can be fabricated using the atomic layer deposition technique. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy both confirmed that isolated Pd single atoms dominantly existed on the graphene support. In selective hydrogenation of 1,3-butadiene, the single-atom Pd1/graphene catalyst showed about 100% butenes selectivity at 95% conversion at a mild reaction condition of about 50 °C, which is likely due to the changes of 1,3-butadiene adsorption mode and enhanced steric effect on the isolated Pd atoms. More importantly, excellent durability against deactivation via either aggregation of metal atoms or carbonaceous deposits during a total 100 h of reaction time on stream was achieved. Therefore, the single-atom catalysts may open up more opportunities to optimize the activity, selectivity, and durability in selective hydrogenation reactions.

  11. Atomic Resolution Imaging of Nanoscale Structural Ordering in a Complex Metal Oxide Catalyst

    KAUST Repository

    Zhu, Yihan

    2012-08-28

    The determination of the atomic structure of a functional material is crucial to understanding its "structure-to-property" relationship (e.g., the active sites in a catalyst), which is however challenging if the structure possesses complex inhomogeneities. Here, we report an atomic structure study of an important MoVTeO complex metal oxide catalyst that is potentially useful for the industrially relevant propane-based BP/SOHIO process. We combined aberration-corrected scanning transmission electron microscopy with synchrotron powder X-ray crystallography to explore the structure at both nanoscopic and macroscopic scales. At the nanoscopic scale, this material exhibits structural and compositional order within nanosized "domains", while the domains show disordered distribution at the macroscopic scale. We proposed that the intradomain compositional ordering and the interdomain electric dipolar interaction synergistically induce the displacement of Te atoms in the Mo-V-O channels, which determines the geometry of the multifunctional metal oxo-active sites.

  12. Growth of carbon nanocone arrays on a metal catalyst: The effect of carbon flux ionization

    International Nuclear Information System (INIS)

    Levchenko, I.; Khachan, J.; Vladimirov, S. V.; Ostrikov, K.

    2008-01-01

    The growth of carbon nanocone arrays on metal catalyst particles by deposition from a low-temperature plasma is studied by multiscale Monte Carlo/surface diffusion numerical simulation. It is demonstrated that the variation in the degree of ionization of the carbon flux provides an effective control of the growth kinetics of the carbon nanocones, and leads to the formation of more uniform arrays of nanostructures. In the case of zero degree of ionization (neutral gas process), a width of the distribution of nanocone heights reaches 360 nm with the nanocone mean height of 150 nm. When the carbon flux of 75% ionization is used, the width of the distribution of nanocone heights decreases to 100 nm, i.e., by a factor of 3.6. A higher degree of ionization leads to a better uniformity of the metal catalyst saturation and the nanocone growth, thus contributing to the formation of more height-uniform arrays of carbon nanostructures.

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

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  14. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

    2017-09-26

    To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

  15. A Phenomenological Study on the Synergistic Role of Precious Metals and the Support in the Steam Reforming of Logistic Fuels on Monometal Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Abdul-Majeed Azad

    2010-01-01

    Full Text Available Clean power source utilizing vast logistic fuel reserves (jet fuels, diesel, and coal would be the main driver in the 21st century for high efficiency. Fuel processors are required to convert these fuels into hydrogen-rich reformate for extended periods in the presence of sulfur, and deliver hydrogen with little or no sulfur to the fuel cell stack. However, the jet and other logistic fuels are invariably sulfur-laden. Sulfur poisons and deactivates the reforming catalyst and therefore, to facilitate continuous uninterrupted operation of logistic fuel processors, robust sulfur-tolerant catalysts ought to be developed. New noble metal-supported ceria-based sulfur-tolerant nanocatalysts were developed and thoroughly characterized. In this paper, the performance of single metal-supported catalysts in the steam-reforming of kerosene, with 260 ppm sulfur is highlighted. It was found that ruthenium-based formulation provided an excellent balance between hydrogen production and stability towards sulfur, while palladium-based catalyst exhibited rapid and steady deactivation due to the highest propensity to sulfur poisoning. The rhodium supported system was found to be most attractive in terms of high hydrogen yield and long-term stability. A mechanistic correlation between the role of the nature of the precious metal and the support for generating clean desulfurized H2-rich reformate is discussed.

  16. A novel dynamic kinetic model of oxygen isotopic exchange on a supported metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Galdikas, Arvaidas; Duprez, Daniel; Descorme, Claude

    2004-09-15

    A time-resolved kinetic analysis has been developed for modeling experimental results of {sup 18}O/{sup 16}O isotopic exchange over oxide-supported metal catalysts. Model is based on two very important points: (1) the parallel calculation of surface and bulk diffusion and (2) the implication of certain O species such as superoxides. The model includes adsorption-desorption processes on metal clusters and oxygen spillover from the metal to the surface of support and vice versa. Different mechanisms of exchange were also taken into account via mononuclear (O atoms, O{sup -}, OH) or binuclear (superoxides) oxygen species. A refined model taking into account surface diffusion, direct exchange on surface of support by binuclear oxygen species and bulk diffusion was also developed. Kinetic (reaction rates and diffusion coefficients) as well as thermodynamic parameters (activation energies) were derived by fitting theoretical and experimental curves of {sup 18}O{sub 2}, {sup 18}O{sup 16}O and {sup 16}O{sub 2} gas phase concentrations versus time. The experimental results of Pt/CeZrO{sub 2} catalyst samples obtained in the 200-450 deg. C range of temperatures are examined. The refined model provides a very good fitting of the kinetic curves recorded with ceria-zirconia-supported catalysts. Moreover, values of diffusion coefficients and activation energies are in good agreement with already published values found by other methods. For a better understanding of all the steps of exchange, the kinetics of {sup 18}O and {sup 16}O distribution on the surface of metal clusters and on the surface of support are calculated and analyzed. On the basis of this model, a computer code is developed for analysis and calculations of kinetic and thermodynamic parameters of automotive catalysts.

  17. Graphene from Alginate Pyrolysis as a Metal-Free Catalyst for Hydrogenation of Nitro Compounds.

    Science.gov (United States)

    Trandafir, Mihaela-Mirela; Florea, Mihaela; Neaţu, Florentina; Primo, Ana; Parvulescu, Vasile I; García, Hermenegildo

    2016-07-07

    Graphene obtained by pyrolysis of alginate at 900 °C under inert atmosphere and exfoliation is used as a metal-free catalyst for reduction of nitro to amino groups with hydrogen as a reagent. The process is general for aromatic and aliphatic, conjugated and isolated nitro groups, and occurs with low selectivity over hydrogenation of carbon-carbon double bonds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Pd Metal Catalysts for Cross-Couplings and Related Reactions in the 21st Century: A Critical Review.

    Science.gov (United States)

    Biffis, Andrea; Centomo, Paolo; Del Zotto, Alessandro; Zecca, Marco

    2018-02-28

    Cross-couplings and related reactions are a class of highly efficient synthetic protocols that are generally promoted by molecular Pd species as catalysts. However, catalysts based on more or less highly dispersed Pd metal have been also employed for this purpose, and their use, which was largely limited to the Heck reaction until the turn of the century, has been extended in recent years to most reactions of this class. This review provides a critical overview on these recent applications of Pd metal catalysts. Particular attention is devoted to the discussion of the mechanistic pathways that have been proposed to explain the catalytic role of Pd metal. Furthermore, the most outstanding Pd metal based catalytic systems that have emerged are illustrated, together with the development of novel approaches to boost the reactivity of Pd metal. A section summarizing the current industrial applications of Pd metal catalyzed reactions of this kind concludes the review.

  19. A Rh III-N-heterocyclic carbene complex from metal-metal singly ...

    Indian Academy of Sciences (India)

    Metal-metal singly bonded [Rh2(CO)4(acac)2][OTf]2 (1) has been synthesized and characterized by spectroscopic and analytical techniques. A density functional theory ... to each rhodium. This work demonstrates the general utility of the metal-metal bonded compounds for the easy synthesis of metal-NHC compounds.

  20. High-Performance Transition Metal Phosphide Alloy Catalyst for Oxygen Evolution Reaction.

    Science.gov (United States)

    Liu, Kewei; Zhang, Changlin; Sun, Yuandong; Zhang, Guanghui; Shen, Xiaochen; Zou, Feng; Zhang, Haichang; Wu, Zhenwei; Wegener, Evan C; Taubert, Clinton J; Miller, Jeffrey T; Peng, Zhenmeng; Zhu, Yu

    2018-01-23

    Oxygen evolution reaction (OER) is a pivotal process in many energy conversion and storage techniques, such as water splitting, regenerative fuel cells, and rechargeable metal-air batteries. The synthesis of stable, efficient, non-noble metal-based electrocatalysts for OER has been a long-standing challenge. In this work, a facile and scalable method to synthesize hollow and conductive iron-cobalt phosphide (Fe-Co-P) alloy nanostructures using an Fe-Co metal organic complex as a precursor is described. The Fe-Co-P alloy exhibits excellent OER activity with a specific current density of 10 mA/cm 2 being achieved at an overpotential as low as 252 mV. The current density at 1.5 V (vs reversible hydrogen electrode) of the Fe-Co-P catalyst is 30.7 mA/cm 2 , which is more than 3 orders of magnitude greater than that obtained with state-of-the-art Fe-Co oxide catalysts. Our mechanistic experiments and theoretical analysis suggest that the electrochemical-induced high-valent iron stabilizes the cobalt in a low-valent state, leading to the simultaneous enhancement of activity and stability of the OER catalyst.

  1. Activated Carbon Supported Mo-Ti-N Binary Transition Metal Nitride as Catalyst for Acetylene Hydrochlorination

    Directory of Open Access Journals (Sweden)

    Hui Dai

    2017-06-01

    Full Text Available Recently, many scientists have focused on the development of green industrial technology. However, the process of synthesizing vinyl chloride faces the problem of Hg pollution. Via a novel approach, we used two elements Mo and Ti to prepare an inexpensive and green binary transition metal nitride (BTMN as the active ingredient in a catalyst with nano-sized particles and an excellent degree of activation, which was supported on activated carbon. When the Mo/Ti mole ratio was 3:1, the conversion of acetylene reached 89% and the selectivity exceeded 98.5%. The doping of Ti in Mo-based catalysts reduced the capacity of adsorption for acetylene and also increased the adsorption of hydrogen chloride. Most importantly, the performance of the BTMN excelled those of the individual transition metal nitrides, due to the synergistic activity between Mo and Ti. This will expand the new epoch of the employment of transition metal nitrides as catalysts in the hydrochlorination of acetylene reaction.

  2. Oxidation of ethoxylated fatty alcohols to alkylpolyglycol carboxylic acids using noble metals as catalysts

    Directory of Open Access Journals (Sweden)

    Sagredos, Angelos

    2009-09-01

    Full Text Available The conversion of ethoxylated fatty alcohols to the corresponding carboxylic acids through dehydrogenation/ oxidation using noble-metal catalysts has been studied. Ethoxylated primary aliphatic alcohols, ethoxylated random secondary aliphatic alcohols and ethoxylated alkylphenols have been converted to the corresponding acids in the presence of a base. The noble metal catalysts Palladium and Platinum were used without significant degradation of the ethoxyl chain in yields that exceeded 90%. On the other hand, the catalysts Rhodium and Ruthenium gave yields of about 80% and 60% respectively.La conversión de alcoholes grasos etoxilados a los correspondientes ácidos carboxílicos por deshidrogenación/ oxidación con metales nobles como catalizador ha sido estudiada. Alcoholes primarios alifáticos etoxilados, alcoholes alifáticos secundarios etoxilados al azar y alquilfenoles etoxilados han sido convertidos a los correspondientes ácidos en presencia de base. Los catalizadores paladio y platino fueron usados sin degradación significativa de las cadenas etoxiladas con un rendimiento que excedió del 90%. Por otra parte catalizadores de rodio y rutenio produjeron rendimientos del 80 y 60%, respectivamente.

  3. Ceria doped mixed metal oxide nanoparticles as oxidation catalysts: Synthesis and their characterization

    OpenAIRE

    Sultana, S.S.P.; Kishore, D.H.V.; Kuniyil, Mufsir; Khan, Mujeeb; Alwarthan, Abdulrahman; Prasad, K.R.S.; Labis, Joselito P.; Adil, S.F.

    2015-01-01

    Mixed metal nanoparticles (NPs) have attracted significant attention as catalysts for various organic transformations. In this study, we have demonstrated the preparation of nickel–manganese mixed metal oxide NPs doped with X% nano cerium oxide (X = 1, 3, 5 mol%) by a facile co-precipitation technique using surfactant and surfactant free methodologies. The as-synthesized materials were calcined at different temperatures (300 °C, 400 °C, and 500 °C), and were characterized using various spectr...

  4. Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating

    Energy Technology Data Exchange (ETDEWEB)

    Abney, Carter W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Patterson, Jacob T. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Gilhula, James C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Wang, Li [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Hensley, Dale K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Chen, Jihua [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Foo, Guo Shiou [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Wu, Zili [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Dai, Sheng [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry

    2017-06-08

    Precise control over the chemical structure of hard-matter materials is a grand challenge of basic science and a prerequisite for the development of advanced catalyst systems. In this work we report the application of a sacrificial metal-organic framework (MOF) template for the synthesis of a porous supported metal oxide catalyst, demonstrating proof-of-concept for a highly generalizable approach to the preparation new catalyst materials. Application of 2,2’-bipyridine-5,5’-dicarboxylic acid as the organic strut in the Ce MOF precursor results in chelation of Cu2+ and affords isolation of the metal oxide precursor. Following pyrolysis of the template, homogeneously dispersed CuO nanoparticles are formed in the resulting porous CeO2 support. By partially substituting non-chelating 1,1’-biphenyl-4,4’-dicarboxylic acid, the Cu2+ loading and dispersion can be finely tuned, allowing precise control over the CuO/CeO2 interface in the final catalyst system. Characterization by x-ray diffraction, x-ray absorption fine structure spectroscopy, and in situ IR spectroscopy/mass spectrometry confirm control over interface formation to be a function of template composition, constituting the first report of a MOF template being used to control interfacial properties in a supported metal oxide. Using CO oxidation as a model reaction, the system with the greatest number of interfaces possessed the lowest activation energy and better activity under differential conditions, but required higher temperature for catalytic onset and displayed inferior efficiency at 100 °C than systems with higher Cu-loading. This finding is attributable to greater CO adsorption in the more heavily-loaded systems, and indicates catalyst performance for these supported oxide systems to be a function of at least two parameters: size of adsorption site and extent of interface. In conclusion, optimization of catalyst materials thus requires precise control

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

    KAUST Repository

    Date, Nandan S

    2018-03-20

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

  6. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

    2017-09-26

    It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

  7. Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts

    International Nuclear Information System (INIS)

    Li, Zhe-Fei; Wang, Yuxuan; Botte, Gerardine G.

    2017-01-01

    Highlights: • A procedure to pretreat electrocatalysts to study the ammonia oxidation is provided. • N ads and O/OH ads were identified as the major deactivation species that prevent ammonia oxidatoin. • The electrocatalytic activity, thermodynamics, and possible deactivation mechanisms for ammonia oxidation were elucidated. • The onset potential for ammonia oxidation is related to the hydrogen binding energy of the catalyst. • Ammonia electro-oxidation involves a complex decoupled electron and proton transfer process. - Abstract: The ammonia electro-oxidation reaction (AOR) has been studied due to its promising applications in ammonia electrolysis, wastewater remediation, direct ammonia fuel cells, and sensors. However, it is difficult to compare and analyze the reported electrocatalytic activity of AOR reliably, likely due to the variation in catalyst synthesis, electrode composition, electrode morphology, and testing protocol. In this paper, the electro-oxidation of ammonia on different carbon-supported precious metal nanoparticle catalysts was revisited. The effect of experimental conditions, electrochemical test parameters, electrocatalytic activity, thermodynamics, and possible deactivation mechanism of the catalysts were investigated. Pt/C catalyst possesses the highest electrocatalytic activity, while Ir/C and Rh/C show lower overpotential. The onset potential of the AOR is related to the hydrogen binding energy of the catalyst. N ads is one major cause of deactivation accompanied with the formation of surface O/OH ads at high potentials. The coulombic efficiency of N ads formation on Pt is about 1% initially and gradually decreases with reaction time. Increase in ammonia concentration leads to increase in current density, while increase in hydroxyl ions concentration can enhance the current density and reduce the overpotential simultaneously. The slopes of AOR onset potential and hydrogen adsorption/desorption potential of Pt/C as a function of p

  8. Chitosan-coated Silica Nanoparticles - A Potential Support for Metal Particles used as Heterogeneous Catalyst

    International Nuclear Information System (INIS)

    Haghighizadeh, A.; Abu Bakar, M.; Ghani, S.A.; Abu Bakar, N.H.H.

    2011-01-01

    In this work a strategy to immobilize noble metal nanoparticles on silica microspheres is proposed. In order to achieve this, monodispersed silica nanoparticles of an average size of 63.5±6.7 nm were synthesized via sol-gel method. Then chitosan was coated onto the silica to create a core/ shell composite with the size range of 66.56±9.78 nm to 79.18±11.87 nm. The noble metal nanoparticles were then synthesized on the shell of the composite through coordination of the respective metal ions to the polymer followed by the subsequent reduction. In this way, the silver particles of average size 6.17±1.83 nm, 9.85±2.60 nm, and 11.80±4.26 nm have been synthesized on the shell successfully. The optimized supported metal particles can be used as a potential heterogeneous catalyst. (author)

  9. Metal–organic and covalent organic frameworks as single-site catalysts

    Science.gov (United States)

    Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-Suarez, A. I.; Sepúlveda-Escribano, A.; Vimont, A.; Clet, G.; Bazin, P.; Kapteijn, F.

    2017-01-01

    Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions. PMID:28338128

  10. The physical and chemical properties of nanostructured mixed-metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Li [Texas A & M Univ., College Station, TX (United States); Goodman, David Wayne [Texas A & M Univ., College Station, TX (United States)

    2016-04-21

    The main targets of this study has been to synthesize well-defined nanoclusters of Ni, Co, Pt, Rh and Pd as well as mixed-metal nanoclusters on ultrathin oxide surfaces and to characterize their detailed morphology using scanning probe techniques. The focus of the research is an understanding of the effects of metal-substrate interactions and overall composition on the structure/stability of single metal and mixed-metal nanoclusters and their catalytic activity.

  11. Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huamin; Lee, Suh-Jane; Olarte, Mariefel V.; Zacher, Alan H.

    2016-08-30

    Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenated to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was

  12. Ligand-Assisted Co-Assembly Approach toward Mesoporous Hybrid Catalysts of Transition-Metal Oxides and Noble Metals: Photochemical Water Splitting.

    Science.gov (United States)

    Liu, Ben; Kuo, Chung-Hao; Chen, Jiejie; Luo, Zhu; Thanneeru, Srinivas; Li, Weikun; Song, Wenqiao; Biswas, Sourav; Suib, Steven L; He, Jie

    2015-07-27

    A bottom-up synthetic approach was developed for the preparation of mesoporous transition-metal-oxide/noble-metal hybrid catalysts through ligand-assisted co-assembly of amphiphilic block-copolymer micelles and polymer-tethered noble-metal nanoparticles (NPs). The synthetic approach offers a general and straightforward method to precisely tune the sizes and loadings of noble-metal NPs in metal oxides. This system thus provides a solid platform to clearly understand the role of noble-metal NPs in photochemical water splitting. The presence of trace amounts of metal NPs (≈0.1 wt %) can enhance the photocatalytic activity for water splitting up to a factor of four. The findings can conceivably be applied to other semiconductors/noble-metal catalysts, which may stand out as a new methodology to build highly efficient solar energy conversion systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage.

    Science.gov (United States)

    Michalsky, R; Avram, A M; Peterson, B A; Pfromm, P H; Peterson, A A

    2015-07-01

    The activity of many heterogeneous catalysts is limited by strong correlations between activation energies and adsorption energies of reaction intermediates. Although the reaction is thermodynamically favourable at ambient temperature and pressure, the catalytic synthesis of ammonia (NH 3 ), a fertilizer and chemical fuel, from N 2 and H 2 requires some of the most extreme conditions of the chemical industry. We demonstrate how ammonia can be produced at ambient pressure from air, water, and concentrated sunlight as renewable source of process heat via nitrogen reduction with a looped metal nitride, followed by separate hydrogenation of the lattice nitrogen into ammonia. Separating ammonia synthesis into two reaction steps introduces an additional degree of freedom when designing catalysts with desirable activation and adsorption energies. We discuss the hydrogenation of alkali and alkaline earth metal nitrides and the reduction of transition metal nitrides to outline a promoting role of lattice hydrogen in ammonia evolution. This is rationalized via electronic structure calculations with the activity of nitrogen vacancies controlling the redox-intercalation of hydrogen and the formation and hydrogenation of adsorbed nitrogen species. The predicted trends are confirmed experimentally with evolution of 56.3, 80.7, and 128 μmol NH 3 per mol metal per min at 1 bar and above 550 °C via reduction of Mn 6 N 2.58 to Mn 4 N and hydrogenation of Ca 3 N 2 and Sr 2 N to Ca 2 NH and SrH 2 , respectively.

  14. Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

    International Nuclear Information System (INIS)

    Sagert, N.H.; Shaw-Wood, P.E.; Pouteau, R.M.L.

    1975-01-01

    Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20 percent of various metal oxides. The oxides used were Cr 2 O 3 , MoO 2 , MnO, WO 2 -WO 3 , and UO 2 . Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide. (author)

  15. ACIDIC REMOVAL OF METALS FROM FLUIDIZED CATALYTIC CRACKING CATALYST WASTE ASSISTED BY ELECTROKINETIC TREATMENT

    Directory of Open Access Journals (Sweden)

    R. B. G. Valt

    2015-06-01

    Full Text Available AbstractOne of the main uses of catalysts in the oil industry is in the fluidized catalytic cracking process, which generates large quantities of waste material after use and regeneration cycles and that can be treated by the electrokinetic remediation technique, in which the contaminant metals are transported by migration. In this study, deactivated FCC catalyst was characterized before and after the electrokinetic remediation process to evaluate the amount of metal removed, and assess structural modifications, in order to indicate a possible use as an adsorbent material. The analyses included pH measurement and the concentration profile of vanadium ions along the reactor, X-ray microtomography, X-ray fluorescence, BET analysis and DTA analysis. The results indicated that 40% of the surface area of the material was recovered in relation to the disabled material, showing an increase in the available area for the adsorption. The remediation process removed nearly 31% of the vanadium and 72% of the P2O5 adhering to the surface of the catalyst, without causing structural or thermal stability changes.

  16. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  17. Highly Active Non-PGM Catalysts Prepared from Metal Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Heather M. Barkholtz

    2015-06-01

    Full Text Available Finding inexpensive alternatives to platinum group metals (PGMs is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs. Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/Nx/C prepared from iron doped zeolitic imidazolate frameworks (ZIFs are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/Nx/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR electrocatalytic activity must be demonstrated in membrane-electrode assemblies (MEAs of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.

  18. Metal (Fe, Co, Ni) supported on different aluminas as Fischer-Tropsch catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Dahlan [Chemistry Education Study Program, Universitas Halu Oleo, Jl. HEA Mokodompit, Kendari 93232 (Indonesia); Marsih, I. Nyoman, E-mail: nyoman@chem.itb.ac.id; Ismunandar [Inorganic and Physical Chemistry Division, Departement of Chemistry, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Makertihartha, I. G. B. N. [Department of Chemical Engineering, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Praserthdam, Piyasan; Panpranot, Joongjai [Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Chulalongkorn University, 254 Phayathai Road, Bangkok 10330 (Thailand)

    2015-09-30

    This research aimed to compare the physico-chemical properties of the same metal M (M = iron, cobalt, nickel) supported on aluminas with different morphology and pore size as Fischer-Tropsch catalyst. The aluminas applied as support were alumina synthesized through hydrothermal process, alumina formed by pretreatment of catapal and commercial alumina which named as Ahy, Aca, and Aco respectively. Ahy has uniform morphology of nanotubes while Aca and Aco showed non-uniform morphology of particle lumps. The particle lumps of Aca were larger than those of Aco. Ahy, Aca, and Aco respectively has average pore diameter of 2.75, 2.86 and 2.9 nm. Metals were deposited on the supports by incipient-wetness impregnation method. The catalysts were characterized by XRD, H{sub 2}-TPR, and H{sub 2} chemisorption. Catalyst acitivity test for Fischer-Tropsch reaction was carried out in a micro reactor at 200 °C and 1 atm, and molar ratio of H{sub 2}/CO = 2:1. The metal oxide particle size increased in the order M/Aco < M/Aca < M/Ahy. The catalysts reducibility also increased according to the order M/Aco < M/Aca < M/Ahy suggesting that the larger metal oxide particles are more reducible. The number of active site was not proportional to the reducibility because during the reduction, larger metal oxide particles were converted into larger metal particles. On the other hand, the number of active sites was inversely proportional to the particle sizes. The number of active site increased in the order M/Ahy < M/Aco < M/Aca. The catalytic activity also increased in the following order M/Ahy < M/Aco < M/Aca. The activity per active site increased according to the order M/Aca < M/Aco < M/Ahy meaning that for M/Ahy, a little increase in active site will lead to a significance increase in catalytic activity. It showed that Ahy has potential for the better support.

  19. Dual catalyst bed concept for catalytic partial oxidation of methane to synthesis gas

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    A system with two catalyst beds instead of one single metal catalyst bed is proposed for catalytic partial oxidation of methane (CPOM) to synthesis gas. In this dual catalyst bed system, an irreducible stable oxide, such as yttrium-stabilized zirconia (YSZ), is used in the first catalyst bed to

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

    NARCIS (Netherlands)

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

    2006-01-01

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

  1. Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

    Science.gov (United States)

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

    2018-04-13

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

  2. Suitable alkaline for graphene peeling grown on metallic catalysts using chemical vapor deposition

    International Nuclear Information System (INIS)

    Karamat, S.; Sonuşen, S.; Çelik, Ü.; Uysallı, Y.; Oral, A.

    2016-01-01

    Graphical abstract: - Highlights: • Graphene layers were grown on Pt and Cu foil via ambient pressure chemical vapor deposition method and for the delicate removal of graphene from metal catalysts, electrolysis method was used by using different alkaline (sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide). • The delamination speed of PMMA/graphene stack was higher during the KOH and LiOH electrolysis as compare to NaOH and Ba(OH) 2 . Ba(OH) 2 is not advisable because of the residues left on the graphene surface which would further trapped in between graphene and SiO 2 /Si surface after transfer. The average peeling time in case of Pt electrode is ∼6 min for KOH and LiOH and ∼15 min for NaOH and Ba(OH) 2 . • Electrolysis method also works for the Cu catalyst. The peeling of graphene was faster in the case of Cu foil due to small size of bubbles which moves faster between the stack and the electrode surface. The average peeling time was ∼3–5 min. • XPS analysis clearly showed that the Pt substrates can be re-used again. Graphene layer was transferred to SiO 2 /Si substrates and to the flexible substrate by using the same peeling method. - Abstract: In chemical vapor deposition, the higher growth temperature roughens the surface of the metal catalyst and a delicate method is necessary for the transfer of graphene from metal catalyst to the desired substrates. In this work, we grow graphene on Pt and Cu foil via ambient pressure chemical vapor deposition (AP-CVD) method and further alkaline water electrolysis was used to peel off graphene from the metallic catalyst. We used different electrolytes i.e., sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) and barium hydroxide Ba(OH) 2 for electrolysis, hydrogen bubbles evolved at the Pt cathode (graphene/Pt/PMMA stack) and as a result graphene layer peeled off from the substrate without damage. The peeling time for KOH and LiOH was ∼6 min and for Na

  3. Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

    Science.gov (United States)

    Park, Paul W.

    2004-03-16

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

  4. Self-Anchored Catalyst Interface Enables Ordered Via Array Formation from Submicrometer to Millimeter Scale for Polycrystalline and Single-Crystalline Silicon.

    Science.gov (United States)

    Kim, Jeong Dong; Kim, Munho; Kong, Lingyu; Mohseni, Parsian K; Ranganathan, Srikanth; Pachamuthu, Jayavel; Chim, Wai Kin; Chiam, Sing Yang; Coleman, James J; Li, Xiuling

    2018-03-14

    Defying text definitions of wet etching, metal-assisted chemical etching (MacEtch), a solution-based, damage-free semiconductor etching method, is directional, where the metal catalyst film sinks with the semiconductor etching front, producing 3D semiconductor structures that are complementary to the metal catalyst film pattern. The same recipe that works perfectly to produce ordered array of nanostructures for single-crystalline Si (c-Si) fails completely when applied to polycrystalline Si (poly-Si) with the same doping type and level. Another long-standing challenge for MacEtch is the difficulty of uniformly etching across feature sizes larger than a few micrometers because of the nature of lateral etching. The issue of interface control between the catalyst and the semiconductor in both lateral and vertical directions over time and over distance needs to be systematically addressed. Here, we present a self-anchored catalyst (SAC) MacEtch method, where a nanoporous catalyst film is used to produce nanowires through the pinholes, which in turn physically anchor the catalyst film from detouring as it descends. The systematic vertical etch rate study as a function of porous catalyst diameter from 200 to 900 nm shows that the SAC-MacEtch not only confines the etching direction but also enhances the etch rate due to the increased liquid access path, significantly delaying the onset of the mass-transport-limited critical diameter compared to nonporous catalyst c-Si counterpart. With this enhanced mass transport approach, vias on multistacks of poly-Si/SiO 2 are also formed with excellent vertical registry through the polystack, even though they are separated by SiO 2 which is readily removed by HF alone with no anisotropy. In addition, 320 μm square through-Si-via (TSV) arrays in 550 μm thick c-Si are realized. The ability of SAC-MacEtch to etch through poly/oxide/poly stack as well as more than half millimeter thick silicon with excellent site specificity for a wide

  5. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

    Science.gov (United States)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

    2018-03-01

    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

  6. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

    Energy Technology Data Exchange (ETDEWEB)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

    2018-01-08

    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.

  7. Long-range electron transfer over graphene-based catalyst for high-performing oxygen reduction reactions: importance of size, N-doping, and metallic impurities.

    Science.gov (United States)

    Choi, Chang Hyuck; Lim, Hyung-Kyu; Chung, Min Wook; Park, Jong Cheol; Shin, Hyeyoung; Kim, Hyungjun; Woo, Seong Ihl

    2014-06-25

    N-doped carbon materials are considered as next-generation oxygen reduction reaction (ORR) catalysts for fuel cells due to their prolonged stability and low cost. However, the underlying mechanism of these catalysts has been only insufficiently identified, preventing the rational design of high-performing catalysts. Here, we show that the first electron is transferred into O2 molecules at the outer Helmholtz plane (ET-OHP) over a long range. This is in sharp contrast to the conventional belief that O2 adsorption must precede the ET step and thus that the active site must possess as good an O2 binding character as that which occurs on metallic catalysts. Based on the ET-OHP mechanism, the location of the electrode potential dominantly characterizes the ORR activity. Accordingly, we demonstrate that the electrode potential can be elevated by reducing the graphene size and/or including metal impurities, thereby enhancing the ORR activity, which can be transferred into single-cell operations with superior stability.

  8. Controlled Polymerization of Isoprene with Chromium-Based Metal-Organic Framework Catalysts: Switching from Cyclic to cis-1,4-Selectivity Depending on Activator.

    Science.gov (United States)

    Gao, Fei; Zhang, Li; Yu, Chao; Yan, Xinwen; Zhang, Shaowen; Li, Xiaofang

    2018-03-05

    Chromium-based metal-organic framework (MOF) Cr-MIL-100/101 activated by activator and aluminum trialkyl compound serve as unique, highly efficient heterogeneous single-site catalysts for the controlled polymerization of isoprene, which not only exhibit quasi-living nature in isoprene polymerization but also unprecedentedly switch from cyclic to cis-1,4-selectivity depending on the activator used to yield low molecular weight cyclic PIPs or extremely high molecular weight cis-1,4-PIPs. Such heterogeneous Cr-MOF catalysts can be recycled approximately five times. Based on nitrogen sorption isotherm tests and powder X-ray diffraction, a cationic mechanism is suggested, in which the polymerization takes place inside the open nanochannels of MOF catalysts and the space confinement effect of narrow open nanochannels originated from the coordination of PhNMe 2 from activator [PhNHMe 2 ][B(C 6 F 5 ) 4 ] with the multiple metal centers of MOF catalysts might give a rational explanation for such controlled adjustment on the PIP's structure and properties. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Minimizing Isolate Catalyst Motion in Metal-Assisted Chemical Etching for Deep Trenching of Silicon Nanohole Array.

    Science.gov (United States)

    Kong, Lingyu; Zhao, Yunshan; Dasgupta, Binayak; Ren, Yi; Hippalgaonkar, Kedar; Li, Xiuling; Chim, Wai Kin; Chiam, Sing Yang

    2017-06-21

    The instability of isolate catalysts during metal-assisted chemical etching is a major hindrance to achieve high aspect ratio structures in the vertical and directional etching of silicon (Si). In this work, we discussed and showed how isolate catalyst motion can be influenced and controlled by the semiconductor doping type and the oxidant concentration ratio. We propose that the triggering event in deviating isolate catalyst motion is brought about by unequal etch rates across the isolate catalyst. This triggering event is indirectly affected by the oxidant concentration ratio through the etching rates. While the triggering events are stochastic, the doping concentration of silicon offers a good control in minimizing isolate catalyst motion. The doping concentration affects the porosity at the etching front, and this directly affects the van der Waals (vdWs) forces between the metal catalyst and Si during etching. A reduction in the vdWs forces resulted in a lower bending torque that can prevent the straying of the isolate catalyst from its directional etching, in the event of unequal etch rates. The key understandings in isolate catalyst motion derived from this work allowed us to demonstrate the fabrication of large area and uniformly ordered sub-500 nm nanoholes array with an unprecedented high aspect ratio of ∼12.

  10. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

    Directory of Open Access Journals (Sweden)

    Matthias Leven

    2013-01-01

    Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

  11. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Alexandre Luiz de Souza; Silva, Cristiano Nunes da; Afonso, Julio Carlos, E-mail: julio@iq.ufrj.b [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica; Mantovano, Jose Luiz [Instituto de Engenharia Nuclear (CNEN/IEN-RJ), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares

    2011-07-01

    This work describes a three-step pre-treatment route for processing spent commercial Ni Mo/Al{sub 2}O{sub 3} catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L{sup -1} sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate. (author)

  12. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Directory of Open Access Journals (Sweden)

    Alexandre Luiz de Souza Pereira

    2011-01-01

    Full Text Available This work describes a three-step pre-treatment route for processing spent commercial NiMo/Al2O3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L-1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate.

  13. Multi-metallic oxides as catalysts for light alcohols and hydrocarbons from synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Perez, Miguel [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico); Diaz, L; Galindo, H de J; Dominguez, J. M; Salmon, Manuel [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)

    1999-08-01

    A series of Cu-Co-Cr oxides doped with alkaline metals (M), were prepared by the coprecipitation method with metal nitrates (Cu{sup I}I, CO{sup I}I, CR{sup I}II) and (M{sub 2})CO{sub 3} in aqueous solution. The calcined products were used as catalysts for the Fisher-Tropsch synthesis in a stainless-steel fixed bed microreactor. The material was characterized by x-ray diffraction, and the specific surface area, pore size and nitrogen adsorption-desorption properties were also determined. The alkaline metals favored the methanol synthesis and prevent the dehydration reactions whereas the hydrocarbon formation is independent to these metals. [Spanish] Una serie de oxidos Cu-Co-Cr soportados con metales alcalinos (M), fueron preparados por el metodo con nitratos metalicos (Cu{sup I}I, CO{sup I}I, CR{sup I}II) y (M{sub 2})CO{sub 3} en soluciones acuosas. Los productos calcinados fueron usados como catalizadores para la sintesis de Fisher-tropsch en la superficie fija de un microreactor de acero inoxidable. El material fue caracterizado por difraccion de rayos X y el area de superficie especifica, el tamano de poro y propiedades de absorcion-desorcion de nitrogeno fueron determinadas. Los metales alcalinos favorecieron la sintesis de metanol y previnieron las reacciones de deshidratacion, mientras que la formacion de hidrocarburos es independiente de estos metales.

  14. Nitrogen and sulfur co-doped carbon with three-dimensional ordered macroporosity: An efficient metal-free oxygen reduction catalyst derived from ionic liquid

    Science.gov (United States)

    Wu, Hui; Shi, Liang; Lei, Jiaheng; Liu, Dan; Qu, Deyu; Xie, Zhizhong; Du, Xiaodi; Yang, Peng; Hu, Xiaosong; Li, Junsheng; Tang, Haolin

    2016-08-01

    The development of efficient and durable catalyst for oxygen reduction reaction (ORR) is critical for the practical application of proton exchange membrane fuel cell (PEMFC). A novel imidazole based ionic liquid is synthesized in this study and used subsequently for the preparation of a N and S co-doped metal-free catalyst with three dimensional ordered microstructure. The catalyst prepared at 1100 °C showed improved ORR catalytic performance and stability compared to commercial Pt/C catalyst. We demonstrate that the high graphitic N content and high degree of graphitization of the synthesized catalyst is responsible for its superb ORR activity. Our results suggest that the N and S co-doped metal-free catalyst reported here is a promising alternative to traditional ORR catalyst based on noble metal. Furthermore, the current study also demonstrate that importance of morphology engineering in the development of high performance ORR catalyst.

  15. A Theoretical Investigation on CO Oxidation by Single-Atom Catalysts M1/γ-Al2O3(M=Pd, Fe, Co, and Ni).

    Science.gov (United States)

    Yang, Tao; Fukuda, Ryoichi; Hosokawa, Saburo; Tanaka, Tsunehiro; Sakaki, Shigeyoshi; Ehara, Masahiro

    2017-04-07

    Single-atom catalysts have attracted much interest recently because of their excellent stability, high catalytic activity, and remarkable atom efficiency. Inspired by the recent experimental discovery of a highly efficient single-atom catalyst Pd 1 /γ-Al 2 O 3 , we conducted a comprehensive DFT study on geometries, stabilities and CO oxidation catalytic activities of M 1 /γ-Al 2 O 3 (M=Pd, Fe, Co, and Ni) by using slab-model. One of the most important results here is that Ni 1 /Al 2 O 3 catalyst exhibits higher activity in CO oxidation than Pd 1 /Al 2 O 3 . The CO oxidation occurs through the Mars van Krevelen mechanism, the rate-determining step of which is the generation of CO 2 from CO through abstraction of surface oxygen. The projected density of states (PDOS) of 2 p orbitals of the surface O, the structure of CO-adsorbed surface, charge polarization of CO and charge transfer from CO to surface are important factors for these catalysts. Although the binding energies of Fe and Co with Al 2 O 3 are very large, those of Pd and Ni are small, indicating that the neighboring O atom is not strongly bound to Pd and Ni, which leads to an enhancement of the reactivity of the O atom toward CO. The metal oxidation state is suggested to be one of the crucial factors for the observed catalytic activity.

  16. In situ Raman studies of single-walled carbon nanotubes grown by local catalyst heating

    Science.gov (United States)

    Dittmer, S.; Olofsson, N.; Ek Weis, J.; Nerushev, O. A.; Gromov, A. V.; Campbell, E. E. B.

    2008-05-01

    Using in situ Raman spectroscopy we investigate single wall carbon nanotube growth on Mo electrodes, using a highly localized resistive heating technique. Small diameter semiconducting single wall nanotubes grow very rapidly when the catalyst support is heated to a temperature of 800 °C. The G/D ratio shows an interesting time-dependent behaviour. It first decreases, indicating the presence of amorphous carbon and then significantly increases again after ca. 5 min growth while retaining the position and shape expected for predominantly semiconducting carbon nanotubes.

  17. Hierarchical zeolites: progress on synthesis and characterization of mesoporous zeolite single crystal catalysts

    DEFF Research Database (Denmark)

    Kustova, Marina; Egeblad, Kresten; Christensen, Claus H.

    2007-01-01

    in a hierarchical pore size distribution. In this work, the preparation of mesoporous ZSM-12 single crystal catalysts using a new improved procedure for directly introducing carbon in the reaction mixture is reported. The microwave heating technique is also applied for the synthesis of mesoporous silicalite-1...... single crystals using this direct introduction of carbon into the reaction mixture. All samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed desorption of ammonia (NH3-TPD), and N-2 adsorption...

  18. Magnetic properties of iron catalyst particles in HiPco single wall carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Bittová, Barbara; Poltierová Vejpravová, Jana; Kalbáč, Martin; Burianová, Simona; Mantlíková, A.; Daniš, S.; Doyle, S.

    2011-01-01

    Roč. 115, č. 35 (2011), s. 17303-17309 ISSN 1932-7447 R&D Projects: GA ČR GAP204/10/1677 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z40400503 Keywords : metal catalyst particles * carbon nanotubes * superparamagnet * core - shell model * inter-particle interactions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.805, year: 2011 http://pubs.acs.org/doi/abs/10.1021/jp203365g

  19. Metal-Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations.

    Science.gov (United States)

    Zhang, Teng; Manna, Kuntal; Lin, Wenbin

    2016-03-09

    New and active earth-abundant metal catalysts are critically needed to replace precious metal-based catalysts for sustainable production of commodity and fine chemicals. We report here the design of highly robust, active, and reusable cobalt-bipyridine- and cobalt-phenanthroline-based metal-organic framework (MOF) catalysts for alkene hydrogenation and hydroboration, aldehyde/ketone hydroboration, and arene C-H borylation. In alkene hydrogenation, the MOF catalysts tolerated a variety of functional groups and displayed unprecedentedly high turnover numbers of ∼2.5 × 10(6) and turnover frequencies of ∼1.1 × 10(5) h(-1). Structural, computational, and spectroscopic studies show that site isolation of the highly reactive (bpy)Co(THF)2 species in the MOFs prevents intermolecular deactivation and stabilizes solution-inaccessible catalysts for broad-scope organic transformations. Computational, spectroscopic, and kinetic evidence further support a hitherto unknown (bpy(•-))Co(I)(THF)2 ground state that coordinates to alkene and dihydrogen and then undergoing σ-complex-assisted metathesis to form (bpy)Co(alkyl)(H). Reductive elimination of alkane followed by alkene binding completes the catalytic cycle. MOFs thus provide a novel platform for discovering new base-metal molecular catalysts and exhibit enormous potential in sustainable chemical catalysis.

  20. Graphene hydrogels with embedded metal nanoparticles as efficient catalysts in 4-nitrophenol reduction and methylene blue decolorization

    Directory of Open Access Journals (Sweden)

    Żelechowska Kamila

    2016-12-01

    Full Text Available Synthesis and characterization of the graphene hydrogels with three different metallic nanoparticles, that is Au, Ag and Cu, respectively is presented. Synthesized in a one-pot approach graphene hydrogels with embedded metallic nanoparticles were tested as heterogeneous catalysts in a model reaction of 4-nitrophenol reduction. The highest activity was obtained for graphene hydrogel with Cu nanoparticles and additional reaction of methylene blued degradation was evaluated using this system. The obtained outstanding catalytic activity arises from the synergistic effect of graphene and metallic nanoparticles. The hydrogel form of the catalyst benefits in the easiness in separation from the reaction mixture (for example using tweezers and reusability.

  1. Nitrogen-Doped Graphene on Transition Metal Substrates as Efficient Bifunctional Catalysts for Oxygen Reduction and Oxygen Evolution Reactions.

    Science.gov (United States)

    Zhou, Si; Liu, Nanshu; Wang, Zhiyu; Zhao, Jijun

    2017-07-12

    Composites of transition metal and carbon-based materials are promising bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and are widely used in rechargeable metal-air batteries. However, the mechanism of their enhanced bicatalytic activities remains elusive. Herein, we construct N-doped graphene supported by Co(111) and Fe(110) substrates as bifunctional catalysts for ORR and OER in alkaline media. First-principles calculations show that these heterostructures possess a large number of active sites for ORR and OER with overpotentials comparable to those of noble metal benchmark catalysts. The catalytic activity is modulated by the coupling strength between graphene and the metal substrates, as well as the charge distribution in the graphitic sheet, which is delicately mediated by N dopants. These theoretical results uncover the key parameters that govern the bicatalytic properties of hybrid materials and help prescribe the principles for designing multifunctional electrocatalysts of high performance.

  2. ZIF-8 with Ferrocene Encapsulated: A Promising Precursor to Single-Atom Fe Embedded Nitrogen-Doped Carbon as Highly Efficient Catalyst for Oxygen Electroreduction.

    Science.gov (United States)

    Wang, Jinpeng; Han, Guokang; Wang, Liguang; Du, Lei; Chen, Guangyu; Gao, Yunzhi; Ma, Yulin; Du, Chunyu; Cheng, Xinqun; Zuo, Pengjian; Yin, Geping

    2018-03-05

    The oxygen reduction reaction (ORR) plays an important role in the fields of energy storage and conversion technologies, including metal-air batteries and fuel cells. The development of nonprecious metal electrocatalysts with both high ORR activity and durability to replace the currently used costly Pt-based catalyst is critical and still a major challenge. Herein, a facile and scalable method is reported to prepare ZIF-8 with single ferrocene molecules trapped within its cavities (Fc@ZIF-8), which is utilized as precursor to porous single-atom Fe embedded nitrogen-doped carbon (Fe-N-C) during high temperature pyrolysis. The catalyst shows a half-wave potential (E 1/2 ) of 0.904 V, 67 mV higher than commercial Pt/C catalyst (0.837 V), which is among the best compared with reported results for ORR. Significant electrochemical properties are attributed to the special configuration of Fc@ZIF-8 transforming into a highly dispersed iron-nitrogen coordination moieties embedded carbon matrix. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Strategies for Probing Nanometer-Scale Electrocatalysts: From Single Particles to Catalyst-Membrane Architectures

    Energy Technology Data Exchange (ETDEWEB)

    Korzeniewski, Carol [Texas Tech Univ., Lubbock, TX (United States). Department of Chemistry & Biochemistry

    2014-01-20

    The project primary objectives are to prepare and elucidate the promoting properties of materials that possess high activity for the conversion of hydrogen and related small molecules (water, oxygen, carbon monoxide and methanol) in polymer electrolyte fuel cells. One area of research has focused on the study of catalyst materials. Protocols were developed for probing the structure and benchmarking the activity of Pt and Pt bimetallic nanometer-scale catalyst against Pt single crystal electrode standards. A second area has targeted fuel cell membrane and the advancement of simple methods mainly based on vibrational spectroscopy that can be applied broadly in the study of membrane structure and transport properties. Infrared and Raman methods combined with least-squares data modeling were applied to investigate and assist the design of robust, proton conductive membranes, which resist reactant crossover.

  4. Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions.

    Science.gov (United States)

    Rodriguez, José A; Illas, Francesc

    2012-01-14

    This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O(2), C(2)H(4), SO(2), thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO(2) at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O(2) and perform the 2CO + O(2)→ 2CO(2) reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS(x) catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical

  5. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination

    Science.gov (United States)

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-01

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

  6. Influence of noble metals on the performance of Co/SiO{sub 2} catalyst for 1-hexene hydroformylation

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, X.Q.; Tsubaki, N.; Sun, S.L.; Fujimoto, K. [Tsing Hua University, Beijing (China). Dept. of Chemistry, State Key Laboratory of C1 Chemistry of Technology

    2002-08-01

    Effect of small amount of Pt, Pd and Ru promoters on the characteristics and performance of Co/SiO{sub 2} catalyst, which was prepared from the mixture of cobalt nitrate and cobalt acetate, was investigated in the hydroformylation of 1-hexene. It was found that the addition of small amount of a noble metal to the supported cobalt catalyst led into great improvement of catalyst activity for hydroformylation of 1-hexene. The 1-hexene conversion as high as 89.7% and oxygenate products selectivity of 88.9% were obtained after reaction of 2 h over Pd promoted CO/SiO{sub 2} catalyst. The increasing of reduction degree, the minimizing of cobalt particle size and the enhancement of carbonyl and linear CO adsorption were responsible for the improved performance of the catalyst. 19 refs., 3 figs., 3 tabs.

  7. A Hafnium-Based Metal-Organic Framework as a Nature-Inspired Tandem Reaction Catalyst.

    Science.gov (United States)

    Beyzavi, M Hassan; Vermeulen, Nicolaas A; Howarth, Ashlee J; Tussupbayev, Samat; League, Aaron B; Schweitzer, Neil M; Gallagher, James R; Platero-Prats, Ana E; Hafezi, Nema; Sarjeant, Amy A; Miller, Jeffrey T; Chapman, Karena W; Stoddart, J Fraser; Cramer, Christopher J; Hupp, Joseph T; Farha, Omar K

    2015-10-28

    Tandem catalytic systems, often inspired by biological systems, offer many advantages in the formation of highly functionalized small molecules. Herein, a new metal-organic framework (MOF) with porphyrinic struts and Hf6 nodes is reported. This MOF demonstrates catalytic efficacy in the tandem oxidation and functionalization of styrene utilizing molecular oxygen as a terminal oxidant. The product, a protected 1,2-aminoalcohol, is formed selectively and with high efficiency using this recyclable heterogeneous catalyst. Significantly, the unusual regioselective transformation occurs only when an Fe-decorated Hf6 node and the Fe-porphyrin strut work in concert. This report is an example of concurrent orthogonal tandem catalysis.

  8. A versatile sonication-assisted deposition-reduction method for preparing supported metal catalysts for catalytic applications.

    Science.gov (United States)

    Padilla, Romen Herrera; Priecel, Peter; Lin, Ming; Lopez-Sanchez, Jose Antonio; Zhong, Ziyi

    2017-03-01

    This work aims to develop a rapid and efficient strategy for preparing supported metal catalysts for catalytic applications. The sonication-assisted reduction-precipitation method was employed to prepare the heterogeneous mono- and bi-metallic catalysts for photocatalytic degradation of methyl orange (MO) and preferential oxidation (PROX) of CO in H 2 -rich gas. In general, there are three advantages for the sonication-assisted method as compared with the conventional methods, including high dispersion of metal nanoparticles on the catalyst support, the much higher deposition efficiency (DE) than those of the deposition-precipitation (DP) and co-precipitation (CP) methods, and the very fast preparation, which only lasts 10-20s for the deposition. In the AuPd/TiO 2 catalysts series, the AuPd(3:1)/TiO 2 catalyst is the most active for MO photocatalytic degradation; while for PROX reaction, Ru/TiO 2 , Au-Cu/SBA-15 and Pt/γ-Al 2 O 3 catalysts are very active, and the last one showed high stability in the lifetime test. The structural characterization revealed that in the AuPd(3:1)/TiO 2 catalyst, Au-Pd alloy particles were formed and a high percentage of Au atoms was located at the surface. Therefore, this sonication-assisted method is efficient and rapid in the preparation of supported metal catalysts with obvious structural characteristics for various catalytic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. New Gateways to the Platinum Group Metal-Catalyzed Direct Deuterium-Labeling Method Utilizing Hydrogen as a Catalyst Activator.

    Science.gov (United States)

    Sawama, Yoshinari; Park, Kwihwan; Yamada, Tsuyoshi; Sajiki, Hironao

    2018-01-01

    Deuterium-labeled compounds are widely utilized in various scientific fields. We summarize the recent advances in the direct deuteration of sugar, saturated fatty acid, and arene derivatives using heterogeneous platinum group metal on carbon catalysts by our research group. Hydrogen gas is a key catalyst-activator to facilitate the present H-D exchange reactions. In this review, the direct activation method of catalysts using in situ-generated hydrogen based on the dehydrogenation of alcohols is introduced. The obtained multiple deuterium-labeled products, including bioactive compounds, are expected to contribute to the development of many scientific investigations.

  10. Kinetics of n-heptane pyrolysis over metal oxide- and synthetic aluminosilicate-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pop, G.; Petre, K.; Pop, E.; Tomi, P.

    1979-01-01

    The kinetics of n-heptane pyrolysis over metal oxide- and synthetic aluminosilicate-based catalysts, including ..cap alpha..-A1/sub 2/0/sub 3/, A1/sub 2/0/sub 3/-CaO, A1/sub 2/0/sub 3/-MgO, and decationated mordenite-type zeolites with the SiO/sub 2/-A1/sub 2/0/sub 3/ ratio (R) of 15-200:1, were studied in a dynamic integral reactor at 650/sup 0/C and 0.015 MPa diluted with steam. The reaction rates and kinetic parameters observed with the mixed oxide and the ..cap alpha..-alumina catalysts were almost identical to those for thermal pyrolysis and were somewhat increased by the addition of K/sub 2/O to these oxides. The zeolites increased the reaction rate by over an order of magnitude and more than halved the activation energy (E). E passed through a strong minimum and the rate of coke formation through a maximum at R approx. 30:1; the rate constant increased with R, but all these parameters stabilized at R Vertical Bar3: 60. The product distributions over the oxide catalysts were similar to those observed in thermal pyrolysis and were consistent with the Rice and Kossiakoff free radical chain mechanism. By contrast, pyrolysis over the zeolites was characterized by a product distribution typical of catalytic cracking by a carbocation mechanism, including larger yields of propylene than of ethylene.

  11. Boron-doped diamond synthesized at high-pressure and high-temperature with metal catalyst

    Science.gov (United States)

    Shakhov, Fedor M.; Abyzov, Andrey M.; Kidalov, Sergey V.; Krasilin, Andrei A.; Lähderanta, Erkki; Lebedev, Vasiliy T.; Shamshur, Dmitriy V.; Takai, Kazuyuki

    2017-04-01

    The boron-doped diamond (BDD) powder consisting of 40-100 μm particles was synthesized at 5 GPa and 1500-1600 °C from a mixture of 50 wt% graphite and 50 wt% Ni-Mn catalyst with an addition of 1 wt% or 5 wt% boron powder. The size of crystal domains of doped and non-doped diamond was evaluated as a coherent scattering region by X-ray diffraction (XRD) and using small-angle neutron scattering (SANS), being ≥180 nm (XRD) and 100 nm (SANS). Magnetic impurities of NiMnx originating from the catalyst in the synthesis, which prevent superconductivity, were detected by magnetization measurements at 2-300 K. X-ray photoelectron spectroscopy, the temperature dependence of the resistivity, XRD, and Raman spectroscopy reveal that the concentration of electrically active boron is as high as (2±1)×1020 cm-3 (0.1 at%). To the best of our knowledge, this is the highest boron content for BDD synthesized in high-pressure high-temperature process with metal catalysts.

  12. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

    Science.gov (United States)

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2003-12-30

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  13. Tandem hydroformylation/hydrogenation of alkenes to normal alcohols using Rh/Ru dual catalyst or Ru single component catalyst.

    Science.gov (United States)

    Takahashi, Kohei; Yamashita, Makoto; Nozaki, Kyoko

    2012-11-14

    The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and (31)P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H(2)/CO pressure clarified different kinetics from the hydrogenation under H(2) and gave a clue to design more active hydrogenation catalysts under H(2)/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported.

  14. Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction.

    Science.gov (United States)

    Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding

    2017-08-28

    A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. The Oxidation of Sulfur-Containing Compounds Using Heterogeneous Catalysts of Transition Metal Oxides Deposited on the Polymeric Matrix

    Science.gov (United States)

    Dinh Vu, Ngo; Dinh Bui, Nhi; Thi Minh, Thao; Thi Thanh Dam, Huong; Thi Tran, Hang

    2016-05-01

    We investigate the activity of heterogeneous catalysts of transition metal oxides deposited on the polymeric matrix in the oxidation of sulfur-containing compounds. It is shown that MnO2-10/CuO-10 has the highest catalytic activity. The physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, including the specific surface area, elongation at break and breaking strength, specific electrical resistance, and volume resistivity were studied by using an Inspekt mini 3 kN universal tensile machine in accordance with TCVN 4509:2006 at a temperature of 20 ± 2°C. Results show that heterogeneous polymeric catalysts were stable under severe reaction conditions. Scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. Microstructural characterization of the catalysts is performed by using x-ray computed tomography. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment.

  16. Fabrication and Performance of Noble Metal Promoted Birnessite Catalysts for Complete Oxidation of Formaldehyde at Low Temperatures.

    Science.gov (United States)

    Liu, Linlin; Tian, Hua; He, Junhui; Wang, Donghui; Ma, Chunyan; Yang, Qiaowen

    2015-04-01

    Noble metal (Au, Ag, Pd and Pt) promoted birnessite (Bir) catalysts were successfully prepared and tested for catalytic oxidation of formaldehyde (HCHO). The catalysts were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), hydrogen temperature programmed reduction (H2-TPR), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and N2 adsorption-desorption. The activities of noble metal (Au, Ag, Pd and Pt) promoted birnessite catalysts follow the order of 1.0Pt/Bir > 1.0Pd/Bir > Bir > 1.0Ag/Bir > 1.0Au/Bir, revealing that the loading of Pd and Pt improves the catalytic activity of birnessite, but the loading of Ag and Au slightly decreases the catalytic activity of birnessite. Effects of the Pt loading amount were also investigated on the activity of Pt/Bir catalysts for HCHO oxidation. Pt/Bir with a Pt loading of 1.5 wt% (1.5 Pt/Bir), which has the best reduction properties, was found to be the most efficient catalyst. Over this catalyst, HCHO could be completely oxidized into CO2 and H2O at 70°. 1.5 Pt/Bir also shows good catalytic stability under the HCHO oxidation atmosphere. The differences in the catalytic activity of these materials are largely attributed to their reducibility as well as the dispersion of metal nanoparticles, but are not directly related to their specific surface areas.

  17. Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

    Science.gov (United States)

    Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

    2018-02-27

    The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

  18. Autothermal reforming catalyst having perovskite structure

    Science.gov (United States)

    Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

    2009-03-24

    The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

  19. PYROLYSIS OF ISOCHRYSIS MICROALGAE WITH METAL OXIDE CATALYSTS FOR BIO-OIL PRODUCTION

    Directory of Open Access Journals (Sweden)

    TEVFİK AYSU

    2016-12-01

    Full Text Available Pyrolysis of Isochrysis microalgae was carried out in a fixed-bed reactor without and with metal oxide catalysts (CeO2, TiO2, Al2O3 at the temperatures of 450, 500 and 550 oC with a constant heating rate of 40 oC/min. The pyrolysis conditions including catalyst and temperature were studied in terms of their effects on the yields of pyrolysis products and quality. The amount of bio-char, bio-oil and gas products was calculated. The composition of the produced bio-oils was determined by Elemental analysis (EA, Fourier transform infrared spectroscopy (FT-IR, proton nuclear magnetic resonance (1H NMR and Gas chromatography/mass spectrometry (GC–MS techniques. As a result of the pyrolysis experiments, it is shown that there have been significant effects of both catalyst and temperature on the conversion of Isochrysis microalgae into solid, liquid (bio-oil and gas products. The highest bio-oil yield (24.30 % including aqueous phase was obtained in the presence of TiO2 (50% as catalyst at 500 °C. 98 different compounds were identified by GC-MS in bio-oils obtained at 500 oC. According to 1H NMR analysis, bio-oils contained ∼60-64 % aliphatic and ∼17-19 % aromatic structural units. EA showed that the bio-oils contained ∼66-69 % C and having 31-34 MJ/kg higher heating values.

  20. Degradation of phenylamine by catalytic wet air oxidation using metal catalysts with modified supports.

    Science.gov (United States)

    Torrellas, Silvia A; Escudero, Gabriel O; Rodriguez, Araceli R; Rodriguez, Juan G

    2015-01-01

    The effect of acid treatments with HCl and HNO3 on the surface area and surface chemistry of three granular activated carbons was studied. These supports were characterized and the hydrochloric acid treatment leads to the best activated carbon support (AC2-C). The catalytic behavior of Pt, Ru and Fe (1 wt.%) supported on granular activated carbon treated with HCl was tested in the phenylamine continuous catalytic wet air oxidation in a three-phase, high-pressure catalytic reactor over a range of reaction temperatures 130-170ºC and total pressure of 1.0-3.0 MPa at LHSV = 0.4-1 h(-1), whereas the phenylamine concentration range and the catalyst loading were 5-16 mol.m(-3) and 0.5-1.5 g, respectively. Activity as well as conversion varied as a function of the metal, the catalyst preparation method and operation conditions. Higher activities were obtained with Pt incorporated on hydrochloric acid -treated activated carbon by the ion exchange method. In steady state, approximately 98% phenylamine conversion, 77% of TOC and 94% of COD removal, was recorded at 150ºC, 11 mol m(-3) of phenylamine concentration and 1.5 g of catalyst, and the selectivity to non-organic compounds was 78%. Several reaction intermediaries were detected. A Langmuir-Hinshelwood model gave an excellent fit of the kinetic data of phenylamine continuous catalytic wet air oxidation over the catalysts of this work.

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

    Science.gov (United States)

    Yik, Edwin Shyn-Lo

    convergence to a single phase is expected and predictable from thermodynamics at a given temperature and sulfur chemical potential, metastability of two phases can exist. We demonstrate, through extensive characterization and kinetic evidence, such behaviors exist in Re, where structural disparities between its phases lead to kinetic hurdles that prevent interconversions between layered ReSx nanostructures and sulfur-covered Re metal clusters. Such features allowed, for the first time, direct comparisons of reaction rates at identical conditions on two disparate phases of the same transition metal identity. Rigorous assessments of kinetic and selectivity data indicated that more universal mechanistic features persist across all catalysts studied, suggesting that differences in their catalytic activity were the result of different densities of HDS sites, which appeared to correlate with their respective metal-sulfur bond energies. Kinetic responses and product distributions indicated that the consumption of thiophene proceeds by the formation of a partially-hydrogenated surface intermediate, which subsequently produces tetrahydrothiophene (THT) and butene/butane (C4) via primary routes on similar types of sites. These sites are formed from desorption of weakly-bound sulfur adatoms on sulfur-covered metal surfaces, which can occur when the heat of sulfur adsorption is sufficiently low at high sulfur coverage as a result of increased sulfur-sulfur repulsive interactions. Relative stabilities and differences in the molecularity of the respective transition states that form THT and C4 dictate product distributions. THT desulfurization to form C4 occurs via readsorption and subsequent dehydrogenation, evidenced by secondary rates that exhibited negative H2 dependences. These behaviors suggest that C-S bond activation occurs on a partially (un)saturated intermediate, analogous to behaviors observed in C-C bond scission reactions of linear and cycloalkanes on hydrogen-covered metal

  2. Synthesis of carbon nanotubes bridging metal electrodes

    International Nuclear Information System (INIS)

    Kotlar, M.; Vojs, M.; Marton, M.; Vesel, M.; Redhammer, R.

    2012-01-01

    In our work we demonstrate growth of carbon nanotubes that can conductively bridge the metal electrodes. The role of different catalysts was examined. Interdigitated metal electrodes are made from copper and we are using bimetal Al/Ni as catalyst for growth of carbon nanotubes. We are using this catalyst composition for growth of the single-walled carbon nanotube network. (authors)

  3. Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C.; Miller, Jeffrey T.; Delferro, Massimiliano; Stair, Peter C.; Marks, Tobin J.

    2016-08-23

    A single-site molybdenum dioxo catalyst, (Oc)2Mo(=O)2@C, was prepared via direct grafting of MoO2Cl2(dme) (dme = 1,2-dimethoxyethane) on high-surface- area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N2 physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H2 (TPR-H2), and temperature-programmed NH3 desorption (TPD-NH3). The single-site nature of the Mo species is corroborated by XPS and TPR-H2 data, and it exhibits the lowest reported MoOx Tmax of reduction reported to date, suggesting a highly reactive MoVI center. (Oc)2Mo(=O)2@C catalyzes the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60-90 °C) and with negligible deactivation. (Oc)2Mo(=O)2@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH = 10.5(8) kcal mol-1 and ΔS = -32(2) eu. The low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and lowcost catalyst with significant potential for transesterification processes.

  4. Transition metals-incorporated zeolites as environmental catalysts for indoor air ozone decomposition.

    Science.gov (United States)

    Mohamed, E F; Awad, G; Zaitan, H; Andriantsiferana, C; Manero, M-H

    2018-04-01

    The present study aimed to prepare catalysts of Fe- and Cu-loaded zeolite via ion-exchange technique using dilute solutions of metal nitrate precursors followed by calcination at 600°C in the air for 4 h. Commercial zeolite ZSM-5 with specific surface area of 400 m 2 /g and diameter particle of 1.2-2 mm was used as a parent support. The prepared catalysts were characterized by Fourier transform infrared spectroscopy analysis. The IR absorbed bands of Cu-ZSM-5 and Fe-ZSM-5 revealed a shift in the frequency and a reduction in the intensity framework. This indicates that both catalysts have a significant change in the number of the zeolite structure bonds. The catalytic activity of the prepared materials compared to the parent zeolite was evaluated for the catalytic ozone decomposition. The ozone stream of the initial concentration (13 g/m 3 ) with air flow rate (Q) of 0.18 m 3 /h was passed through a glass jacket column reactor filled with a fixed bed of 40 g zeolites. It was showed that the ozone removal efficiency by Cu-ZSM-5 and Fe-ZSM-5 was obviously higher than that found with the parent ZSM-5. In terms of O 3 removal efficiency, zeolite samples could be ranked as follows: Fe-ZSM-5 > Cu-ZSM-5> parent ZSM-5. The results revealed about 90% O 3 removal efficiency for Fe-ZSM-5 and 70% for Cu-ZSM-5 as compared to nearly 40% for the parent zeolite. Consequently, the incorporation of Fe and Cu metals onto the zeolite surface plays a key role for enhancing the gaseous ozone elimination.

  5. Metal Oxide Supported Vanadium Substituted Keggin Type Polyoxometalates as Catalyst For Oxidation of Dibenzothiophene

    Science.gov (United States)

    Lesbani, Aldes; Novri Meilyana, Sarah; Karim, Nofi; Hidayati, Nurlisa; Said, Muhammad; Mohadi, Risfidian; Miksusanti

    2018-01-01

    Supported polyoxometalatate H4[γ-H2SiV2W10O40]·nH2O with metal oxide i.e. silica, titanium, and tantalum was successfully synthesized via wet impregnation method to form H4[γ-H2SiV2W10O40]·nH2O-Si, H4[γ-H2SiV2W10O40]·nH2O-Ti, and H4[γ-H2SiV2W10O40]·nH2O-Ta. Characterization was performed using FTIR spectroscopy, X-Ray analyses, and morphology analyses using SEM. All compounds were used as the catalyst for desulfurization of dibenzothiophene (DBT). Silica and titanium supported polyoxometalate H4[γ-H2SiV2W10O40]·nH2O better than tantalum due to retaining crystallinity after impregnation process. On the other hand, compound H H4[γ-H2SiV2W10O40]·nH2O-Ta showed high catalytic activity than other supported metal oxides for desulfurization of DBT. Optimization desulfurization process resulted in 99% conversion of DBT under a mild condition at 70 °C, 0.1 g catalyst, and reaction for 3 hours. Regeneration studies showed catalyst H4[γ-H2SiV2W10O40]·nH2O-Ti was remaining catalytic activity for desulfurization of DBT.

  6. Large-scale synthesis of coiled-like shaped carbon nanotubes using bi-metal catalyst

    Science.gov (United States)

    Krishna, Vemula Mohana; Somanathan, T.; Manikandan, E.; Umar, Ahmad; Maaza, M.

    2018-02-01

    Carbon nanomaterials (CNMs), especially carbon nanotubes (CNTs) with coiled structure exhibit scientifically fascinating. They may be projected as an innovative preference to future technological materials. Coiled carbon nanotubes (c-CNTs) on a large-scale were successfully synthesized with the help of bi-metal substituted α-alumina nanoparticles catalyst via chemical vapor deposition (CVD) technique. Highly spring-like carbon nanostructures were observed by field emission scanning electron microscope (FESEM) examination. Furthermore, the obtained material has high purity, which correlates the X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) analysis. Raman spectroscopy reveals that the carbon multi layers are well graphitized and crystalline, even if they have defects in its structure due to coiled morphology. High-resolution transmission electron microscope (HRTEM) describes internal structure and dia of the product. Ultimately, results support the activity of bi-metal impregnated α-alumina nanoparticles catalyst to determine the high yield, graphitization and internal structure of the material. We have also studied the purified c-CNTs magnetic properties at room temperature and will be an added advantage in several applications.

  7. Metal Phosphides as Co-Catalysts for Photocatalytic and Photoelectrocatalytic Water Splitting.

    Science.gov (United States)

    Cao, Shuang; Wang, Chuan-Jun; Fu, Wen-Fu; Chen, Yong

    2017-11-23

    Solar-to-hydrogen conversion based on photocatalytic and photoelectrocatalytic water splitting is considered as a promising technology for sustainable hydrogen production. Developing earth-abundant H 2 -production materials with robust activity and stability has become the mainstream in this field. Due to the unique properties and characteristics, transition metal phosphides (TMPs) have been proven to be high performance co-catalysts to replace some of the classic precious metal materials in photocatalytic water splitting. In this Minireview, we summarize the recent significant progress of TMPs as cocatalysts for water splitting reaction with high activity and stability. Firstly, the characteristic of TMPs is briefly introduced. Then, we mainly discuss the recent research efforts toward their application as photocatalytic co-catalysts in photocatalytic H 2 -production, O 2 -evolution and photoelectrochemical water splitting. Finally, the catalytic mechanism, current existing challenges and future working directions for improving the performance of TMPs are proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

    Science.gov (United States)

    Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

    2018-01-01

    Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

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

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz

    2009-12-01

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

  10. Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

    Science.gov (United States)

    Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

    2018-03-01

    Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

  11. Synthesis of High-quality Single- and Double-walled Carbon Nanotubes on Fe/MgO Catalysts

    Directory of Open Access Journals (Sweden)

    Mehran B. Kashi

    2016-06-01

    Full Text Available In this study, Fe/MgO catalysts with three different iron contents (5, 10, and 15 wt.% were prepared by three catalyst preparation methods: impregnation, solution combustion synthesis, and co-calcination of metal ni‐ trates. The resulting catalysts were subjected to methane at 900°C in order to grow carbon nanotubes (CNTs. The powders and products were then studied by X-ray diffraction (XRD, differential thermal analysis (DTA, scanning and transmission electron microscopy (SEM and TEM, and Raman spectroscopy. Formation of MgFe2O4 upon heating the catalysts to 900°C was confirmed by XRD. After the growth step, corresponding peaks of MgFe2O4 disappeared and metallic iron peaks appeared, indicating that MgFe2O4 is the responsible phase for production of iron nanoparticles. HRTEM images showed that the product on the 5 wt.% catalysts was mostly SWNTs and DWNTs with no evidence of carbon nanofi‐ bres or multi-walled carbon nanotubes on the co-calcina‐ tion catalyst. Furthermore, ID/IG ratios obtained from Raman spectra were all below 0.1, except for one sample, showing the good quality of the products.

  12. Interaction of NO2 with model NSR catalysts: metal-oxide interaction controls initial NOx storage mechanism.

    Science.gov (United States)

    Desikusumastuti, Aine; Staudt, Thorsten; Qin, Zhihui; Happel, Markus; Laurin, Mathias; Lykhach, Yaroslava; Shaikhutdinov, Shamil; Rohr, Friedemann; Libuda, Jörg

    2008-10-24

    Using scanning tunneling microscopy (STM), molecular-beam (MB) methods and time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we investigate the mechanism of initial NO(x) uptake on a model nitrogen storage and reduction (NSR) catalyst. The model system is prepared by co-deposition of Pd metal particles and Ba-containing oxide particles onto an ordered alumina film on NiAl(110). We show that the metal-oxide interaction between the active noble metal particles and the NO(x) storage compound in NSR model catalysts plays an important role in the reaction mechanism. We suggest that strong interaction facilitates reverse spillover of activated oxygen species from the NO(x) storage compound to the metal. This process leads to partial oxidation of the metal nanoparticles and simultaneous stabilization of the surface nitrite intermediate.

  13. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1996-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  14. Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip

    Science.gov (United States)

    Kittrell, W. Carter; Wang, Yuhuang; Kim, Myung Jong; Hauge, Robert H.; Smalley, Richard E.; Marek leg, Irene Morin

    2010-06-01

    The present invention is directed to fibers of epitaxially grown single-wall carbon nanotubes (SWNTs) and methods of making same. Such methods generally comprise the steps of: (a) providing a spun SWNT fiber; (b) cutting the fiber substantially perpendicular to the fiber axis to yield a cut fiber; (c) etching the cut fiber at its end with a plasma to yield an etched cut fiber; (d) depositing metal catalyst on the etched cut fiber end to form a continuous SWNT fiber precursor; and (e) introducing feedstock gases under SWNT growth conditions to grow the continuous SWNT fiber precursor into a continuous SWNT fiber.

  15. Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compounds.

    Science.gov (United States)

    Barakat, Tarek; Rooke, Joanna C; Tidahy, Haingomalala Lucette; Hosseini, Mahsa; Cousin, Renaud; Lamonier, Jean-François; Giraudon, Jean-Marc; De Weireld, Guy; Su, Bao-Lian; Siffert, Stéphane

    2011-10-17

    The use of porous materials to eliminate volatile organic compounds (VOCs) has proven very effective towards achieving sustainability and environmental protection goals. The activity of zeolites and macro-mesoporous metal-oxide supports in the total oxidation of VOCs has been investigated, with and without noble-metal deposition, to develop highly active catalyst systems where the formation of by-products was minimal. The first catalysts employed were zeolites, which offered a good activity in the oxidation of VOCs, but were rapidly deactivated by coke deposition. The effects of the acido-basicity and ionic exchange of these zeolites showed that a higher basicity was related to exchanged ions with lower electronegativities, resulting in better catalytic performances in the elimination of VOCs. Following on from this work, noble metals were deposited onto macro-mesoporous metal-oxide supports to form mono and bimetallic catalysts. These were then tested in the oxidation of toluene to study their catalytic performance and their deactivation process. PdAu/TiO(2) and PdAu/TiO(2) -ZrO(2) 80/20 catalysts demonstrated the best activity and life span in the oxidation of toluene and propene and offered the lowest temperatures for a 50 % conversion of VOCs and the lowest coke content after catalytic testing. Different characterization techniques were employed to explain the changes occurring in catalyst structure during the oxidation of toluene and propene. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Comparison of UV and visible Raman spectroscopy of bulk metal molybdate and metal vanadate catalysts.

    Science.gov (United States)

    Tian, Hanjing; Wachs, Israel E; Briand, Laura E

    2005-12-15

    The visible (532 and 442 nm) and UV (325 nm) Raman spectra of bulk mixed metal oxides (metal molybdates and metal vanadates) were compared on the same spectrometer, for the first time, to allow examination of how varying the excitation energy from visible to UV affects the resulting Raman spectra. The quality of the Raman spectra was found to be a strong function of the absorption properties of the bulk mixed oxide. For bulk mixed metal oxides that absorb weakly in the visible and UV regions, both the visible and UV Raman spectra were of high quality and exhibit identical vibrational bands, but with slightly different relative intensities. For bulk mixed metal oxides that absorb strongly in the UV and visible regions and/or strongly in the UV and weakly in the visible regions, the visible Raman spectra are much richer in structural information and of higher resolution than the corresponding UV Raman spectra. This is a consequence of the strong UV absorption that significantly reduces the sampling volume and number of scatterers giving rise to the Raman signal. The shallower escape depth of UV Raman, however, was not sufficient to detect vibrations from the surface metal oxide species that are present on the outermost surface layer of these crystalline mixed metal oxide phases as previously suggested. It was also demonstrated that there is no sample damage by the more energetic UV excitation when very low laser powers and fast detectors are employed, thus avoiding the need of complicated fluidized bed sample arrangements sometimes used for UV Raman investigations. The current comparative Raman investigation carefully documents, for the first time, the advantages and disadvantages of applying different excitation energies in collecting Raman spectra of bulk mixed metal oxide materials.

  17. Steam reforming of biomass gasification tar using benzene as a model compound over various Ni supported metal oxide catalysts.

    Science.gov (United States)

    Park, Hyun Ju; Park, Sung Hoon; Sohn, Jung Min; Park, Junhong; Jeon, Jong-Ki; Kim, Seung-Soo; Park, Young-Kwon

    2010-01-01

    The steam reforming of benzene as a model compound of biomass gasification tar was carried out over various Ni/metal oxide catalysts. The effects of the support, temperature, Ni-precursor, Ni loading and reaction time were examined, and their catalytic performance was compared with that of a commercial Ni catalyst. Among the Ni/metal oxide catalysts used, 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) showed the highest catalytic performance owing to its greater redox characteristics and increased surface area, irrespective of the reaction temperature. The catalytic activity of 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) was higher than that of the commercial Ni catalyst. Moreover, the catalyst activity was retained due to its excellent resistance to coke deposition even after 5h. The Ni-precursor played a critical role in the catalytic activity. With the exception of nickel nitrate, all the Ni-precursors (chloride and sulfate) caused deactivation of the catalyst.

  18. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

    Science.gov (United States)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

    2018-01-10

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  20. Metallic cobalt nanoparticles imbedded into ordered mesoporous carbon: A non-precious metal catalyst with excellent hydrogenation performance.

    Science.gov (United States)

    Liu, Jiangyong; Wang, Zihao; Yan, Xiaodong; Jian, Panming

    2017-11-01

    Ordered mesoporous carbon (OMC)-metal composites have attracted great attention owing to their combination of high surface area, controlled pore size distribution and physicochemical properties of metals. Herein, we report the cobalt nanoparticles/ordered mesoporous carbon (CoNPs@OMC) composite prepared by a one-step carbonization/reduction process assisted by a hydrothermal pre-reaction. The CoNPs@OMC composite presents a high specific surface area of 544m 2 g -1 , and the CoNPs are uniformly imbedded or confined in the ordered mesoporous carbon matrix. When used as a non-precious metal-containing catalyst for hydrogenation reduction of p-nitrophenol and nitrobenzene, it demonstrates high efficiency and good cycling stability. Furthermore, the CoNPs@OMC composite can be directly used to catalyze the Fischer-Tropsch synthesis for the high-pressure CO hydrogenation, and presents a good catalytic selectivity for C 5 + hydrocarbons. The excellent catalytic performance of the CoNPs@OMC composite can be ascribed to synergistic effect between the high specific surface area, mesoporous structure and well-imbedded CoNPs in the carbon matrix. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Metal-induced rapid transformation of diamond into single and multilayer graphene on wafer scale.

    Science.gov (United States)

    Berman, Diana; Deshmukh, Sanket A; Narayanan, Badri; Sankaranarayanan, Subramanian K R S; Yan, Zhong; Balandin, Alexander A; Zinovev, Alexander; Rosenmann, Daniel; Sumant, Anirudha V

    2016-07-04

    The degradation of intrinsic properties of graphene during the transfer process constitutes a major challenge in graphene device fabrication, stimulating the need for direct growth of graphene on dielectric substrates. Previous attempts of metal-induced transformation of diamond and silicon carbide into graphene suffers from metal contamination and inability to scale graphene growth over large area. Here, we introduce a direct approach to transform polycrystalline diamond into high-quality graphene layers on wafer scale (4 inch in diameter) using a rapid thermal annealing process facilitated by a nickel, Ni thin film catalyst on top. We show that the process can be tuned to grow single or multilayer graphene with good electronic properties. Molecular dynamics simulations elucidate the mechanism of graphene growth on polycrystalline diamond. In addition, we demonstrate the lateral growth of free-standing graphene over micron-sized pre-fabricated holes, opening exciting opportunities for future graphene/diamond-based electronics.

  2. Amino-functionalized metal-organic frameworks as tunable heterogeneous basic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, M.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2011-07-01

    Metal-organic framework (MOF) materials have been explored for applications in heterogeneous catalysis in recent years. In addition to the use of MOFs as supports for the deposition of highly dispersed metal particles, the incorporation of active centers such as coordinatively unsaturated metal sites and the functionalization of the organic linkers with acidic or basic groups seems to be most promising. In our contribution, three different MOFs carrying amino groups at their organic linkers, namely Fe-MIL-101-NH{sub 2} (S{sub BET} = 3438 m{sup 2}g{sup -1}), Al-MIL-101-NH{sub 2} (S{sub BET} = 3099 m{sup 2}g{sup -1}) and CAU-1 (S{sub BET} = 1492 m{sup 2}g{sup -1}), were synthesized and tested in the Knoevenagel condensation of benzaldehyde with malononitrile and with ethyl cyanoacetate, respectively. It is shown that the expected products benzylidenemalononitrile (BzMN) and ethyl a-cyanocinnamate (EtCC) are formed with selectivities of more than 99 % and yields of 90 to 95 % after 3 h (for BzMN). Due to the very small pore windows of CAU-1 (0.3 to 0.4 nm) the reaction proceeds much slower over this catalyst in comparison to the amino-MIL-101 derivatives, which possess open pore windows of up to 1.6 nm. Finally, leaching tests confirm that the reaction is heterogeneously catalyzed. Moreover, the catalysts are recyclable without significant loss of activity. (orig.)

  3. Noble metals decorated hierarchical maghemite magnetic tubes as an efficient recyclable catalyst.

    Science.gov (United States)

    Purbia, Rahul; Paria, Santanu

    2018-02-01

    The noble metal nanocatalysts on high surface area magnetic material supports have huge technological importance in the field of catalysis. The green synthesis of magnetic-noble metal hybrid material has another technological importance. In this study, we report a novel, efficient, and sustainable synthesis methodology for Au nanoparticles (NPs) deposited hierarchical magnetic maghemite (γ-Fe 2 O 3 ) tubes. In this methodology, the green tea extract was used as a reducing agent for both iron oxide and Au NPs synthesis. The natural cotton fibers were used as a sacrificial template to obtain porous and high surface area (90m 2 /g) magnetic γ-Fe 2 O 3 tubes. Further, the Au NPs (7±2nm) were in situ deposited onto the tubes surface after reduction of Au salt by green tea extract. The XPS spectra was confirmed the presence of negatively charged Au on the iron oxide supports due to charge transfer process and strong metal-support material electronic interaction. The Au NPs decorated γ-Fe 2 O 3 tubes were possessed 18emu/g saturation magnetization at room temperature which is large enough for the magnetic separation. The synthesized material was showed very good catalytic activity for the hydrogenation reaction of 4-nitrophenol to aminophenol conversion. As the catalyst has very good magnetic property, the reusability of catalyst was checked after magnetic separation and found only 0.29% reduction in catalytic activity after the sixth cycle. Further, the Ag and Pd NPs decorated γ-Fe 2 O 3 tubes were also synthesized and tested for the same catalytic reaction and found the highest activity for Pd. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Single sheet metal oxides and hydroxides

    DEFF Research Database (Denmark)

    Huang, Lizhi

    The synthesis of layered double hydroxides (LDHs) provides a relatively easy and traditional way to build versatile chemical compounds with a rough control of the bulk structure. The delamination of LDHs to form their single host layers (2D nanosheets) and the capability to reassemble them offer ......) Delamination of the LDHs structure (oxGRC12) with the formation of single sheet iron (hydr)oxide (SSI). (3) Assembly of the new 2D nanosheets layer by layer to achieve desired functionalities....

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

    Science.gov (United States)

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

    2015-09-01

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

  6. Catalytic Formylation of Primary and Secondary Amines with CO2and H2Using Abundant-Metal Catalysts.

    Science.gov (United States)

    Affan, Mohammad A; Jessop, Philip G

    2017-06-19

    Catalytic hydrogenation of CO 2 is an efficient and selective way to prepare formic acid derivatives, but most of the highly active catalysts used for this purpose require precious metals. In this study, in situ abundant-metal complexes have been evaluated as potential catalysts for CO 2 hydrogenation to prepare formamides, including N-formylmorpholine, 2-ethylhexylformamide, and dimethylformamide, from the corresponding amines. From these initial screening results, the most active catalysts for these reactions were found to be MX 2 /dmpe in situ catalysts (M = Fe(II), Ni(II); X = Cl - , CH 3 CO 2 - , acac - ; dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. The optimal reaction conditions were found to be 100-135 °C and a total pressure of 100 bar. Morpholine was formylated with a TON value of up to 18000, which is the highest TON for the hydrogenation of CO 2 to formamides using any abundant-metal-phosphine complex. With an appropriate selection of catalyst and reaction conditions, >90-98% conversion of amine to formamide could be achieved.

  7. Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh32Ru-SnX3 (X = Cl or Br

    Directory of Open Access Journals (Sweden)

    Ana Cláudia Bernardes Silva

    2003-06-01

    Full Text Available In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh32Ru-SnX3 (X = Cl or Br complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR (Temperature Programmed Reduction experiments carried out with these RuSn catalysts suggested a strong interaction between Ruthenium and Tin. Mössbauer measurements showed that these materials when exposed to air are immediately oxidized to form Sn (IV. It was shown that upon controlled reduction conditions with H2 it is possible to reduce selectively Sn to different oxidation states and different phases. The Sn oxidation state showed significant effect on the catalytic hydrogenation of 1,5-cyclooctadiene. The use of these single source precursors with a controlled decomposition/reduction procedure allows the preparation of unique catalysts with an intimate interaction between the components ruthenium and tin and the possibility of varying the Sn oxidation state around the Ru metal.

  8. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

    Science.gov (United States)

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

    2015-09-01

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

  9. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

    Energy Technology Data Exchange (ETDEWEB)

    Altman, Eric I. [Yale Univ., New Haven, CT (United States)

    2015-10-06

    The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO2 surfaces. Building on this work on anatase, the mechanism by which TiO2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

  10. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  11. Why Does Industry Not Use Immobilized Transition Metal Complexes as Catalysts?

    NARCIS (Netherlands)

    Huebner, Sandra; de Vries, Johannes G.; Farina, Vittorio

    2016-01-01

    Much effort has gone into the immobilization of homogeneous catalysts based on the idea that in this way the catalysts could be not only separated more easily from the product but also reused several times, thus reducing the cost of the catalyst use. So far none of these immobilized catalysts have

  12. Synthesis of Supported Ultrafine Non-noble Subnanometer-Scale Metal Particles Derived from Metal-Organic Frameworks as Highly Efficient Heterogeneous Catalysts.

    Science.gov (United States)

    Kang, Xinchen; Liu, Huizhen; Hou, Minqiang; Sun, Xiaofu; Han, Hongling; Jiang, Tao; Zhang, Zhaofu; Han, Buxing

    2016-01-18

    The properties of supported non-noble metal particles with a size of less than 1 nm are unknown because their synthesis is a challenge. A strategy has now been created to immobilize ultrafine non-noble metal particles on supports using metal-organic frameworks (MOFs) as metal precursors. Ni/SiO2 and Co/SiO2 catalysts were synthesized with an average metal particle size of 0.9 nm. The metal nanoparticles were immobilized uniformly on the support with a metal loading of about 20 wt%. Interestingly, the ultrafine non-noble metal particles exhibited very high activity for liquid-phase hydrogenation of benzene to cyclohexane even at 80 °C, while Ni/SiO2 with larger Ni particles fabricated by a conventional method was not active under the same conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Single-photon imaging in complementary metal oxide semiconductor processes

    NARCIS (Netherlands)

    Charbon, E.

    2014-01-01

    This paper describes the basics of single-photon counting in complementary metal oxide semiconductors, through single-photon avalanche diodes (SPADs), and the making of miniaturized pixels with photon-counting capability based on SPADs. Some applications, which may take advantage of SPAD image

  14. Single-crystal metal growth on amorphous insulating substrates.

    Science.gov (United States)

    Zhang, Kai; Pitner, Xue Bai; Yang, Rui; Nix, William D; Plummer, James D; Fan, Jonathan A

    2018-01-23

    Metal structures on insulators are essential components in advanced electronic and nanooptical systems. Their electronic and optical properties are closely tied to their crystal quality, due to the strong dependence of carrier transport and band structure on defects and grain boundaries. Here we report a method for creating patterned single-crystal metal microstructures on amorphous insulating substrates, using liquid phase epitaxy. In this process, the patterned metal microstructures are encapsulated in an insulating crucible, together with a small seed of a differing material. The system is heated to temperatures above the metal melting point, followed by cooling and metal crystallization. During the heating process, the metal and seed form a high-melting-point solid solution, which directs liquid epitaxial metal growth. High yield of single-crystal metal with different sizes is confirmed with electron backscatter diffraction images, after removing the insulating crucible. Unexpectedly, the metal microstructures crystallize with the [Formula: see text] direction normal to the plane of the film. This platform technology will enable the large-scale integration of high-performance plasmonic and electronic nanosystems.

  15. Photo-electrocatalytic hydrogen generation at dye-sensitised electrodes functionalised with a heterogeneous metal catalyst

    International Nuclear Information System (INIS)

    Hoogeveen, Dijon A.; Fournier, Maxime; Bonke, Shannon A.; Fang, Xi-Ya; Mozer, Attila J.; Mishra, Amaresh; Bäuerle, Peter; Simonov, Alexandr N.; Spiccia, Leone

    2016-01-01

    Dye-sensitised photocathodes promoting hydrogen evolution are usually coupled to a catalyst to improve the reaction rate. Herein, we report on the first successful integration of a heterogeneous metal particulate catalyst, viz., Pt aggregates electrodeposited from acidic solutions on the surface of a NiO-based photocathode sensitised with a p-type perylenemonoimid-sexithiophene-triphenylamine dye (PMI-6T-TPA). The platinised dye-NiO electrodes generate photocurrent density of ca −0.03 mA cm −2 (geom.) with 100% faradaic efficiency for the H 2 evolution at 0.059 V vs. reversible hydrogen electrode under 1 sun visible light irradiation (AM1.5G, 100 mW cm −2 , λ > 400 nm) for more than 10 hours in 0.1 M H 2 SO 4 (aq.). The Pt-free dye-NiO and dye-free Pt-modified NiO cathodes show no photo-electrocatalytic hydrogen evolution under these conditions. The performance of these Pt-modified PMI-6T-TPA-based photoelectrodes compares well to that of previously reported dye-sensitised photocathodes for H 2 evolution.

  16. Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

    Science.gov (United States)

    Liu, Yuanyue; Wu, Jingjie; Hackenberg, Ken P.; Zhang, Jing; Wang, Y. Morris; Yang, Yingchao; Keyshar, Kunttal; Gu, Jing; Ogitsu, Tadashi; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M.; Wood, Brandon C.; Yakobson, Boris I.

    2017-09-01

    Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm-2 current density at an overpotential of ˜50-60 mV with a loading of 10-55 μg cm-2, surpassing other reported MX2 candidates without any performance-enhancing additives.

  17. Half-sandwich group 4 metal siloxy and silsesquioxane complexes : Soluble model systems for silica-grafted olefin polymerization catalysts

    NARCIS (Netherlands)

    Duchateau, R; Cremer, U; Harmsen, RJ; Mohamud, SI; Abbenhuis, HCL; van Santen, RA; Meetsma, A; Thiele, SKH; van Tol, MFH; Kranenburg, M

    1999-01-01

    The cuboctameric hydroxysilsesquioxane (c-C5H9)(7)Si8O12(OH) (2), obtained after hydrolysis of (c-C5H9)(7)Si8O12Cl (1), and triphenylsilanol have been applied as model supports for silica-grafted olefin polymerization catalysts. The ligands were introduced on group 4 metals by either chloride

  18. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides

    NARCIS (Netherlands)

    Hereijgers, B.P.C.; Weckhuysen, B.M.

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with

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

    DEFF Research Database (Denmark)

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

    2015-01-01

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

  20. Three dimensional metal/N-doped nanoplate carbon catalysts for oxygen reduction, the reason for using a layered nanoreactor.

    Science.gov (United States)

    Yeganeh Ghotbi, Mohammad; Javanmard, Arash; Soleimani, Hassan

    2018-02-21

    A layered nanoreactor (zinc hydroxide gallate/nitrate nanohybrid) has been designed as a nano-vessel to confine the gallate/nitrate reaction inside zinc hydroxide layers for production of metal/nitrogen-doped carbon catalysts. Metals (Fe 2+ , Co 2+ and Ni 2+ ) doped and bare zinc hydroxide nitrates (ZHN) were synthesized as the α-phase hydroxide hosts. By an incomplete ion-exchange process, nitrate anions between the layers of the hosts were then partially replaced by the gallate anions to produce the layered nanoreactors. Under heat-treatment, the reaction between the remaining un-exchanged nitrate anions and the organic moiety inside the basal spacing of each nanohybrid plate resulted in obtaining highly porous 3D metal/nitrogen-doped carbon nanosheets. These catalysts were then used as extremely efficient electrocatalysts for catalyzing oxygen reduction reaction (ORR). This study is intended to show the way to get maximum electrocatalytic activity of the metal/N-doped carbon catalysts toward the ORR. This exceptionally high ORR performance originates from the increased available surface, the best pore size range and the uniform distribution of the active sites in the produced catalysts, all provided by the use of new idea of the layered nanoreactor.

  1. Influence of Multi-Valency, Electrostatics and Molecular Recognition on the Adsorption of Transition Metal Complexes on Metal Oxides: A Molecular Approach to Catalyst Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, Robert M. [Pennsylvania State Univ., University Park, PA (United States)

    2017-03-31

    In this work, we have primarily utilized isothermal titration calorimetry (ITC) and complimentary catalyst characterization techniques to study and assess the impact of solution conditions (i.e., solid-liquid) interface on the synthesis of heterogeneous and electro-catalysts. Isothermal titration calorimetry is well-known technique from biochemistry/physics, but has been applied to a far lesser extent to characterize buried solid-liquid interfaces in materials science. We demonstrate the utility and unique information provided by ITC for two distinct catalytic systems. We explored the thermodynamics associated catalyst synthesis for two systems: (i) ion-exchange or strong electrostatic adsorption for Pt and Pd salts on silica and alumina materials (ii) adsorption to provide covalent attachment of metal and metal-oxo clusters to Dion-Jacobsen perovskite materials.

  2. Mechanistic studies of the reactions of 2-methylpropene with deuterium over supported metal catalysts

    International Nuclear Information System (INIS)

    Brown, R.; Kemball, C.; Sadler, I.H.

    1989-01-01

    Deuterium NMR spectroscopy, gas chromatography and mass spectrometry have been used to examine the products from the reaction of 2-methylpropene with deuterium over supported metal catalysts. The detailed information, so obtained, about the number, location and grouping of deuterium atoms in both the exchanged alkenes and the 2-methylpropanes formed by addition provided evidence about possible mechanisms. With palladium, exchange was faster than addition and the deuterium atoms were randomly distributed in the alkene, probably through a π-allyl dissociative mechanism. With platinum and rhodium, exchange occurred preferentially in the methylene groups of the alkene and the results indicated a dissociative mechanism involving adsorbed vinyl intermediates together with some intramolecular double-bond movement through a π-allyl type of species. Relatively little exchange occurred with iridium. (author)

  3. Recent developments in atom transfer radical polymerization (ATRP): methods to reduce metal catalyst concentrations.

    Science.gov (United States)

    Lou, Qin; Shipp, Devon A

    2012-10-08

    Atom transfer radical polymerization (ATRP) was initially developed in the mid-1990s, and with continued refinement and use has led to significant discoveries in new materials. However, metal contamination of the polymer product is an issue that has proven detrimental to widespread industrial application of ATRP. The laboratories of K. Matyjaszewski have made significant progress towards removing this impediment, leading the development of "activators regenerated by electron transfer" ATRP (ARGET ATRP) and electrochemically mediated ATRP (eATRP) technologies. These variants of ATRP allow polymers to be produced with great molecular weight and functionality control but at significantly reduced catalyst concentrations, typically at parts per million levels. This Concept examines these polymerizations in terms of their mechanism and outcomes, and is aimed at giving the reader an overview of recent developments in the field of ATRP. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Applications of Immobilized Bio-Catalyst in Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Qi Wang

    2018-04-01

    Full Text Available Immobilization of bio-catalysts in solid porous materials has attracted much attention in the last few decades due to its vast application potential in ex vivo catalysis. Despite the high efficiency and selectivity of enzymatic catalytic processes, enzymes may suffer from denaturation under industrial production conditions, which, in turn, diminish their catalytic performances and long-term recyclability. Metal-organic frameworks (MOFs, as a growing type of hybrid materials, have been identified as promising platforms for enzyme immobilization owing to their enormous structural and functional tunability, and extraordinary porosity. This review mainly focuses on the applications of enzyme@MOFs hybrid materials in catalysis, sensing, and detection. The improvements of catalytic activity and robustness of encapsulated enzymes over the free counterpart are discussed in detail.

  5. Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts.

    Science.gov (United States)

    Bernskoetter, Wesley H; Hazari, Nilay

    2017-04-18

    New and sustainable energy vectors are required as a consequence of the environmental issues associated with the continued use of fossil fuels. H 2 is a potential clean energy source, but as a result of problems associated with its storage and transport as a gas, chemical H 2 storage (CHS), which involves the dehydrogenation of small molecules, is an attractive alternative. In principle, formic acid (FA, 4.4 wt % H 2 ) and methanol (MeOH, 12.6 wt % H 2 ) can be obtained renewably and are excellent prospective liquid CHS materials. In addition, MeOH has considerable potential both as a direct replacement for gasoline and as a fuel cell input. The current commercial syntheses of FA and MeOH, however, use nonrenewable feedstocks and will not facilitate the use of these molecules for CHS. An appealing option for the sustainable synthesis of both FA and MeOH, which could be implemented on a large scale, is the direct metal catalyzed hydrogenation of CO 2 . Furthermore, given that CO 2 is a readily available, nontoxic and inexpensive source of carbon, it is expected that there will be economic and environmental benefits from using CO 2 as a feedstock. One strategy to facilitate both the dehydrogenation of FA and MeOH and the hydrogenation of CO 2 and H 2 to FA and MeOH is to utilize a homogeneous transition metal catalyst. In particular, the development of catalysts based on first row transition metals, which are cheaper, and more abundant than their precious metal counterparts, is desirable. In this Account, we describe recent advances in the development of iron and cobalt systems for the hydrogenation of CO 2 to FA and MeOH and the dehydrogenation of FA and MeOH and provide a brief comparison between precious metal and base metal systems. We highlight the different ligands that have been used to stabilize first row transition metal catalysts and discuss the use of additives to promote catalytic activity. In particular, the Account focuses on the crucial role that

  6. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts.

    Science.gov (United States)

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

    2009-09-10

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

  7. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

    Science.gov (United States)

    Franco, Ana; De, Sudipta; Balu, Alina M; Garcia, Araceli; Luque, Rafael

    2017-01-01

    Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H 2 O 2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  8. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin

    Directory of Open Access Journals (Sweden)

    Ana Franco

    2017-07-01

    Full Text Available Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc. have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H2O2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  9. Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

    Science.gov (United States)

    Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

    2018-04-01

    As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

  10. Growth Mechanism of Single-Walled Carbon Nanotubes on Iron–Copper Catalyst and Chirality Studies by Electron Diffraction

    DEFF Research Database (Denmark)

    He, Maoshuai; Liu, Bilu; Chernov, Alexander I.

    2012-01-01

    Chiralities of single-walled carbon nanotubes grown on an atomic layer deposition prepared bimetallic FeCu/MgO catalyst were evaluated quantitatively using nanobeam electron diffraction. The results reveal that the growth yields nearly 90% semiconducting tubes, 45% of which are of the (6,5) type....... by impregnation, showing similar catalytic performance as the atomic layer deposition-prepared catalyst, yielding single-walled carbon nanotubes with a similar narrow chirality distribution.......Chiralities of single-walled carbon nanotubes grown on an atomic layer deposition prepared bimetallic FeCu/MgO catalyst were evaluated quantitatively using nanobeam electron diffraction. The results reveal that the growth yields nearly 90% semiconducting tubes, 45% of which are of the (6,5) type....... The growth mechanisms as well as the roles of different components in the catalyst were studied in situ using environmental transmission electron microscopy and infrared spectroscopy. On the basis of the understanding of carbon nanotube growth mechanisms, an MgO-supported FeCu catalyst was prepared...

  11. Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst.

    Science.gov (United States)

    Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng; Gao, Zehua; Luo, Zhiheng; Wang, Xu; Zeng, Rui; Li, Aowen; Li, Hongliang; Wang, Menglin; Zheng, Xusheng; Zhu, Junfa; Zhang, Wenhua; Ma, Chao; Si, Rui; Zeng, Jie

    2016-12-22

    Rh-based heterogeneous catalysts generally have limited selectivity relative to their homogeneous counterparts in hydroformylation reactions despite of the convenience of catalyst separation in heterogeneous catalysis. Here, we develop CoO-supported Rh single-atom catalysts (Rh/CoO) with remarkable activity and selectivity towards propene hydroformylation. By increasing Rh mass loading, isolated Rh atoms switch to aggregated clusters of different atomicity. During the hydroformylation, Rh/CoO achieves the optimal selectivity of 94.4% for butyraldehyde and the highest turnover frequency number of 2,065 h -1 among the obtained atomic-scale Rh-based catalysts. Mechanistic studies reveal that a structural reconstruction of Rh single atoms in Rh/CoO occurs during the catalytic process, facilitating the adsorption and activation of reactants. In kinetic view, linear products are determined as the dominating products by analysing reaction paths deriving from the two most stable co-adsorbed configurations. As a bridge of homogeneous and heterogeneous catalysis, single-atom catalysts can be potentially applied in other industrial reactions.

  12. Combined high-pressure cell-ultrahigh vacuum system for fast testing of model metal alloy catalysts using scanning mass spectrometry

    DEFF Research Database (Denmark)

    Johansson, Martin; Jørgensen, Jan Hoffmann; Chorkendorff, Ib

    2004-01-01

    An apparatus for fabrication, surface analysis in ultrahigh vacuum, and testing of the catalytic activity of model metal alloy catalysts is described. Arrays of model catalysts are produced by electron-beam deposition of up to four metals simultaneously onto a substrate. The surface analysis...... be studied on a substrate 10 mm in diameter. A high pressure cell with an all-metal sealed ultrahigh vacuum lock is also described as part of the work. ©2004 American Institute of Physics....

  13. Recent Developments in Single-Walled Carbon Nanotube Thin Films Fabricated by Dry Floating Catalyst Chemical Vapor Deposition.

    Science.gov (United States)

    Zhang, Qiang; Wei, Nan; Laiho, Patrik; Kauppinen, Esko I

    2017-11-27

    Transparent conducting films (TCFs) are critical components of many optoelectronic devices that pervade modern technology. Due to their excellent optoelectronic properties and flexibility, single-walled carbon nanotube (SWNT) films are regarded as an important alternative to doped metal oxides or brittle and expensive ceramic materials. Compared with liquid-phase processing, the dry floating catalyst chemical vapor deposition (FCCVD) method without dispersion of carbon nanotubes (CNTs) in solution is more direct and simpler. By overcoming the tradeoff between CNT length and solubility during film fabrication, the dry FCCVD method enables production of films that contain longer CNTs and offer excellent optoelectronic properties. This review focuses on fabrication of SWNT films using the dry FCCVD method, covering SWNT synthesis, thin-film fabrication and performance regulation, the morphology of SWNTs and bundles, transparency and conductivity characteristics, random bundle films, patterned films, individual CNT networks, and various applications, especially as TCFs in touch displays. Films based on SWNTs produced by the dry FCCVD method are already commercially available for application in touch display devices. Further research on the dry FCCVD method could advance development of not only industrial applications of CNTs but also the fundamental science of related nanostructured materials and nanodevices.

  14. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

    Science.gov (United States)

    Luo, Si

    Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been

  15. Surface tailored single walled carbon nanotubes as catalyst support for direct methanol fuel cell

    Science.gov (United States)

    Kireeti, Kota V. M. K.; Jha, Neetu

    2017-10-01

    A strategy for tuning the surface property of Single Walled Carbon Nanotubes (SWNTs) for enhanced methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) along with methanol tolerance is presented. The surface functionality is tailored using controlled acid and base treatment. Acid treatment leads to the attachment of carboxylic carbon (CC) fragments to SWNT making it hydrophilic (P3-SWNT). Base treatment of P3-SWNT with 0.05 M NaOH reduces the CCs and makes it hydrophobic (P33-SWNT). Pt catalyst supported on the P3-SWNT possesses enhanced MOR whereas that supported on P33-SWNT not only enhances ORR kinetics but also possess good tolerance towards methanol oxidation as verified by the electrochemical technique.

  16. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A method to explore the quantitative interactions between metal and ceria for M/CeO2 catalysts

    Science.gov (United States)

    Zhu, Kong-Jie; Liu, Jie; Yang, Yan-Ju; Xu, Yu-Xing; Teng, Bo-Tao; Wen, Xiao-Dong; Fan, Maohong

    2018-03-01

    To explore the quantitative relationship of metal interaction with ceria plays a key role in the theoretical design of M/CeO2 catalysts, especially for the new hot topic of atomically dispersed catalysts. A method to quantitatively explore the interactions between metal and ceria is proposed in the present work on the basis of the qualitative analysis of the effects of different factors on metal adsorption at different ceria surfaces by using Ag/CeO2 as a case. Two parameters are firstly presented, Ep which converts the total adsorption energy into the interaction energy per Agsbnd O bond, and θdiff which measures the deviation of Agsbnd Osbnd Ce bond angle from the angle of the sp3 orbital hybridization of O atom. Using the two parameters, the quantitative relationship of the interaction energy between Ag and ceria is established. There is a linear correlation between Ep and dAgsbndO with θdiff. The higher θdiff, the weaker Ep, and the longer Agsbnd O bond. This method is also suitable for other metals (Cu, Ni, Pd, and Rh, etc.) on ceria. It is the first time to establish the quantitative relationship for the interaction between metal and ceria, and sheds light into the theoretical design of M/CeO2 catalysts.

  18. Development of a Hemispherical Metal Diaphragm for Single-Cycle Liquid-Metal Positive Expulsion Systems

    National Research Council Canada - National Science Library

    Gorland, Sol

    1965-01-01

    This report presents experimental results pertaining to the design and development of a metallic expulsion diaphragm for single-cycle positive expulsion of high-temperature liquid in an agravity condition...

  19. Stability investigation of a high number density Pt1/Fe2O3single-atom catalyst under different gas environments by HAADF-STEM.

    Science.gov (United States)

    Duan, Sibin; Wang, Rongming; Liu, Jingyue

    2018-05-18

    Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt 1 /Fe 2 O 3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water-gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe 2 O 3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H 2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H 2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H 2 O molecules to the CO or H 2 significantly accelerates the sintering of the Fe 2 O 3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal-support interaction.

  20. Functionalised metal-organic frameworks : A novel approach to stabilising single metal atoms

    NARCIS (Netherlands)

    Szilagyi, P.A.; Rogers, D. M.; Zaiser, I.; Callini, E; Turner, Stuart; Borgschulte, A; Züttel, A.; Geerlings, J.J.C.; Hirscher, M; Dam, B.

    2017-01-01

    We have investigated the potential of metal-organic frameworks for immobilising single atoms of transition metals using a model system of Pd supported on NH2-MIL-101(Cr). Our transmission electron microscopy and in situ Raman spectroscopy results give evidence for the first time that

  1. 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.

  2. Recyclable Earth-Abundant Metal Nanoparticle Catalysts for Selective Transfer Hydrogenation of Levulinic Acid to Produce γ-Valerolactone.

    Science.gov (United States)

    Gowda, Ravikumar R; Chen, Eugene Y-X

    2016-01-01

    Nanoparticles (NPs) derived from earth-abundant metal(0) carbonyls catalyze conversion of bio-derived levulinic acid into γ-valerolactone in up to 93% isolated yield. This sustainable and green route uses non-precious metal catalysts and can be performed in aqueous or ethanol solution without using hydrogen gas as the hydrogen source. Generation of metal NPs using microwave irradiation greatly enhances the rate of the conversion, enables the use of ethanol as both solvent and hydrogen source without forming the undesired ethyl levulinate, and affords recyclable polymer-stabilized NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2012-04-11

    A new class of core-corona structured bifunctional catalyst (CCBC) consisting of lanthanum nickelate centers supporting nitrogen-doped carbon nanotubes (NCNT) has been developed for rechargeable metal-air battery application. The nanostructured design of the catalyst allows the core and corona to catalyze the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), respectively. These materials displayed exemplary OER and ORR activity through half-cell testing, comparable to state of the art commercial lanthanum nickelate (LaNiO(3)) and carbon-supported platinum (Pt/C), with added bifunctional capabilities allowing metal-air battery rechargeability. LaNiO(3) and Pt/C are currently the most accepted benchmark electrocatalyst materials for the OER and ORR, respectively; thus with comparable activity toward both of these reactions, CCBC are presented as a novel, inexpensive catalyst component for the cathode of rechargeable metal-air batteries. Moreover, after full-range degradation testing (FDT) CCBC retained excellent activity, retaining 3 and 13 times greater ORR and OER current upon comparison to state of the art Pt/C. Zinc-air battery performances of CCBC is in good agreement with the half-cell experiments with this bifunctional electrocatalyst displaying high activity and stability during battery discharge, charge, and cycling processes. Owing to its outstanding performance toward both the OER and ORR, comparable with the highest performing commercial catalysts to date for each of the respective reaction, coupled with high stability and rechargeability, CCBC is presented as a novel class of bifunctional catalyst material that is very applicable to future generation rechargeable metal-air batteries. © 2012 American Chemical Society

  4. Airborne concentrations of metals and total dust during solid catalyst loading and unloading operations at a petroleum refinery.

    Science.gov (United States)

    Lewis, Ryan C; Gaffney, Shannon H; Le, Matthew H; Unice, Ken M; Paustenbach, Dennis J

    2012-09-01

    Workers handle catalysts extensively at petroleum refineries throughout the world each year; however, little information is available regarding the airborne concentrations and plausible exposures during this type of work. In this paper, we evaluated the airborne concentrations of 15 metals and total dust generated during solid catalyst loading and unloading operations at one of the largest petroleum refineries in the world using historical industrial hygiene samples collected between 1989 and 2006. The total dust and metals, which included aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, platinum, silicon, silver, vanadium, and zinc, were evaluated in relation to the handling of four different types of solid catalysts associated with three major types of catalytic processes. Consideration was given to the known components of the solid catalysts and any metals that were likely deposited onto them during use. A total of 180 analytical results were included in this analysis, representing 13 personal and 54 area samples. Of the long-term personal samples, airborne concentrations of metals ranged from <0.001 to 2.9mg/m(3), and, in all but one case, resulted in concentrations below the current U.S. Occupational Safety and Health Administration's Permissible Exposure Limits and the American Conference of Governmental Industrial Hygienists' Threshold Limit Values. The arithmetic mean total dust concentration resulting from long-term personal samples was 0.31mg/m(3). The data presented here are the most complete set of its kind in the open literature, and are useful for understanding the potential exposures during solid catalyst handling activities at this petroleum refinery and perhaps other modern refineries during the timeframe examined. Copyright © 2011 Elsevier GmbH. All rights reserved.

  5. Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons

    Directory of Open Access Journals (Sweden)

    Aurora J. Cruz-Cabeza

    2012-01-01

    Full Text Available Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Brönsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Brönsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion, the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite. We propose different reactions mechanisms in order to explain the final product distributions.

  6. Recycling CO 2 ? Computational Considerations of the Activation of CO 2 with Homogeneous Transition Metal Catalysts

    KAUST Repository

    Drees, Markus

    2012-08-10

    Faced with depleting fossil carbon sources, the search for alternative energy carriers and energy storage possibilities has become an important issue. Nature utilizes carbon dioxide as starting material for storing sun energy in plant hydrocarbons. A similar approach, storing energy from renewable sources in chemical bonds with CO 2 as starting material, may lead to partial recycling of CO 2 created by human industrial activities. Unfortunately, currently available routes for the transformation of CO 2 involve high temperatures and are often not selective. With the development of more sophisticated methods and better software, theoretical studies have become both increasingly widespread and useful. This concept article summarizes theoretical investigations of the current state of the feasibility of CO 2 activation with molecular transition metal catalysts, highlighting the most promising reactions of CO 2 with olefins to industrially relevant acrylic acid/acrylates, and the insertion of CO 2 into metal-element bonds, particularly for the synthesis of cyclic carbonates and polymers. Rapidly improving computational power and methods help to increase the importance and accuracy of calculations continuously and make computational chemistry a useful tool helping to solve some of the most important questions for the future. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Rare metal fission products in nuclear spent fuel as catalysts for hydrogen production by water electrolysis

    International Nuclear Information System (INIS)

    Ozawa, Masaki

    2004-01-01

    Separation and utilization of rare metal fission products (RMFP) in nuclear spent fuel were studied to apply them as a catalyst for hydrogen generation by water electrolysis. The RMFP, namely Pd, Ru, Rh and Tc, etc, are abundant, more than ca. 30kg per metric ton of a typical fast reactor spent fuel. The RMFP can be selectively separated from high level liquid waste (HLLW) by catalytic electrolytic extraction (CEE) method. Specific metallic cations such as Pd 2+ , which originate in the solutions, may act as promoters (i.e., Pd adatom ) or mediators, thereby accelerating electrochemical deposition of RuNO 3+ , Rh 3+ and ReO 4 - (simulator TcO 4 - ). In utilizing CEE method, electrodeposited electrodes were prepared, and successively dedicated to the water (alkaline or artificial sea water) electrolysis tests. Among the RMFP deposited electrodes, maximum potential shifting for hydrogen evolution to noble side was observed for the quaternary, Pd-Ru-Rh-Re (3.5:4:1:1), deposit Pt electrode, with suggesting the highest cathodic currents for hydrogen evolution both in alkaline solution and artificial sea water. The electro analytic activity of quaternary, Pd-Ru-Rh-Re (3.5:4:1:1), deposit Pt electrode exceeded that of Pt electrode by ca. twice both in alkaline solution and artificial sea water. The paper conclusively proposes RMFP generated by nuclear fission to utilize as an alternative material for hydrogen production with a novel vision to bridge nuclear and hydrogen energy systems. (author)

  8. Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

    Science.gov (United States)

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

  9. Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Alperovich, Igor; Smolentsev, Grigory; Moonshiram, Dooshaye; Jurss, Jonah W.; Concepcion, Javier J.; Meyer, Thomas J.; Soldatov, Alexander; Pushkar, Yulia (UNC); (Purdue); (SFU-Russia); (Lund)

    2015-09-17

    L{sub 2,3}-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[Ru{sub 2}{sup III}O(H{sub 2}O){sub 2}(bpy){sub 4}]{sup 4+} water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex show considerably different splitting of the Ru L{sub 2,3} absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L{sub 2,3}-edges XAS spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L{sub 2,3}-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals.

  10. Carbon nanotubes and other nanostructures as support material for nanoparticulate noble-metal catalysts in fuel cells

    DEFF Research Database (Denmark)

    Veltzé, Sune; Larsen, Mikkel Juul; Elina, Yli-Rantala

    or platinum-alloy catalysts in the electrodes are required. To maximize the utilization of the noble metal it is frequently deposited as nanoparticles (1–5 nm) on a stabilizing support of carbon black. Carbon black provides good anchoring of the catalyst particles, but is prone to severe destructive oxidation...... carbon black they can conduct electrons to and from the reaction sites, and in addition their resistance to electrochemical degradation is better than that of carbon black due to their much higher structural perfection. This latter feature is indeed highly desired with a view to the durability...... for difficulties in contacting the nanotubes with other substances in the electrode or electrode preparation. Other promising candidate structures for catalyst support include carbon nanofibers (CNF) and various modifications of CNTs. We present some of our work with the investigation of surface properties...

  11. Carbon Nanotubes and Other Nanostructures as Support Material for Nanoparticulate Noble-Metal Catalysts in Fuel Cells

    DEFF Research Database (Denmark)

    Larsen, Mikkel Juul; Veltzé, Sune; Skou, Eivind Morten

    or platinum-alloy catalysts in the electrodes are required. To maximize the utilization of the noble metal it is frequently deposited as nanoparticles (1-5 nm) on a stabilizing support of carbon black. Carbon black provides good anchoring of the catalyst particles, but is prone to severe destructive oxidation...... carbon black they can conduct electrons to and from the reaction sites, and in addition their resistance to electrochemical degradation is better than that of carbon black due to their much higher structural perfection. This latter feature is indeed highly desired with a view to the durability...... for difficulties in contacting the nanotubes with other substances in the electrode or electrode preparation. Other promising candidate structures for catalyst support include carbon nanofibers (CNF) and various modifications of CNTs. We present some of our work with the investigation of surface properties...

  12. Synthesis and characterization of group V metal carbide and nitride catalysts

    Science.gov (United States)

    Kwon, Heock-Hoi

    1998-11-01

    Group V transition metal carbides and nitrides were prepared via the temperature programmed reaction (TPR) of corresponding oxides with NHsb3 or a CHsb4/Hsb2 mixture. Except for the tantalum compounds, phase-pure carbides and nitrides were prepared. The vanadium carbides and nitrides were the most active and selective catalysts. Therefore the principal focus of the research was the preparation, characterization, and evaluation of high surface area vanadium nitride catalysts. A series of vanadium nitrides with surface areas up to 60 msp2/g was prepared. Thermal gravimetric analysis coupled with x-ray diffraction and scanning electron microscopy indicated that the solid-state reaction proceeded by the sequential reduction of Vsb2Osb5 to VOsb{0.9} and concluded with the topotactic substitution of nitrogen for oxygen in VOsb{0.9}. The transformation of Vsb2Osb5 to VN was pseudomorphic. An experimental design was executed to determine effects of the heating rates and space velocities on the VN microstructures. The heating rates had minor effects on the surface areas and pore size distributions; however, increasing the space velocity significantly increased the surface area. The materials were mostly mesoporous. Oxygen chemisorption on the vanadium nitrides scaled linearly with the surface area. The corresponding O/Vsbsurface ratio was ≈0.6. The vanadium nitrides were active for butane activation and pyridine hydrodenitrogenation. During butane activation, their selectivities towards dehydrogenation products were as high as 98%. The major product in pyridine hydrodenitrogenation was pentane. The reaction rates increased almost linearly with the surface area suggesting that these reactions were structure insensitive. The vanadium nitrides were not active for crotonaldehyde hydrogenation; however, they catalyzed an interesting ring formation reaction that produced methylbenzaldehyde and xylene from crotonaldehyde. A new method was demonstrated for the production of very

  13. Biomass Conversion Strategies and the Renewable Production of Hydrogen using Heterogeneous Metal Catalysts

    Science.gov (United States)

    Carrasquillo-Flores, Ronald

    Biomass is a renewable carbon source that can be processed into fuels and chemicals in a biorefinery. However, there are a number of challenges that need to be overcome for biomass utilization to be viable. The work presented herein aims to address two existing challenges in biomass processing schemes, namely the efficient utilization of all fractions of lignocellulosic biomass and the renewable production of the hydrogen necessary to reduce the oxygen functionalities native in biomass. First, lignin was depolymerized to produce a renewable phenolic solvent mixture. Biphasic reactions with this solvent and aqueous solution of glucose or xylose produce 5-hydroxymethylfurfural (HMF) and furfural, respectively, at high yields. HMF and furfuryl alcohol could also be upgraded into levulinic acid at high yields. The yields are due to the capacity of the solvent to partition these molecules and prevent their degradation. Second, propyl guaiacol, a component of the phenolic solvent, was used for biphasic reactions where ball milled biomass substrates were used. These substrates are converted to furfural and HMF at high yields due to the partition of these molecules into the solvent and the on-demand production of glucose and xylose from the substrate, minimizing the formation of humins. A study of the water-gas shift reaction over Pt-based catalysts was conducted. Alloying Pt with Re was found to increase the catalytic activity and microkinetic modeling revealed Pt is a good representation of the active site and Re acts as a promoter slightly destabilizing CO binding. A study on formic acid decomposition over Au catalysts was performed. Experiments, density functional theory and microkinetic modeling results indicate the reaction proceeds completely on highly undercoordinated Au atoms with any high coordination atom being largely inert. Motivated by the results on Au catalysts, the metal-support interaction was investigated for the reverse water-gas shift reaction. Using a

  14. Extending Tabletop XUV Spectroscopy to the Liquid Phase to Examine Transition Metal Catalysts

    Science.gov (United States)

    Benke, Kristin; Ryland, Elizabeth S.; Vura-Weis, Josh

    2017-06-01

    M-edge spectroscopy of first row transition metals (3p to 3d excitation) is the low energy analogue of more well-known K- and L-edge spectroscopy, but can be implemented without the use of a synchrotron. Instead, M-edge spectroscopy can be performed as a tabletop method, relying on high harmonic generation (HHG) to produce ultrashort (˜ 20 fs) pulses of extreme ultraviolet (XUV) light in the range of 10-100s of eV. We have shown tabletop M-edge spectroscopy to be a valuable tool in determining the electronic structure of metal-centered coordination complexes and have demonstrated its capacity to yield element-specific information about a compound's oxidation state, spin state, and ligand field. The power of this technique to distinguish these features makes it a promising addition to the arsenal of methods used to study metal-centered catalysts. A catalytic reaction can be initiated photochemically and the XUV probe can be used to track oxidative and structural changes to identify the key intermediates. Until recently tabletop XUV spectroscopy has been performed on thin film samples, but in order to examine homogeneous catalysis, the technique must be adapted to look at samples in the liquid phase. The challenges of adapting tabletop XUV spectroscopy to the liquid phase lie in the lower attenuation length of XUV light compared to soft and hard x-rays and the lower flux compared to synchrotron methods. As a result, the sample must be limited to a sub-micron thickness as well as isolated from the vacuum environment required for x-ray spectroscopy. I am developing a liquid flow cell that relies on confining the sample between two x-ray transmissive SiN membranes, as has been demonstrated for use at synchrotrons, but adapted to the unique difficulties encountered in tabletop XUV spectroscopy.

  15. Molecular Mixed-Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts.

    Science.gov (United States)

    Suseno, Sandy; McCrory, Charles C L; Tran, Rosalie; Gul, Sheraz; Yano, Junko; Agapie, Theodor

    2015-09-14

    Well-defined mixed-metal [CoMn3 O4 ] and [NiMn3 O4 ] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts' heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni-Mn oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3 O4 cubane-like geometry was maintained in the absence of thermal treatment (2-Ni). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in Photosystem II, including the MMn3 O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Single crystalline metal films as substrates for graphene growth

    Energy Technology Data Exchange (ETDEWEB)

    Zeller, Patrick; Henss, Ann-Kathrin; Wintterlin, Joost [Department Chemie, Ludwig-Maximilians-Universitaet Muenchen (Germany); Weinl, Michael; Schreck, Matthias [Institut fuer Physik, Universitaet Augsburg (Germany); Speck, Florian; Ostler, Markus [Lehrstuhl fuer Technische Physik, Universitaet Erlangen-Nuernberg, Erlangen (Germany); Institut fuer Physik, Technische Universitaet Chemnitz (Germany); Seyller, Thomas [Institut fuer Physik, Technische Universitaet Chemnitz (Germany)

    2017-11-15

    Single crystalline metal films deposited on YSZ-buffered Si(111) wafers were investigated with respect to their suitability as substrates for epitaxial graphene. Graphene was grown by CVD of ethylene on Ru(0001), Ir(111), and Ni(111) films in UHV. For analysis a variety of surface science methods were used. By an initial annealing step the surface quality of the films was strongly improved. The temperature treatments of the metal films caused a pattern of slip lines, formed by thermal stress in the films, which, however, did not affect the graphene quality and even prevented wrinkle formation. Graphene was successfully grown on all three types of metal films in a quality comparable to graphene grown on bulk single crystals of the same metals. In the case of the Ni(111) films the originally obtained domain structure of rotational graphene phases could be transformed into a single domain by annealing. This healing process is based on the control of the equilibrium between graphene and dissolved carbon in the film. For the system graphene/Ni(111) the metal, after graphene growth, could be removed from underneath the epitaxial graphene layer by a pure gas phase reaction, using the reaction of CO with Ni to give gaseous Ni(CO){sub 4}. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    Energy Technology Data Exchange (ETDEWEB)

    T. Brent Gunnoe

    2011-02-17

    Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials. A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt

  18. A Comparative Study of Mn/Co Binary Metal Catalysts Supported on Two Commercial Diatomaceous Earths for Oxidation of Benzene

    Directory of Open Access Journals (Sweden)

    Marco Tomatis

    2018-03-01

    Full Text Available Two commercial diatomaceous earths were used as supports for the preparation of Mn/Co binary metal catalysts at different metal loads (5 to 10 wt % Mn and 5 to 15 wt % Co by incipient wetness deposition. The activity of the prepared catalysts towards the complete oxidation of benzene to CO2 and water was investigated between 100 and 400 °C. Raw supports and synthesized catalysts were characterized by XRD, N2 physisorption, SEM-EDS, H2-TPR, and TPD. The purification treatment of food-grade diatomite significantly affected the crystallinity of this support while reducing its specific surface area (SSA. A loss of SSA, associated with the increase in the metal load, was observed on samples prepared on natural diatomite, while the opposite trend occurred with food-grade diatomite-supported catalysts. Metal nanoparticles of around 50 nm diameter were observed on the catalysts’ surface by SEM analysis. EDS analysis confirmed the uniform deposition of the active phases on the support’s surface. A larger H2 consumption was found by TPR analysis of natural diatomite-based samples in comparison to those prepared at the same metal load on food-grade diatomite. During the catalytic oxidation experiment, over 90% conversion of benzene were achieved at a reaction temperature of 225 °C by all of the prepared samples. In addition, the formation of coke during the oxidation tests was demonstrated by TGA analysis and the soluble fraction of the produced coke was characterized by GC-MS.

  19. NO reduction by CO over noble-metal catalysts under cycled feedstreams

    International Nuclear Information System (INIS)

    Muraki, H.; Fujitani, Y.

    1986-01-01

    The reduction of NO with CO was studied over α-Al/sub 2/O/sub 3/-supported Pt, Pd, Rh, Ru, and Ir catalysts. The activities were measured by using cycled feeds and steady noncycled feed. The activity sequence of the catalysts tested was Rh > Ru > Ir > Pd > Pt. The activities of Pt and Pd catalysts were increased under the cycled feed. The periodic operation effect on the Pt catalyst was more predominant than that on the Pd catalyst. The order of periodic operation effect corresponded to the order of their susceptibility to CO self-poisoning

  20. Effects of particulates, heavy metals and acid gas on the removals of NO and PAHs by V2O5-WO3 catalysts in waste incineration system.

    Science.gov (United States)

    Chang, Feng-Yim; Chen, Jyh-Cherng; Wey, Ming-Yen; Tsai, Shih-An

    2009-10-15

    This study investigated the activities of prepared and commercial V(2)O(5)-WO(3) catalysts for simultaneous removals of NO and polycyclic aromatic hydrocarbons (PAHs) and the influences of particulates, heavy metals, SO(2), and HCl on the performances of catalysts. The experiments were carried out in a laboratory-scale waste incineration system equipped with a catalyst reactor. The DREs of PAHs by prepared and commercial V(2)O(5)-WO(3) catalysts were 64% and 72%, respectively. Increasing the particulate concentrations in flue gas suppressed the DRE of PAHs, but increasing the carbon content on surface of catalysts promotes the NO conversions. The DRE of PAHs by the catalysts was significantly decreased by the increased concentrations of heavy metal Cd, but was promoted by high concentration of Pb. The influence level of SO(2) was higher than HCl on the performances of V(2)O(5)-WO(3) catalysts for PAHs removal, but was lower than HCl for NO removal. Prepared and commercial V(2)O(5)-WO(3) catalysts have similar trends on the effects of particulates, heavy metals, SO(2), and HCl. The results of ESCA analysis reveal that the presence of these pollutants on the surface of catalysts did not change the chemical state of V and W.

  1. Metal-nanoparticle single-electron transistors fabricated using electromigration

    DEFF Research Database (Denmark)

    Bolotin, K I; Kuemmeth, Ferdinand; Pasupathy, A N

    2004-01-01

    We have fabricated single-electron transistors from individual metal nanoparticles using a geometry that provides improved coupling between the particle and the gate electrode. This is accomplished by incorporating a nanoparticle into a gap created between two electrodes using electromigration, all...

  2. A Single-Site Iron(III-Salan Catalyst for Converting COS to Sulfur-Containing Polymers

    Directory of Open Access Journals (Sweden)

    Ge-Ge Gu

    2017-10-01

    Full Text Available An iron(III complex of tetradentate N,N′-disubstituted bis(aminophenoxide (designated as salan, a saturated version of the corresponding salen ligand with a sterically hindered organic base anchored on the ligand framework, can selectively mediate the conversion of carbonyl sulfide to sulfur-containing polymers by the copolymerization with epoxides. This single-site catalyst exhibits broad substrate scope, and the resultant copolymers have completely alternating structures. In addition, this catalyst is efficient in producing diblock copolymers, suggesting a living polymerization nature.

  3. Oxygen reduction and evolution at single-metal active sites

    DEFF Research Database (Denmark)

    Calle-Vallejo, F.; Martínez, J.I.; García Lastra, Juan Maria

    2013-01-01

    overpotentials and is made of precious materials. A possible solution is the use of non-noble electrocatalysts with single-metal active sites. Here, on the basis of DFT calculations of adsorbed intermediates and a thermodynamic analysis, we compare the oxygen reduction (ORR) and evolution (OER) activities...... of functionalized graphitic materials and gas-phase porphyrins with late transition metals. We find that both kinds of materials follow approximately the same activity trends, and active sites with transition metals from groups 7 to 9 may be good ORR and OER electrocatalysts. However, spin analyses show more...... flexibility in the possible oxidation states of the metal atoms in solid electrocatalysts, while in porphyrins they must be +2. These observations reveal that the catalytic activity of these materials is mainly due to nearest-neighbor interactions. Based on this, we propose that this class of electrocatalysts...

  4. Bimetal catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-10-03

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

  5. Selective Degradation of Organic Pollutants Using an Efficient Metal-Free Catalyst Derived from Carbonized Polypyrrole via Peroxymonosulfate Activation.

    Science.gov (United States)

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

    2017-10-03

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

  6. Aromatic hydrocarbon production via eucalyptus urophylla pyrolysis over several metal modified ZSM-5 catalysts – an analysis by py-GC/MS

    Science.gov (United States)

    Metal modified HZSM-5 catalysts were prepared by ion exchange of NH4ZSM-5 (SIO2/Al2O3 = 23) using gallium, molybdenum, nickel and zinc, and their combinations thereof. The prepared catalysts were used to evaluate catalytic pyrolysis for the conversion of Eucalyptus urophylla to fuels and chemicals, ...

  7. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

    Science.gov (United States)

    Murahashi, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

  8. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    Science.gov (United States)

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  9. Chromium-based metal-organic framework MIL-101 as a highly effective catalyst in plasma for toluene removal

    Science.gov (United States)

    Wu, Junliang; Xia, Qibin; Xiao, Jing; Li, Zhong

    2017-11-01

    Catalytic performance of MIL-101—a type of chromium-based metal-organic frameworks (MOFs)—in a plasma catalysis system for toluene removal was experimentally studied. The MIL-101 was synthesized using a hydrothermal method, and its catalytic performance was compared to two other catalysts, Cr2O3/γ-Al2O3 and γ-Al2O3, in a dielectric barrier discharge (DBD) reactor. Results showed that the presence of a catalyst in plasma changed the voltage and current characteristic substantially, and promoted the performance of the plasma reactor. Among the catalysts, the MIL-101 exhibited a significantly high toluene conversion, which was 20% and 35% higher than Cr2O3/γ-Al2O3 and γ-Al2O3, respectively, under the same testing conditions, as well as higher carbon balance and CO2 selectivity. The analysis of by-products on the surfaces of the catalysts before and after reaction demonstrated that MIL-101 had better resistance towards by-products accumulation compared to Cr2O3/γ-Al2O3 and γ-Al2O3. The loading of MnO x on MIL-101 further promoted its catalytic performance. MIL-101 exhibits attractive catalytic properties as a catalyst in a plasma catalysis system for the decomposition of volatile organic compounds.

  10. Chromium-based metal-organic framework MIL-101 as a highly effective catalyst in plasma for toluene removal

    International Nuclear Information System (INIS)

    Wu, Junliang; Xia, Qibin; Xiao, Jing; Li, Zhong

    2017-01-01

    Catalytic performance of MIL-101—a type of chromium-based metal-organic frameworks (MOFs)—in a plasma catalysis system for toluene removal was experimentally studied. The MIL-101 was synthesized using a hydrothermal method, and its catalytic performance was compared to two other catalysts, Cr 2 O 3 / γ -Al 2 O 3 and γ -Al 2 O 3 , in a dielectric barrier discharge (DBD) reactor. Results showed that the presence of a catalyst in plasma changed the voltage and current characteristic substantially, and promoted the performance of the plasma reactor. Among the catalysts, the MIL-101 exhibited a significantly high toluene conversion, which was 20% and 35% higher than Cr 2 O 3 / γ -Al 2 O 3 and γ -Al 2 O 3 , respectively, under the same testing conditions, as well as higher carbon balance and CO 2 selectivity. The analysis of by-products on the surfaces of the catalysts before and after reaction demonstrated that MIL-101 had better resistance towards by-products accumulation compared to Cr 2 O 3 / γ -Al 2 O 3 and γ -Al 2 O 3 . The loading of MnO x on MIL-101 further promoted its catalytic performance. MIL-101 exhibits attractive catalytic properties as a catalyst in a plasma catalysis system for the decomposition of volatile organic compounds. (paper)

  11. Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

    Science.gov (United States)

    Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

    2003-09-23

    Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

  12. Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

    Energy Technology Data Exchange (ETDEWEB)

    Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan; Velikokhatnyi, Oleg

    2017-02-07

    The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

  13. Effectiveness of non-noble metal based diesel oxidation catalysts on particle number emissions from diesel and biodiesel exhaust.

    Science.gov (United States)

    Shukla, Pravesh Chandra; Gupta, Tarun; Labhasetwar, Nitin Kumar; Khobaragade, Rohini; Gupta, Neeraj K; Agarwal, Avinash Kumar

    2017-01-01

    Two new formulations of non-noble metal based diesel oxidation catalysts based on CoCe based mixed oxide (DOC 2 ) and perovskite catalysts (DOC 3 ) were prepared and retrofitted in a 4-cylinder diesel engine fueled by diesel and Karanja biodiesel blend (KB20). In this study, their effectiveness in reducing raw exhaust particulate emissions vis-à-vis a commercial diesel oxidation catalyst (DOC 1 ) was evaluated. Emission characteristics such as particle number-size distribution, mass-size distribution, and surface area-size distribution, total particle number concentration and count mean diameter as a function of engine load at constant engine speed were evaluated. Variations in total particle number concentration as a function of engine speed were also determined. The prepared DOCs and the commercial DOC showed varying degrees of performance as a function of engine operating conditions. Overall, effectiveness of the prepared DOC's appeared to be more fuel specific. For diesel exhaust, overall performance of DOC 1 was more effective compared to both prepared DOCs, with DOC 2 being superior to DOC 3 . In case of KB20 exhaust, the overall performance of DOC 2 was either more effective or nearly comparable to DOC 1, while DOC 3 being not so effective. This showed that the DOCs based on CoCe based mixed oxide catalysts have potential to replace commercial noble metal based DOC's, especially in engines fueled by biodiesel. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Hydrogen cold plasma for synthesizing Pd/C catalysts: the effect of support–metal ion interaction

    Science.gov (United States)

    Zhuang, LI; Xiuling, ZHANG; Yuzhuo, ZHANG; Dongzhi, DUAN; Lanbo, DI

    2018-01-01

    It has been found that cold plasma is a facile and environmentally benign method for synthesizing supported metal catalysts, and great efforts have been devoted to enlarging its applications. However, little work has been done to disclose the influence mechanism, which is significant for controllable synthesis. In this work, hydrogen cold plasma was adopted to synthesize a palladium catalyst supported on activated carbon (Pd/C-P) using H2PdCl4 as a Pd precursor followed by calcination in hydrogen gas to remove the chlorine ions. The Pd/C-P catalyst was found to be made of larger Pd nanoparticles showing a decreased migration to the support outer surface than that prepared by the conventional thermal hydrogen reduction method (Pd/C-C). Meanwhile, the pore diameter of the activated carbon support is small (∼4 nm). Therefore, Pd/C-P exhibits lower CO oxidation activity than Pd/C-C. It was proposed that the strong interaction between the activated carbon and {{{{PdCl}}}4}2-, and the enhanced metal–support interaction caused by hydrogen cold plasma reduction made it difficult for Pd nanoparticles to migrate to the support outer surface. The larger-sized Pd nanoparticles for Pd/C-P may be due to the Coulomb interaction resulting in the disturbance of the metal–support interaction. This work has important guiding significance for the controllable synthesis of supported metal catalysts by hydrogen cold plasma.

  15. In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

    Science.gov (United States)

    Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

    2013-08-07

    In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually

  16. Metal catalysts supported on activated carbon fibers for removal of polycyclic aromatic hydrocarbons from incineration flue gas.

    Science.gov (United States)

    Lin, Chiou-Liang; Cheng, Yu-Hsiang; Liu, Zhen-Shu; Chen, Jian-Yuan

    2011-12-15

    The aim of this research was to use metal catalysts supported on activated carbon fibers (ACFs) to remove 16 species of polycyclic aromatic hydrocarbons (PAHs) from incineration flue gas. We tested three different metal loadings (0.11 wt%, 0.29 wt%, and 0.34 wt%) and metals (Pt, Pd, and Cu), and two different pretreatment solutions (HNO(3) and NaOH). The results demonstrated that the ACF-supported metal catalysts removed the PAHs through adsorption and catalysis. Among the three metals, Pt was most easily adsorbed on the ACFs and was the most active in oxidation of PAHs. The mesopore volumes and density of new functional groups increased significantly after the ACFs were pretreated with either solutions, and this increased the measured metal loading in HNO(3)-0.48% Pd/ACFs and NaOH-0.52% Pd/ACFs. These data confirm that improved PAH removal can be achieved with HNO(3)-0.48% Pd/ACFs and NaOH-0.52% Pd/ACFs. Copyright © 2011 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2016-12-22

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

  18. Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts.

    Science.gov (United States)

    Shaffer, David W; Xie, Yan; Szalda, David J; Concepcion, Javier J

    2017-11-01

    A critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s -1 , faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2 ] (bpH 2 cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediates O-O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.

  19. Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

    International Nuclear Information System (INIS)

    Shaffer, David W.; Xie, Yan; Szalda, David J.; Concepcion, Javier J.

    2017-01-01

    Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1 , faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2 ] (bpH 2 cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediates O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.

  20. 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, the author 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, they 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. In the second part of this dissertation, the author used laser-induced native fluorescence coupled with capillary electrophoresis (LINF-CE) and microscope imaging to study the single cell degranulation. On the basis of good temporal correlation with events observed through an optical microscope, they have identified individual peaks in the fluorescence electropherograms as serotonin released from the granular core on contact with the surrounding fluid.

  1. 3 D characterization of gold nanoparticles supported on heavy metal oxide catalysts by HAADF-STEM electron tomography.

    Science.gov (United States)

    González, J C; Hernández, J C; López-Haro, M; del Río, E; Delgado, J J; Hungría, A B; Trasobares, S; Bernal, S; Midgley, P A; Calvino, José Juan

    2009-01-01

    Living on the edge: Three-dimensional reconstructions from electron tomography data recorded from Au/Ce(0.50)Tb(0.12)Zr(0.38)O(2-x) catalysts show that gold nanoparticles (see picture; yellow) are preferentially located on stepped facets and nanocrystal boundaries. An epitaxial relationship between the metal and support plays a key role in the structural stabilization of the gold nanoparticles.

  2. On possibility of preparation of catalysts for ammonia synthesis based on cyanocomplexes of some d-metals

    International Nuclear Information System (INIS)

    Sergeeva, A.N.; Dovgej, V.V.; Pavlenko, L.I.; Zubritskaya, D.I.; Tkachenko, Zh.I.; Okorskaya, A.P.; Lyubchenko, Yu.A.

    1983-01-01

    The catalytic properties of the systems prepared on the basis of coordination cyanides of iron, ruthenium, osmium, rhenium, molydenum, vanadium and other d-metals in the ammonia synthesis reaction are studied. It has been found that thermal stability of catalytic systems containing vanadium and molybdenum is considerably higher than that of the industrial sample of similar type containing aluminium. The systems prepared on the basis of hexacyanoferrates, ruthenates and osmates can be referred to low-temperature type catalysts

  3. Shuttling single metal atom into and out of a metal nanoparticle.

    Science.gov (United States)

    Wang, Shuxin; Abroshan, Hadi; Liu, Chong; Luo, Tian-Yi; Zhu, Manzhou; Kim, Hyung J; Rosi, Nathaniel L; Jin, Rongchao

    2017-10-10

    It has long been a challenge to dope metal nanoparticles with a specific number of heterometal atoms at specific positions. This becomes even more challenging if the heterometal belongs to the same group as the host metal because of the high tendency of forming a distribution of alloy nanoparticles with different numbers of dopants due to the similarities of metals in outmost electron configuration. Herein we report a new strategy for shuttling a single Ag or Cu atom into a centrally hollow, rod-shaped Au 24 nanoparticle, forming AgAu 24 and CuAu 24 nanoparticles in a highly controllable manner. Through a combined approach of experiment and theory, we explain the shuttling pathways of single dopants into and out of the nanoparticles. This study shows that the single dopant is shuttled into the hollow Au 24 nanoparticle either through the apex or side entry, while shuttling a metal atom out of the Au 25 to form the Au 24 nanoparticle occurs mainly through the side entry.Doping a metal nanocluster with heteroatoms dramatically changes its properties, but it remains difficult to dope with single-atom control. Here, the authors devise a strategy to dope single atoms of Ag or Cu into hollow Au nanoclusters, creating precise alloy nanoparticles atom-by-atom.

  4. An introduction to catalyst

    International Nuclear Information System (INIS)

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  5. A New Energy-Saving Catalytic System: Carbon Dioxide Activation by a Metal/Carbon Catalyst.

    Science.gov (United States)

    Yun, Danim; Park, Dae Sung; Lee, Kyung Rok; Yun, Yang Sik; Kim, Tae Yong; Park, Hongseok; Lee, Hyunjoo; Yi, Jongheop

    2017-09-22

    The conversion of CO 2 into useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO 2 means that a lot of energy is required for its conversion into chemicals. Here, we suggest a new catalytic system with an alternative heating system that allows minimal energy consumption during CO 2 conversion. In this system, electrical energy is transferred as heat energy to the carbon-supported metal catalyst. Fast ramping rates allow high operating temperatures (T app =250 °C) to be reached within 5 min, which leads to an 80-fold decrease of energy consumption in methane reforming using CO 2 (DRM). In addition, the consumed energy normalized by time during the DRM reaction in this current-assisted catalysis is sixfold lower (11.0 kJ min -1 ) than that in conventional heating systems (68.4 kJ min -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Evaluation of potential for reuse of industrial wastewater using metal-immobilized catalysts and reverse osmosis.

    Science.gov (United States)

    Choi, Jeongyun; Chung, Jinwook

    2015-04-01

    This report describes a novel technology of reusing the wastewater discharged from the display manufacturing industry through an advanced oxidation process (AOP) with a metal-immobilized catalyst and reverse osmosis (RO) in the pilot scale. The reclaimed water generated from the etching and cleaning processes in display manufacturing facilities was low-strength organic wastewater and was required to be recycled to secure a water source. For the reuse of reclaimed water to ultrapure water (UPW), a combination of solid-phase AOP and RO was implemented. The removal efficiency of TOC by solid-phase AOP and RO was 92%. Specifically, the optimal acid, pH, and H2O2 concentrations in the solid-phase AOP were determined. With regard to water quality and operating costs, the combination of solid-phase AOP and RO was superior to activated carbon/RO and ultraviolet AOP/anion polisher/coal carbon. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Single-magnet rotary flowmeter for liquid metals

    OpenAIRE

    Priede, Jānis; Buchenau, Dominique; Gerbeth, Gunter

    2010-01-01

    We present a theory of single-magnet flowmeter for liquid metals and compare it with experimental results. The flowmeter consists of a freely rotating permanent magnet, which is magnetized perpendicularly to the axle it is mounted on. When such a magnet is placed close to a tube carrying liquid metal flow, it rotates so that the driving torque due to the eddy currents induced by the flow is balanced by the braking torque induced by the rotation itself. The equilibrium rotation rate, which var...

  8. Optics of a single ultrasharp groove in metal

    DEFF Research Database (Denmark)

    Søndergaard, Thomas; Bozhevolnyi, Sergey I

    2016-01-01

    Optical properties of a single ultrasharp groove of subwavelength width cut in an otherwise flat metal surface are examined theoretically. We calculate optical extinction, scattering, and absorption cross-section spectra for a wide range of groove profiles, establishing several fundamental trends...... absorption spectra. For ultrasharp grooves, oscillations in all spectra can be suppressed by increasing the groove depth. Finally, the level of absorption relative to that of scattering increases as the top groove width decreases, a trend that is analogous to that found when decreasing the size of metal...

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

    Science.gov (United States)

    Bhandari, Pushpak

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

  10. Catalysts prepared by interaction of transition metal organometallic compounds with the surface of supporters

    International Nuclear Information System (INIS)

    Ryndin, Yu.A.; Kuznetsov, B.N.; Moroz, Eh.M.; Tripol'skij, A.A.; Ermakov, Yu.I.

    1977-01-01

    The phase composition and dispersion of the catalyst (W + Pt)/SiO 2 , subjected to oxidation and reduction at an elevated temperature was investigated by roentgenographic methods (radial distribution of atoms and broadening of X-ray lines). The X-ray data are compared with the results of chemisorption measurements of platinum dispersion in the specimens and their activity in reactions of benzene hydration and ethane hydrogenolysis. It has been established that catalysts reduced at 600 deg C and not subjected to oxidation, as well as catalysts oxidized at 200 deg C and then reduced at 600 deg C are characterized by a high platinum dispersion. The dispersion catalysts are noted for their activity in the reaction of benzene hydration and ethane hydrogenolysis. On the other hand, the activity of catalysts oxidized and reduced in rigid conditions (600 deg C, air) is much lower and is close to the activity of the coarsely dispersed PtSiO 2 catalyst

  11. Recovery of platinum-group metals (PGMS from spent automotive catalysts: Part II: Automotive catalysts: Structures and principle of operation

    Directory of Open Access Journals (Sweden)

    Dimitrijević Mile D.

    2015-01-01

    Full Text Available Catalytic converters are incorporated into motor vehicle emission systems (passenger cars, trucks and other motor vehicles, as well as civil and agricultural machines, as of lately to reduce air pollution as well as to meet the emission standards. Their purpose is to convert toxic emissions generated by combustion of liquid fossil fuels into less harmful products. In catalytic converters, rhodium is used for the reduction of gasses, whereas platinum and palladium are used for the oxidation of gasses. This paper presents the structure and operating principle of automotive catalysts in view of the fact that cars are the most prevalent motor vehicles worldwide and due to the fact that the production of cars with gasoline and diesel engines will dominate until at least 2020.

  12. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    Science.gov (United States)

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-12-01

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Selective alkane activation with single-site atoms on amorphous support

    Science.gov (United States)

    Hock, Adam S.; Schweitzer, Neil M.; Miller, Jeffrey T.; Hu, Bo

    2015-11-24

    The present invention relates generally to catalysts and methods for use in olefin production. More particularly, the present invention relates to novel amorphously supported single-center, Lewis acid metal ions and use of the same as catalysts.

  14. Integrated Transmission Electron and Single-Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

    NARCIS (Netherlands)

    Hendriks, Frank C.|info:eu-repo/dai/nl/412642697; Mohammadian, Sajjad|info:eu-repo/dai/nl/374721327; Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Kalirai, Samanbir; Meirer, Florian; Vogt, Eelco T. C.|info:eu-repo/dai/nl/073717398; Bruijnincx, Pieter C. A.|info:eu-repo/dai/nl/33799529X; Gerritsen, Hans|info:eu-repo/dai/nl/071548777; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2018-01-01

    Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron

  15. Ring Opening of Naphthenic Molecules Over Metal Containing Mesoporous Y Zeolite Catalyst.

    Science.gov (United States)

    Lee, You-Jin; Kim, Eun Sang; Kim, Tae-Wan; Kim, Chul-Ung; Jeong, Kwang-Eun; Lee, Chang-Ha; Jeong, Soon-Yong

    2015-07-01

    Mesoporous Y zeolite (Meso-Y) with a uniform mesopore was synthesized via pseudomorphic syn- thesis. The Meso-Y supported Ni-W catalyst (NiW/Meso-Y) was introduced as a catalyst for the selective ring opening of naphthenic rings. The catalytic test for the ring opening of naphthalene as a model compound of multi-ring aromatics was performed using a batch-type reaction system with both sulfided 20 wt% NiW/Meso-Y and NiW/Y catalysts under different reaction conditions. The catalytic results reveal that the Meso-Y supported NiW catalyst experiences a naphthalene conversion similar to the NiW/Y catalyst, but the NiW/Meso-Y catalyst has higher product yields for BTEX (benzene, toluene, ethyl benzene, and xylene) and the middle distillate than those of the NiW/Y catalyst at a low reaction temperature. These results suggest that the mesoporosity of the NiW/Meso-Y catalyst is more advantageous for the ring opening reaction of multi-ring aromatics due to the easier access for the bulky molecules compared to the NiW/Y catalyst.

  16. Process integration for material synthesis from a deactivated catalyst: Studies on the interaction of metal ions between two immiscible phases.

    Science.gov (United States)

    Mishra, D; Sahu, K K; Agrawal, A

    2018-02-15

    Present investigation deals with the treatment of deactivated Co-Mn bromide catalyst for the recovery of Co and Mn as Co metal powder and chemical manganese dioxide by an integrated process comprising of a selective metal ion transfer from an aqueous solution containing a mixture of metal ions with a saponified solution of di-2ethyl-hexyl phosphoric acid, followed by selective scrubbing and metal stripping. The pure metal solutions so obtained were subjected to precipitation and hydrothermal treatment to obtain a desired material. The deactivated catalyst was leached by H 2 SO 4 in presence of H 2 O 2 followed by removing Fe, Si etc. The purified leach liquor of composition: 6.9g/L Co, 9.4g/L Mn was used for detail study to optimize the best conditions for the separation of Co from Mn. Experimental observations show that the extraction of both increased with increasing equilibrium pH and the concentration of the organic, with a separation factor of about 10, at equilibrium pH of 3. A quantitative extraction of Mn was possible with 20% D2EHPA in three stage counter-current extraction. After Co scrubbing, Mn was stripped with dilute H 2 SO 4 and high pure spherical shaped CMD was produced. Co in the raffinate was recovered as powder by hydrothermal H 2 - reduction. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Determination of platinum group metal catalyst residues in active pharmaceutical ingredients by means of total reflection X-ray spectrometry

    Science.gov (United States)

    Marguí, Eva; Queralt, Ignasi; Hidalgo, Manuela

    2013-08-01

    The control of metal catalyst residues (i.e., platinum group metals (PGMs)) in different stages of the manufacturing processes of the active pharmaceutical ingredients (APIs) and, especially, in the final product is crucial. For API specimens, there are strict guidelines to limit the levels of metal residues based on their individual levels of safety concern. For PGMs the concentration limit has been established at 10 mg/kg in the API. Therefore great effort is currently being devoted to the development of new and simple procedures to control metals in pharmaceuticals. In the present work, an analytical methodology based on benchtop total reflection X-ray fluorescence spectrometry (TXRF) has been developed for the rapid and simple determination of some PGM catalyst impurities (Rh, Pd, Ir and Pt) in different types of API samples. An evaluation of different sample treatments (dissolution and digestion of the solid pharmaceutical samples) has been carried out and the developed methodologies have been validated according to the analytical parameters to be considered and acceptance criteria for PGM determination according to the United States Pharmacopeia (USP). Limits of quantification obtained for PGM metals were in the range of 2-4 mg/kg which are satisfactory according to current legislation. From the obtained results it is shown that the developed TXRF method can be implemented in the pharmaceutical industries to increase productivity of the laboratory; offering an interesting and complementary analytical tool to other atomic spectroscopic methods.

  18. 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.

  19. Pyrolysis of marine biomass to produce bio-oil and its upgrading using a novel multi-metal catalyst prepared from the spent car catalytic converter.

    Science.gov (United States)

    Sabegh, Mahzad Yaghmaei; Norouzi, Omid; Jafarian, Sajedeh; Khosh, Akram Ghanbari; Tavasoli, Ahmad

    2018-02-01

    In order to reduce the economic and environmental consequences caused by spent car catalyst, we herein report for the first time a novel promising multi-metal catalyst prepared from spent car catalytic converters to upgrade the pyrolysis bio-oils. The physico-chemical properties of prepared catalyst were characterized by XRD, EDS, FESEM, and FT-IR analyses. The thermal stability of the multi-metal catalyst was studied with TGA. To investigate the activity of the catalyst, Conversion of Cladophora glomerata (C. glomerata) into bio-products was carried out via a fixed bed reactor with and without catalyst at the temperature of 500°C. Although the catalyst didn't catalyze the gasification reaction, bio-oil was upgraded over the catalyst. The main effect of the catalyst on the bio-oil components is deoxygenating of nitrogen compounds and promotion the ketonization reaction, which converts acid to ketone and declines the corrosive nature of bio-oil. Copyright © 2017. Published by Elsevier Ltd.

  20. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    Directory of Open Access Journals (Sweden)

    Wan Azelee Wan Abu Bakar

    2015-09-01

    Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.