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Sample records for active catalyst species

  1. Preparation of active HDS catalysts by controlling the dispersion of active species

    NASA Astrophysics Data System (ADS)

    Inamura, Kazuhiro; Uchikawa, Kei; Matsuda, Satoshi; Akai, Yoshio

    1997-11-01

    It is demonstrated that the structural control of the metal ion precursors in the impregnating solution by adding the chelating agents is effective to prepare the higher active CoMo supported on alumina catalysts ( Co-Mo/Al 2O 3) for hydrodesulfurization (HDS). Coordination structures of the Co and Mo complexes in the CoMo impregnating solution and distributions of the Co and Mo complexes were evaluated by spectroscopic characterization techniques and by using a computational calculation, respectively. An addition of a chelating agent, such as NTA (nitrilotriacetic acid) and Glu (L-glutamic acid), in the CoMo solution results in the selective formation of the Co complexes, while the amount of the Mo complex is negligibly small at the practical pH of 9.2. The addition of the chelating agent increases the thiophene HDS activity of the sulfided catalysts typically by 50%, compared with that prepared without the chelating agent. Dispersion results of Co and Mo species on both oxidic and sulfided catalysts indicate that the higher HDS activity is explained by the higher degree of surface exposure of Co sites (namely the dispersion of Co) rather than that of Mo sites. The selective formation of the Co-chelate complexes keeps Co ions stable in solution up to high concentration. Furthermore, the Co complexes are estimated to be stable on the support even in the initial step of calcination, which would depress the formation of crystalline Co compounds, such as CoAl 2O 4 and CoMoO 4. These effects result in the higher dispersion of the active Co surface species.

  2. Catalyst activator

    DOEpatents

    McAdon, Mark H.; Nickias, Peter N.; Marks, Tobin J.; Schwartz, David J.

    2001-01-01

    A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.

  3. Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts.

    PubMed

    Widmann, D; Behm, R J

    2014-03-18

    Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently. This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even at the extremely low concentrations present under realistic reaction conditions. Different types of pulse experiments were performed, during which the highly dispersed, realistic powder catalysts are exposed to very low amounts of reactants, CO and/or O2, in order to form and reactively remove Oact species and gain information on their formation, nature, and the active site for Oact formation. Our investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 °C and higher is a highly stable atomic species, which at 80 °C is formed only at the perimeter of the Au-oxide interface and whose reactive removal by CO is activated, but not its formation. From these findings, it is concluded that surface lattice oxygen represents the Oact species for the CO oxidation. Accordingly, the CO oxidation proceeds via a Au-assisted Mars-van Krevelen mechanism, during which surface lattice oxygen close to the Au NPs is removed by reaction

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

    PubMed Central

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

    2016-01-01

    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. PMID:27538720

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

    PubMed

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

    2016-01-01

    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. PMID:27538720

  6. The formation and degradation of active species during methanol conversion over protonated zeotype catalysts.

    PubMed

    Olsbye, U; Svelle, S; Lillerud, K P; Wei, Z H; Chen, Y Y; Li, J F; Wang, J G; Fan, W B

    2015-10-21

    The methanol to hydrocarbon (MTH) process provides an efficient route for the conversion of carbon-based feedstocks into olefins, aromatics and gasoline. Still, there is room for improvements in product selectivity and catalytic stability. This task calls for a fundamental understanding of the formation, catalytic mechanism and degradation of active sites. The autocatalytic feature of the MTH process implies that hydrocarbons are active species on the one hand and deactivating species on the other hand. The steady-state performance of such species has been thoroughly studied and reviewed. However, the mechanism of formation of the initial hydrocarbon species (i.e.; the first C-C bond) and the evolution of active species into deactivating coke species have received less attention. Therefore, this review focuses on the significant progress recently achieved in these two stages by a combination of theoretical calculations, model studies, operando spectroscopy and catalytic tests. PMID:26185806

  7. An in-depth understanding of the bimetallic effects and coked carbon species on an active bimetallic Ni(Co)/Al2O3 dry reforming catalyst.

    PubMed

    Liao, Xin; Gerdts, Rihards; Parker, Stewart F; Chi, Lina; Zhao, Yongxiang; Hill, Martyn; Guo, Junqiu; Jones, Martin O; Jiang, Zheng

    2016-06-29

    Ni/Al2O3, Co/Al2O3 and bimetallic Ni(Co)/Al2O3 catalysts were prepared using an impregnation method and employed in CO2 dry reforming of methane under coking-favored conditions. The spent catalysts were carefully characterized using typical characterization technologies and inelastic neutron scattering spectroscopy. The bimetallic catalyst exhibited a superior activity and anti-coking performance compared to Ni/Al2O3, while the most resistant to coking behavior was Co/Al2O3. The enhanced activity of the Ni(Co)/Al2O3 bimetallic catalyst is attributed to the reduced particle size of metallic species and resistance to forming stable filamentous carbon. The overall carbon deposition on the spent bimetallic catalyst is comparable to that of the spent Ni/Al2O3 catalyst, whereas the carbon deposited on the bimetallic catalyst is mainly less-stable carbonaceous species as confirmed by SEM, TPO, Raman and INS characterization. This study provides an in depth understanding of alloy effects in catalysts, the chemical nature of coked carbon on spent Ni-based catalysts and, hopefully, inspires the creative design of a new bimetallic catalyst for dry reforming reactions. PMID:27326792

  8. Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

    NASA Astrophysics Data System (ADS)

    Zhang, Libo; Zhou, Gang

    2016-04-01

    The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO2 is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximate to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.

  9. Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study.

    PubMed

    Zhang, Libo; Zhou, Gang

    2016-04-14

    The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO2 is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximate to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs. PMID:27083744

  10. Nickel as a co-catalyst for photocatalytic hydrogen evolution on graphitic-carbon nitride (sg-CN): what is the nature of the active species?

    PubMed

    Indra, Arindam; Menezes, Prashanth W; Kailasam, Kamalakannan; Hollmann, Dirk; Schröder, Marc; Thomas, Arne; Brückner, Angelika; Driess, Matthias

    2016-01-01

    The nature of a nickel-based co-catalyst deposited on a sol-gel prepared porous graphitic-carbon nitride (sg-CN), for photocatalytic H2 production from water, has been investigated. The formation of the active catalytic species, charge separation and recombination of the photogenerated electrons and holes during photochemical H2 evolution has been determined for the first time using in situ EPR spectroscopy. PMID:26498497

  11. In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity.

    PubMed

    Trześniewski, Bartek J; Diaz-Morales, Oscar; Vermaas, David A; Longo, Alessandro; Bras, Wim; Koper, Marc T M; Smith, Wilson A

    2015-12-01

    Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni(Fe)-B(i)) and nickel oxyhydroxide (Ni(Fe)OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO(-)), which can be described as adsorbed "active oxygen". Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV-vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs. PMID:26544169

  12. Preparation of new catalysts by the immobilization of palladium(II) species onto silica: an investigation of their catalytic activity for the cyclization of aminoalkynes.

    PubMed

    Richmond, M K; Scott, S L; Alper, H

    2001-10-31

    Silica-immobilized palladium catalysts are readily prepared by treating partially dehydroxylated silica with solutions of the palladium(II) complexes, cis-[PdMeXL2] (X = Me, L2 = dmpe; X = Cl, L2 = dmpe, dppe, phen, bipy, 2PMe3), trans-[PdMeXL2] (X = Cl, NO3, OTf, L = PMe3; X = Cl, L = PPh3), or [PdPh(OH)L]2 (L = PPh3, PCy3), at room temperature. A chemisorption reaction is presumed to occur on the surface Si-OH groups, with elimination of 1 equiv of methane, benzene, or water and the initial formation of a covalent Pd-O bond to the silica surface. The amount of chemisorbed material is strongly dependent on the nature of the complex employed, and the Pd content of the materials, determined by ICP analysis, was found to vary widely (from 1.47 to 0.021 wt %). It appears that the complexes stabilized by more basic ligands undergo a more facile reaction with the surface. The catalytic activity of the materials was first tested in the cyclization of 6-aminohex-1-yne. Higher conversions were found for those catalysts containing more basic ligands, due to the higher loadings, and for those complexes containing more weakly coordinating anions. Silica/trans-[PdMe(NO3)(PMe3)2] was identified as the best catalyst and was used to test the generality of the catalytic cyclization method with two other alkynes, namely, 5-phenyl-4-pentyn-1-amine and 6-phenyl-5-hexyn-1-amine. The catalysts prepared here show rates comparable to, or greater than, those found for homogeneous late transition metal complexes, including their molecular precursors. Furthermore, the supported catalysts are only slightly air-sensitive and can be recycled, after filtration in air, with only moderate loss of activity. PMID:11673983

  13. Activation Energies of Plasmonic Catalysts.

    PubMed

    Kim, Youngsoo; Dumett Torres, Daniel; Jain, Prashant K

    2016-05-11

    The activation energy of a catalytic reaction serves not only as a metric of the efficacy of a catalyst but also as a potential indicator of mechanistic differences between the catalytic and noncatalytic reaction. However, activation energies are quite underutilized in the field of photocatalysis. We characterize in detail the effect of visible light excitation on the activation enthalpy of an electron transfer reaction photocatalyzed by plasmonic Au nanoparticles. We find that in the presence of visible light photoexcitation, the activation enthalpy of the Au nanoparticle-catalyzed electron transfer reaction is significantly reduced. The reduction in the activation enthalpy depends on the excitation wavelength, the incident laser power, and the strength of a hole scavenger. On the basis of these results, we argue that the activation enthalpy reduction is directly related to the photoelectrochemical potential built-up on the Au nanoparticle under steady-state light excitation, analogous to electrochemical activation. Under optimum light excitation conditions, a potential as high as 240 mV is measured. The findings constitute more precise insights into the mechanistic role and energetic contribution of plasmonic excitation to chemical reactions catalyzed by transition metal nanoparticles. PMID:27064549

  14. Highly Stable and Active Catalyst for Sabatier Reactions

    NASA Technical Reports Server (NTRS)

    Hu, Jianli; Brooks, Kriston P.

    2012-01-01

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

  15. Immobilisation of homogeneous olefin polymerisation catalysts. Factors influencing activity and stability.

    PubMed

    Severn, John R; Chadwick, John C

    2013-07-01

    The activity and stability of homogeneous olefin polymerisation catalysts, when immobilised on a support, are dependent on both chemical and physical effects. Chemical factors affecting catalyst activity include the ease of formation of the active species, which is strongly dependent on the transition metal. Catalyst productivity is dependent on the balance between activity and stability. Immobilisation can lead to a lower proportion of active species and therefore lower initial polymerisation activity, but nevertheless give higher polymer yields in cases where increased catalyst stability is obtained. Important physical factors are support porosity and the ability of a support to undergo progressive fragmentation during polymerisation, facilitating monomer diffusion through the growing catalyst/polymer particle. This article illustrates the importance of these factors in olefin polymerisation with both early- and late-transition metal catalysts, with particular reference to the use of silica and magnesium chloride supports as well as to effects of immobilisation on polymer structure and properties. PMID:23467461

  16. Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity

    SciTech Connect

    Gao, Feng; Washton, Nancy M.; Wang, Yilin; Kollar, Marton; Szanyi, Janos; Peden, Charles HF

    2015-09-03

    Cu/SSZ-13 catalysts with three Si/Al ratios of 6, 12 and 35 were synthesized with Cu incorporation via solution ion exchange. The implications of varying Si/Al ratios on the nature of the multiple Cu species that can be present in the SSZ-13 zeolite are a major focus of this work, as highlighted by the results of a variety of catalyst characterization and reaction kinetics measurements. Specifically, catalysts were characterized with surface area/pore volume measurements, temperature programmed reduction by H2 (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), and DRIFTS and solid-state nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties were examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions on selected catalysts under differential conditions. Besides indicating possible variably active multiple Cu species for these reactions, the measurements are also used to untangle some of the complexities caused by the interplay between redox of Cu ion centers and Brønsted acidity. All three reactions appear to follow a redox reaction mechanism, yet the roles of Brønsted acidity are quite different. For NO oxidation, increasing Si/Al ratio lowers Cu redox barriers, thus enhancing reaction rates. Brønsted acidity appears to play essentially no role for this reaction. For standard NH3-SCR, residual Brønsted acidity plays a significant beneficial role at both low- and high-temperature regimes. For NH3 oxidation, no clear trend is observed suggesting both Cu ion center redox and Brønsted acidity play important and perhaps competing roles. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of

  17. Upgrading of coal-derived liquids. 1. Catalytic activities of zeolite catalysts and commercial HDS catalysts

    SciTech Connect

    Yoshida, R.; Hara, S.; Yoshida, T.; Yokoyama, S.; Nakata, Y.; Goto, Y.; Maekawa, Y.

    1983-01-01

    The applicability of various zeolite catalysts and commercial hydrodesulfurization (HDS) catalysts to the secondary hydrotreatment of coal-derived liquids was examined in relation to the chemical structure of upgraded liquids. The catalytic activities of zeolite catalysts for HI conversion is lower than are the activities of Ni-Mo, Ni-Co-Mo, Co-Mo and Ni-W catalysts. However, as regards hydrogenation and the removal of nitrogen, zeolite catalysts such as natural clinoptilolite and mordenite have almost the same activity as do Co-Mo and Ni-W catalysts. As to the removal of oxygen, it was proved that zeolite catalysts had a functionality to remove oxygen as CO/sub x/ gas, and HDS catalysts had a high activity for hydrodeoxygenation. 10 references, 3 figures, 4 tables.

  18. Activity and selectivity of molybdenum catalysts in coal liquefaction reactions

    SciTech Connect

    Curtis, C.W.; Pellegrino, J.L. )

    1988-06-01

    During coal liquefaction, coal fragments forming a liquid product with reduced heteroatom content. Coal can be considered to be a large network of polynuclear aromatic species connected by heteroatoms and alkyl bridging structures. Predominant heteroatoms contained in coal are sulfur, oxygen, and nitrogen. Predominant alkyl bridges are methylene and ethylene structures. The purpose of this work is to evaluate how effectively three different molybdenum catalysts promote reactions involving heteroatom removal and cleavage of alkyl bridge structures. The reactions studied include: hydrogenation (HYD), hydrodeoxygenation (HDO), hydrosulfurization (HDS), hydrodenitrogenation (HDN) and hydrocracking (HYC). Both model and coal liquefaction reactions were performed to test the activity and selectivity of three different molybdenum catalysts. The three catalysts used were molybdenum napththenate, molybdenum supported on gamma alumina (Mo/Al/sub 2/O/sub 3/) and precipitated, poorly crystalline molybdenum disulfide (MoS/sub 2/). The model compounds, chosen to mimic coal structure, on which the effectiveness of the catalysts for the model reactions was tested were: 1-methylnaphthalene, representing aromatic hydrocarbons, for hydrogenation; 1-naphthol, representing oxygen containing compounds, for deoxygenation; benzothiophene, representing sulfur containing compounds, for desulfurization; indole, representing nitrogen containing compounds, for denitrogenation; and bibenzyl, representing alkyl bridging structures, for hydrocracking. Catalytic reactions of combinations of reactants were performed to simulate a complex coal matrix. Thermal and catalytic coal liquefaction reactions were performed using Illinois No. 6 coal with anthracene as a solvent. The efficacy of the catalysts was determined by comparing the product and compound class fractions obtained from the liquefaction reactions.

  19. Support chemistry, surface area, and preparation effects on sulfided NiMo catalyst activity

    SciTech Connect

    Gardner, T.J.; McLaughlin, L.I.; Sandoval, R.S.

    1996-06-01

    Hydrous Metal Oxides (HMOs) are chemically synthesized materials which contain a homogeneous distribution of ion exchangeable alkali cations that provide charge compensation to the metal-oxygen framework. In terms of the major types of inorganic ion exchangers defined by Clearfield, these amorphous HMO materials are similar to both hydrous oxides and layered oxide ion exchangers (e.g., alkali metal titanates). For catalyst applications, the HMO material serves as an ion exchangeable support which facilitates the uniform incorporation of catalyst precursor species. Following catalyst precursor incorporation, an activation step is required to convert the catalyst precursor to the desired active phase. Considerable process development activities at Sandia National Laboratories related to HMO materials have resulted in bulk hydrous titanium oxide (HTO)- and silica-doped hydrous titanium oxide (HTO:Si)-supported NiMo catalysts that are more active in model reactions which simulate direct coal liquefaction (e.g., pyrene hydrogenation) than commercial {gamma}-Al{sub 2}O{sub 3}-supported NiMo catalysts. However, a fundamental explanation does not exist for the enhanced activity of these novel catalyst materials; possible reasons include fundamental differences in support chemistry relative to commercial oxides, high surface area, or catalyst preparation effects (ion exchange vs. incipient wetness impregnation techniques). The goals of this paper are to identify the key factors which control sulfided NiMo catalyst activity, including those characteristics of HTO- and HTO:Si-supported NiMo catalysts which uniquely set them apart from conventional oxide supports.

  20. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

    Alcohol transformation to transportation fuel range hydrocarbon on HZSM-5 (SiO2 / Al2O3 = 30) catalyst was studied at 360oC and 300psig. Product distributions and catalyst life were compared using methanol, ethanol, 1-propanol or 1-butanol as a feed. The catalyst life for 1-propanol and 1-butanol was more than double compared to that for methanol and ethanol. For all the alcohols studied, the product distributions (classified to paraffin, olefin, napthene, aromatic and naphthalene compounds) varied with time on stream (TOS). At 24 hours TOS, liquid product from 1-propanol and 1-butanol transformation primarily contains higher olefin compounds. The alcohol transformation process to higher hydrocarbon involves a complex set of reaction pathways such as dehydration, oligomerization, dehydrocyclization, and hydrogenation. Compared to ethylene generated from methanol and ethanol, oligomerization of propylene and butylene has a lower activation energy and can readily take place on weaker acidic sites. On the other hand, dehydrocyclization of propylene and butylene to form the cyclic compounds requires the sits with stronger acid strength. Combination of the above mentioned reasons are the primary reasons for olefin rich product generated in the later stage of the time on stream and for the extended catalyst life time for 1 propanol and 1 butanol compared to methanol and ethanol conversion over HZSM-5.

  1. Understanding high-yield catalyst-free growth of horizontally aligned single-walled carbon nanotubes nucleated by activated C60 species.

    PubMed

    Ibrahim, Imad; Bachmatiuk, Alicja; Grimm, Daniel; Popov, Alexey; Makharza, Sami; Knupfer, Martin; Büchner, Bernd; Cuniberti, Gianaurelio; Rümmeli, Mark H

    2012-12-21

    Our understanding of the catalyst-free growth of single-walled carbon nanotubes by chemical vapor deposition is limited. Toward improving our knowledge base, we conducted systematic investigations into the initial preparation of C(60) fullerenes as nucleation precursors for single-wall and even double-wall carbon nanotube fabrication. The role of the dispersing media is shown to be crucial and is related to the initial fullerene cluster size. Oxygen-based groups, in particular, epoxy groups, are shown to be vital prior to actual growth. Moreover, the presence of oxygen groups during the growth phase is necessary for tube development. We also demonstrate the possibility of fabricating the tubes in crossbar configurations with bespoke crossing angles in a single synthesis step, unlike other routes which require at least two synthesis steps. The systematic studies significantly advance our understanding of the growth mechanisms involved in all-carbon catalyst-free growth of single- and double-walled carbon nanotubes. PMID:23186015

  2. Oxygen-assisted reduction of Au species on Au/SiO2 catalyst in room temperature CO oxidation

    SciTech Connect

    Wu, Zili; Zhou, Shenghu; Zhu, Haoguo; Dai, Sheng; Overbury, Steven {Steve} H

    2008-01-01

    An unexpected oxygen-assisted reduction of cationic Au species by CO was found on a Au/SiO2 catalyst at room temperature; CO oxidation activity increases simultaneously with the reduction of Au species, suggesting the key role of metallic Au played in CO oxidation on Au/SiO2.

  3. Process of activation of a palladium catalyst system

    DOEpatents

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-08-02

    Improved processes for activating a catalyst system used for the reduction of nitrogen oxides are provided. In one embodiment, the catalyst system is activated by passing an activation gas stream having an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen over the catalyst system and increasing a temperature of the catalyst system to a temperature of at least 180.degree. C. at a heating rate of from 1-20.degree./min. Use of activation processes described herein leads to a catalyst system with superior NOx reduction capabilities.

  4. Phase-Transfer Activation of Transition Metal Catalysts.

    PubMed

    Tuba, Robert; Xi, Zhenxing; Bazzi, Hassan S; Gladysz, John A

    2015-11-01

    With metal-based catalysts, it is quite common that a ligand (L) must first dissociate from a catalyst precursor (L'n M-L) to activate the catalyst. The resulting coordinatively unsaturated active species (L'n M) can either back react with the ligand in a k-1 step, or combine with the substrate in a k2 step. When dissociation is not rate determining and k-1 [L] is greater than or comparable to k2 [substrate], this slows the rate of reaction. By introducing a phase label onto the ligand L and providing a suitable orthogonal liquid or solid phase, dramatic rate accelerations can be achieved. This phenomenon is termed "phase-transfer activation". In this Concept, some historical antecedents are reviewed, followed by successful applications involving fluorous/organic and aqueous/organic liquid/liquid biphasic catalysis, and liquid/solid biphasic catalysis. Variants that include a chemical trap for the phase-labeled ligands are also described. PMID:26338471

  5. Activation of catalysts for synthesizing methanol from synthesis gas

    DOEpatents

    Blum, David B.; Gelbein, Abraham P.

    1985-01-01

    A method for activating a methanol synthesis catalyst is disclosed. In this method, the catalyst is slurried in an inert liquid and is activated by a reducing gas stream. The activation step occurs in-situ. That is, it is conducted in the same reactor as is the subsequent step of synthesizing methanol from a methanol gas stream catalyzed by the activated catalyst still dispersed in a slurry.

  6. Novel catalyst for the removal of aromatic sulfur species from refinery streams

    NASA Astrophysics Data System (ADS)

    Petzold, Franz Georg

    2011-12-01

    A novel catalyst with hydro-desulfurization and hydrogenation capabilities was tested with the aim of producing ultra-low sulfur and aromatics diesel oil. The catalytically active phase is nickel in a reduced valence state on a carrier made of zinc oxide nanowires and alumina. Based on the reactive adsorption principle, it was speculated that enhanced metal-support interactions and short diffusion paths between nickel and zinc oxide could lead to improved activity and sulfur uptake capacity. Zinc oxide nanowires, proposed here as a novel catalyst support, were produced in appreciable quantities in a microwave-induced plasma jet reactor. After purification and decoration with an active nickel phase, the nanowires underwent extensive characterization, which revealed promising properties. On-stream hydrogenation activity and sulfur uptake was tested on a model diesel oil spiked with difficult-to-remove organic sulfur species. It was observed that the proposed catalyst system, as it was assembled in this project, is inferior to existing hydro-desulfurization products. Nevertheless, this undertaking was a first crude attempt and the concept of reactive adsorption was sufficiently demonstrated, which can hopefully be improved upon with succeeding trials.

  7. Reduction of low temperature engine pollutants by understanding the exhaust species interactions in a diesel oxidation catalyst.

    PubMed

    Lefort, I; Herreros, J M; Tsolakis, A

    2014-02-18

    The interactions between exhaust gas species and their effect (promotion or inhibition) on the light-off and activity of a diesel oxidation catalyst (DOC) for the removal of pollutants are studied, using actual engine exhaust gases from the combustion of diesel, alternative fuels (rapeseed methyl ester and gas-to-liquid fuel) and diesel/propane dual fuel combustion. The activity of the catalyst was recorded during a heating temperature ramp where carbon monoxide (CO) and hydrocarbon (HC) light-off curves were obtained. From the catalyst activity tests, it was found that the presence of species including CO, medium-heavy HC, alkenes, alkanes, and NOx and their concentration influence the catalyst ability to reduce CO and total HC emissions before release to the atmosphere. CO could inhibit itself and other species oxidation (e.g., light and medium-heavy hydrocarbons) while suffering from competitive adsorption with NO. Hydrocarbon species were also found to inhibit their own oxidation as well as CO through adsorption competition. On the other hand, NO2 was found to promote low temperature HC oxidation through its partial reduction, forming NO. The understanding of these exhaust species interactions within the DOC could aid the design of an efficient aftertreatment system for the removal of diesel exhaust pollutants. PMID:24450781

  8. The role of copper species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction

    NASA Astrophysics Data System (ADS)

    Liang, Chunxia; Li, Xinyong; Qu, Zhenping; Tade, Moses; Liu, Shaomin

    2012-02-01

    UV-vis spectra, XRD, H2-TPR, TEM and ESR were used to characterize a series of Cu/γ-Al2O3 catalysts, which were prepared by incipient wetness impregnation using copper nitrate, copper acetate or copper sulfate as precursors, to study the role of Cu species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction. It was found that the mixture of CuO phase and CuAl2O4 phase formed on various Cu/γ-Al2O3 catalysts, and the Cu species and dispersion had significant influence on the Cu/γ-Al2O3 activity. Highly dispersed CuO phase on the support would be related with its high activity for the NH3-SCO reaction.

  9. Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents

    PubMed Central

    2016-01-01

    Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed. PMID:27610418

  10. Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents.

    PubMed

    Mougel, Victor; Chan, Ka-Wing; Siddiqi, Georges; Kawakita, Kento; Nagae, Haruki; Tsurugi, Hayato; Mashima, Kazushi; Safonova, Olga; Copéret, Christophe

    2016-08-24

    Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed. PMID:27610418

  11. Activation of molecular catalysts using semiconductor quantum dots

    DOEpatents

    Meyer, Thomas J.; Sykora, Milan; Klimov, Victor I.

    2011-10-04

    Photocatalytic materials based on coupling of semiconductor nanocrystalline quantum dots (NQD) and molecular catalysts. These materials have capability to drive or catalyze non-spontaneous chemical reactions in the presence of visible radiation, ultraviolet radiation, or both. The NQD functions in these materials as a light absorber and charge generator. Following light absorption, the NQD activates a molecular catalyst adsorbed on the surface of the NQD via transfer of one or more charges (either electrons or electron-holes) from the NQD to the molecular catalyst. The activated molecular catalyst can then drive a chemical reaction. A photoelectrolytic device that includes such photocatalytic materials is also described.

  12. Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

    PubMed Central

    Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

    2014-01-01

    A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

  13. Method for regeneration and activity improvement of syngas conversion catalyst

    DOEpatents

    Lucki, Stanley J.; Brennan, James A.

    1980-01-01

    A method is disclosed for the treatment of single particle iron-containing syngas (synthes.s gas) conversion catalysts comprising iron, a crystalline acidic aluminosilicate zeolite having a silica to alumina ratio of at least 12, a pore size greater than about 5 Angstrom units and a constraint index of about 1-12 and a matrix. The catalyst does not contain promoters and the treatment is applicable to either the regeneration of said spent single particle iron-containing catalyst or for the initial activation of fresh catalyst. The treatment involves air oxidation, hydrogen reduction, followed by a second air oxidation and contact of the iron-containing single particle catalyst with syngas prior to its use for the catalytic conversion of said syngas. The single particle iron-containing catalysts are prepared from a water insoluble organic iron compound.

  14. Catalytic deactivation of methane steam reforming catalysts. I. Activation

    SciTech Connect

    Agnelli, M.E.; Demicheli, M.C.; Ponzi, E.N.

    1987-08-01

    An alumina-supported catalyst was studied both in its original state and after activation and sintering. Chemical composition and textural properties were determined, and crystalline compounds were identified. Active-phase and support transformations occurring during activation were determined by differential thermoanalysis (DTA), temperature-programmed reduction (TPR), and X-ray diffraction. The catalyst activated by means of various procedures was characterized by measuring crystallite size.

  15. Comparison of the activities of fine-particle size catalysts

    SciTech Connect

    Stohl, F.V.; Diegert, K.V.; Goodnow, D.C.

    1994-12-31

    The objectives of Sandia`s fine-particle size catalyst testing project are to evaluate and compare the activities of the fine-particle size catalysts being developed in DOE/PETCs Advanced Research Coal Liquefaction Program by using standard coal liquefaction test procedures. The standard procedures use Blind Canyon coal, phenanthrene as the reaction solvent, and a factorial experimental design with temperatures from 350{degrees}C to 400{degrees}C, reaction times from 20 to 60 minutes, and catalyst loadings up to 1 wt%. Catalytic activity is measured in terms of tetrahydrofuran conversion, heptane conversion, the amount of 9,10-dihydrophenanthrene in the product, and the gas yield. Several catalysts have been evaluated including a commercially available pyrite, a sulfated iron oxide from the University of Pittsburgh, and several preparations of 6-line ferrihydrites from Pacific Northwest Laboratories. Results have demonstrated that significant differences in activity can be detected among these catalysts.

  16. Highly active water-soluble olefin metathesis catalyst.

    PubMed

    Hong, Soon Hyeok; Grubbs, Robert H

    2006-03-22

    A novel water-soluble ruthenium olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated saturated 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligand is reported. The catalyst displays improved activity in ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis reactions in aqueous media. PMID:16536510

  17. Role of surface Ni and Ce species of Ni/CeO2 catalyst in CO2 methanation

    NASA Astrophysics Data System (ADS)

    Zhou, Guilin; Liu, Huiran; Cui, Kaikai; Jia, Aiping; Hu, Gengshen; Jiao, Zhaojie; Liu, Yunqi; Zhang, Xianming

    2016-10-01

    CeO2, which was used as support to prepare mesoporous Ni/CeO2 catalyst, was prepared by the hard-template method. The prepared NiO/CeO2 precursor and Ni/CeO2 catalyst were studied by H2-TPR, in-situ XPS, and in-situ FT-IR. The catalytic properties of the prepared Ni/CeO2 catalyst were also investigated by CO2 catalytic hydrogenation methanation. H2-TPR and in-situ XPS results showed that metal Ni species and surface oxygen vacancies could be formed by H2 reduction. In-situ FT-IR and in-situ XPS results indicated that CO2 molecules could be reduced by active metal Ni species and surface oxygen vacancies to generate active CO species and promote CO2 methanation. The Ni/CeO2 catalyst presented the high CO2 methanation activity, and CO2 conversion and CH4 selectivity reached 91.1% and 100% at 340 °C and atmospheric pressure.

  18. The role of catalyst activation on the activity and attrition of precipitated iron Fischer-Tropsch catalysts

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Harrington, M.S.; Coulter, K.E.; Sault, A.G.; Jackson, N.B.

    1995-12-31

    The results of this work indicate that magnetite is not catalytically active for Fischer-Tropsch Synthesis (FTS) in precipitated, unsupported iron catalysts, but the formation of the carbide phase is necessary to obtain FTS activity. The transformation of magnetite to carbide, though essential to obtain FTS activity, also causes the catalyst to break down. This can lead to severe problems during operation in a commercial slurry phase reactor. The results presented here imply that activation and attrition are simultaneous and complementary processes. In another study, we show that the catalyst can also under go attrition on a micron scale which is caused by lack of strength of the forces binding the catalyst primary particles in the agglomerates. Both these processes can make wax separation and product recovery extremely difficult. In this study, we have also shown that H{sub 2} reduction of this catalyst to metallic iron is detrimental to subsequent catalyst activity and causes a loss of surface area due to sintering of the iron crystallites. Reduction to metallic Fe also causes impurities such as S to segregate to the surface causing a complete loss of FTS activity. It has been shown that even submonolayer amounts of S can cause a dramatic decrease in FTS activity, hence reduction to metallic Fe should be avoided during activation of these catalysts. We have shown, however, that a mild H{sub 2} reduction to magnetite does not lead to S segregation to the surface, and is therefore acceptable.

  19. Removal and Transformation of Sulfur Species During Regeneration of Poisoned Nickel Biomass Conditioning Catalysts

    SciTech Connect

    Yung, M. M.; Cheah, S.; Kuhn, J. N.; Magrini-Bair, K. A.

    2012-01-01

    Sulfur K-edge XANES was used to monitor sulfur species transforming from sulfides to sulfates during steam + air regeneration on a Ni/Mg/K/Al{sub 2}O{sub 3} catalyst used to condition biomass-derived syngas. The catalyst was tested for multiple reaction/regeneration cycles. Post-reaction samples showed the presence of sulfides on the H{sub 2}S-poisoned nickel catalyst. Although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H{sub 2} reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.

  20. Morphology-dependent bactericidal activities of Ag/CeO2 catalysts against Escherichia coli.

    PubMed

    Wang, Lian; He, Hong; Yu, Yunbo; Sun, Li; Liu, Sijin; Zhang, Changbin; He, Lian

    2014-06-01

    Silver-loaded CeO2 nanomaterials (Ag/CeO2) including Ag/CeO2 nanorods, nanocubes, nanoparticles were prepared with hydrothermal and impregnation methods. Catalytic inactivation of Escherichia coli with Ag/CeO2 catalysts through the formation of reactive oxygen species (ROS) was investigated. For comparison purposes, the bactericidal activities of CeO2 nanorods, nanocubes and nanoparticles were also studied. There was a 3-4 log order improvement in the inactivation of E. coli with Ag/CeO2 catalysts compared with CeO2 catalysts. Temperature-programmed reduction of H2 showed that Ag/CeO2 catalysts had higher catalytic oxidation ability than CeO2 catalysts, which was the reason for that Ag/CeO2 catalysts exhibited stronger bactericidal activities than CeO2 catalysts. Further, the bactericidal activities of CeO2 and Ag/CeO2 depend on their shapes. Results of 5,5-dimethyl-1-pyrroline-N-oxide spin-trapping measurements by electron spin resonance and addition of catalase as a scavenger indicated the formation of OH, O2(-), and H2O2, which caused the obvious bactericidal activity of catalysts. The stronger chemical bond between Ag and CeO2 nanorods led to lower Ag(+) elution concentrations. The toxicity of Ag(+) eluted from the catalysts did not play an important role during the bactericidal process. Experimental results also indicated that Ag/CeO2 induced the production of intracellular ROS and disruption of the cell wall and cell membrane. A possible production mechanism of ROS and bactericidal mechanism of catalytic oxidation were proposed. PMID:24662462

  1. Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts.

    PubMed

    Wang, Lu-Cun; Friend, C M; Fushimi, Rebecca; Madix, Robert J

    2016-07-01

    The activation of molecular O2 as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O2 activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O2 dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O2 dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O2 dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction. PMID:27376884

  2. Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.

    PubMed

    Wang, Liang; Zhang, Bingsen; Meng, Xiangju; Su, Dang Sheng; Xiao, Feng-Shou

    2014-06-01

    A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229 m(2)  g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites. PMID:24861954

  3. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity

    NASA Astrophysics Data System (ADS)

    Balof, Shawna Lynn

    2011-12-01

    Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH-responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for

  4. Near-ambient XPS characterization of interfacial copper species in ceria-supported copper catalysts.

    PubMed

    Monte, Manuel; Munuera, Guillermo; Costa, Dominique; Conesa, José C; Martínez-Arias, Arturo

    2015-11-28

    Catalysts based on combinations of copper and cerium oxides are interesting alternatives to noble metal ones for processes involved in the production/purification of hydrogen produced from hydrocarbons or biomass like the water-gas shift or the preferential oxidation of CO reactions. Active sites for such processes have been proposed to correspond to reduced species formed at the interface between both oxides. The present work provides direct evidence of reduced copper species located at the interface and observed during the course of near-ambient XPS experiments performed over samples of copper oxide supported on ceria nanospheres and nanocubes subjected to interaction with CO at different temperatures. The analysis of XPS results is based on DFT+U calculations employed as a complementary method for the analysis of redox properties of the catalysts and core-level shifts produced upon such redox changes. Differences observed in interfacial redox properties as a function of the ceria support morphology appear to be most useful to explain catalytic properties of this type of system for mentioned processes. PMID:26497369

  5. Nanoscale attrition during activation of precipitated iron Fischer- Tropsch catalysts: Implications for catalyst design

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Jin, Y.; Brooks, R.P.; Wilder, J.A.; Harrington, M.S.; Sault, A.G.; Jackson, N.B.

    1996-06-01

    This work has shown that the kaolin binder that has been used in commercial Fischer-Tropsch Synthesis catalysts doe not offer any significant attrition resistance. This is due in part to its morphology (plate-like) and to its particle size being much greater than the primary crystallite size of the iron oxide catalyst. From a microscopic examination of these catalysts, it appears that if the nanoscale attrition of the iron catalyst is to be avoided, the iron must be well dispersed on the binder, and the binder must provide an interlocking microstructure that provides strength and stability to the 30-70 {mu}m agglomerates. The study of Fe/SiO{sub 2} catalysts has shown that co-precipitation of the iron and silica leads to formation of an amorphous glassy phase which is difficult to reduce even at 723K. On the other hand, when the iron was precipitated on a preformed silica, 25-40% of the iron could be reduced and carbided. The supported iron catalyst, after reduction, formed 15-20 nm iron carbide particles that look very similar to those on the unsupported catalyst. The major difference is these nanometer sized particles are anchored on a support and therefore would not be expected to breakup further and contribute to the fines generated as catalyst attrition proceeds. However, since only a fraction of the silica-supported iron can be reduced to the active carbide phase, our present efforts are devoted to moderating the Fe/SiO{sub 2} interaction by introducing an interfacial oxide phase. We are also studying the role of added Cu on the ease of reducibility of Fe/SiO{sub 2}. The implication of this work is that other binder materials should be explored that have a morphology that can strengthen the agglomerates and minimize the Fe-SiO{sub 2} interfacial reactions. This work is presently underway in our laboratory.

  6. Highly Active Multidentate Ligand-Based Alkyne Metathesis Catalysts.

    PubMed

    Du, Ya; Yang, Haishen; Zhu, Chengpu; Ortiz, Michael; Okochi, Kenji D; Shoemaker, Richard; Jin, Yinghua; Zhang, Wei

    2016-06-01

    Alkyne metathesis catalysts composed of molybdenum(VI) propylidyne and multidentate tris(2-hydroxylbenzyl)methane ligands have been developed, which exhibit excellent stability (remains active in solution for months at room temperature), high activity, and broad functional-group tolerance. The homodimerization and cyclooligomerization of monopropynyl or dipropynyl substrates, including challenging heterocycle substrates (e.g., pyridine), proceed efficiently at 40-55 °C in a closed system. The ligand structure and catalytic activity relationship has been investigated, which shows that the ortho groups of the multidentate phenol ligands are critical to the stability and activity of such a catalyst system. PMID:27113640

  7. Support effects on hydrotreating activity of NiMo catalysts

    SciTech Connect

    Dominguez-Crespo, M.A. Arce-Estrada, E.M.; Torres-Huerta, A.M.

    2007-10-15

    The effect of the gamma alumina particle size on the catalytic activity of NiMoS{sub x} catalysts prepared by precipitation method of aluminum acetate at pH = 10 was studied. The structural characterization of the supports was measured by using XRD, pyridine FTIR-TPD and nitrogen physisorption. NiMo catalysts were characterized during the preparation steps (annealing and sulfidation) using transmission electron microscopy (TEM). Hydrogen TPR studies of the NiMo catalysts were also carried out in order to correlate their hydrogenating properties and their catalytic functionality. Catalytic tests were carried out in a pilot plant at 613, 633 and 653 K temperatures. The results showed that the rate constants of hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatizing (HDA) at 613-653 K decreased in the following order: A > B > C corresponding to the increase of NiMoS particle size associated to these catalysts.

  8. Cationic zinc enolates as highly active catalysts for acrylate polymerization.

    PubMed

    Garner, Logan E; Zhu, Hongping; Hlavinka, Mark L; Hagadorn, John R; Chen, Eugene Y-X

    2006-11-22

    Unprecedented cationic zinc enolates have been generated by a novel activation route involving the amido to imino ligand transformation with B(C6F5)3, structurally characterized, and utilized as highly active catalysts for the production of high molecular weight polyacrylates at ambient temperature. PMID:17105289

  9. Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer

    NASA Astrophysics Data System (ADS)

    Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-aki

    2015-04-01

    Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp 2 carbon network of the HB-FePc catalysts may occur up to 900°C.

  10. CATALYST ACTIVITY MAINTENANCE FOR THE LIQUID PHASE SYNTHESIS GAS-TO-DIMETHYL ETHER PROCESS PART II: DEVELOPMENT OF ALUMINUM PHOSPHATE AS THE DEHYDRATION CATALYST FOR THE SINGLE-STEP LIQUID PHASE SYNGAS-TO-DME PROCESS

    SciTech Connect

    Xiang-Dong Peng

    2002-05-01

    At the heart of the single-step liquid phase syngas-to-DME process (LPDME{trademark}) is a catalyst system that can be active as well as stable. In the Alternative Fuels I program, a dual-catalyst system containing a Cu-based commercial methanol synthesis catalyst (BASF S3-86) and a commercial dehydration material ({gamma}-alumina) was demonstrated. It provided the productivity and selectivity expected from the LPDME process. However, the catalyst system deactivated too rapidly to warrant a viable commercial process [1]. The mechanistic investigation in the early part of the DOE's Alternative Fuels II program revealed that the accelerated catalyst deactivation under LPDME conditions is due to detrimental interaction between the methanol synthesis catalyst and methanol dehydration catalyst [2,3]. The interaction was attributed to migration of Cu- and/or Zn-containing species from the synthesis catalyst to the dehydration catalyst. Identification of a dehydration catalyst that did not lead to this detrimental interaction while retaining adequate dehydration activity was elusive. Twenty-nine different dehydration materials were tested, but none showed the desired performance [2]. The search came to a turning point when aluminum phosphate was tested. This amorphous material is prepared by precipitating a solution containing Al(NO{sub 3}){sub 3} and H{sub 3}PO{sub 4} with NH{sub 4}OH, followed by washing, drying and calcination. The aluminum phosphate catalyst has adequate dehydration activity and good stability. It can co-exist with the Cu-based methanol synthesis catalyst without negatively affecting the latter catalyst's stability. This report documents the details of the development of this catalyst. These include initial leads, efforts in improving activity and stability, investigation and development of the best preparation parameters and procedures, mechanistic understanding and resulting preparation guidelines, and the accomplishments of this work.

  11. Identification of copper species present in Cu-ZSM-5 catalysts for NO{sub x} reduction

    SciTech Connect

    Millar, G.J.; Canning, A.; Rose, G.; Wood, B.; Trewartha, L.; Mackinnon, I.D.R.

    1999-04-25

    The structure of Cu-ZSM-5 catalysts that show activity for direct NO decomposition and selective catalytic reduction of NO{sub x} by hydrocarbons has been investigated by a multitude of modern surface analysis and spectroscopy techniques including X-ray photoelectron spectroscopy, thermogravimetric analysis, and in situ Fourier transform infrared spectroscopy. A series of four catalysts were prepared by exchange of Na-ZSM-5 with dilute copper acetate, and the copper loading was controlled by variation of the solution pH. Underexchanged catalysts contained isolated Cu{sup 2+}OH{sup {minus}}(H{sub 2}O) species and as the copper loading was increased Cu{sup 2+} ions incorporated into the zeolite lattice appeared. The sites at which the latter two copper species were located were fundamentally different. The Cu{sup 2+}OH{sup {minus}}(H{sub 2}O) moieties were bound to two lattice oxygen ions and associated with two framework aluminum ions. Once the Cu-ZSM-5 samples attained high levels of exchange, the development of [Cu({mu}-OH){sub 2}Cu]{sub n}{sup 2+}OH{sup {minus}}(H{sub 2}O) species along with a small concentration of Cu(OH){sub 2} was observed. On activation in helium to 500 C the Cu{sup 2+}OH{sup {minus}}(H{sub 2}O) species transformed into Cu{sup 2+}O{sup {minus}} and Cu{sup +} moieties, whereas the Cu{sup 2+} ions were apparently unaffected by this treatment (apart from the loss of ligated water molecules). Calcination of the precursors resulted in the formation of Cu{sup 2+}O{sub 2}{sup {minus}} and a one-dimensional CuO species. Temperature-programmed desorption studies revealed that oxygen was removed from the latter two species at 407 and 575 C, respectively.

  12. Catalyst dispersion and activity under conditions of temperature- staged liquefaction

    SciTech Connect

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1991-09-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation. Liquefaction experiments of solvent-treated and untreated Blind Canyon (DECS-6) and Texas lignite (DECS-1) have been performed using ammonium tetrathiomolybdate (ATTM) and bis (dicarbonylcyclopentadienyl) iron (CPI) as catalyst precursors using temperature-staged conditions (275{degrees}C, 30 min; 425{degrees}C, 30 min). Solid state {sup 13}C NMR analysis was carried out for each coal and for selected residues. 12 refs., 14 figs., 9 tabs.

  13. Characterization of the activity and stability of supported cobalt catalysts for the steam reforming of ethanol

    NASA Astrophysics Data System (ADS)

    Batista, Marcelo S.; Santos, Rudye K. S.; Assaf, Elisabete M.; Assaf, José M.; Ticianelli, Edson A.

    This paper reports results of studies of the catalytic activity and stability of supported cobalt catalysts for steam reforming of ethanol. Co/Al 2O 3, Co/SiO 2, and Co/MgO catalysts were prepared by an impregnation method and characterized by X-ray diffraction, atomic absorption spectroscopy, Raman spectroscopy, and temperature programmed reduction with hydrogen. The results showed the presence of Co 3O 4 and CoO x species interacting with Al 2O 3 or MgO and formed after a calcination step. It was evident that only Co 0 sites are active for the steam reforming of ethanol. All materials showed high levels of ethanol conversion, with molar yields of about 70% of hydrogen and 30% of CO+CO 2+CH 4 in the gaseous mixture. The Co/Al 2O 3 catalyst also produced ethylene through a dehydration reaction of ethanol. It is proposed that the methane formation on Co/SiO 2 catalysts occurs by methanation of CO and by ethanol decomposition. After 9 h of reaction, 14-24% (w/w) of carbon was deposited on all catalysts, indicating that a well characterized deactivation of the materials is due to coke deposition.

  14. Integration of molecular and enzymatic catalysts on graphene for biomimetic generation of antithrombotic species

    NASA Astrophysics Data System (ADS)

    Xue, Teng; Peng, Bo; Xue, Min; Zhong, Xing; Chiu, Chin-Yi; Yang, Si; Qu, Yongquan; Ruan, Lingyan; Jiang, Shan; Dubin, Sergey; Kaner, Richard B.; Zink, Jeffrey I.; Meyerhoff, Mark E.; Duan, Xiangfeng; Huang, Yu

    2014-02-01

    The integration of multiple synergistic catalytic systems can enable the creation of biocompatible enzymatic mimics for cascading reactions under physiologically relevant conditions. Here we report the design of a graphene-haemin-glucose oxidase conjugate as a tandem catalyst, in which graphene functions as a unique support to integrate molecular catalyst haemin and enzymatic catalyst glucose oxidase for biomimetic generation of antithrombotic species. Monomeric haemin can be conjugated with graphene through π-π interactions to function as an effective catalyst for the oxidation of endogenous L-arginine by hydrogen peroxide. Furthermore, glucose oxidase can be covalently linked onto graphene for local generation of hydrogen peroxide through the oxidation of blood glucose. Thus, the integrated graphene-haemin-glucose oxidase catalysts can readily enable the continuous generation of nitroxyl, an antithrombotic species, from physiologically abundant glucose and L-arginine. Finally, we demonstrate that the conjugates can be embedded within polyurethane to create a long-lasting antithrombotic coating for blood-contacting biomedical devices.

  15. Activity and selectivity of molybdenum catalysts in coal liquefaction reactions

    SciTech Connect

    Curtis, C.W.; Pellegrino, J.L. )

    1988-01-01

    The purpose of this work is to evaluate how effectively three different molybdenum catalysts promote reactions involving heteroatom removal and cleavage of alkyl bridge hydrodeoxygenation (HDO), hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrocracking (HYC). Both model and coal liquefaction reactions were performed to test the activity and selectivity of three different molybdenum catalysts. The three catalysts used were molybdenum naphthenate, molybdenum supported on gamma alumina (Mo/Al{sub 2}O{sub 3}) and precipitated, poorly crystalline molybdenum disulfide (MoS{sub 2}). The model compounds, chosen to mimic coal structure, on which the effectiveness of the catalysts for the model reactions was tested were: 1-methylnaphthalene, representing aromatic hydrocarbons, for hydrogenation; 1-naphthol, representing oxygen containing compounds, for deoxygenation; benzothiophene, representing sulfur containing compounds, for desulfurization; indole, representing nitrogen containing compounds, for denitrogenation; and bibenzyl, representing alkyl bridging structures, for hydrocracking. Catalytic reactions of combinations of reactants were performed to simulate a complex coal matrix. Thermal and catalytic coal liquefaction reactions were performed using Illinois No. 6 coal with anthracene as a solvent. The efficacy of the catalysts was determined by comparing the product and compound class fractions obtained from the liquefaction reactions.

  16. Activity and Stability of Nanoscale Oxygen Reduction Catalysts

    SciTech Connect

    Shao-Horn, Yang

    2015-07-28

    Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

  17. Modeling Species Inhibition and Competitive Adsorption in Urea-SCR Catalysts

    SciTech Connect

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Lee, Jong H.

    2012-04-16

    Although the urea-SCR technology exhibits high NOx reduction efficiency over a wide range of temperatures among the lean NOx reduction technologies, further improvement in low-temperature performance is required to meet the future emission standards and to lower the system cost. In order to improve the catalyst technologies and optimize the system performance, it is critical to understand the reaction mechanisms and catalyst behaviors with respect to operating conditions. Urea-SCR catalysts exhibit poor NOx reduction performance at low temperature operating conditions (T < 150 C). We postulate that the poor performance is either due to NH3 storage inhibition by species like hydrocarbons or due to competitive adsorption between NH3 and other adsorbates such as H2O and hydrocarbons in the exhaust stream. In this paper we attempt to develop one-dimensional models to characterize inhibition and competitive adsorption in Fe-zeolite based urea-SCR catalysts based on bench reactor experiments. We further use the competitive adsorption (CA) model to develop a standard SCR model based on previously identified kinetics. Simulation results indicate that the CA model predicts catalyst outlet NO and NH3 concentrations with minimal root mean square error.

  18. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR.

    PubMed

    Johnson, Robert L; Perras, Frédéric A; Kobayashi, Takeshi; Schwartz, Thomas J; Dumesic, James A; Shanks, Brent H; Pruski, Marek

    2016-01-31

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticle catalysts. By offering >2500-fold time savings, the technique enabled the observation of (13)C-(13)C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface. PMID:26675287

  19. Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO

    NASA Astrophysics Data System (ADS)

    Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher

    2016-05-01

    Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25- nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts.

  20. Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO.

    PubMed

    Alfonso, Dominic R; Kauffman, Douglas; Matranga, Christopher

    2016-05-14

    Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25 (-) nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts. PMID:27179498

  1. NREL Team Creates High-Activity, Durable Platinum Extended Surface Catalyst for Fuel Cells (Fact Sheet)

    SciTech Connect

    Not Available

    2011-02-01

    Researchers with NREL's Fuel Cell team showed that platinum can replace copper nanowires in such a way that high-surface-area and high-specific-activity catalysts are produced, potentially allowing for lower-cost catalysts.

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

    NASA Astrophysics Data System (ADS)

    Li, Baitao; Zhu, Yanrun; Jin, Xiaojing

    2015-01-01

    Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted "pH-adjusting" technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co3O4 particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was more beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H2O2) at 70 °C.

  3. Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species.

    PubMed

    Perea-Buceta, Jesus E; Fernández, Israel; Heikkinen, Sami; Axenov, Kirill; King, Alistair W T; Niemi, Teemu; Nieger, Martin; Leskelä, Markku; Repo, Timo

    2015-11-23

    The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson's catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored. PMID:26437764

  4. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    PubMed Central

    Guo, Wei; Vlachos, Dionisios G.

    2015-01-01

    Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N−H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design. PMID:26443525

  5. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

  6. Influences of impregnation procedure on the SCR activity and alkali resistance of V2O5-WO3/TiO2 catalyst

    NASA Astrophysics Data System (ADS)

    Yu, Wenchao; Wu, Xiaodong; Si, Zhichun; Weng, Duan

    2013-10-01

    V2O5-WO3/TiO2 catalysts were prepared by wet and dry impregnation methods, respectively, and the deactivation effects of KCl on their NH3-SCR activities were investigated. The catalysts were characterized by powder X-ray diffraction (XRD), inductively coupled plasma (ICP), Brunauer-Emmett-Teller (BET), Raman, H2 temperature-programmed reaction (TPR), infrared spectra (IR) and NH3 oxidation. The wet-impregnated catalyst shows higher SCR activities before and after the alkali poisoning compared with the dry-impregnated one. The Raman results show that more polymeric vanadia species appear on the wet-impregnated sample, whereas the isolated form is predominant on the dry-impregnated sample. The transformation of vanadia from isolated to polymeric species increases the acidity of the catalyst and the NH3 oxidation activity. The activation of the adsorbed ammonia appears to be a determinant of the SCR reaction over V2O5-WO3/TiO2 catalysts, and is responsible for the higher activity of the wet-impregnated catalyst. Furthermore, the isolated vanadia species is more likely to combine with potassium to produce inert materials, and hereby the dry-impregnated catalyst is more severely deactivated.

  7. Pd/MgO: Catalyst characterization and phenol hydrogenation activity

    SciTech Connect

    Claus, P.; Berndt, H.; Mohr, C.; Radnik, J.; Shin, E.J.; Keane, M.A.

    2000-05-15

    The gas-phase hydrogenation of phenol has been studied over a 1% w/w Pd/MgO catalyst prepared by impregnation of MgO with (NH{sub 4}){sub 2}PdCl{sub 6}. The catalyst precursor was activated by precalcination in air at 473 K followed by reduction in hydrogen at 573 K. Temperature-programmed reduction/desorption has revealed the presence of ammonium carbonate and/or ammonium hydrogen carbonate on the active surface in addition to a metallic palladium component. Whereas the latter was not detectable by X-ray diffraction due to the high metal dispersion, transmission electron microscopy revealed that the mean palladium particle diameter is 1.3 {+-} 0.2 nm, which corresponds to a palladium dispersion of D{sub Pd} = 71%. Impregnation followed by calcination is shown to transform MgO to Mg(OH){sub 2} while the additional reduction step generates a surface phase that is composed of both needle-like Periclase MgO and Mg(OH){sub 2}. X-ray photoelectron spectrometric analyses of the activated catalyst has established the presence of zero-valent palladium which appears to be electron rich as a result of metal-support interaction; a degree of palladium charging is also evident as well as residual surface chlorine. The effects on fractional phenol conversion and reaction selectivity of varying such process variables as reaction time, temperature, and phenol molar feed rate are considered and the possibility of thermodynamic limitations is addressed. Hydrogenation was observed to proceed in a stepwise fashion with cyclohexanone as the partially hydrogenated product and cyclohexanol as the fully hydrogenated product. The catalyst delivered a 96% selectivity with respect to cyclohexanone production at 423 K but the cyclohexanone yield decreased at higher temperatures as conversion declined and cyclohexanol was increasingly preferred. Conversion and selectivity were both stable with prolonged catalyst use, i.e., time on stream in excess of 55 h.

  8. Highly active composite catalysts for reforming of methane into syngas

    SciTech Connect

    Inui, T.; Saigo, K.; Ichino, K.

    1997-12-31

    Development in highly active catalysts for the reforming of methane with H{sub 2}O, CO{sub 2}, H{sub 2}O + CO{sub 2}, and partial oxidation of methane was conducted to produce hydrogen with high reaction rates. A Ni-based four component catalyst, Ni-Ce{sub 2}O{sub 3}-Pt-Rh supported on an alumina wash-coated ceramic fiber in a plate shape was suitable for the objective reaction. By combining the catalytic combustion reaction, methane conversion was markedly enhanced. Furthermore, by combining the combustion of ethane or ethylene, significantly high space-time yields of hydrogen such as 6,731 mol/1-h or 6,907 mol/l{center_dot}h, respectively at 700{degrees}C. In a reaction of CH{sub 4}-CO{sub 2}-H{sub 2}O-O{sub 2} on the four component catalyst, an extraordinary high space-time yield of hydrogen, 12,190 mol/l{center_dot}h was realized even under the very rapid operation conditions as 3 m-sec short contact time.

  9. AgI/TiO2 nanobelts monolithic catalyst with enhanced visible light photocatalytic activity.

    PubMed

    Yi, Junhui; Huang, Lingling; Wang, Hongjuan; Yu, Hao; Peng, Feng

    2015-03-01

    AgI nanoparticles (NPs) have been decorated on the TiO2 nanobelts (NBs) immobilized on a metal Ti substrate by a simple impregnating-precipitation method. The as-achieved AgI/TiO2 monolithic catalyst exhibits a high and stable visible photocatalytic activity toward acid orange II (AO-II) degradation, which is attributed to the suitable energy band match of AgI NPs and TiO2 NBs, leading to the efficient transfer of photo-generated electrons. In addition, it was found that ·O2(-) radicals and h(+) are the main reactive species for the degradation of AO-II under visible light irradiation. A reasonable photocatalytic mechanism of AgI/TiO2 photocatalyst toward AO-II degradation was discussed. This monolithic catalyst provides an advantage over the drawback encountered with powder suspension. PMID:25463235

  10. Sol immobilization technique: a delicate balance between activity, selectivity and stability for gold catalyst

    SciTech Connect

    Villa, Alberto; Wang, Di; Veith, Gabriel M; Prati, Laura

    2013-01-01

    Sol immobilization is a widely used method to prepare gold catalysts. The presence of the protective layer can have a significant influence on catalyst properties by mediating metal-support and reactantmetal interactions. This paper details the effect of a polyvinyl alcohol (PVA) protecting groups on the activity of a supported gold catalysts as well as its selectivity towards glycerol oxidation.

  11. Oxidation of ammonia to nitrogen over Pt/Fe/ZSM5 catalyst: influence of catalyst support on the low temperature activity.

    PubMed

    Kim, Min-Sung; Lee, Dae-Won; Chung, Sang-Ho; Hong, Yoon-Ki; Lee, Seong Ho; Oh, Seong-Hoon; Cho, Il-Hyoung; Lee, Kwan-Young

    2012-10-30

    In this study, Pt/Fe/ZSM5 catalysts were applied to oxidation of ammonia, where the catalysts showed good low-temperature activity (≤ 200°C) for converting ammonia into nitrogen. With 1.5% Pt/0.5% Fe/ZSM5 catalyst, we could obtain 81% NH(3) conversion and 93% N(2) selectivity at 175°C at the short contact-time of w/f=0.00012 g min/mL. Through the characterization studies using high-resolution transmission electron microscopy (HRTEM) and X-ray spectroscopies (XRD, XPS), we could find that the active species was collaborating Pt/Fe species, which structure and activity were largely influenced by support material - in a positive way by ZSM5, rather than by Al(2)O(3) and SiO(2). When using ZSM5 as the support material, Pt was highly dispersed exclusively on the Fe oxide, and the valence state and dispersion of Pt changed according to Fe loading amount. PMID:22954598

  12. Antifungal activity of some Cuban Zanthoxylum species.

    PubMed

    Diéguez-Hurtado, R; Garrido-Garrido, G; Prieto-González, S; Iznaga, Y; González, L; Molina-Torres, J; Curini, M; Epifano, F; Marcotullio, M C

    2003-06-01

    Ethanolic extracts of the trunk bark of Zanthoxylum fagara, Z. elephantiasis and Z. martinicense showed activity against different species of fungi. No antibacterial activity was detected. PMID:12781811

  13. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    PubMed

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

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene. PMID:26928967

  14. Understanding support mediated activity by investigating highly active, thermally stable, silica supported gold catalysts

    SciTech Connect

    Veith, Gabriel M; Lupini, Andrew R; Rashkeev, Sergey; Pennycook, Stephen J; Schwartz, Viviane; Mullins, David R; Dudney, Nancy J

    2009-01-01

    2.5 nm gold nanoparticles were grown on a fumed silica support using the physical vapor deposition technique magnetron sputtering. Combining electron microscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and catalytic studies revealed that the silica supported gold catalysts are thermally stable when annealed in an oxygen containing environment up to at least 500oC. This surprising stability is attributed to the absence of residual halide impurities and a strong bond between gold and defects at the silica surface (2.7 - 3.8 eV), as estimated from density functional theory (DFT) calculations. The Au/SiO2 catalysts are slightly less active for CO oxidation than the prototypical Au/TiO2 catalysts, however they can be regenerated far more easily, fully recovering the activity of a freshly prepared catalyst after deactivation.

  15. On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2014-01-07

    We model N{sub 2} desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N{sub 2} desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

  16. Redox properties and VOC oxidation activity of Cu catalysts supported on Ce₁-xSmxOδ mixed oxides.

    PubMed

    Konsolakis, Michalis; Carabineiro, Sónia A C; Tavares, Pedro B; Figueiredo, José L

    2013-10-15

    A series of Cu catalysts supported on Ce1-xSmxOδ mixed oxides with different molar contents (x=0, 0.25, 0.5, 0.75 and 1), was prepared by wet impregnation and evaluated for volatile organic compounds (VOC) abatement, employing ethyl acetate as model molecule. An extensive characterization study was undertaken in order to correlate the morphological, structural and surface properties of catalysts with their oxidation activity. The optimum performance was obtained with Cu/CeO2 catalyst, which offers complete conversion of ethyl acetate into CO2 at temperatures as low as 260°C. The catalytic performance of Cu/Ce1-xSmxOδ was interpreted on the basis of characterization studies, showing that incorporation of samarium in ceria has a detrimental effect on the textural characteristics and reducibility of catalysts. Moreover, high Sm/Ce atomic ratios (from 1 to 3) resulted in a more reduced copper species, compared to CeO2-rich supports, suggesting the inability of these species to take part in the redox mechanism of VOC abatement. Sm/Ce surface atomic ratios are always much higher than the nominal ratios indicating an impoverishment of catalyst surface in cerium oxide, which is detrimental for VOC activity. PMID:23995554

  17. Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis.

    PubMed

    Marx, Vanessa M; Sullivan, Alexandra H; Melaimi, Mohand; Virgil, Scott C; Keitz, Benjamin K; Weinberger, David S; Bertrand, Guy; Grubbs, Robert H

    2015-02-01

    An expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340,000, at a catalyst loading of only 1 ppm. This is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products. PMID:25522160

  18. Pollution Control Meets Sustainability: Structure-Activity Studies on New Iron Oxide-Based CO Oxidation Catalysts.

    PubMed

    Schoch, Roland; Bauer, Matthias

    2016-08-01

    A new class of catalysts for the oxidation of CO based on iron oxide as a biocompatible, earth-abundant and non-toxic metal is presented. The catalytic activities achieved with these catalysts provide promising milestones towards the substitution of noble metals in CO oxidation catalysts. The catalysts can be obtained by using iron core-shell nanoparticle precursors. The metal used for the shell material determines whether the iron core is integrated in or isolated from the support. The active iron site is effectively integrated into the γ-Al2 O3 support if an aluminum shell is present in the core-shell precursor. When the metal used for the shell is different from the support, an isolated structure is formed. Using this directed synthesis approach, different iron oxide species can be obtained and their structural differences are linked to distinct catalytic activities, as demonstrated by combined in-depth analytical studies using XRD, X-ray absorption spectroscopy (XAS), UV/Vis, and Brunauer-Emmett-Teller (BET) analysis. The key species responsible for high catalytic activity is identified as isolated tetrahedrally coordinated Fe(III) centers, whereas aggregation leads to a reduction in activity. PMID:27440425

  19. Highly durable and active non-precious air cathode catalyst for zinc air battery

    NASA Astrophysics Data System (ADS)

    Chen, Zhu; Choi, Ja-Yeon; Wang, Haijiang; Li, Hui; Chen, Zhongwei

    The electrochemical stability of non-precious FeCo-EDA and commercial Pt/C cathode catalysts for zinc air battery have been compared using accelerated degradation test (ADT) in alkaline condition. Outstanding oxygen reduction reaction (ORR) stability of the FeCo-EDA catalyst was observed compared with the commercial Pt/C catalyst. The FeCo-EDA catalyst retained 80% of the initial mass activity for ORR whereas the commercial Pt/C catalyst retained only 32% of the initial mass activity after ADT. Additionally, the FeCo-EDA catalyst exhibited a nearly three times higher mass activity compared to that of the commercial Pt/C catalyst after ADT. Furthermore, single cell test of the FeCo-EDA and Pt/C catalysts was performed where both catalysts exhibited pseudolinear behaviour in the 12-500 mA cm -2 range. In addition, 67% higher peak power density was observed from the FeCo-EDA catalyst compared with commercial Pt/C. Based on the half cell and single cell tests the non-precious FeCo-EDA catalyst is a very promising ORR electrocatalyst for zinc air battery.

  20. Nanoscale attrition during activation of precipitated iron Fischer-Tropsch catalysts: Implications for catalyst design

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Jin, Y.; Brooks, R.P.; Wilder, J.A.

    1996-12-31

    The Fischer-Tropsch Synthesis (FTS) for the production of liquid hydrocarbons from coal-based synthesis gas has been the subject of renewed interest for conversion of coal to liquid fuels. The use of synthesis gas from modem energy-efficient gasifiers requires catalysts that can operate under low H{sub 2}/CO ratios, typically 0.7-0.9. Since the FTS stoichiometry requires a H{sub 2}/CO ratio of 2.0, catalysts that operate at lower ratios must catalyze the water gas shift reaction to make up the deficit in H{sub 2}. The use of iron-based catalysts for the process is attractive in view of their low cost, ready availability and high water-gas shift reactivity. Furthermore, iron catalysts at elevated pressures (10-15 atmospheres) produce the desired range of liquid hydrocarbons. AU these features make the use of Fe as an F-T catalyst extremely desirable. Since the reaction is highly exothermic, the preferred reactor type for industrial operation is the slurry bubble column reactor. The catalyst for this reactor is precipitated iron oxide which is spray dried to yield particles with diameter of 30-70 {mu}m. One major limitation of these catalysts is that they tend to undergo attrition during use, leading to problems in catalyst separation and recovery of liquid products from the reactor.

  1. Effects of H/sub 2/O and CO/sub 2/ on the activity and composition of iron Fischer-Tropsch catalysts

    SciTech Connect

    McDonald, M.A.

    1986-01-01

    The composition of an iron Fischer-Tropsch (F-T) catalyst is strongly affected by the % conversion of H/sub 2/-CO syngas. At low % conversion, the strongly reducing syngas mixture tends to covert metallic or oxidic iron species to a bulk iron carbide phase or phases. As % syngas conversion increases, H/sub 2/ and CO are converted to organic products, and to H/sub 2/O and CO/sub 2/. The gas mixture can therefore oxidize an iron catalyst. However, the catalyst's synthesis behavior (activity, selectivity, activity and selectivity maintenance) also depends strongly on % syngas conversion. Thus, an iron catalyst's composition and synthesis behavior are not easily correlated under typical F-T reaction conditions. This study was designed to determine how the build-up of H/sub 2/O and CO/sub 2/ during reaction affect F-T catalyst composition and synthesis behavior. Reaction rate measurements were conducted at differential % syngas conversion using catalyst wafers mounted in an in-situ cell. This cell allowed Mossbauer effect spectroscopy of the used catalyst for determination of the catalyst composition. Additional H/sub 2/O and CO/sub 2/ were added to syngas to determine the effects on catalyst composition, activity and selectivity. Furthermore, these experiments were carried out at pressures well above atmospheric, the pressure range required for good iron F-T catalyst behavior. Thus, results presented here are more closely related to the state of working F-T catalysts than are previous in-situ Mossbauer studies of iron catalysts, which were done almost exclusively at atmospheric pressure. This paper focuses on initial experiments involving the addition of only H/sub 2/O, not CO/sub 2/, to a syngas stream.

  2. An Auger electron spectroscopy study of the activation of iron Fischer-Tropsch catalysts. II. Carbon monoxide activation

    SciTech Connect

    Sault, A.G. ); Datye, A.K. )

    1993-03-01

    Activation procedures can have a dramatic effect on the activity of iron-based catalysts for Fischer-Tropsch (F-T) synthesis. CO conversion over a 100 Fe/3 Cu/0.2 K catalyst (parts by weight) can vary by nearly a factor of 3, depending on activation treatment. In contrast, a 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst displays little dependence of F-T activity on activation treatment. An ultra-high vacuum surface analysis chamber coupled to an atmospheric reactor has been used to measure the surface composition of these catalysts following activation in carbon monoxide at 280[degrees]C, while transmission electron microscopy (TEM) and BET surface area measurements have been used to investigate catalyst morphology. CO activation of the 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst at 280[degrees]C results in partial reduction of iron to a mixture of Fe[sub x]O and Fe[sub 3]O[sub 4], and an overall surface composition very similar to that obtained following hydrogen activation at 220 or 280[degrees]C, consistent with the invariance of F-T activity with activation treatment for this catalyst. Activation of the 100 Fe/3 Cu/0.2 K catalyst in CO at 280[degrees]C results in the formation of iron carbide particles, growth of graphitic carbon (C[sub g]) filaments, and formation of a thick, porous, C[sub g] layer covering the carbide particles. Differences in F-T activity between the hydrogen- and CO-activated 100 Fe/3 Cu/0.2 K catalyst are discussed in terms of surface composition and catalyst morphology. The difference in sensitivity of the two catalysts to activation conditions is related to differences in the extent of reduction of the catalysts. 45 refs., 4 figs., 1 tab.

  3. An Auger electron spectroscopy study of the activation of iron Fischer-Tropsch catalysts. I. Hydrogen activation

    SciTech Connect

    Sault, A.G. )

    1993-03-01

    Activation procedures can have a dramatic effect on the activity of iron-based catalysts for Fischer-Tropsch (F-T) synthesis. CO conversion over a 100 Fe/3 Cu/0.2 K catalyst (parts by weight) can vary by nearly a factor of 3, depending on activation. In contrast, a 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst displays only minor variations in activity with activation conditions. An ultra-high vacuum surface analysis chamber coupled to an atmospheric pressure reactor has been used to measure the surface compositions of these catalysts following various hydrogen activation procedures. Activation of the 100 Fe/3 Cu/0.2 K catalyst in H[sub 2] results in rapid reduction of iron to the metallic state, and segregation of sulfur to the catalyst surface. The sulfur arises from bulk sulfate impurities present in the metal nitrates used to prepare the catalyst. Sulfur coverage increases with both activation time and temperature, due to an increase in the rate of sulfur diffusion with temperature. F-T activity of this catalyst varies inversely with sulfur coverage, consistent with the well-known poisoning effect of sulfur on F-T synthesis. For the 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst no significant variations in surface composition are observed as a function of hydrogen activation temperature, consistent with the absence of any variations in catalyst activity. Only partial reduction of iron to a mixture of Fe[sub x]O and Fe[sub 3]O[sub 4] is observed for this catalyst for all activation conditions investigated. Using electron beam effects to remove potassium and silica shows that one or both of these components inhibits reduction of iron to the metallic state in the 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst. 48 refs., 3 tabs.

  4. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale

    NASA Astrophysics Data System (ADS)

    Shan, Shiyao; Petkov, Valeri; Prasai, Binay; Wu, Jinfang; Joseph, Pharrah; Skeete, Zakiya; Kim, Eunjoo; Mott, Derrick; Malis, Oana; Luo, Jin; Zhong, Chuan-Jian

    2015-11-01

    The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo phase

  5. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    DOE PAGESBeta

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

  6. Evaluation of fine-particle catalysts: Activity testing results and phase identification using Mossbauer spectroscopy

    SciTech Connect

    Stohl, F.V.; Diegert, K.V.; Goodnow, D.; Rao, K.R.P.M.; Huggins, F.; Huffman, G.P.

    1994-10-01

    To evaluate and compare the activities/selectivities of fine- particle size catalysts being developed in the DOE/PETC Advanced Research (AR) Coal Liquefaction program by using standard coal liquefaction activity test procedures. Previously reported results have described the standard test procedure that was developed at Sandia to evaluate fine-particle size iron catalysts being developed in DOE/PETC`s AR Coal Liquefaction Program. This test uses DECS-17 Blind Canyon Coal, phenanthrene as the reaction solvent, and a factorial experimental design that enables evaluation of a catalyst over ranges of temperature (350 to 400{degrees}C), time (20 to 60 minutes), and catalyst loading (0 to 1 wt% on a dmmf coal basis). Testing has been performed on Pacific Northwest Laboratories` (PNL) 6-line ferrihydrite catalyst. Results showed that this catalyst is more active than the University of Pittsburgh`s sulfated iron oxide catalyst that was evaluated previously. PNL has also produced two additional batches of catalyst in an effort to optimize their preparation procedures for larger batches. Sandia has observed significant differences in activities among these three catalysts; these differences might be due to particle size effects, the type of drying procedure, or the amount of moisture present. Mossbauer characterization of the iron phases in the coal, catalyst precursors, and tetrahydrofuran (THF) insoluble material from liquefaction reactions has been performed on the University of Pittsburgh`s catalyst and the first PNL catalyst that was tested at Sandia. The Mossbauer results were obtained at the University of Kentucky and will be presented. Future work will include testing additional catalysts being developed in the AR Coal Liquefaction Program, developing procedures to characterize reaction products, and determining the kinetics of the reactions.

  7. Development of highly active and stable hybrid cathode catalyst for PEMFCs

    NASA Astrophysics Data System (ADS)

    Jung, Won Suk

    Polymer electrolyte membrane fuel cells (PEMFCs) are attractive power sources of the future for a variety of applications including portable electronics, stationary power, and automobile application. However, sluggish cathode kinetics, high Pt cost, and durability issues inhibit the commercialization of PEMFCs. To overcome these drawbacks, research has been focused on alloying Pt with transition metals since alloy catalysts show significantly improved catalytic properties like high activity, selectivity, and durability. However, Pt-alloy catalysts synthesized using the conventional impregnation method exhibit uneven particle size and poor particle distribution resulting in poor performance and/or durability in PEMFCs. In this dissertation, a novel catalyst synthesis methodology is developed and compared with catalysts prepared using impregnation method and commercial catalysts. Two approaches are investigated for the catalyst development. The catalyst durability was studied under U. S. DRIVE Fuel Cell Tech Team suggested protocols. In the first approach, the carbon composite catalyst (CCC) having active sites for oxygen reduction reaction (ORR) is employed as a support for the synthesis of Pt/CCC catalyst. The structural and electrochemical properties of Pt/CCC catalyst are investigated using high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, while RDE and fuel cell testing are carried out to study the electrochemical properties. The synergistic effect of CCC and Pt is confirmed by the observed high activity towards ORR for the Pt/CCC catalyst. The second approach is the synthesis of Co-doped hybrid cathode catalysts (Co-doped Pt/CCC) by diffusing the Co metal present within the CCC support into the Pt nanoparticles during heat-treatment. The optimized Co-doped Pt/CCC catalyst performed better than the commercial catalysts and the catalyst prepared using the impregnation method in PEMFCs and showed high

  8. High-activity mesoporous Pt/Ru catalysts for methanol oxidation.

    PubMed

    Franceschini, Esteban A; Bruno, Mariano M; Williams, Federico J; Viva, Federico A; Corti, Horacio R

    2013-11-13

    High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores. PMID:24083938

  9. Nanoporous gold as an active low temperature catalyst toward CO oxidation in hydrogen-rich stream

    PubMed Central

    Li, Dongwei; Zhu, Ye; Wang, Hui; Ding, Yi

    2013-01-01

    Preferential CO oxidation (PROX) was investigated by using dealloyed nanoporous gold (NPG) catalyst under ambient conditions. Systematic investigations were carried out to characterize its catalytic performance by varying reaction parameters such as temperature and co-existence of CO2 and H2O, which revealed that NPG was a highly active and selective catalyst for PROX, especially at low temperature. At 20°C, the exit CO concentration could be reduced to less than 2 ppm with a turnover frequency of 4.1 × 10−2 s−1 at a space velocity of 120,000 mL h−1 g−1cat. and its high activity could retain for more than 24 hours. The presence of residual Ag species in the structure did not seem to improve the intrinsic activity of NPG for PROX; however, they contributed to the stabilization of the NPG structure and apparent catalytic activity. These results indicated that NPG might be readily applicable for hydrogen purification in fuel cell applications. PMID:24145317

  10. Nanoporous gold as an active low temperature catalyst toward CO oxidation in hydrogen-rich stream.

    PubMed

    Li, Dongwei; Zhu, Ye; Wang, Hui; Ding, Yi

    2013-01-01

    Preferential CO oxidation (PROX) was investigated by using dealloyed nanoporous gold (NPG) catalyst under ambient conditions. Systematic investigations were carried out to characterize its catalytic performance by varying reaction parameters such as temperature and co-existence of CO2 and H2O, which revealed that NPG was a highly active and selective catalyst for PROX, especially at low temperature. At 20°C, the exit CO concentration could be reduced to less than 2 ppm with a turnover frequency of 4.1 × 10(-2) s(-1) at a space velocity of 120,000 mL h(-1) g(-1)cat. and its high activity could retain for more than 24 hours. The presence of residual Ag species in the structure did not seem to improve the intrinsic activity of NPG for PROX; however, they contributed to the stabilization of the NPG structure and apparent catalytic activity. These results indicated that NPG might be readily applicable for hydrogen purification in fuel cell applications. PMID:24145317

  11. Highly active copper-network catalyst for the direct aldol reaction.

    PubMed

    Ohta, Hidetoshi; Uozumi, Yasuhiro; Yamada, Yoichi M A

    2011-09-01

    The development of a highly active solid-phase catechol-copper network catalyst for direct aldol reaction is described. The catalyst was prepared from an alkyl-chain-linked bis(catechol) and a copper(II) complex. The direct aldol reaction between carbonyl compounds (aldehydes and ketones) and methyl isocyanoacetate was carried out using 0.1-1 mol% [Cu] catalyst to give the corresponding oxazolines at yields of up to 99% and a trans/cis ratio of >99:1. The catalyst was reused with no loss of catalytic activity. A plausible reaction pathway is also described. PMID:21751405

  12. Oxovanadium(V) tetrathiacalix[4]arene complexes and their activity as oxidation catalysts.

    PubMed

    Hoppe, Elke; Limberg, Christian

    2007-01-01

    With the aim of modeling reactive moieties and relevant intermediates on the surfaces of vanadium oxide based catalysts during oxygenation/dehydrogenation of organic substrates, mono- and dinuclear vanadium oxo complexes of doubly deprotonated p-tert-butylated tetrathiacalix[4]arene (H4TC) have been synthesized and characterized: PPh4[(H2TC)VOCl(2)] (1) and (PPh4)2[{(H2TC)V(O)(mu-O)}2] (2). According to the NMR spectra of the dissolved complexes they both retain the structures adopted in the crystalline state, as revealed by single-crystal X-ray crystallography. Compounds 1 and 2 were tested as catalysts for the oxidation of alcohols with O(2) at 80 degrees C. Both 1 and 2 efficiently catalyze the oxidation of benzyl alcohol, crotyl alcohol, 1-phenyl-1-propanol, and fluorenol, and in most cases dinuclear complex 2 is more active than mononuclear complex 1. Moreover, the two thiacalixarene complexes 1 and 2 are in many instances more active than oxovanadium(V) complexes containing "classical" calixarene ligands tested previously. Complexes 1 and 2 also show significant activity in the oxidation of dihydroanthracene. Further investigations led to the conclusion that 1 acts as precatalyst that is converted to the active species PPh4[(TC)V==O] (3) at 80 degrees C by double intramolecular HCl elimination. For complex 2, the results of mechanistic investigations indicated that the oxidation chemistry takes place at the bridging oxo ligands and that the two vanadium centers cooperate during the process. The intermediate (PPh4)2[{H2TCV(O)}2(mu-OH)(mu-OC13H9)] (4) was isolated and characterized, also with respect to its reactivity, and the results afforded a mechanistic proposal for a reasonable catalytic cycle. The implications which these findings gathered in solution may have for oxidation mechanisms on the surfaces of V-based heterogeneous catalysts are discussed. PMID:17566134

  13. Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

  14. Modeling Species Inhibition of NO Oxidation in Urea-SCR Catalysts for Diesel Engine NOx Control

    SciTech Connect

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Tran, Diana N.; Lee, Jong H.; Herling, Darrell R.

    2011-04-20

    Urea-selective catalytic reduction (SCR) catalysts are regarded as the leading NOx aftertreatment technology to meet the 2010 NOx emission standards for on-highway vehicles running on heavy-duty diesel engines. However, issues such as low NOx conversion at low temperature conditions still exist due to various factors, including incomplete urea thermolysis, inhibition of SCR reactions by hydrocarbons and H2O. We have observed a noticeable reduction in the standard SCR reaction efficiency at low temperature with increasing water content. We observed a similar effect when hydrocarbons are present in the stream. This effect is absent under fast SCR conditions where NO ~ NO2 in the feed gas. As a first step in understanding the effects of such inhibition on SCR reaction steps, kinetic models that predict the inhibition behavior of H2O and hydrocarbons on NO oxidation are presented in the paper. A one-dimensional SCR model was developed based on conservation of species equations and was coded as a C-language S-function and implemented in Matlab/Simulink environment. NO oxidation and NO2 dissociation kinetics were defined as a function of the respective adsorbate’s storage in the Fe-zeolite SCR catalyst. The corresponding kinetic models were then validated on temperature ramp tests that showed good match with the test data. Such inhibition models will improve the accuracy of model based control design for integrated DPF-SCR aftertreatment systems.

  15. Modeling Species Inhibition of NO oxidation in Urea-SCR Catalysts for Diesel Engine NOx Control

    SciTech Connect

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Tran, Diana N.; Lee, Jong H.; Herling, Darrell R.

    2010-09-15

    Urea-selective catalytic reduction (SCR) catalysts are regarded as the leading NOx aftertreatment technology to meet the 2010 NOx emission standards for on-highway vehicles running on heavy-duty diesel engines. However, issues such as low NOx conversion at low temperature conditions still exist due to various factors, including incomplete urea thermolysis, inhibition of SCR reactions by hydrocarbons and H2O. We have observed a noticeable reduction in the standard SCR reaction efficiency at low temperature with increasing water content. We observed a similar effect when hydrocarbons are present in the stream. This effect is absent under fast SCR conditions where NO ~ NO2 in the feed gas. As a first step in understanding the effects of such inhibition on SCR reaction steps, kinetic models that predict the inhibition behavior of H2O and hydrocarbons on NO oxidation are presented in the paper. A one-dimensional SCR model was developed based on conservation of species equations and was coded as a C-language S-function and implemented in Matlab/Simulink environment. NO oxidation and NO2 dissociation kinetics were defined as a function of the respective adsorbate’s storage in the SCR catalyst. The corresponding kinetic models were then validated on temperature ramp tests that showed good match with the test data.

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

    SciTech Connect

    Li, Baitao Zhu, Yanrun; Jin, Xiaojing

    2015-01-15

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

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

    PubMed

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

    2011-01-01

    This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions.H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

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

    PubMed Central

    2011-01-01

    This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

  19. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  20. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  1. Sunlight-driven copper-catalyst activation applied to photolatent click chemistry.

    PubMed

    Beniazza, Rédouane; Lambert, Romain; Harmand, Lydie; Molton, Florian; Duboc, Carole; Denisov, Sergey; Jonusauskas, Gedeminas; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc

    2014-10-01

    The synthesis, full characterization, photoreduction properties, and catalytic activity for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction of a copper(II)-DMEDA (N,N'-dimethylethylendiamine) complex is reported. Spectroscopic studies (UV/Vis, EPR) demonstrated that under daylight illumination highly effective copper(II) to copper(I) reduction occurs in this complex. These findings are in agreement with a high photoreduction quantum yield value of 0.22 in MeOH, and a value approaching unity as determined in THF. The reduction process, which can also be conducted by irradiation at 365 nm by using a standard TLC (thin layer chromatography) lamp, is ascribed to a highly efficient photoinduced electron transfer (PET) process mediated by the benzophenone photosensitizer present in the carboxylate counterion. Having deaerated the reaction mixture, the photogenerated copper(I) species proved to be highly active for the CuAAC reaction, demonstrated by reactions conducted with low catalyst loading (0.5 mol %) on a range of clickable protected and non-protected mono- and disaccharides. Once initiated, the reaction can be stopped at any time on introducing air into the reaction medium. Deoxygenation followed by irradiation restores the activity, making the copper(II)-DMEDA complex a switchable catalyst of practical value. PMID:25171758

  2. DRIFTS-QMS study of room temperature CO oxidation on Au/SiO2 catalyst: nature and role of different Au species

    SciTech Connect

    Wu, Zili; Zhou, Shenghu; Zhu, Haoguo; Dai, Sheng; Overbury, Steven {Steve} H

    2009-01-01

    The nature and role of different Au species on a Au/SiO2 catalyst in room temperature (rt) CO oxidation have been studied by operando diffuse reflectance infrared spectroscopy (DRIFT) coupled with quadruple mass spectrometry (QMS). It has shown that different pretreatments (oxidative and reductive) of Au/SiO2 have significant effect on the nature of Au species and thus the CO oxidation performance. High temperature (500 C) O2-treatment leads to cationic Au species which is inactive for rt CO oxidation. Reductive treatment (either H2 or CO) results in metallic Au species that are immediately active for rt CO oxidation. Furthermore, CO oxidation activity is found in good correlation with the reduction degree of Au species, a clear indication of the essential role of metallic Au species played in rt CO oxidation. The accompanying slight deactivation with the oxidation of metallic Au species on reductively treated Au/SiO2 in CO oxidation suggests that cationic Au species may play a negative role in rt CO oxidation. The effect of water in rt CO oxidation on Au/SiO2 was also investigated. Two positive roles played by water in CO oxidation have been identified: activation of O2 and reduction of cationic Au species.

  3. Use of H2S to Probe the Active Sites in FeNC Catalysts for the Oxygen Reduction Reaction (ORR) in Acidic Media

    SciTech Connect

    Singh, Deepika; Mamtani, Kuldeep; Bruening, Christopher R.; Miller, Jeffrey T.; Ozkan, Umit S.

    2014-10-01

    H2S has been used as a probe molecule both in an “in situ” poisoning experiment and in intermediate-temperature heat-treatment steps during and after the preparation of FeNC catalysts in an attempt to analyze its effect on their ORR activity. The heat treatments were employed either on the ball-milled precursor of FeNC or after the Ar-NH3 high temperature heat treatments. ORR activity of the H2S-treated catalysts was seen to be significantly lower than the sulfur-free catalysts, whether the sulfur exposure was during a half-cell testing, or as an intermediate-temperature exposure to H2S. The incorporation of sulfur species and interaction of Fe with sulfur were confirmed by characterization using XPS, EXAFS, TPO, and TPD. This study provides crucial evidence regarding differences in active sites in FeNC versus nitrogen-containing carbon nanostructured (CNx) catalysts.

  4. Understanding Iron-based catalysts with efficient Oxygen reduction activity from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Hafiz, Hasnain; Barbiellini, B.; Jia, Q.; Tylus, U.; Strickland, K.; Bansil, A.; Mukerjee, S.

    2015-03-01

    Catalysts based on Fe/N/C clusters can support the oxygen-reduction reaction (ORR) without the use of expensive metals such as platinum. These systems can also prevent some poisonous species to block the active sites from the reactant. We have performed spin-polarized calculations on various Fe/N/C fragments using the Vienna Ab initio Simulation Package (VASP) code. Some results are compared to similar calculations obtained with the Gaussian code. We investigate the partial density of states (PDOS) of the 3d orbitals near the Fermi level and calculate the binding energies of several ligands. Correlations of the binding energies with the 3d electronic PDOS's are used to propose electronic descriptors of the ORR associated with the 3d states of Fe. We also suggest a structural model for the most active site with a ferrous ion (Fe2+) in the high spin state or the so-called Doublet 3 (D3).

  5. Activation and promotion studies in a mixed slurry reactor with an iron-manganese Fischer-Tropsch catalyst

    SciTech Connect

    Pennline, H.W.; Zarochak, M.F.; Stencel, J.M.; Diehl, J.R.

    1987-03-01

    Synthesis gas was reacted over a coprecipitated iron-manganese Fischer-Tropsch catalyst in a slurry reactor. The effect of various activation parameters - temperature, pressure, and gas composition - on subsequent catalyst activity and product selectivity was investigated. The gas composition had the most dramatic effect on the catalyst activation and the ensuing synthesis gas conversion. The effect of potassium promotion on catalyst activity and product selectivity was also studied in slurry reactor tests.

  6. Effect of Mo on the active sites of VPO catalysts upon the selective oxidation of n-butane

    SciTech Connect

    Irusta, S.; Boix, A.; Pierini, B.; Caspani, C.; Petunchi, J.

    1999-10-25

    The effect of the addition of Mo to VPO formulations on the physiochemical and catalytic properties of VPO solids was studied using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Laser Raman spectroscopy (LRS), temperature-programmed reduction, and a flow reactor system. The addition of Mo to the oxides increases the activity and selectivity of the VPO catalysts. The promoting effect is a function of both the Mo loading and the way such cation was added to the VPO matrix. The best catalyst was obtained when 1% Mo was impregnated on the NOHPO{sub 4}-0.5H{sub 2}O phase. At 400 C 36% of molar yield to maleic anhydride was obtained in this catalyst against 12% of the unpromoted catalysts and only 3% of the solids where Mo was added during the phosphatation step. The impregnated 1% Mo catalyst achieved a molar yield of 50% after 700 h under reaction stream (equilibrated catalysts). (VO){sub 2}P{sub 2}O{sub 7} was the only phase detected by XRD and LRS in all the catalysts studied. They showed comparable BET surface areas and crystallinity after 400 h under reaction conditions. A local order distortion of the O{sub 3}-P-O-P-O{sub 3} structure was detected by LRS in the impregnated Mo VPO catalysts. After 400 h on stream, both promoted and unpromoted solids only showed V{sup IV} on the surface layer. The main effect on the addition of Mo by impregnation to VPO oxides was enhanced by the very strong Lewis acid sites and the liability of the oxygen of (VO){sub 2}P{sub 2}O{sub 7}. This suggests that the promoting effect is more electronic in nature than structural. Polymeric MO{sub 3} species were detected neither by TPR nor by LRS. All the promoted catalysts presented a surface molybdenum enrichment but whereas the coprecipitated Mo VPO solid only shows surface Mo{sup VI}, both Mo{sup VI} coexist in the impregnated catalyst.

  7. Texas Endangered Species Activity Book.

    ERIC Educational Resources Information Center

    Jackson, Kathleen Marie; Campbell, Linda

    This publication is the result of the Texas Parks and Wildlife Division's (TPWD's) commitment to education and the fertile partnerships formed between TPWD biologists and educators. This activity book brings together the expertise and practical knowledge of a classroom teacher with the technical knowledge and skills of a TPWD biologist and artist.…

  8. Effects of various poisoning compounds on the activity and stereospecificity of heterogeneous Ziegler-Natta catalyst

    NASA Astrophysics Data System (ADS)

    Tangjituabun, Kitti; Kim, Sang Yull; Hiraoka, Yuichi; Taniike, Toshiaki; Terano, Minoru; Jongsomjit, Bunjerd; Praserthdam, Piyasan

    2008-04-01

    A TiCl4/ethylbenzoate/MgCl2 Ziegler-Natta catalyst was pretreated with chemically different poisoning compounds to investigate their effects on the catalyst activity and stereospecificity for propylene polymerization. The poisoning power on the activity was in the order of methanol > acetone > ethyl acetate. A kinetic analysis using the stopped-flow method revealed that addition of the poisoning materials decreased the activity through the reduction of the number of active sites, whereas the catalyst isospecificity was hardly affected by these materials.

  9. Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

    DOE PAGESBeta

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; Debe, Mark; Steinbach, Andrew J.; Guetaz, L.

    2015-04-10

    In this study, the nanoscale morphology of highly active Pt3Ni7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure plays in surfacemore » area, activity, and durability.« less

  10. Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

    SciTech Connect

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; Debe, Mark; Steinbach, Andrew J.; Guetaz, L.

    2015-04-10

    In this study, the nanoscale morphology of highly active Pt3Ni7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure plays in surface area, activity, and durability.

  11. Photogeneration of active formate decomposition catalysts to produce hydrogen from formate and water

    DOEpatents

    King, Jr., Allen D.; King, Robert B.; Sailers, III, Earl L.

    1983-02-08

    A process for producing hydrogen from formate and water by photogenerating an active formate decomposition catalyst from transition metal carbonyl precursor catalysts at relatively low temperatures and otherwise mild conditions is disclosed. Additionally, this process may be expanded to include the generation of formate from carbon monoxide and hydroxide such that the result is the water gas shift reaction.

  12. Catalyst dispersion and activity under conditions of temperature- staged liquefaction. [Catalyst precursors for molybdenum-based catalyst and iron-based catalyst

    SciTech Connect

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1992-07-01

    Two coals, a Texas subbituminous C and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling and catalyst impregnation on liquefaction conversion behavior in temperature staged reactions for 30 minutes each at 275{degree} and 425{degree}C in H{sub 2} and 95:5 H{sub 2}:H{sub 2}S atmospheres. Methanol, pyridine, tetrahydrofuran, and tetrabutylammonium hydroxide were used as swelling agents. Molybdenum-based catalyst precursors were ammonium tetrathiomolybdate, molybdenum trisulfide, molybdenum hexacarbonyl, and bis(tricarbonylcyclopentadienyl-molybdenum). Ferrous sulfate and bis(dicarbonylcyclo-pentadienyliron) served as iron-based catalyst precursors. In addition, ion exchange was used for loading iron onto the subbituminous coal. For most experiments, liquefaction in H{sub 2}:H{sub 2}S was superior to that in H{sub 2}, regardless of the catalyst precursor. The benefit of the H{sub 2}S was greater for the subbituminous, presumably because of its higher iron content relative to the hvab coal. Tetrabutylammonium hydroxide was the only swelling agent to enhance conversion of the hvab coal significantly; it also caused a remarkable increase in conversion of the subbituminous coal. The combined application of solvent swelling and catalyst impregnation also improves liquefaction, mainly through increased oil yields from the hvab coal and increased asphaltenes from the subbituminous. A remarkable effect from use of ammonium tetrathiomolybdate as a catalyst precursor is substantial increase in pristane and phytane yields. Our findings suggest that these compounds are, at least in part, bound to the coal matrix.

  13. Active Gold-Ceria and Gold-Ceria/titania Catalysts for CO Oxidation. From Single-Crystal Model Catalysts to Powder Catalysts

    SciTech Connect

    Rodriguez, Jose A.; Si, Rui; Evans, Jaime; Xu, Wenqian; Hanson, Jonathan C.; Tao, Jing; Zhu, Yimei

    2014-07-23

    We studied CO oxidation on model and powder catalysts of Au-CeO2 and Au-CeOx/TiO2. Phenomena observed in Au-CeO2(1 1 1) and Au-CeO2/TiO2(1 1 0) provided useful concepts for designing and preparing highly active and stable Au-CeOx/TiO2 powder catalysts for CO oxidation. Small particles of Au dispersed on CeO2(1 1 1) displayed high catalytic activity, making Au-CeO2(1 1 1) a better CO oxidation catalyst than Au-TiO2(1 1 0) or Au-MgO(1 0 0). An excellent support for gold was found after depositing nanoparticles of ceria on TiO2(1 1 0). The CeOx nanoparticles act as nucleation centers for gold, improving dispersion of the supported metal and helping in the creation of reaction sites efficient for the adsorption of CO and the dissociation of the O2 molecule. High-surface area catalysts were prepared by depositing gold on ceria nanorods and CeOx/TiO2 powders. The samples were tested for the low-temperature (10–70 °C) oxygen-rich (1%CO/4%O2/He) CO oxidation reaction after pre-oxidation (20%O2/He, 300 °C) and pre-reduction (5%H2/He, 300 °C) treatments. Moreover, synchrotron-based operando X-ray diffraction (XRD) and X-ray absorption (XAS) spectroscopy were used to study the Au-CeO2 and Au-CeOx/TiO2 catalysts under reaction conditions. Our operando findings indicate that the most active phase of these catalysts for low-temperature CO oxidation consist of small particles of metallic Au dispersed on CeO2 or CeOx/TiO2.

  14. Irreversible Catalyst Activation Enables Hyperpolarization and Water Solubility for NMR Signal Amplification by Reversible Exchange

    PubMed Central

    2015-01-01

    Activation of a catalyst [IrCl(COD)(IMes)] (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; COD = cyclooctadiene)] for signal amplification by reversible exchange (SABRE) was monitored by in situ hyperpolarized proton NMR at 9.4 T. During the catalyst-activation process, the COD moiety undergoes hydrogenation that leads to its complete removal from the Ir complex. A transient hydride intermediate of the catalyst is observed via its hyperpolarized signatures, which could not be detected using conventional nonhyperpolarized solution NMR. SABRE enhancement of the pyridine substrate can be fully rendered only after removal of the COD moiety; failure to properly activate the catalyst in the presence of sufficient substrate can lead to irreversible deactivation consistent with oligomerization of the catalyst molecules. Following catalyst activation, results from selective RF-saturation studies support the hypothesis that substrate polarization at high field arises from nuclear cross-relaxation with hyperpolarized 1H spins of the hydride/orthohydrogen spin bath. Importantly, the chemical changes that accompanied the catalyst’s full activation were also found to endow the catalyst with water solubility, here used to demonstrate SABRE hyperpolarization of nicotinamide in water without the need for any organic cosolvent—paving the way to various biomedical applications of SABRE hyperpolarization methods. PMID:25372972

  15. Copper catalyst activation driven by photoinduced electron transfer: a prototype photolatent click catalyst.

    PubMed

    Harmand, Lydie; Cadet, Sarah; Kauffmann, Brice; Scarpantonio, Luca; Batat, Pinar; Jonusauskas, Gediminas; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc

    2012-07-16

    PET cat. While the copper(II) tren ketoprofenate precatalyst 1 (see picture) is inactive at room temperature in methanol, it is quantitatively and rapidly reduced to its cuprous state upon light irradiation to provide a highly reactive click catalyst. By simply introducing air into the reaction medium the catalysis can be switched off and then switched on again by bubbling argon followed by irradiation. PMID:22777953

  16. Transformation of Sulfur Species during Steam/Air Regeneration on a Ni Biomass Conditioning Catalyst

    SciTech Connect

    Yung, M. M.; Cheah, S.; Magrini-Bair, K.; Kuhn, J. N.

    2012-07-06

    Sulfur K-edge XANES identified transformation of sulfides to sulfates during combined steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. This catalyst was tested over multiple reaction/regeneration/reduction cycles. Postreaction catalysts showed the presence of sulfides on H2S-poisoned sites. Although H2S was observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst, and a transformation from sulfides to sulfates was observed. Following the oxidative regeneration, the subsequent H2 reduction led to a partial reduction of sulfates back to sulfides, indicating the difficulty and sensitivity in achieving complete sulfur removal during regeneration for biomass-conditioning catalysts.

  17. Activity and stability of nanostructured gold-cerium oxide catalysts for the water-gas shift reaction

    NASA Astrophysics Data System (ADS)

    Fu, Qi

    Advanced low-temperature water-gas shift (LTS) catalysts of high activity and stability are under development to produce essentially CO-free hydrogen to feed PEM fuel cells for power generation. Materials based on nanocrystalline cerium oxide (ceria) are among the most promising LTS catalysts. Understanding the structural properties relationship with the WGS activity is fundamentally important in order to rational design the catalysts. Various gold structures, such as metallic gold nanoparticles, cluster and cations were found in gold-ceria sample containing 4--8 at% gold. To discriminate between the various gold species, leaching of the gold-ceria in sodium cyanide was conducted. The metallic gold and all other gold species not in close association with ceria were removed by leaching. A small amount of gold remained in the leached samples. The exact content of non-leachable gold was a function of the parent catalyst properties. Similar data were collected from Pt-ceria samples. STEM or HRTEM, coupled with EDX showed no gold or platinum particles remaining; only what appeared to be very fine clusters or atomically dispersed gold or platinum. Cationic gold or platinum was identified in these samples by XPS. The unexpected finding was that the catalytic activity of the leached samples was similar or slightly better than that of the parent catalyst after removal of the metallic gold or platinum particles by cyanide leaching. Thus, metallic nanoparticles are not necessary; they are mere spectators in the water-gas shift reaction. Nonmetallic gold or platinum species strongly associated with surface cerium-oxygen groups are responsible for the activity, since the extra gold or platinum present in the parent material does not increase the reaction rate; nor does it change the activation energy of the reaction. The importance of the oxide support properties became clear by this work. The amount of gold or platinum retained in active form depends on the surface properties

  18. Microwave and Beam Activation of Nanostructured Catalysts for Environmentally Friendly, Energy Efficient Heavy Crude Oil Processing

    SciTech Connect

    2009-03-01

    This factsheet describes a study whose goal is initial evaluation and development of energy efficient processes which take advantage of the benefits offered by nanostructured catalysts which can be activated by microwave, RF, or radiation beams.

  19. Crystallographic dependence of CO activation on cobalt catalysts: HCP versus FCC.

    PubMed

    Liu, Jin-Xun; Su, Hai-Yan; Sun, Da-Peng; Zhang, Bing-Yan; Li, Wei-Xue

    2013-11-01

    Identifying the structure sensitivity of catalysts in reactions, such as Fischer-Tropsch synthesis from CO and H2 over cobalt catalysts, is an important yet challenging issue in heterogeneous catalysis. Based on a first-principles kinetic study, we find for the first time that CO activation on hexagonal close-packed (HCP) Co not only has much higher intrinsic activity than that of face centered-cubic (FCC) Co but also prefers a different reaction route, i.e., direct dissociation with HCP Co but H-assisted dissociation on the FCC Co. The origin is identified from the formation of various denser yet favorable active sites on HCP Co not available for FCC Co, due to their distinct crystallographic structure and morphology. The great dependence of the activity on the crystallographic structure and morphology of the catalysts revealed here may open a new avenue for better, stable catalysts with maximum mass-specific reactivity. PMID:24147726

  20. Activation studies with a precipitated iron catalyst for Fischer-Tropsch synthesis. II. Reaction studies

    SciTech Connect

    Bukur, D.B.; Nowicki, L.; Manne, R.K.; Lang, Xiaosu

    1995-09-01

    Effects of pretreatment conditions on catalyst performance (activity, selectivity, and stability with time) during Fischer-Tropsch (FT) synthesis were studied in a fixed-bed reactor using a commercial precipitated iron catalyst (100 Fe/5 Cu/4.2K/25 SiO{sub 2} on a mass basis). The catalyst activity increased slightly with time-on-stream after hydrogen reductions, which was accompanied with conversion of metallic iron and part of iron oxides to {epsilon}{prime}-carbide ({epsilon}{prime}-Fe{sub 22}C). Initial activity of the H{sub 2}-reduced catalyst at 280{degrees}C for 8 or 24 h was markedly lower than that obtained in other tests. This is attributed to slow carburization of large oxide particles and partial poisoning of catalyst sites by migration of sulfur from the bulk to the surface of the catalyst during the reduction. Pretreatments with carbon monoxide and syngas resulted in partial conversion of Fe{sub 2}O{sub 3} to {chi}-carbide ({chi}-Fe{sub 5}C{sub 2}). During FT synthesis the CO- and the syngas-pretreated catalyst deactivated slowly with time-on-stream, due to partial conversion of {chi}-carbide to less active iron oxide phases and buildup of carbonaceous deposits which block the active sites. The hydrogen-reduced catalyst at 280{degrees}C, for 1-24h, produced more methane and gaseous hydrocarbons than the CO- or the syngas-pretreated catalyst and favored secondary reactions (1-olefin hydrogenation, isomerization, and readsorption). 41 refs., 5 figs., 2 tabs.

  1. Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Final report

    SciTech Connect

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1993-02-01

    This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275{degrees}C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

  2. Catalyst dispersion and activity under conditions of temperature-staged liquefaction

    SciTech Connect

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1993-02-01

    This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275[degrees]C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

  3. Surface Chemistry and Properties of Oxides as Catalyst Supports

    SciTech Connect

    DeBusk, Melanie Moses; Narula, Chaitanya Kumar; Contescu, Cristian I

    2015-01-01

    Heterogeneous catalysis relies on metal-oxides as supports for the catalysts. Catalyst supports are an indispensable component of most heterogeneous catalysts, but the role of the support is often minimized in light of the one played by the catalytically active species it supports. The active species of supported catalysts are located on the surface of the support where their contact with liquid or gas phase reactants will be greatest. Considering that support plays a major role in distribution and stability of active species, the absorption and retention of reactive species, and in some cases in catalytic reaction, the properties and chemistry that can occur at the surface of an oxide support are important for understanding their impact on the activity of a supported catalyst. This chapter examines this rich surface chemistry and properties of oxides used as catalyst supports, and explores the influence of their interaction with the active species.

  4. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

    NASA Astrophysics Data System (ADS)

    Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; Zegkinoglou, Ioannis; Sinev, Ilya; Choi, Yong-Wook; Kisslinger, Kim; Stach, Eric A.; Yang, Judith C.; Strasser, Peter; Cuenya, Beatriz Roldan

    2016-06-01

    There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides are surprisingly resistant to reduction and copper+ species remain on the surface during the reaction. Our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper+ is key for lowering the onset potential and enhancing ethylene selectivity.

  5. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene.

    PubMed

    Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S; Zegkinoglou, Ioannis; Sinev, Ilya; Choi, Yong-Wook; Kisslinger, Kim; Stach, Eric A; Yang, Judith C; Strasser, Peter; Cuenya, Beatriz Roldan

    2016-01-01

    There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides are surprisingly resistant to reduction and copper(+) species remain on the surface during the reaction. Our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper(+) is key for lowering the onset potential and enhancing ethylene selectivity. PMID:27356485

  6. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

    PubMed Central

    Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; Zegkinoglou, Ioannis; Sinev, Ilya; Choi, Yong-Wook; Kisslinger, Kim; Stach, Eric A.; Yang, Judith C.; Strasser, Peter; Cuenya, Beatriz Roldan

    2016-01-01

    There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides are surprisingly resistant to reduction and copper+ species remain on the surface during the reaction. Our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper+ is key for lowering the onset potential and enhancing ethylene selectivity. PMID:27356485

  7. Activity, short-term stability (poisoning tolerance) and durability of carbon supported Pt-Pr catalysts for ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Corradini, Patricia G.; Antolini, Ermete; Perez, Joelma

    2014-04-01

    Pt-Pr/C electrocatalysts were prepared by a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation, their short term stability and durability were compared to that of commercial Pt/C and Pt-Sn/C (3:1) catalysts. By derivative voltammetry (DV) it was found that ethanol electro-oxidation takes place by two main pathways at different potentials. It was observed that, in the presence of Pr, ethanol electro-oxidation takes place mostly through the pathway at lower potential, which is the most interesting for fuel cell application. The Pt-Pr/C catalysts were less tolerant to poisoning by ethanol oxidation intermediate species than Pt/C. Durability test by a repetitive potential cycling under Ar atmosphere revealed a good structural stability of Pt-Pr/C catalysts. A repetitive potential cycling under CO atmosphere carried out on the Pt-Pr/C (1:1) catalyst, instead, indicated a structural change, likely by formation of a core-shell structure.

  8. Shape-selective catalysts for Fischer-Tropsch chemistry : iron-containing particulate catalysts. Activity report : January 1, 2001 - December 31, 2004.

    SciTech Connect

    Cronauer, D.; Chemical Engineering

    2006-05-12

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry--specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It is desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The goal is to produce shape-selective catalysts that have the potential to limit the formation of longchain products and yet retain the active metal sites in a protected 'cage'. This cage also restricts their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. This activity report centers upon this first stage of experimentation with particulate FT catalysts. (For reference, a second experimental stage is under way to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes.) To date, experimentation has centered upon the evaluation of a sample of iron-based, spray-dried catalyst prepared by B.H. Davis of the Center of Applied Energy Research (CAER) and samples of his catalyst onto which inorganic 'shells' were deposited. The reference CAER catalyst contained a high level of dispersed fine particles, a portion of which was removed by differential settling. Reaction conditions have been established using a FT laboratory unit such that reasonable levels of CO conversion can be achieved, where therefore a valid catalyst comparison can be made. A wide range of catalytic activities was observed with SiO{sub 2}-coated FT catalysts. Two techniques were used for SiO{sub 2}coating. The first involved a caustic precipitation of SiO{sub 2} from an

  9. Structure and activity of tellurium/molybdenum oxide acrylonitrile catalysts. [Ammoxidation

    SciTech Connect

    Bart, J.C.J.; Giordano, N.

    1980-08-01

    The tellurium/molybdenum mixed oxides ((TeMo)O) catalyst system was investigated as part of the development of an industrial cerium/tellurium/molybdenum mixed oxides catalyst for propylene ammoxidation Catalysts containing 25% active phase on silica were prepared, characterized by BET surface area measurement, mercury porosimetry, X-ray diffraction, and optical microscopy, and tested for the ammoxidation of propylene at 400/sup 0/-460/sup 0/C in a flow reactor. The results suggested that Te/sub 2/MoO/sub 7/ is the active phase. The mechanism probably involves activation of propylene on a tellurium site and oxygen insertion at isolated and highly distorted MoO/sub 6/ octahedral sites. The addition of cerium to the binary catalyst prevents the reductive degradation of (TeMo)O which occurs under reactor flow conditions by a phase-separation process.

  10. Causes of Activation and Deactivation of Modified Nanogold Catalysts during Prolonged Storage and Redox Treatments.

    PubMed

    Kolobova, Ekaterina; Kotolevich, Yulia; Pakrieva, Ekaterina; Mamontov, Grigory; Farías, Mario H; Bogdanchikova, Nina; Cortés Corberán, Vicente; Pestryakov, Alexey

    2016-01-01

    The catalytic properties of modified Au/TiO₂ catalysts for low-temperature CO oxidation are affected by deactivation and reactivation after long-term storage and by redox treatments. The effect of these phenomena on the catalysts was studied by HRTEM, BET, SEM, FTIR CO, XPS and H₂ TPR methods. The main cause for the deactivation and reactivation of catalytic properties is the variation in the electronic state of the supported gold, mainly, the proportion of singly charged ions Au⁺. The most active samples are those with the highest proportion of singly charged gold ions, while catalysts with a high content of trivalent gold ions are inactive at low-temperatures. Active states of gold, resistant to changes caused by the reaction process and storage conditions, can be stabilized by modification of the titanium oxide support with transition metals oxides. The catalyst modified with lanthanum oxide shows the highest stability and activity. PMID:27089310

  11. Sulphate-activated growth of bamboo-like carbon nanotubes over copper catalysts

    NASA Astrophysics Data System (ADS)

    Lin, Jarrn-Horng; Chen, Ching-Shiun; Zeng, Zhi-Yan; Chang, Chia-Wei; Chen, Hsiu-Wei

    2012-07-01

    A sulphate-activated mechanism is proposed to describe the growth of bamboo-like carbon nanotubes (CNTs) over copper catalysts using chemical vapour deposition with helium-diluted ethylene. Sulphate-assisted copper catalysts afford a high-yield growth of bamboo-like CNTs at a mild temperature, 800 °C however, non-sulphate-assisted copper catalysts, e.g., copper acetate and copper nitrate prepared catalysts, were inert to CNT growth and only gave amorphous carbons (a-C) surrounding copper nanoparticles under the same conditions. Nevertheless, the addition of sulphate ions in the preparation step for the two inert catalysts can activate their abilities for CNT growth with remarkable yields. Furthermore, Raman spectra analysis demonstrates a linear dependence between the concentration of sulphate ions in copper catalysts and the ratio of CNT-a-C in the as-grown carbon soot. The sulphate-activated effect on CNT growth over copper catalysts could be related to a three-way interaction of sulphate ions, copper nanoparticles and support. In situ TEM images of an as-grown CNT irradiated by electron beams without the inlet of carbon sources reveal a new pathway of carbon diffusion through the bulk of copper nanoparticles and an enlarged inner-wall thickness of the on-site CNT. This carbon diffusion model over copper catalysts can provide new insights into the CNT growth mechanism over non-magnetic metal catalysts.A sulphate-activated mechanism is proposed to describe the growth of bamboo-like carbon nanotubes (CNTs) over copper catalysts using chemical vapour deposition with helium-diluted ethylene. Sulphate-assisted copper catalysts afford a high-yield growth of bamboo-like CNTs at a mild temperature, 800 °C however, non-sulphate-assisted copper catalysts, e.g., copper acetate and copper nitrate prepared catalysts, were inert to CNT growth and only gave amorphous carbons (a-C) surrounding copper nanoparticles under the same conditions. Nevertheless, the addition of

  12. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale.

    PubMed

    Shan, Shiyao; Petkov, Valeri; Prasai, Binay; Wu, Jinfang; Joseph, Pharrah; Skeete, Zakiya; Kim, Eunjoo; Mott, Derrick; Malis, Oana; Luo, Jin; Zhong, Chuan-Jian

    2015-12-01

    The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo

  13. Morphological effects of the nanostructured ceria support on the activity and stability of CuO/CeO2 catalysts for the water-gas shift reaction.

    PubMed

    Yao, S Y; Xu, W Q; Johnston-Peck, A C; Zhao, F Z; Liu, Z Y; Luo, S; Senanayake, S D; Martínez-Arias, A; Liu, W J; Rodriguez, J A

    2014-08-28

    Three CuO/CeO2 catalyst with different morphologies of ceria, namely nanospheres, nanorods and nanocubes, were synthesized and used to catalyze the water-gas shift (WGS) reaction. The reactivity tests showed that the Cu supported on the ceria nanospheres exhibited both the highest activity and superior stability when compared with the nanocube and nanorod ceria catalysts. Operando X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) methods were used to characterize these catalysts in their working state. High resolution electron microscopy (HRTEM, STEM) was used to look at the local atomic structure and nano-scale morphology. Our results show that the morphology of the ceria support, which can involve different crystal faces and concentrations of defects and imperfections, has a critical impact on the catalytic properties and influences: (1) the dispersion of CuO in the as-synthesized catalyst; (2) the particle size of metallic Cu upon reduction during the WGS reaction, (3) the stability of the metallic Cu upon variations of temperature, and (4) the dissociation of water on the ceria support. The nanosphere ceria catalyst showed an excellent water dissociation capability, the best dispersion of Cu and a strong Cu-Ce interaction, therefore delivering the best performance among the three WGS catalysts. The metallic Cu, which is the active species during the WGS reaction, was more stabilized on the nanospheres than on the nanorods and nanocubes and thus led to a better stability of the nanosphere catalyst than the other two architectures. Each catalyst exhibited a distinctive line-shape in the 800-1600 cm(-1) region of the DRIFTS spectra, pointing to the existence of different types of carbonate or carboxylate species as surface intermediates for the WGS. PMID:25012908

  14. Degradation of organic pollutants in wastewater by bicarbonate-activated hydrogen peroxide with a supported cobalt catalyst.

    PubMed

    Zhou, Li; Song, Wei; Chen, Zhuqi; Yin, Guochuan

    2013-04-16

    Developing novel technologies to cleanup wastewater has attracted attention for a long while in academic and industrial communities not only for environmental issues but also for recycling water sources. This work demonstrates that bicarbonate-activated H2O2 can be applied as a novel oxidant source in pollutant degradation. Using a supported cobalt catalyst, bicarbonate-activated H2O2 can efficiently degrade various dyes and phenol at ambient temperature. Because the reaction media remains weakly basic during degradation, the cobalt leaching from the solid catalyst has been efficiently avoided and the lifetime of the catalyst can be extended to above 180 h without significant activity loss in a fixed-bed test. Different scavengers, including ascorbic acid, t-butanol, sodium azide, benzoquinone, and tiron, have been tested to identify the active species, which may be involved in pollutant degradation, and it was found that singlet oxygen and the carbonate radical may play a key role in the degradation process. PMID:23495717

  15. Effect of Support on the Activity of Ag-based Catalysts for Formaldehyde Oxidation

    PubMed Central

    Zhang, Jianghao; Li, Yaobin; Zhang, Yan; Chen, Min; Wang, Lian; Zhang, Changbin; He, Hong

    2015-01-01

    Ag-based catalysts with different supports (TiO2, Al2O3 and CeO2) were prepared by impregnation method and subsequently tested for the catalytic oxidation of formaldehyde (HCHO) at low temperature. The Ag/TiO2 catalyst showed the distinctive catalytic performance, achieving the complete HCHO conversion at around 95 °C. In contrast, the Ag/Al2O3 and Ag/CeO2 catalysts displayed much lower activity and the 100% conversion was reached at 110 °C and higher than 125 °C, respectively. The Ag-based catalysts were next characterized by several methods. The characterization results revealed that supports have the dramatic influence on the Ag particle sizes and dispersion. Kinetic tests showed that the Ag based catalyst on the TiO2, Al2O3 or CeO2 supports have the similar apparent activation energy of 65 kJ mol−1, indicating that the catalytic mechanism keep immutability over these three catalysts. Therefore, Ag particle size and dispersion was confirmed to be the main factor affecting the catalytic performance for HCHO oxidation. The Ag/TiO2 catalyst has the highest Ag dispersion and the smallest Ag particle size, accordingly presenting the best catalytic performance for HCHO oxidation. PMID:26263506

  16. Decoupling HZSM-5 catalyst activity from deactivation during upgrading of pyrolysis oil vapors.

    PubMed

    Wan, Shaolong; Waters, Christopher; Stevens, Adam; Gumidyala, Abhishek; Jentoft, Rolf; Lobban, Lance; Resasco, Daniel; Mallinson, Richard; Crossley, Steven

    2015-02-01

    The independent evaluation of catalyst activity and stability during the catalytic pyrolysis of biomass is challenging because of the nature of the reaction system and rapid catalyst deactivation that force the use of excess catalyst. In this contribution we use a modified pyroprobe system in which pulses of pyrolysis vapors are converted over a series of HZSM-5 catalysts in a separate fixed-bed reactor controlled independently. Both the reactor-bed temperature and the Si/Al ratio of the zeolite are varied to evaluate catalyst activity and deactivation rates independently both on a constant surface area and constant acid site basis. Results show that there is an optimum catalyst-bed temperature for the production of aromatics, above which the production of light gases increases and that of aromatics decrease. Zeolites with lower Si/Al ratios give comparable initial rates for aromatics production, but far more rapid catalyst deactivation rates than those with higher Si/Al ratios. PMID:25504857

  17. Method of treating intermetallic alloy hydrogenation/oxidation catalysts for improved impurity poisoning resistance, regeneration and increased activity

    DOEpatents

    Wright, Randy B.

    1992-01-01

    Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation).

  18. Iridium Ziegler-Type Hydrogenation Catalysts Made from [(1,5-COD)Ir( -O2C8H15)]2 and AlEt3: Spectroscopic and Kinetic Evidence for the Irn Species Present and for Nanoparticles as the Fastest Catalyst

    SciTech Connect

    Alley, W.; Hamdemir, I; Wang, Q; Frenkel, A; Li, L; Yang, J; Menard, L; Nuzzo, R; Ozkar, S; Finke, R

    2010-01-01

    Ziegler-type hydrogenation catalysts, those made from a group 8-10 transition metal precatalyst and an AlR{sub 3} cocatalyst, are often used for large scale industrial polymer hydrogenation; note that Ziegler-type hydrogenation catalysts are not the same as Ziegler-Natta polymerization catalysts. A review of prior studies of Ziegler-type hydrogenation catalysts (Alley et al. J. Mol. Catal. A: Chem. 2010, 315, 1-27) reveals that a {approx}50 year old problem is identifying the metal species present before, during, and after Ziegler-type hydrogenation catalysis, and which species are the kinetically best, fastest catalysts-that is, which species are the true hydrogenation catalysts. Also of significant interest is whether what we have termed 'Ziegler nanoclusters' are present and what their relative catalytic activity is. Reported herein is the characterization of an Ir Ziegler-type hydrogenation catalyst, a valuable model (vide infra) for the Co-based industrial Ziegler-type hydrogenation catalyst, made from the crystallographically characterized [(1,5-COD)Ir({mu}-O{sub 2}C{sub 8}H{sub 15})]{sub 2} precatalyst plus AlEt{sub 3}. Characterization of this Ir model system is accomplished before and after catalysis using a battery of physical methods including Z-contrast scanning transmission electron microscopy (STEM), high resolution (HR)TEM, and X-ray absorption fine structure (XAFS) spectroscopy. Kinetic studies plus Hg(0) poisoning experiments are then employed to probe which species are the fastest catalysts. The main findings herein are that (i) a combination of the catalyst precursors [(1,5-COD)Ir({mu}-O{sub 2}C{sub 8}H{sub 15})]{sub 2} and AlEt{sub 3} gives catalytically active solutions containing a broad distribution of Ir{sub n} species ranging from monometallic Ir complexes to nanometer scale, noncrystalline Ir{sub n} nanoclusters (up to Ir{sub {approx}100} by Z-contrast STEM) with the estimated mean Ir species being 0.5-0.7 nm, Ir{sub {approx}4-15} clusters

  19. An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

    NASA Astrophysics Data System (ADS)

    Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

    2012-10-01

    The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.

  20. An alternative approach to PEPPSI catalysts: from palladium isonitriles to highly active unsymmetrically substituted PEPPSI catalysts.

    PubMed

    Zeiler, Anna; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2015-07-27

    A series of new pyridine-enhanced precatalyst preparation, stabilization, and initiation (PEPPSI)-type complexes bearing different types of carbene ligands was prepared by the modular and convergent template synthesis strategy. Nitrogen acyclic carbenes, saturated and unsaturated five-membered NHC, saturated six-membered NHCs, and five-membered N-heterocyclic oxo-carbene (NHOC) ligands on palladium were prepared this way. These new organometallic compounds then were tested in Suzuki and Negishi cross-coupling reactions by using substrates with one or two substituents in ortho-position of the new CC bond being formed. Both aryl chlorides and bromides were tested as coupling partners. In some cases, the new ligands gave results similar to Organ's successful IPr-based and IPent-based PEPPSI derivatives, with aryl bromides 0.05 mol % catalyst load still gave satisfactory results, with aryl chlorides 0.5 mol % were needed. PMID:26096141

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

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

  2. Role of pH in the formation of structurally stable and catalytically active supported gold catalysts

    SciTech Connect

    Veith, Gabriel M; Lupini, Andrew R; Dudney, Nancy J

    2009-01-01

    We report the investigation of titania (Degussa P25) supported gold catalysts prepared by magnetron sputtering. Catalysts grown on natural fumed titania were structurally unstable, resulting in the rapid coarsening of 2.4 nm gold clusters into large {approx}20 nm gold clusters in a few days at room temperature under normal atmospheric conditions. However, treating the titania support powder to a mock deposition-precipitation process, at pH 4, followed by the subsequent deposition of gold onto this treated powder produced a remarkable enhancement in gold particle stability and a 20-fold enhancement of catalytic activity. Furthermore, it was found that treating the titania under basic conditions (pH 10) resulted in a further enhancement of structural stability and a further doubling of the reaction rate to 0.28 mol of CO/mol of Au {center_dot} s. This enhancement cannot be attributed to removing surface Cl{sup -} species from the titania, the formation of oxygen vacancies on the TiO{sub 2} surface, or an electronic effect. Instead, it appears to be associated with the formation of strongly bound hydroxyl species on the TiO{sub 2} surface. The formation of surface hydroxyls during the deposition-precipitation method is coincidental and contributes significantly to the properties of Au/TiO{sub 2} catalysts.

  3. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts.

    PubMed

    Bu, Quan; Lei, Hanwu; Wang, Lu; Wei, Yi; Zhu, Lei; Liu, Yupeng; Liang, Jing; Tang, Juming

    2013-08-01

    The effects of different activated carbon (AC) catalysts based on various carbon sources on products yield and chemical compositions of upgraded pyrolysis oils were investigated using microwave pyrolysis of Douglas fir sawdust pellets. Results showed that high amounts of phenols were obtained (74.61% and 74.77% in the upgraded bio-oils by DARCO MRX (wood based) and DARCO 830 (lignite coal based) activated carbons, respectively). The catalysts recycling test of the selected catalysts indicated that the carbon catalysts can be reused for at least 3-4 times and produced high concentrations of phenol and phenolic compounds. The chemical reaction mechanism for phenolics production during microwave pyrolysis of biomass was analyzed. PMID:23765005

  4. The role of adsorbed hydrogen species in the dehydrogenation and hydrocracking of saturated hydrocarbons on supported metal catalysts

    NASA Astrophysics Data System (ADS)

    Babenkova, L. V.; Naidina, I. N.

    1994-07-01

    The role of certain hydrogen absorption complexes in the dehydrogenation and hydrocracking of hydrocarbons on low-percentage one-component, (Pt, Pd/Al2O3) and bimetallic (Pd-Co, Pd-Ce, Pt-Co, Pt-Sn/Al2O3) catalysts is discussed. It is shown that the combination of metals in reduced forms and forms oxidised to different extents on the catalyst surfaces is responsible for their high capacity for the chemisorption of hydrogen, the wide range of its energetic inhomogeneity, and the high activity of the catalysts in the conversion of saturated hydrocarbons. Catalysts containing on the surface mainly sites for the type Hδ- chemisorption are the most active in the dehydrogenation of hydrocarbons, whereas specimens chemisorbing hydrogen mainly in the Hδ+ form are the most active in the hydrockracking of hydrocarbons. It is concluded that the strongly bound atomic hydrogen Hδ+ plays a dual role, since it not only participates directly in the dehydrogenation reaction but also promotes the reduction of the electron-deficient surface centres, which optimises the number of centres for the activation of C-H bonds. The bibliography includes 75 references.

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

    PubMed

    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 (57)Fe 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. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

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

    PubMed Central

    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

  8. Activation and deactivation of a robust immobilized Cp*Ir-transfer hydrogenation catalyst: a multielement in situ X-ray absorption spectroscopy study.

    PubMed

    Sherborne, Grant J; Chapman, Michael R; Blacker, A John; Bourne, Richard A; Chamberlain, Thomas W; Crossley, Benjamin D; Lucas, Stephanie J; McGowan, Patrick C; Newton, Mark A; Screen, Thomas E O; Thompson, Paul; Willans, Charlotte E; Nguyen, Bao N

    2015-04-01

    A highly robust immobilized [Cp*IrCl2]2 precatalyst on Wang resin for transfer hydrogenation, which can be recycled up to 30 times, was studied using a novel combination of X-ray absorption spectroscopy (XAS) at Ir L3-edge, Cl K-edge, and K K-edge. These culminate in in situ XAS experiments that link structural changes of the Ir complex with its catalytic activity and its deactivation. Mercury poisoning and "hot filtration" experiments ruled out leached Ir as the active catalyst. Spectroscopic evidence indicates the exchange of one chloride ligand with an alkoxide to generate the active precatalyst. The exchange of the second chloride ligand, however, leads to a potassium alkoxide-iridate species as the deactivated form of this immobilized catalyst. These findings could be widely applicable to the many homogeneous transfer hydrogenation catalysts with Cp*IrCl substructure. PMID:25768298

  9. Hemolytic activity of dermatophytes species isolated from clinical specimens.

    PubMed

    Aktas, E; Yıgıt, N

    2015-03-01

    Hemolytic activity was recently reported for several pathogenic fungal species, such as Aspergillus, Candida, Trichophyton, Penicillium and Fusarium. Based on a number of mechanistic and characterization studies, several fungal hemolysins have been proposed as virulence factors. Hemolysins lyse red blood cells resulting in the release of iron, an important growth factor for microbes especially during infection. The requirement of iron in fungal growth is necessary for metabolic processes and as a catalyst for various biochemical processes. Expression of a hemolytic protein with capabilities to lyse red blood cells has also been suggested to provide a survival strategy for fungi during opportunistic infections. The aims of this study were to investigate the hemolytic activities of dermatophytes species isolated from patients with dermatophytosis. Hair, skin and nail samples of patients were examined with direct microscopy using potassium hydroxide and cultivated on Mycobiotic agar and Sabouraud's dextrose agar. To determine hemolytic activities of dermatophytes species, they were subcultured on Columbia Agar with 5% sheep blood and incubated for 7-14 days at 25°C in aerobic conditions. Media which displayed hemolysis were further incubated for 1-5 days at 37°C to increase hemolytic activity. In this study, 66 dermatophytes strains were isolated from clinical specimens and were identified by six different species: 43 (65.1%) Trichophyton rubrum, 7 (10.7%) Trichophyton mentagrophytes, 5 (7.6%) Microsporum canis, 5 (7.6%) Trichophyton tonsurans, 4 (6.0%) Epidermophyton floccosum and 2 (3.0%) Trichophyton violaceum. Twenty-one T. rubrum strains showed incomplete (alpha) hemolysis and nine T. rubrum strains showed complete (beta) hemolysis, whereas hemolysis was absent in 13 T. rubrum strains. Four T. mentagrophytes strains showed complete hemolysis and three T. tonsurans strains showed incomplete hemolysis. However, M. canis, E. floccosum and T. violaceum species had

  10. Spectroscopic and XRD characterisation of zeolite catalysts active for the oxidative methylation of benzene with methane

    NASA Astrophysics Data System (ADS)

    Adebajo, Moses O.; Long, Mervyn A.; Frost, Ray L.

    2004-03-01

    The benzene methylation with methane over zeolite catalysts was previously shown in our laboratory to require the presence of oxygen. Thus, a two-step mechanism involving the intermediate formation of methanol by partial oxidation of methane followed by the methylation of benzene with methanol in the second step, was postulated. This paper now reports the results of the characterisation of the zeolite catalysts used for the oxidative benzene methylation reaction in order to provide some information about their composition, structure, properties and their behaviour before and after the reaction. The catalysts were characterised by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), FT-IR and solid state NMR. XRD results indicate that the crystalline structures of all the ZSM-5 and H-beta catalysts remained unchanged after batch reaction of benzene with methane over the catalysts in agreement with the observation that the catalysts recovered from the reactor could be reused without loss of activity. Elemental analyses and FT-IR data show that as the level of metal ion exchange increases, the Brönsted acid concentration decreases but this metal ion exchange does not totally remove Brönsted acidity. FT-IR results further show that only a small amount of acid sites is actually necessary for a catalyst to be active since used catalysts containing highly reduced Brönsted acidity are found to be reusable without any loss of their activity. 29Si and 27Al magic angle spinning (MAS) NMR together with FT-IR spectra also show that all the active zeolites catalysts contain some extra-framework octahedral aluminium in addition to the normal tetrahedral framework aluminium. The presence of this extra-lattice aluminium does not, however, have any adverse effect on the crystallinity of the catalysts both before and after oxidative benzene methylation reaction. There appears also to be no significant dealumination

  11. Activity and selectivity of Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl

    SciTech Connect

    Song, C.; Schmidt, E.; Schobert, H.H.

    1995-12-31

    Various iron containing catalysts have been investigated for their use in hydroliquefaction of coal ever since Bergius demonstrated the feasibility of the process. Conventional iron catalysts have been widely used either unsupported or as catalysts dispersed directly onto coal. Iron catalysts have generally a lower cost and lower environmental detriment than Mo, Ni and Co catalyst precursors. The search for active high surface area iron particles has become recently an important pan in the development of a cost effective direct coal liquefaction process. To examine what determines the activity and selectivity of Fe catalysts for hydrogenation and hydrocracking, various molecular precursors with Fe in different chemical environments have been tested in this work to help understand the influence of precursor structure and the effect of sulfur addition on the activity and selectivity of resulting Fe catalysts in model reactions of 4-(naphthylmethyl)bibenzyl (NMBB).

  12. Fischer Tropsch synthesis : influence of Mn on the carburization rates and activities of Fe-based catalysts by TPR-EXAFS/XANES and catalyst testing.

    SciTech Connect

    Ribeiro, M. C.; Jacobs, G.; Pendyala, R.; Davis, B. H.; Cronauer, D. C.; Kropf, A. J.; Marshall, C. L.

    2011-03-24

    Fe-based catalysts containing different amounts of Mn were tested for Fischer-Tropsch synthesis using a stirred tank reactor at 270 C, 1.21 MPa, and H{sub 2}:CO = 0.7. Catalyst activation by carburization with 10% CO/He was followed by Temperature Programmed Reduction/X-ray Absorption Spectroscopy (TPR-EXAFS/XANES) from room temperature to 300 C. {gamma}-Fe{sub 2}O{sub 3} was converted into iron carbides, whereas MnO{sub x} was reduced to oxygen deficient MnO. Mn hindered Fe carburization, such that the carburized catalyst displayed higher Fe{sub 3}O{sub 4} content than the catalyst without Mn. EXAFS fitting indicates that the carburized catalyst contained a mixture of Hgg carbide, Fe{sub 3}O{sub 4}, and Mn oxides. Increasing Mn content led to higher CH{sub 4} and light product selectivities, and lower light olefin selectivities. Higher and stable conversions were obtained with a catalyst containing an almost equimolar Fe/Mn ratio relative to the catalyst without Mn. Selectivity trends are attributed to the higher WGS rates observed on the FeMn catalysts, consistent with the structural differences observed.

  13. Acidic Properties and Structure-Activity Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy.

    PubMed

    Zheng, Anmin; Li, Shenhui; Liu, Shang-Bin; Deng, Feng

    2016-04-19

    Solid acid materials with tunable structural and acidic properties are promising heterogeneous catalysts for manipulating and/or emulating the activity and selectivity of industrially important catalytic reactions. On the other hand, the performances of acid-catalyzed reactions are mostly dictated by the acidic features, namely, type (Brønsted vs Lewis acidity), amount, strength, and local environment of acid sites. The latter is relevant to their location (intra- vs extracrystalline), and possible confinement and Brønsted-Lewis acid synergy effects that may strongly affect the host-guest interactions, reaction mechanism, and shape selectivity of the catalytic system. This account aims to highlight some important applications of state-of-the-art solid-state NMR (SSNMR) techniques for exploring the structural and acidic properties of solid acid catalysts as well as their catalytic performances and relevant reaction pathway invoked. In addition, density functional theory (DFT) calculations may be exploited in conjunction with experimental SSNMR studies to verify the structure-activity correlations of the catalytic system at a microscopic scale. We describe in this Account the developments and applications of advanced ex situ and/or in situ SSNMR techniques, such as two-dimensional (2D) double-quantum magic-angle spinning (DQ MAS) homonuclear correlation spectroscopy for structural investigation of solid acids as well as study of their acidic properties. Moreover, the energies and electronic structures of the catalysts and detailed catalytic reaction processes, including the identification of reaction species, elucidation of reaction mechanism, and verification of structure-activity correlations, made available by DFT theoretical calculations were also discussed. Relevant discussions will focus primarily on results obtained from our laboratories in the past decade, including (i) quantitative and qualitative acidity characterization utilizing assorted probe molecules

  14. A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.

    1992-01-01

    An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ligands'' with localized surface orbitals perturbed only by these ligands''. These complexes'' are based on a twelve coordinate species with the ligands'' attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  15. A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.

    1992-11-01

    An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ``ligands`` with localized surface orbitals perturbed only by these ``ligands``. These ``complexes`` are based on a twelve coordinate species with the ``ligands`` attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  16. Antifungal activity of five species of Polygala

    PubMed Central

    Johann, Susana; Mendes, Beatriz G.; Missau, Fabiana C.; de Resende, Maria A.; Pizzolatti, Moacir G.

    2011-01-01

    Crude extracts and fractions of five species of Polygala – P. campestris, P. cyparissias, P. paniculata, P. pulchella and P. sabulosa – were investigated for their in vitro antifungal activity against opportunistic Candida species, Cryptococcus gattii and Sporothrix schenckii with bioautographic and microdilution assays. In the bioautographic assays, the major extracts were active against the fungi tested. In the minimal concentration inhibitory (MIC) assay, the hexane extract of P. paniculata and EtOAc fraction of P. sabulosa showed the best antifungal activity, with MIC values of 60 and 30 μg/mL, respectively, against C. tropicalis, C. gattii and S. schenckii. The compounds isolated from P. sabulosa prenyloxycoumarin and 1,2,3,4,5,6-hexanehexol displayed antifungal activity against S. schenckii (with MICs of 125 μg/mL and 250 μg/mL, respectively) and C. gattii (both with MICs of 250 μg/mL). Rutin and aurapten isolated from P. paniculata showed antifungal activity against C. gattii with MIC values of 60 and 250 μg/mL, respectively. In the antifungal screening, few of the isolated compounds showed good antifungal inhibition. The compound α-spinasterol showed broad activity against the species tested, while rutin had the best activity with the lowest MIC values for the microorganisms tested. These two compounds may be chemically modified by the introduction of a substitute group that would alter several physico-chemical properties of the molecule, such as hydrophobicity, electronic density and steric strain. PMID:24031724

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

    SciTech Connect

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

    2000-04-01

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

  18. Development of Highly Active and Regioselective Catalysts for the Copolymerization of Epoxides with Cyclic Anhydrides: An Unanticipated Effect of Electronic Variation.

    PubMed

    DiCiccio, Angela M; Longo, Julie M; Rodríguez-Calero, Gabriel G; Coates, Geoffrey W

    2016-06-01

    Recent developments in polyester synthesis have established several systems based on zinc, chromium, cobalt, and aluminum catalysts for the ring-opening alternating copolymerization of epoxides with cyclic anhydrides. However, to date, regioselective processes for this copolymerization have remained relatively unexplored. Herein we report the development of a highly active, regioselective system for the copolymerization of a variety of terminal epoxides and cyclic anhydrides. Unexpectedly, electron withdrawing substituents on the salen framework resulted in a more redox stable Co(III) species and longer catalyst lifetime. Using enantiopure propylene oxide, we synthesized semicrystalline polyesters via the copolymerization of a range of epoxide/anhydride monomer pairs. PMID:27171536

  19. Effects of coordination number of Au catalyst on oxygen species and their catalytic roles

    NASA Astrophysics Data System (ADS)

    Ouyang, Gen; Zhu, Kong-Jie; Zhang, Lei; Cui, Peng-Fei; Teng, Bo-Tao; Wen, Xiao-Dong

    2016-11-01

    To explore the effects of coordination number of Au nanoparticles on oxygen species and their catalytic roles is very important in gold catalysis. Based on the systematic study of oxygen adsorption on Au(997) by density functional theory calculation, the quantitative correlation for different oxygen species with coverage and Au coordination number is established in theory. The only O adatoms near step area with relatively low Au coordination numbers exist at low coverage (<1/18 ML), O adatoms adsorb at terrace areas with relatively high Au coordination numbers at medium coverage (1/18-2/9 ML); while oxygen islands form at high coverage (>2/9 ML). The theoretical predictions are in good agreement with the experimental observations in TDS spectrum. On the basis of Langmuir-Hinschelwood and Eley-Rideal mechanisms for NO oxidation, the activities of the three different oxygen species also exhibit correlation with Au coordination number. The oxygen island shows the highest oxidation activity, followed by the O adatom at terrace surface; while the O adatom near step area has the lowest oxidative performance. This work will shed light into the understanding of gold catalysis.

  20. Computational approaches to the determination of active site structures and reaction mechanisms in heterogeneous catalysts.

    PubMed

    Catlow, C R A; French, S A; Sokol, A A; Thomas, J M

    2005-04-15

    We apply quantum chemical methods to the study of active site structures and reaction mechanisms in mesoporous silica and metal oxide catalysts. Our approach is based on the use of both molecular cluster and embedded cluster (QM/MM) techniques, where the active site and molecular complex are described using density functional theory (DFT) and the embedding matrix simulated by shell model potentials. We consider three case studies: alkene epoxidation over the microporous TS-1 catalyst; methanol synthesis on ZnO and Cu/ZnO and C-H bond activation over Li-doped MgO. PMID:15901543

  1. Effect of thermal treatments on the properties of nickel and cobalt activated-charcoal-supported catalysts

    SciTech Connect

    Gandia, L.M.; Montes, M. )

    1994-02-01

    The effect of thermal pretreatment in N[sub 2] up to 723 K and the activation treatments in H[sub 2] and an inert atmosphere on the properties of Ni and Co activated-charcoal-supported catalysts were studied. Catalysts were characterized by means of N[sub 2] adsorption at 77 K, H[sub 2] chemisorption at room temperature, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The catalysts' activity and selectivity for acetone hydrogenation to 2-propanol under unusual and severe conditions (473 K and high overall acetone conversion) were also measured. TGA and XRD evidence was found for the charcoal-support-promoted NiO and CoO reduction to the metallic states when the catalysts were subjected to an inert atmosphere above 723 K caused a loss of acetone hydrogenation activity (calculated on a metal load basis) for both the Ni and Co activated-charcoal-supported catalysts, with respect to that of the low-temperature (573 K) activation treatments. In a series of activated-charcoal-supported Ni catalysts, a large decrease in the H[sub 2] chemisorption uptake was also found for a sample pretreated in N[sub 2] at 723 K prior to H[sub 2] reduction. These results were not due to nickel or cobalt sintering, as shown by XRD line broadening measurements. The catalytic activity loss was accompanied by a decrease (in the case of Ni) and an increase (in the case of Co) in the 2-propanol selectivity. 44 refs., 13 figs., 3 tabs.

  2. C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

    PubMed

    Shul'pin, Georgiy B

    2013-09-28

    This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

  3. Bulk binary ZrO2-based oxides as highly active alternative-type catalysts for non-oxidative isobutane dehydrogenation.

    PubMed

    Otroshchenko, Tatyana; Radnik, Jörg; Schneider, Matthias; Rodemerck, Uwe; Linke, David; Kondratenko, Evgenii V

    2016-06-21

    Bulk binary ZrO2-based oxides efficiently catalyse non-oxidative dehydrogenation of isobutane to isobutylene. Their activity strongly depends on the kind of second metal oxide. So designed CrZrOx showed superior activity to industrially relevant catalysts with supported Pt or CrOx species. It was also stable under alternating dehydrogenation and oxidative regeneration cycles over ca. 110 h under different reaction conditions between 550 and 600 °C. PMID:27277540

  4. Development of catalytically active and highly stable catalyst supports for polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Taekeun; Xie, Tianyuan; Jung, Wonsuk; Gadala-Maria, Francis; Ganesan, Prabhu; Popov, Branko N.

    2015-01-01

    Novel procedures are developed for the synthesis of highly stable carbon composite catalyst supports (CCCS-800 °C and CCCS-1100 °C) and an activated carbon composite catalyst support (A-CCCS). These supports are synthesized through: (i) surface modification with acids and inclusion of oxygen groups, (ii) metal-catalyzed pyrolysis, and (iii) chemical leaching to remove excess metal used to dope the support. The procedure results in increasing carbon graphitization and inclusion of non-metallic active sites on the support surface. Catalytic activity of CCCS indicates an onset potential of 0.86 V for the oxygen reduction reaction (ORR) with well-defined kinetic and mass-transfer regions and ∼2.5% H2O2 production in rotating ring disk electrode (RRDE) studies. Support stability studies at 1.2 V constant potential holding for 400 h indicate high stability for the 30% Pt/A-CCCS catalyst with a cell potential loss of 27 mV at 800 mA cm-2 under H2-air, 32% mass activity loss, and 30% ECSA loss. Performance evaluation in polymer electrolyte membrane (PEM) fuel cell shows power densities (rated) of 0.18 and 0.23 gPt kW-1 for the 30% Pt/A-CCCS and 30% Pt/CCCS-800 °C catalysts, respectively. The stabilities of various supports developed in this study are compared with those of a commercial Pt/C catalyst.

  5. Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

    SciTech Connect

    Islam, A. E.; Zakharov, D.; Stach, E. A.; Nikoleav, P.; Amama, P. B.; Sargent, G.; Saber, S.; Huffman, D.; Erford, M.; Semiatin, S. L.; Maruyama, B.

    2015-09-16

    Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. As a result, with the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

  6. Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

    DOE PAGESBeta

    Islam, A. E.; Zakharov, D.; Stach, E. A.; Nikoleav, P.; Amama, P. B.; Sargent, G.; Saber, S.; Huffman, D.; Erford, M.; Semiatin, S. L.; et al

    2015-09-16

    Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only inmore » the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. As a result, with the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.« less

  7. Fe/S doped granular activated carbon as a highly active heterogeneous persulfate catalyst toward the degradation of Orange G and diethyl phthalate.

    PubMed

    Pu, Mengjie; Ma, Yongwen; Wan, Jinquan; Wang, Yan; Huang, Mingzhi; Chen, Yangmei

    2014-03-15

    Fe/S doped granular activated carbon (Fe/SGAC) was synthesized with ferric nitrate, Na2S2O3 and (NH4)2S2O8 via an impregnation-precipitation, reduction-oxidation combining with aqueous-phase synthesis method treatment. Surface density of functional groups, surface area changes as well as the chemical state inside Fe/SGAC catalyst were studied by Boehm titration, N2 adsorption and X-ray photoelectron spectroscopy (XPS). The reactivity of the catalysts was tested by degrading Orange G (OG) and diethyl phthalate (DEP). The Fe/SGAC catalysts could significantly enhance the removal rate of OG as compared to persulfate alone and PS/GAC. And the catalytic capacity was also enhanced by S doping. But the degradation of DEP under the similar condition was inhibited by adsorption process because of the different hydrophobicities of OG and DEP molecule. Fe2O3/FeOOH (Fe(3+)) (represents ferrihydrite) together with FeO/Fe3O4 (Fe(2+)) and Fe2O3-satellite, which provide the new active site for persulfate catalyst was found to be the major components of iron element in Fe/SGAC catalyst; the existence of FeS2(S(-)) for sulfur element verified the assumption that the doped S element promoted the electron transfer between the persulfate species and iron oxide at the interface. COD removal experiment further confirmed that mostly contaminant removal was owed to the Fe/SGAC catalytic persulfate oxidation process. PMID:24461853

  8. Antibacterial activity of some Artemisia species extract.

    PubMed

    Poiată, Antonia; Tuchiluş, Cristina; Ivănescu, Bianca; Ionescu, A; Lazăr, M I

    2009-01-01

    The antimicrobial activities of ethanol, methanol and hexane extracts from Artemisia absinthium, Artemisia annua and Artemisia vulgaris were studied. Plant extracts were tested against five Gram-positive bacteria, two Gram-negative bacteria and one fungal strain. The results indicated that Artemisia annua alcoholic extracts are more effective against tested microorganisms. However, all plants extracts have moderate or no activity against Gram-negative bacteria. The obtained results confirm the justification of extracts of Artemisia species use in traditional medicine as treatment for microbial infections. PMID:20191854

  9. ZrO2 -Based Alternatives to Conventional Propane Dehydrogenation Catalysts: Active Sites, Design, and Performance.

    PubMed

    Otroshchenko, Tatyana; Sokolov, Sergey; Stoyanova, Mariana; Kondratenko, Vita A; Rodemerck, Uwe; Linke, David; Kondratenko, Evgenii V

    2015-12-21

    Non-oxidative dehydrogenation of propane to propene is an established large-scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO2 promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO2 promoter and/or supporting tiny amounts of hydrogenation-active metal. Accordingly designed Cu(0.05 wt %)/ZrO2 -La2 O3 showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625 °C. PMID:26566072

  10. Copper on responsive polymer microgels: a recyclable catalyst exhibiting tunable catalytic activity.

    PubMed

    Wu, Qingshi; Cheng, Han; Chang, Aiping; Bai, Xue; Lu, Fan; Wu, Weitai

    2014-11-25

    Copper has been immobilized on a chitosan-based responsive polymer microgel by simply stirring the microgel dispersion with copper sulfate. The ensuing catalyst is highly active for a model azide-alkyne [3+2]-cycloaddition reaction, and can be recycled at least 5 times; the catalytic activity can be tuned via swelling-deswelling transitions of the polymer gels. PMID:25283806

  11. Modification of isomerization activity and selectivity over sulfated zirconia catalysts

    SciTech Connect

    Soled, S.L.; Iglesia, E.; Kramer, G.M.; McVicker, G.B.

    1993-12-31

    The family of anion-modified oxide strong solid acid catalysts (oxides of Zr, Ti, Sn, or Fe, modified with sulfate) that have been recently reported in the literature were examined for the isomerization of C{sub 5}-C{sub 8} n-paraffins. Isomerization of C{sub 7+} feeds on conventional solid and liquid acids leads to extensive cracking; in particular, paraffins with seven or more carbon atoms are known to undergo acid cracking to undesirable light gases during isomerization over acid catalysts; thus, commercial isomerization practice is limited to C{sub 4}-C{sub 6} feeds. Cracking occurs because isobutane and propane are excellent leaving groups in carbonium ion rearrangements. Since both isomerization and cracking occur on strong acid sites it has been difficult to control one at the expense of the other. The authors have observed that low levels of that low levels of adamantane, a hydride transfer agent, added to a heptane or octain feed will double the isomerization rate while dramatically limiting cracking reactions. The adamantane enhances the rate determining hydride transfer step and limits the surface residence time of carbocation intermediates. This behavior contrasts with that of aromatic addition where poisoning of strong acid sites inhibits cracking but dramatically decreases the isomerization rate. This paper will suggest a mechanism that involves a nonfunctional acid catalyzed chain mechanism proceeding through intermolecular hydride transfer reactions. Finally we will discuss the remaining issues in obtaining a viable C{sub 7}+ isomerization process.

  12. Probing the coordinative unsaturation and local environment of Ti³⁺ sites in an activated high-yield Ziegler-Natta catalyst.

    PubMed

    Morra, Elena; Giamello, Elio; Van Doorslaer, Sabine; Antinucci, Giuseppe; D'Amore, Maddalena; Busico, Vincenzo; Chiesa, Mario

    2015-04-13

    The typical activation of a fourth generation Ziegler-Natta catalyst TiCl4/MgCl2/phthalate with triethyl aluminum generates Ti(3+) centers that are investigated by multi-frequency continuous wave and pulse EPR methods. Two families of isolated, molecule-like Ti(3+) species have been identified. A comparison of the experimentally derived g tensors and (35,37)Cl hyperfine and nuclear-quadrupole tensors with DFT-computed values suggests that the dominant EPR-active Ti(3+)  species is located on MgCl2(110) surfaces (or equivalent MgCl2 terminations with tetra-coordinated Mg). O2 reactivity tests show that a fraction of these Ti sites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization. PMID:25706346

  13. Photo-enhanced activity of Pt and Pt-Ru catalysts towards the electro-oxidation of methanol

    NASA Astrophysics Data System (ADS)

    Arulmani, Dheevesh V.; Eastcott, Jennie I.; Mavilla, Stephanie G.; Easton, E. Bradley

    2014-02-01

    Electrocatalyst materials, consisting of Pt or Pt-Ru supported on carbon with and without TiO2, are evaluated for their activity towards the methanol oxidation reaction (MOR) in 1.0 M H2SO4 at 25 °C in the presence and absence of visible light irradiation. Electrochemical studies showed that enhanced MOR activity is achieved upon irradiation with visible light for each catalyst, in both the presence and absence of TiO2. Irradiation leads to no improvement in activity towards the formic acid oxidation reaction (FAOR) indicating that irradiation aids in the removal of adsorbed intermediate species, such as CO, during MOR. While the presence of a TiO2 support does lead to an increase in activity upon irradiation, about 50% of the improvements arise solely from the irradiation of the metal-containing electrocatalysts themselves.

  14. Fraction of platinum surface covered with carbonaceous species following hydrogenolysis of hexane on platinum alumina catalysts

    SciTech Connect

    Rivera Latas, F.J.

    1986-01-01

    Catalytic naphtha reforming plays a major role in satisfying the demand for unleaded, high octane gasoline. Hydrogen containing carbonaceous deposits (coke) accumulation on the surface of the catalysts during reforming operation. This study investigated the following question: what is the fraction of the platinum surface covered with the deposits following a typical reforming reaction. These observations prompted us to prepare a platinum-alumina catalyst with a high metal content (5%) to enhance the sensitivity of experiments designed to examine the platinum surface following hexane hydrogenolysis. The reaction was selected because it is a good model reaction for catalytic reforming and it was also studied by the Somorjai group in the higher temperature range of their work. Hydrogenolysis of hexane was carried out in a flow system for 3 h at 713 K, at atmospheric pressure, and around 0.1 total conversion. The catalyst was cooled down to room temperature in the reactant mixture, and the fraction of surface platinum atoms exposed was measured in situ by four independent methods: titration of adsorbed oxygen by dihydrogen, chemisorption of carbon monoxide, infra-red spectroscopy of carbon monoxide bonded to platinum, and rate of ethylene hydrogenation. Independent gravimetric studies showed that coke deposits of around 1% by weight were formed on the same catalyst during hydrogenolysis of hexane under similar conditions. Each of the four methods indicate that approximately 50% of the platinum surface remains exposed under the conditions.

  15. Results of catalyst testing using iron-based catalysts

    SciTech Connect

    Linehan, J.C.; Darab, J.G.; Matson, D.W.

    1993-03-01

    As coal liquefaction catalysts, iron-based products are generally inferior to the more expensive molybdenum, cobalt, or nickel-based materials. However, the lower costs of production and recovery (or in the case of some iron catalysts, non-recovery) give the iron-based materials a potential economic advantage over the more efficient precious and semi-precious metal catalysts for this application. Recent research has shown that a number of different iron-containing materials can be successfully utilized as coal liquefaction catalysts or as catalyst. Pyrrhotite (Fe{sub 1-x}S) or a similar iron-sulfide phase is commonly believed to be the active catalyst in coal liquefaction and model compound pyrolysis reactions, although no specific phase has been yet been isolated as the actual catalyst species. The active iron-containing catalyst is usually generated in situ from an iron-oxide precursor and an elemental sulfur source under reducing conditions in the reactor vessel. Most research has concentrated on the use of common iron-oxide phases such as hematite or goethite (and their derivatives) as the iron-bearing precursor, or on non-specific iron materials produced by the reaction of various iron salts and compounds in the coal or liquefaction reactor. To our knowledge there has been no systematic effort to determine the optimum iron-containing precursor phase for producing active coal liquefaction catalysts, despite the fact that there are over ten iron-(hydroxy)oxide phases which can be easily synthesized in the laboratory. We have undertaken a systematic study to identify the most active iron-oxide catalyst precursor phases, the co-catalysts, and the coal pretreatments which will provide optimum yields in coal liquefaction processes.

  16. Results of catalyst testing using iron-based catalysts

    SciTech Connect

    Linehan, J.C.; Darab, J.G.; Matson, D.W.

    1993-03-01

    As coal liquefaction catalysts, iron-based products are generally inferior to the more expensive molybdenum, cobalt, or nickel-based materials. However, the lower costs of production and recovery (or in the case of some iron catalysts, non-recovery) give the iron-based materials a potential economic advantage over the more efficient precious and semi-precious metal catalysts for this application. Recent research has shown that a number of different iron-containing materials can be successfully utilized as coal liquefaction catalysts or as catalyst. Pyrrhotite (Fe[sub 1-x]S) or a similar iron-sulfide phase is commonly believed to be the active catalyst in coal liquefaction and model compound pyrolysis reactions, although no specific phase has been yet been isolated as the actual catalyst species. The active iron-containing catalyst is usually generated in situ from an iron-oxide precursor and an elemental sulfur source under reducing conditions in the reactor vessel. Most research has concentrated on the use of common iron-oxide phases such as hematite or goethite (and their derivatives) as the iron-bearing precursor, or on non-specific iron materials produced by the reaction of various iron salts and compounds in the coal or liquefaction reactor. To our knowledge there has been no systematic effort to determine the optimum iron-containing precursor phase for producing active coal liquefaction catalysts, despite the fact that there are over ten iron-(hydroxy)oxide phases which can be easily synthesized in the laboratory. We have undertaken a systematic study to identify the most active iron-oxide catalyst precursor phases, the co-catalysts, and the coal pretreatments which will provide optimum yields in coal liquefaction processes.

  17. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    PubMed

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-01-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation. PMID:25740709

  18. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado; Dugulan, A. Iulian; Nasalevich, Maxim A.; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A.; Koeken, Ard C. J.; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R.; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  19. Synthesis of highly dispersed and active palladium/carbon nanofiber catalyst for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Yue-Jiang; Yang, Hou-Hua; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2011-05-01

    Highly dispersed and active palladium/carbon nanofiber (Pd/CNF) catalyst is synthesized by NaBH4 reduction with trisodium citrate as the stabilizing agent. The obtained Pd/CNF catalyst is characterized by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The results show that the Pd nanoparticles with an average particle size of ca. 3.8 nm are highly dispersed on the CNF support even with a small ratio of citrate to Pd precursor, which is believed to be due to the pH adjustment of citrate stabilized colloidal Pd nanoparticles. The cyclic voltammetry and chronoamperometry techniques show that the obtained Pd/CNF catalyst exhibits good catalytic activity and stability for the electrooxidation of formic acid.

  20. Air Oxidation of Activated Carbon to Synthesize a Biomimetic Catalyst for Hydrolysis of Cellulose.

    PubMed

    Shrotri, Abhijit; Kobayashi, Hirokazu; Fukuoka, Atsushi

    2016-06-01

    Oxygenated carbon catalyzes the hydrolysis of cellulose present in lignocellulosic biomass by utilizing the weakly acidic functional groups on its surface. Here we report the synthesis of a biomimetic carbon catalyst by simple and economical air-oxidation of a commercially available activated carbon. Air- oxidation at 450-500 °C introduced 2000-2400 μmol g(-1) of oxygenated functional groups on the material with minor changes in the textural properties. Selectivity towards the formation of carboxylic groups on the catalyst surface increased with the increase in oxidation temperature. The degree of oxidation on carbon catalyst was found to be proportional to its activity for hydrolysis of cellulose. The hydrolysis of eucalyptus in the presence of carbon oxidized at 475 °C afforded glucose yield of 77 % and xylose yield of 67 %. PMID:27115288

  1. Catalyst activation, deactivation, and degradation in palladium-mediated Negishi cross-coupling reactions.

    PubMed

    Böck, Katharina; Feil, Julia E; Karaghiosoff, Konstantin; Koszinowski, Konrad

    2015-03-27

    Pd-mediated Negishi cross-coupling reactions were studied by a combination of kinetic measurements, electrospray-ionization (ESI) mass spectrometry, (31)P NMR and UV/Vis spectroscopy. The kinetic measurements point to a rate-determining oxidative addition. Surprisingly, this step seems to involve not only the Pd catalyst and the aryl halide substrate, but also the organozinc reagent. In this context, the ESI-mass spectrometric observation of heterobimetallic Pd-Zn complexes [L2 PdZnR](+) (L=S-PHOS, R=Bu, Ph, Bn) is particularly revealing. The inferred presence of these and related neutral complexes with a direct Pd-Zn interaction in solution explains how the organozinc reagent can modulate the reactivity of the Pd catalyst. Previous theoretical calculations by González-Pérez et al. (Organometallics- 2012, 31, 2053) suggest that the complexation by the organozinc reagent lowers the activity of the Pd catalyst. Presumably, a similar effect also causes the rate decrease observed upon addition of ZnBr2 . In contrast, added LiBr apparently counteracts the formation of Pd-Zn complexes and restores the high activity of the Pd catalyst. At longer reaction times, deactivation processes due to degradation of the S-PHOS ligand and aggregation of the Pd catalyst come into play, thus further contributing to the appreciable complexity of the title reaction. PMID:25709062

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

    PubMed

    Kondrat, Simon A; Smith, Paul J; Wells, Peter P; Chater, Philip A; Carter, James H; Morgan, David J; Fiordaliso, Elisabetta M; Wagner, Jakob B; Davies, Thomas E; Lu, Li; Bartley, Jonathan K; Taylor, Stuart H; Spencer, Michael S; Kiely, Christopher J; Kelly, Gordon J; Park, Colin W; Rosseinsky, Matthew J; Hutchings, Graham J

    2016-03-01

    Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable--and hence little known and largely ignored--georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions--a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts. PMID:26878237

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

    NASA Astrophysics Data System (ADS)

    Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.; Chater, Philip A.; Carter, James H.; Morgan, David J.; Fiordaliso, Elisabetta M.; Wagner, Jakob B.; Davies, Thomas E.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.; Rosseinsky, Matthew J.; Hutchings, Graham J.

    2016-03-01

    Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored—georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

  4. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    PubMed

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction. PMID:27433672

  5. Phytochemistry and biological activities of Phlomis species.

    PubMed

    Limem-Ben Amor, Ilef; Boubaker, Jihed; Ben Sgaier, Mohamed; Skandrani, Ines; Bhouri, Wissem; Neffati, Aicha; Kilani, Soumaya; Bouhlel, Ines; Ghedira, Kamel; Chekir-Ghedira, Leila

    2009-09-01

    The genus Phlomis L. belongs to the Lamiaceae family and encompasses 100 species native to Turkey, North Africa, Europe and Asia. It is a popular herbal tea enjoyed for its taste and aroma. Phlomis species are used to treat various conditions such as diabetes, gastric ulcer, hemorrhoids, inflammation, and wounds. This review aims to summarize recent research on the phytochemistry and pharmacological properties of the genus Phlomis, with particular emphasis on its ethnobotanical uses. The essential oil of Phomis is composed of four chemotypes dominated by monoterpenes (alpha-pinene, limonene and linalool), sesquiterpenes (germacrene D and beta-caryophyllene), aliphalic compounds (9,12,15-octadecatrienoic acid methyl ester), fatty acids (hexadecanoic acid) and other components (trans-phytol, 9,12,15-octadecatrien-1-ol). Flavonoids, iridoids and phenylethyl alcohol constitute the main compounds isolated from Phlomis extracts. The pharmacological activities of some Phlomis species have been investigated. They are described according to antidiabetic, antinociceptive, antiulcerogenic, protection of the vascular system, anti-inflammatory, antiallergic, anticancer, antimicrobial and antioxidant properties. PMID:19563875

  6. Commercial runs show TiO/sub 2/ Claus catalyst retains activity

    SciTech Connect

    Nougayrede, J.; Philippe, A.; Quesmerel, E.; Vermeersch, R.

    1987-08-10

    Commercial data are given for the CRS 31 Claus catalyst, jointly developed by Rhone Poulenc and Societe Nationale Elf Aquitane (Production) (SNEA). The data confirm laboratory results that show the catalyst's ability to deliver more complete hydrolysis in the first reactor of Claus sulfur recovery plants, and its ability to maintain activity in the second and third reactors. The most important losses in sulfur yields in Claus plants generally come from COS and CS/sub 2/ formed in the thermal steps of the process in the first reactor, and from the low Claus activity of alumina-based catalysts in the second and third reactors. In the first reactor, loaded with alumina-based catalyst, hydrolysis is only partial. Low Claus activity in second and third reactors is caused by the inevitable sulfation of the alumina. Catalytic-activity decrease of aluminas is caused particularly by the presence of oxygen, even in trace amounts, in the Claus gases. Therefore, in the first reactor, the CS/sub 2/ hydrolysis rate is lowered in the subsequent reactors, the H/sub 2/ + SO/sub 2/ conversion significantly drops. The chemical composition of CRS 31, TiO/sub 2/ only, in the same operating conditions, causes a significant improvement in activity because of its increased resistance to sulfation. The economics of the process are given.

  7. Rapid mechanochemical synthesis of VOx/TiO2 as highly active catalyst for HCB removal.

    PubMed

    Zhang, Shuzhen; Huang, Jun; Yang, Yang; Li, Yuancheng; Wang, Bin; Wang, Yujue; Deng, Shubo; Yu, Gang

    2015-12-01

    A rapid (1.5h) one-step ball milling (BM) method was developed to synthesize VOx/TiO2 (VTi-BM) and WOx or MoOx doped VOx/TiO2 (VWTi-BM or VMoTi-BM). Catalytic activity on gaseous POPs removal was tested using hexachlorobenzene (HCB) as surrogate. Catalytic performance decreased in the order of VWTi-BM (T50%=230°C)>VMoTi-BM (260°C)>VTi-BM (270°C)>VTi-WI (300°C; VOx/TiO2 synthesized by wetness impregnation method). The intermediates from oxidation of HCB were analyzed by off gas analysis, from which 2,2,4,5-tetrachloro-4-cyclopentene-1,3-dione (TCCD), dichloromaleic anhydride (DCMA) and tetrachloro-1,4-bezoquinone (TCBQ) were identified. Furthermore, a possible mechanism for the oxidation of HCB over VOx/TiO2 catalysts was proposed. Mechanism studies showed that BM samples possess better dispersion of the VOx species and more surface chemisorbed oxygen. Doping WOx or MoOx into VOx/TiO2 by ball milling can further enhance catalytic performance by increasing surface acid sites. PMID:26218787

  8. Evidences of the presence of different types of active sites for the oxygen reduction reaction with Fe/N/C based catalysts

    NASA Astrophysics Data System (ADS)

    Pérez-Alonso, Francisco J.; Domínguez, Carlota; Al-Thabaiti, Shaeel A.; Al-Youbi, Abdulrahman O.; Abdel Salam, Mohamed; Alshehri, Abdulmohsen A.; Retuerto, María; Peña, Miguel A.; Rojas, Sergio

    2016-09-01

    Fe/N/C catalysts are very active for the oxygen reduction reaction (ORR); however, the nature of the active site(s) is not fully understood. In this work, we study the performance of different types of N/C and Fe/N/C catalysts for the ORR, and the effect of the addition of NaCN. Phthalocyanine and graphene have been studied as model metal-free catalysts for the ORR. Fe-phthalocyanine (FePhcy), Fe-phthalocyanine dispersed in graphene (FePhcy/G) and Fe/N/G, have been used as model Fe-containing catalysts. FePhcy and FePhcy/G only contain Fe atoms coordinated to 4 nitrogen atoms. On the other hand, different species such as Fe-Nx and Fe3C coexist in Fe/N/G. In addition, Csbnd C ensembles are present in the graphene present in FePhcy/G and Fe/N/G. The ORR activity is characteristic of each catalyst, being the highest for the catalysts containing FeN4 ensembles. The addition of CN- results in the selective poisoning of the Fe-containing sites but it does not suppress the ORR activity of the Graphene containing samples. In-situ infrared spectroscopy studies during the ORR reveal that CN- poisoning of the Fe sites is reversible, desorbing at potentials less positive than ca. 600 mV. As a consequence, the ORR activity of the Fe-containing sites is recovered gradually.

  9. Morphology and activity of vanadium-containing catalysts for the selective oxidation of benzene to maleic anhydride

    NASA Astrophysics Data System (ADS)

    Dosumov, K.; Ergazieva, G. E.

    2012-11-01

    The morphology and activity of vanadium catalysts are studied using a number of physicochemical methods: electron microscopy, electron paramagnetic resonance, and infrared spectroscopy. It is found that the active agent of the conversion of benzene to maleic anhydride over modified vanadium catalysts is the V4+ ion in the vanadyl configuration.

  10. Structure-activity relationship of Au-ZrO2 catalyst on formation of hydroxyl groups and its influence on CO oxidation

    SciTech Connect

    Karwacki, Christopher J; Ganesh, Panchapakesan; Kent, P. R. C.; Gordon, Wesley O; Peterson, Gregory W; Niu, Jun Jie; Gogotsi, Yury G.

    2013-01-01

    The effect of changes in morphology and surface hydroxyl species upon thermal treatment of zirconia on the oxidation activity of Au/ZrO2 catalyst was studied. We observed using transmission Fourier transform infrared (FTIR) spectroscopy progressive changes in the presence of monodentate (type I), bidentate (type II) and hydrogen bridged species (type III) for each of the thermally treated (85 to 500 C) supports consisting of bare zirconia and Au/ZrO2 catalysts. Furthermore, structural changes in zirconia were accompanied by an increase in crystal size (7 to 58 nm) and contraction of the supports porosity (SSA 532 to 7 m2 g 1) with increasing thermal treatment. Deposition of gold nanoparticles under similar preparation conditions on different thermally treated zirconia resulted in changes in the mean gold cluster size, ranging from 3.7 to 5.6 nm. Changes in the surface hydroxyl species, support structure and size of the gold centers are important parameters responsible for the observed decrease (>90%) in CO conversion activity for the Au/ZrO2 catalysts. Density functional theory calculations provide evidence of increased CO binding to Au nanoclusters in the presence of surface hydroxyls on zirconia, which increases charge transfer at the perimeter of the gold nanocluster on zirconia support. This further helps in reducing a model CO-oxidation reaction barrier in the presence of surface hydroxyls. This work demonstrates the need to understand the structure activity relationship of both the support and active particles for the design of catalytic materials.

  11. Structure–activity relationship of Au/ZrO2 catalyst on formation of hydroxyl groups and its influence on CO oxidation

    SciTech Connect

    Karwacki, Christopher J.; Ganesh, P.; Kent, Paul R. C.; Gordon, Wesley O.; Peterson, Gregory W.; Niu, Jun Jie; Gogotsi, Yury

    2013-01-01

    The effect of changes in morphology and surface hydroxyl species upon thermal treatment of zirconia on the oxidation activity of Au/ZrO2 catalyst was studied. We observed using transmission fourier transform infrared (FTIR) spectroscopy progressive changes in the presence of monodentate (type I), bidentate (type II) and hydrogen bridged species (type III) for each of the thermally treated (85 to 500 C) supports consisting of bare zirconia and Au/ZrO2 catalysts. Furthermore, structural changes in zirconia were accompanied by an increase in crystal size (7 to 58 nm) and contraction of the supports porosity (SSA 532 to 7 m2/g) with increasing thermal treatment. Deposition of gold nanoparticles under similar preparation conditions on different thermally treated zirconia resulted in changes in the mean gold cluster size, ranging from 3.7 to 5.6 nm. Changes in the surface hydroxyl species, support structure and size of the gold centers are important parameters responsible for the observed decrease (> 90 %) in CO conversion activity for the Au/ZrO2 catalysts. Density functional theory calculations provide evidence of increased CO binding to Au nanoclusters in the presence of surface hydroxyls on zirconia, which increases charge transfer at the perimeter of the gold nanocluster on zirconia support. This further helps in reducing a model CO-oxidation reaction barrier in the presence of surface hydroxyls. This work demonstrates the need to understand the structure-activity relationship of both the support and active particles for the design of catalytic materials.

  12. Highly Active Carbon Supported Pd-Ag Nanofacets Catalysts for Hydrogen Production from HCOOH.

    PubMed

    Wang, Wenhui; He, Ting; Liu, Xuehua; He, Weina; Cong, Hengjiang; Shen, Yangbin; Yan, Liuming; Zhang, Xuetong; Zhang, Jinping; Zhou, Xiaochun

    2016-08-17

    Hydrogen is regarded as a future sustainable and clean energy carrier. Formic acid is a safe and sustainable hydrogen storage medium with many advantages, including high hydrogen content, nontoxicity, and low cost. In this work, a series of highly active catalysts for hydrogen production from formic acid are successfully synthesized by controllably depositing Pd onto Ag nanoplates with different Ag nanofacets, such as Ag{111}, Ag{100}, and the nanofacet on hexagonal close packing Ag crystal (Ag{hcp}). Then, the Pd-Ag nanoplate catalysts are supported on Vulcan XC-72 carbon black to prevent the aggregation of the catalysts. The research reveals that the high activity is attributed to the formation of Pd-Ag alloy nanofacets, such as Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp}. The activity order of these Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}. Particularly, the activity of Pd-Ag{hcp} is up to an extremely high value, i.e., TOF{hcp} = 19 000 ± 1630 h(-1) at 90 °C (lower limit value), which is more than 800 times higher than our previous quasi-spherical Pd-Ag alloy nanocatalyst. The initial activity of Pd-Ag{hcp} even reaches (3.13 ± 0.19) × 10(6) h(-1) at 90 °C. This research not only presents highly active catalysts for hydrogen generation but also shows that the facet on the hcp Ag crystal can act as a potentially highly active catalyst. PMID:27454194

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

    PubMed

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

    2016-09-01

    The application of catalytically coated metallic foams in catalytic processes has a high potential for exothermic catalytic reactions such as CO2 methanation or Fischer-Tropsch synthesis due to good heat conductivity, improved turbulent flow properties and high catalyst efficiencies. But the preparation of homogenous catalyst coats without pore blocking is challenging with conventional wash coating techniques. Here, we report on a stable and additive free colloidal CoAlOOH suspension (sol) for the preparation of catalytically active Co/Al2O3 xerogel catalysts and coatings. Powders with 18wt% Co3O4 prepared from this additive free synthesis route show a catalytic activity in Fischer-Tropsch synthesis and CO2 methanation which is similar to a catalyst prepared by incipient wetness impregnation (IWI) after activating the material under flowing hydrogen at 430°C. Yet, the xerogel catalyst exhibits a much higher thermal stability as compared to the IWI catalyst, as demonstrated in catalytic tests after different heat agings between 430°C and 580°C. It was also found that the addition of polyethylene glycol (PEG) to the sol influences the catalytic properties of the formed xerogels negatively. Only non-reducible cobalt spinels were formed from a CoAlOOH sol with 20wt% PEG. Metallic foams with pores sizes between 450 and 1200μm were coated with the additive free CoAlOOH sol, which resulted in homogenous xerogel layers. First catalytic tests of the coated metal foams (1200μm) showed good performance in CO2 methanation. PMID:27240245

  14. Antimicrobial activities of some Euphorbia species.

    PubMed

    Kirbag, Sevda; Erecevit, Pınar; Zengin, Fikriye; Guvenc, Ayşe Nilay

    2013-01-01

    In this study, the antimicrobial activities of methanolic extracts and latex of some Euphorbia species used for medical purposes in Turkey were investigated. The extracts of Euphorbia aleppica L., Euphorbia szovitsii Fisch.&Mey. var. harputensis Aznav. ex M. S. Khan, Euphorbia falcata L. sub. falcata var. falcata, Euphorbia denticulata Lam., Euphorbia macroclada Boiss., Euphorbia cheiradenia Boiss.&Hohen, Euphorbia virgata Waldst.&Kit., Euphorbia petiolata Banks&Sol. were prepared with methanol. The antimicrobial activities of these extracts were examined on test microorganisms as follows: Staphylococcus aureus COWAN 1, Bacillus megaterium DSM 32, Proteus vulgaris FMC 1, Klebsiella pneumonia FMC 5, Escherichia coli ATCC 25922, Pseudomonas aeruginosa DSM 50071, Candida albicans FMC 17, Candida glabrata ATCC 66032, Epidermophyton sp. and Trichophyton sp. by the disc diffusion methods and well agar method. The MIC values of extracts were determined according to the broth microdulitions method. Results indicated that extracts of Euphorbia species inhibited the growth of tested microorganisms in the different ratio. Also, the MIC values of extracts were determined as 31,2-1000 µg. PMID:24311840

  15. Impact of transition metal on nitrogen retention and activity of iron-nitrogen-carbon oxygen reduction catalysts.

    PubMed

    Ganesan, Selvarani; Leonard, Nathaniel; Barton, Scott Calabrese

    2014-03-14

    Iron based nitrogen doped carbon (FeNC) catalysts are synthesized by high-pressure pyrolysis of carbon and melamine with varying amounts of iron acetate in a closed, constant-volume reactor. The optimum nominal amount of Fe (1.2 wt%) in FeNC catalysts is established through oxygen reduction reaction (ORR) polarization. Since the quantity of iron used in FeNCs is very small, the amount of Fe retained in FeNC catalysts after leaching is determined by UV-VIS spectroscopy. As nitrogen is considered to be a component of active sites, the amount of bulk and surface nitrogen retention in FeNC catalysts are measured using elemental analysis and X-ray photoelectron spectroscopy, respectively. It is found that increasing nominal Fe content in FeNC catalysts leads to a decreased level of nitrogen retention. Thermogravimetric analysis demonstrates that increasing nominal Fe content leads to increased weight loss during pyrolysis, particularly at high temperatures. Catalysts are also prepared in the absence of iron source, and with iron removed by washing with hot aqua regia post-pyrolysis. FeNC catalysts prepared with no Fe show high retained nitrogen content but poor ORR activity, and aqua regia washed catalysts demonstrate similar activity to Fe-free catalysts, indicating that Fe is an active site component. PMID:24457909

  16. The leguminous species Anthyllis vulneraria as a Zn-hyperaccumulator and eco-Zn catalyst resources.

    PubMed

    Grison, Claire M; Mazel, Marine; Sellini, Amandine; Escande, Vincent; Biton, Jacques; Grison, Claude

    2015-04-01

    Anthyllis vulneraria was highlighted here as a Zn-hyperaccumulator for the development of a pilot phytoextraction process in the mine site of Les Avinières in the district of Saint-Laurent-Le-Minier. A. vulneraria appeared to hyperaccumulate the highest concentration of Zn in shoots with a better metal selectivity relative to Cd and Pb than the reference Zn-hyperaccumulator Noccea caerulescens. A bigger biomass production associated to a higher Zn concentration conducted A. vulneraria to the highest total zinc gain per hectare per year. As a legume, A. vulneraria was infected by rhizobia symbionts. Inoculation of A. vulneraria seeds showed a positive impact on Zn hyperaccumulation. A large-scale culture process of symbiotic rhizobia of A. vulneraria was investigated and optimized to allow large-scale inoculation process. Contaminated shoots of A. vulneraria were not considered as wastes and were recovered as Eco-Zn catalyst in particular, examples of organic synthesis, electrophilic aromatic substitution. Eco-Zn catalyst was much more efficient than conventional catalysts and allowed greener chemical processes. PMID:25253057

  17. Alkene Isomerization Using a Solid Acid as Activator and Support for a Homogeneous Catalyst

    ERIC Educational Resources Information Center

    Seen, Andrew J.

    2004-01-01

    An upper-level undergraduate experiment that, in addition to introducing students to catalysis using an air sensitive transition-metal complex, introduces the use of a solid acid as an activator and support for the catalyst is developed. The increased stability acquired in the course of the process affords the opportunity to characterize the…

  18. The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.; Cole, F.

    1992-11-01

    An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  19. The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.; Cole, F.

    1992-01-01

    An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  20. Graphene-supported hemin as a highly active biomimetic oxidation catalyst.

    PubMed

    Xue, Teng; Jiang, Shan; Qu, Yongquan; Su, Qiao; Cheng, Rui; Dubin, Sergey; Chiu, Chin-Yi; Kaner, Richard; Huang, Yu; Duan, Xiangfeng

    2012-04-16

    Well supported: stable hemin-graphene conjugates formed by immobilization of monomeric hemin on graphene, showed excellent catalytic activity, more than 10 times better than that of the recently developed hemin-hydrogel system and 100 times better than that of unsupported hemin. The catalysts also showed excellent binding affinities and catalytic efficiencies approaching that of natural enzymes. PMID:22368046

  1. Ligand-free Heck reaction: Pd(OAc)2 as an active catalyst revisited.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Yang, Zhi

    2003-09-19

    Palladium acetate was shown to be an extremely active catalyst for the Heck reaction of aryl bromides. Both the base and the solvent were found to have a fundamental influence on the efficiency of the reaction, with K(3)PO(4) and N,N-dimethylacetamide being the optimal base and solvent, respectively. PMID:12968913

  2. PREPARATION, CHARACTERIZATION AND ACTIVITY OF AL2O3-SUPPORTED V2O5 CATALYSTS

    EPA Science Inventory

    A series of activated alumina supported vanadium oxide catalysts with various V2O5 loadings ranging from 5 to 25 wt% has been prepared by wet impregnation technique. A combination of various physico-chemical techniques such as BET surface areas, oxygen chemisorption, X-ray diffra...

  3. Active sites for NO reduction over Fe-ZSM-5 catalysts.

    PubMed

    Schwidder, M; Santhosh Kumar, M; Brückner, A; Grünert, W

    2005-02-14

    A study of Fe-ZSM-5 catalysts with variable amounts of isolated, oligomeric and heavily aggregated Fe3+ oxo sites (as evidenced by UV-Vis and EPR spectroscopic data) and their catalytic properties in the selective catalytic reduction of NO by isobutane or by NH3 is presented, which allows development of a unified concept of the active Fe sites in these reactions, according to which isolated Fe sites catalyse both SCR reactions while oligomeric sites, though also involved in the selective reduction path, limit the catalyst performance by causing the total oxidation of the reductant. PMID:15685345

  4. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    PubMed

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism. PMID:24025780

  5. A packed bed membrane reactor for production of biodiesel using activated carbon supported catalyst.

    PubMed

    Baroutian, Saeid; Aroua, Mohamed K; Raman, Abdul Aziz A; Sulaiman, Nik M N

    2011-01-01

    In this study, a novel continuous reactor has been developed to produce high quality methyl esters (biodiesel) from palm oil. A microporous TiO2/Al2O3 membrane was packed with potassium hydroxide catalyst supported on palm shell activated carbon. The central composite design (CCD) of response surface methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst amount and cross flow circulation velocity on the production of biodiesel in the packed bed membrane reactor. The highest conversion of palm oil to biodiesel in the reactor was obtained at 70 °C employing 157.04 g catalyst per unit volume of the reactor and 0.21 cm/s cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. High quality palm oil biodiesel was produced by combination of heterogeneous alkali transesterification and separation processes in the packed bed membrane reactor. PMID:20888219

  6. Novel catalysts for methane activation. Quarterly report No. 3, April 1, 1993--June 30, 1993

    SciTech Connect

    Hirschon, A.S.; Malhotra, R.; Wilson, R.B.

    1993-08-31

    The objectives of this project are to test novel fullerene based catalysts for application in methane activation. Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane conversion to higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with the synthesis and characterization of the fullerenes and fullerene soots, Task 2 with the testing of the catalysts, and Task 3 with the evaluation of the results and technical reporting requirements. This quarter we prepared fuuerene soot and metallized fullerene soot and rebuilt our experimental testing system to be more suitable for the evaluation of the catalysts. The results and accomplishments are presented.

  7. Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters

    SciTech Connect

    Esswein, AJ; Surendranath, Y; Reece, SY; Nocera, DG

    2011-02-01

    A high surface area electrode is functionalized with cobalt-based oxygen evolving catalysts (Co-OEC = electrodeposited from pH 7 phosphate, Pi, pH 8.5 methylphosphonate, MePi, and pH 9.2 borate electrolyte, Bi). Co-OEC prepared from MePi and operated in Pi and Bi achieves a current density of 100 mA cm(-2) for water oxidation at 442 and 363 mV overpotential, respectively. The catalyst retains activity in near-neutral pH buffered electrolyte in natural waters such as those from the Charles River (Cambridge, MA) and seawater (Woods Hole, MA). The efficacy and ease of operation of anodes functionalized with Co-OEC at appreciable current density together with its ability to operate in near neutral pH buffered natural water sources bodes well for the translation of this catalyst to a viable renewable energy storage technology.

  8. Toward Design of Synergistically Active Carbon-Based Catalysts for Electrocatalytic Hydrogen Evolution

    PubMed Central

    2015-01-01

    Replacement of precious Pt catalyst with cost-effective alternatives would be significantly beneficial for hydrogen production via electrocatalytic hydrogen evolution reaction (HER). All candidates thus far are exclusively metallic catalysts, which suffer inherent corrosion and oxidation susceptibility during acidic proton-exchange membrane electrolysis. Herein, based on theoretical predictions, we designed and synthesized nitrogen (N) and phosphorus (P) dual-doped graphene as a nonmetallic electrocatalyst for sustainable and efficient hydrogen production. The N and P heteroatoms could coactivate the adjacent C atom in the graphene matrix by affecting its valence orbital energy levels to induce a synergistically enhanced reactivity toward HER. As a result, the dual-doped graphene showed higher electrocatalytic HER activity than single-doped ones and comparable performance to some of the traditional metallic catalysts. PMID:24779586

  9. Activity and structure of perovskites as diesel reforming catalysts for solid oxide fuel cells.

    SciTech Connect

    Liu, D.-J.; Krumpelt, M.; Chemical Engineering

    2005-01-01

    Recent progress in developing perovskite materials as more cost-effective catalysts in autothermal reforming (ATR) of diesel fuel to hydrogen-rich reformate for solid oxide fuel cell (SOFC) application is reported. Perovskite-type metal oxides with B sites partially exchanged by ruthenium were prepared and evaluated under ATR reaction conditions. The hydrogen yield, reforming efficiency, and CO{sub x} selectivity of these catalysts were investigated using diesel surrogate fuel with 50 ppm sulfur. The catalyst performances have approached or exceeded a benchmark, high-cost rhodium-based material. In parallel with the reactivity study, we also investigated the physical properties of B-site doped perovskites and their impact on the reforming performance using various characterization techniques such as BET, X-ray powder diffraction, temperature programmable reduction, scanning electron microscopy, and synchrotron X-ray absorption spectroscopy. We found that ruthenium is highly dispersed into perovskite lattice and its redox behavior is directly associated with reforming activity.

  10. Atmospheric-Pressure DBD Cold Plasma for Preparation of High Active Au/P25 Catalysts for Low-Temperature CO Oxidation

    NASA Astrophysics Data System (ADS)

    Di, Lanbo; Zhan, Zhibin; Zhang, Xiuling; Qi, Bin; Xu, Weijie

    2016-05-01

    Cold plasma generated by dielectric barrier discharge (DBD) at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts (Au/P25-P) with the assistance of the deposition-precipitation procedure. The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated. CO oxidation was performed to investigate the catalytic activity of the Au/P25 catalysts. The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process, and Au/P25-P (4 min) exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies. In order to form more oxygen vacancies active species, Au/P25-P was calcined to obtain Au/P25-PC catalysts. Interestingly, Au/P25-PC exhibited the highest activity for CO oxidation among the Au/P25 samples. The results of transmission electron microscopy (TEM) indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC. Atmospheric-pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts. supported by National Natural Science Foundation of China (Nos. 11505019, 21173028), the Science and Technology Research Project of Liaoning Provincial Education Department (No. L2013464), the Scientific Research Foundation for the Doctor of Liaoning Province (No. 20131004), and the Dalian Jinzhou New District Science and Technology Plan Project (No. KJCX-ZTPY-2014-0001)

  11. The selectivity and activity of catalyst for CO hydrogenation to methanol and hydrocarbon: A comparative study on Cu, Co and Ni surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Jingbo; Kawazoe, Yoshiyuki; Sun, Qiang; Chan, Siewhwa; Su, Haibin

    2016-03-01

    Typical Fischer-Tropsch catalysts display different selectivity and activity in catalyzing CO hydrogenation to diverse products. In this work, the preferable routes for CH3OH formation on Cu, chain growth on Co and CH4 formation on Ni are identified guided by the comprehensive reaction network that is mapped out by density function theory calculations. The difference in selectivity among catalysts is controlled delicately by several reactions, including CH3O + H ↔ CH3OH, CH3 + H ↔ CH4 and CH2 + CO ↔ CH2CO. The equilibrium shifts of CH2O + H ↔ CH3O and CH2 + H ↔ CH3 also make an impact on selectivity. The distinct selectivity can be understood further with the activity of catalysts. Our results show that the ability of surface to absorb species increases in the order Cu < Ni < Co. Generally, Cu catalyzes the association reaction better than Co and Ni, while Co facilitates the dissociation reaction. Two key factors, thermodynamic effect and kinetic effect, are identified in determining the activity of catalyst. We proof that surface with strong binding capability promotes the dissociation reaction, meanwhile impedes the association reaction when the thermodynamic effect is dominant in determining the barrier height. The Brønsted-Evans-Polanyi relation is observed for C-O bond breaking reactions. In addition, kinetic effect also affects the barrier when special transition state exists. The tilt of CO at the transition state for COH formation and chain growth reactions introduces the interaction of atom O with surface. The stronger binding of atom O on Co is crucial to branch the selectivity of Co to chain growth rather than methane. Present study provides a comprehensive picture on the activity and selectivity of catalysts, which is the essential to develop novel catalyst for syngas conversion.

  12. Method of treating intermetallic alloy hydrogenation/oxidation catalysts for improved impurity poisoning resistance, regeneration and increased activity

    DOEpatents

    Wright, R.B.

    1992-01-14

    Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation). 23 figs.

  13. Pt5Gd as a highly active and stable catalyst for oxygen electroreduction.

    PubMed

    Escudero-Escribano, María; Verdaguer-Casadevall, Arnau; Malacrida, Paolo; Grønbjerg, Ulrik; Knudsen, Brian P; Jepsen, Anders K; Rossmeisl, Jan; Stephens, Ifan E L; Chorkendorff, Ib

    2012-10-10

    The activity and stability of Pt(5)Gd for the oxygen reduction reaction (ORR) have been studied, using a combination of electrochemical measurements, angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and density functional theory calculations. Sputter-cleaned, polycrystalline Pt(5)Gd shows a 5-fold increase in ORR activity, relative to pure Pt at 0.9 V, approaching the most active in the literature for catalysts prepared in this way. AR-XPS profiles after electrochemical measurements in 0.1 M HClO(4) show the formation of a thick Pt overlayer on the bulk Pt(5)Gd, and the enhanced ORR activity can be explained by means of compressive strain effects. Furthermore, these novel bimetallic electrocatalysts are highly stable, which, in combination with their enhanced activity, makes them very promising for the development of new cathode catalysts for fuel cells. PMID:22998588

  14. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

    DOE PAGESBeta

    Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; Zegkinoglou, Ioannis; Sinev, Ilya; Choi, Yong-Wook; Kisslinger, Kim; Stach, Eric A.; Yang, Judith C.; Strasser, Peter; et al

    2016-06-30

    There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides aremore » surprisingly resistant to reduction and copper+ species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper+ is key for lowering the onset potential and enhancing ethylene selectivity.« less

  15. Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane.

    PubMed

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

    2012-11-01

    LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance. PMID:23039114

  16. Synthesis, characterization and catalytic activity of carbon-silica hybrid catalyst from rice straw

    NASA Astrophysics Data System (ADS)

    Janaun, J.; Safie, N. N.; Siambun, N. J.

    2016-07-01

    The hybrid-carbon catalyst has been studied because of its promising potential to have high porosity and surface area to be used in biodiesel production. Silica has been used as the support to produce hybrid carbon catalyst due to its mesoporous structure and high surface area properties. The chemical synthesis of silica-carbon hybrid is expensive and involves more complicated preparation steps. The presence of natural silica in rice plants especially rice husk has received much attention in research because of the potential as a source for solid acid catalyst synthesis. But study on rice straw, which is available abundantly as agricultural waste is limited. In this study, rice straw undergone pyrolysis and functionalized using fuming sulphuric acid to anchor -SO3H groups. The presence of silica and the physiochemical properties of the catalyst produced were studied before and after sulphonation. The catalytic activity of hybrid carbon silica acid catalyst, (H-CSAC) in esterification of oleic acid with methanol was also studied. The results showed the presence of silica-carbon which had amorphous structure and highly porous. The carbon surface consisted of higher silica composition, had lower S element detected as compared to the surface that had high carbon content but lower silica composition. This was likely due to the fact that Si element which was bonded to oxygen was highly stable and unlikely to break the bond and react with -SO3H ions. H-CSAC conversions were 23.04 %, 35.52 % and 34.2 7% at 333.15 K, 343.15 K and 353.15 K, respectively. From this research, rice straw can be used as carbon precursor to produce hybrid carbon-silica catalyst and has shown catalytic activity in biodiesel production. Rate equation obtained is also presented.

  17. A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

    PubMed Central

    Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

    2011-01-01

    Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

  18. Enhanced activity of urea electrooxidation on nickel catalysts supported on tungsten carbides/carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Du, Tingting; Cheng, Jin; Xie, Xing; Yang, Bolun; Li, Mingtao

    2015-04-01

    Nickel nanoparticles with tungsten carbides supported on the multi-walled carbon nanotubes, noted as Ni-WC/MWCNT catalyst, is prepared through an impregnation method and used for the electrooxidation of urea in alkaline conditions. The micro-morphology and composition of the Ni-WC/MWCNT particles are determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The electrooxidation activity and conductivity of the catalyst are investigated by cyclic voltammetry and electrochemical impedance spectroscopy, respectively. Characterization results indicate that the Ni nanoparticles are uniformly distributed on the WC/MWCNT framework, and the Ni-WC/MWCNT catalyst shows an improved activity for the urea electrooxidation. The current densities of Ni-WC/MWCNT are over 3 times and 15 times higher than those of the Ni-WC/C and Ni/C catalysts, respectively, and the electrochemical impedance also decreases markedly. The higher activity on Ni-WC/MWCNT is attributed to the support effect of MWCNT as well as the synergistic effect between Ni and WC.

  19. Electrochemical catalyst recovery method

    DOEpatents

    Silva, L.J.; Bray, L.A.

    1995-05-30

    A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

  20. Electrochemical catalyst recovery method

    DOEpatents

    Silva, Laura J.; Bray, Lane A.

    1995-01-01

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

  1. In situ-generated metal oxide catalyst during CO oxidation reaction transformed from redox-active metal-organic framework-supported palladium nanoparticles

    PubMed Central

    2012-01-01

    The preparation of redox-active metal-organic framework (ra-MOF)-supported Pd nanoparticles (NPs) via the redox couple-driven method is reported, which can yield unprotected metallic NPs at room temperature within 10 min without the use of reducing agents. The Pd@ra-MOF has been exploited as a precursor of an active catalyst for CO oxidation. Under the CO oxidation reaction condition, Pd@ra-MOF is transformed into a PdOx-NiOy/C nanocomposite to generate catalytically active species in situ, and the resultant nanocatalyst shows sustainable activity through synergistic stabilization. PMID:22898143

  2. A highly active water-soluble cross-coupling catalyst based on dendritic polyglycerol N-heterocyclic carbene palladium complexes.

    PubMed

    Meise, Markus; Haag, Rainer

    2008-01-01

    A new water-soluble polyglycerol derivative functionalized with N-heterocyclic carbene palladium complexes was prepared and applied as catalyst for Suzuki cross-coupling reactions in water. The complex displays a metal loading of around 65 metal centers per dendrimeric molecule, which is estimated to contain 130 chelating groups and thus corresponds approximately to the formation of 2:1 NHC/metal complexes. Monomeric analogues were also synthesized to validate the reactivity of the dendritic catalyst. Both types of catalysts were tested with various aryl bromides and arylboronic acids. Turnover frequencies of up to 2586 h(-1) at 80 degrees C were observed with the dendritic catalyst along with turnover numbers of up to 59 000, which are among the highest turnover numbers reported for polymer-supported catalysts in neat water. The dendritic catalyst could be used (reused) in five consecutive reactions without loss in activity. PMID:18702166

  3. In situ generated highly active copper oxide catalysts for the oxygen evolution reaction at low overpotential in alkaline solutions.

    PubMed

    Liu, Xiang; Cui, Shengsheng; Qian, Manman; Sun, Zijun; Du, Pingwu

    2016-04-25

    Developing efficient water oxidation catalysts made up of earth-abundant elements has attracted much attention as a step toward for future clean energy production. Herein we report a simple one-step method to generate a low cost copper oxide catalyst film in situ from a copper(ii) ethylenediamine complex. The resulting catalyst has excellent activity toward the oxygen evolution reaction in alkaline solutions. A catalytic current density of 1.0 mA cm(-2) and 10 mA cm(-2) for the catalyst film requires the overpotentials of only ∼370 mV and ∼475 mV in 1.0 M KOH, respectively. This catalytic performance shows that the new catalyst is one of the best Cu-based heterogeneous OER catalysts to date. PMID:27020763

  4. Low-temperature catalyst activator: mechanism of dense carbon nanotube forest growth studied using synchrotron radiation

    PubMed Central

    Takashima, Akito; Izumi, Yudai; Ikenaga, Eiji; Ohkochi, Takuo; Kotsugi, Masato; Matsushita, Tomohiro; Muro, Takayuki; Kawabata, Akio; Murakami, Tomo; Nihei, Mizuhisa; Yokoyama, Naoki

    2014-01-01

    The mechanism of the one-order-of-magnitude increase in the density of vertically aligned carbon nanotubes (CNTs) achieved by a recently developed thermal chemical vapor deposition process was studied using synchrotron radiation spectroscopic techniques. In the developed process, a Ti film is used as the underlayer for an Fe catalyst film. A characteristic point of this process is that C2H2 feeding for the catalyst starts at a low temperature of 450°C, whereas conventional feeding temperatures are ∼800°C. Photoemission spectroscopy using soft and hard X-rays revealed that the Ti underlayer reduced the initially oxidized Fe layer at 450°C. A photoemission intensity analysis also suggested that the oxidized Ti layer at 450°C behaved as a support for nanoparticle formation of the reduced Fe, which is required for dense CNT growth. In fact, a CNT growth experiment, where the catalyst chemical state was monitored in situ by X-ray absorption spectroscopy, showed that the reduced Fe yielded a CNT forest at 450°C. Contrarily, an Fe layer without the Ti underlayer did not yield such a CNT forest at 450°C. Photoemission electron microscopy showed that catalyst annealing at the conventional feeding temperature of 800°C caused excess catalyst agglomeration, which should lead to sparse CNTs. In conclusion, in the developed growth process, the low-temperature catalyst activation by the Ti underlayer before the excess Fe agglomeration realised the CNT densification. PMID:25075343

  5. In-situ Moessbauer Spectroscopy of Supported Iron Fischer-Tropsch Catalysts During Activation

    SciTech Connect

    Motjope, Thato R.; Dlamini, Thulani H.

    2005-04-26

    The behavior of Fe based catalysts supported on ZrO2, SiO2, {gamma}-Al2O3, CeO2 and TiO2 during calcination, reduction and FT synthesis have been studied via in situ Moessbauer spectroscopy. It was found that the type of metal support interaction i.e. surface migration or bulk diffusion during calcination was dependant on the type of support used. Surface migration of Fe3+ during calcination was dominant for ZrO2, CeO2 and {gamma}-Al2O3 and this resulted in the sintering of {alpha}-Fe2O3 crystallites. Whereas bulk diffusion was observed mainly for the catalysts prepared using SiO2 and TiO2, causing a stabilization of the small crystallites of Fe3+ that interacted strongly with the support. Upon reduction, the large crystallites of {alpha}-Fe2O3 were found to reduce readily compared to the small crystallites of Fe3+, except for the catalyst prepared using {gamma}-Al2O3, as a support, where the presence of Al3+ resulted in the formation of spinel like species with the formula (Fe{sup 3+}{sub 2-x}Al{sup 3+}{sub x}Fe{sup 2+})O{sub 4} which are resistant to reduction. Upon exposure to synthesis gas, it was found that catalysts supported on ZrO2 and CeO2 carburized readily resulting in the formation of circa 80% {chi}-Fe2.5C. From this study it was observed that {gamma}-Al2O3 is not the preferred support for Fe based FT catalysts, as it forms the least amount of Fe carbides during FT synthesis.

  6. Influence of liquid medium on the activity of a low-alpha Fischer-Tropsch catalyst

    SciTech Connect

    Gormley, R.J.; Zarochak, M.F.; Deffenbaugh, P.W.; Rao, K.R.P.M.

    1995-12-31

    The purpose of this research was to measure activity, selectivity, and the maintenance of these properties in slurry autoclave experiments with a Fischer-Tropsch (FT) catalyst that was used in the {open_quotes}FT II{close_quotes} bubble-column test, conducted at the Alternative Fuels Development Unit (AFDU) at LaPorte, Texas during May 1994. The catalyst contained iron, copper, and potassium and was formulated to produce mainly hydrocarbons in the gasoline range with lesser production of diesel-range products and wax. The probability of chain growth was thus deliberately kept low. Principal goals of the autoclave work have been to find the true activity of this catalyst in a stirred tank reactor, unhindered by heat or mass transfer effects, and to obtain a steady conversion and selectivity over the approximately 15 days of each test. Slurry autoclave testing of the catalyst in heavier waxes also allows insight into operation of larger slurry bubble column reactors. The stability of reactor operation in these experiments, particularly at loadings exceeding 20 weight %, suggests the likely stability of operations on a larger scale.

  7. Catalyst suppliers consolidate further, offer more catalysts

    SciTech Connect

    Rhodes, A.K.

    1995-10-02

    The list of suppliers of catalysts to the petroleum refining industry has decreased by five since Oil and Gas Journal`s survey of refining catalysts and catalytic additives was last published. Despite the consolidation, the list of catalyst designations has grown to about 950 in this latest survey, compared to 820 listed in 1993. The table divides the catalysts by use and gives data on their primary differentiating characteristics, feedstock, products, form, bulk density,catalyst support, active agents, availability, and manufactures.

  8. Study of the active surface on titanium oxide catalysts for the oxidation of hydrogen sulfide

    SciTech Connect

    Khanmamedov, T.K.; Kalinkin, A.V.; Rakhimova, N.R.

    1989-02-01

    A study was carried out on the change in the composition of a Ti-Mo-W catalyst depending on the conditions for their treatment by H/sub 2/S-SO/sub 2/ and H/sub 2/S-O/sub 2/ gas mixtures, which serve as models for the technological gases in Klaus apparatuses and the direct catalytic oxidation of H/sub 2/S. X-ray photoelectron spectroscopy was used to establish the formation of sulfur as S/sup 2/minus// and S/sup 6+/ on the surface. The presence of S/sup 6+/ along with the changes in E/sub b/ of the electrons in the T-Mo-W catalyst indicates the formation of MoS/sub 2/ and TiO(SO/sub 4/) species.

  9. Investigation of the Structure and Active Sites of TiO2 Nanorod Supported VOx Catalysts by High-Field and Fast-Spinning 51V MAS NMR

    SciTech Connect

    Hu, Jian Z.; Xu, Suochang; Li, Weizhen; Hu, Mary Y.; Deng, Xuchu; Dixon, David A.; Vasiliu, Monica; Craciun, Raluca; Wang, Yong; Bao, Xinhe; Peden, Charles HF

    2015-07-02

    Supported VOx/TiO2-Rod catalysts were studied by 51V MAS NMR at high field using a sample spinning rate of 55 kHz. The superior spectral resolution allows for the observation of at least five vanadate species. The assignment of these vanadate species was carried out by quantum mechanical calculations of 51V NMR chemical shifts of model V-surface structures. Methanol oxidative dehydrogenation (ODH) was used to establish the correlation between the reaction rate and the various surface V-sites. It is found that monomeric V-species dominated the catalyst at low vanadium loadings with two peaks observed at about -502 and -529 ppm. V-dimers with two bridged oxygen appeare at about -555 ppm. Vanadate dimers and polyvanadates connected by one bridged oxygen atom between two adjacent V atoms resonate at about -630 ppm. A positive correlation is found between the V-dimers related to the -555 ppm peak and the ODH rate while a better correlation is obtained by including monomeric contributions. This result indicates that surface V-dimers related to the -555 ppm peak are the major active sites for ODH reaction despite mono-V species are more catalytic active but their relative ratios are decreased dramatically at high V-loadings. Furthermore, a portion of the V-species is found invisible. In particular, the level of such invisibility increases with decreased level of V-loading, suggesting the existence of paramagnetic V-species at the surface.

  10. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    DOE PAGESBeta

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; et al

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.« less

  11. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    SciTech Connect

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; Jia, Chun -Jia; Schueth, Ferdi

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

  12. Synergy between Two Metal Catalysts: A Highly Active Silica-Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane.

    PubMed

    Samantaray, Manoja K; Dey, Raju; Kavitake, Santosh; Abou-Hamad, Edy; Bendjeriou-Sedjerari, Anissa; Hamieh, Ali; Basset, Jean-Marie

    2016-07-13

    A well-defined, silica-supported bimetallic precatalyst [≡Si-O-W(Me)5≡Si-O-Zr(Np)3] (4) has been synthesized for the first time by successively grafting two organometallic complexes [W(Me)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple-quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON = 1436) than the monometallic W hydride (TON = 650) in the metathesis of n-decane at 150 °C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation that occurs on Zr. The produced olefin resulting from a β-H elimination undergoes easy metathesis on W. PMID:27248839

  13. Promoting effect of vanadium on catalytic activity of Pt/Ce-Zr-O diesel oxidation catalysts.

    PubMed

    Huang, Haifeng; Jiang, Bo; Gu, Lei; Qi, Zhonghua; Lu, Hanfeng

    2015-07-01

    A series of Pt-V/Ce-Zr-O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt-V/Ce-Zr-O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer-Emmett-Teller method, X-ray diffraction, H2 temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce-Zr-O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation. PMID:26141886

  14. Highly active non-PGM catalysts prepared from metal organic frameworks

    DOE PAGESBeta

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; Xu, Tao; Liu, Di -Jia

    2015-06-11

    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 demonstratedmore » 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.« less

  15. Highly active non-PGM catalysts prepared from metal organic frameworks

    SciTech Connect

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; Xu, Tao; Liu, Di -Jia

    2015-06-11

    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.

  16. The Economics of Saving Endangered Species: A Teaching Activity.

    ERIC Educational Resources Information Center

    Schug, Mark C.; Shaw, Jane S.

    1997-01-01

    Argues that well-intentioned government policies, such as the Endangered Species Act, can actually cause harm to endangered species by creating disincentives to preserving the habitat for endangered species. Maintains that the use of incentives can lead to voluntary species protection. Includes instructions for an in-class teaching activity. (MJP)

  17. ALTERNATIVE ROUTES FOR CATALYST PREPARATION: USE OF ULTRASOUND AND MICROWAVE IRRADIATION FOR THE PREPARATION OF VANADIUM PHOSPHORUS OXIDE CATALYST AND ITS ACTIVITY FOR HYDROCARBON OXIDATION

    EPA Science Inventory

    Vanadium phosphorus oxide (VPO) is a well-known catalyst used for the vapor phase n-butane oxidation to maleic anhydride. It is prepared by a variety of methods, all of which, however, eventually result in the same active phase. The two main methods for the preparation of its pr...

  18. Catalytic oxidation of pulping effluent by activated carbon-supported heterogeneous catalysts.

    PubMed

    Yadav, Bholu Ram; Garg, Anurag

    2016-01-01

    The present study deals with the non-catalytic and catalytic wet oxidation (CWO) for the removal of persistent organic compounds from the pulping effluent. Two activated carbon-supported heterogeneous catalysts (Cu/Ce/AC and Cu/Mn/AC) were used for CWO after characterization by the following techniques: temperature-programmed reduction, Fourier transform infrared spectroscopy and thermo-gravimetric analysis. The oxidation reaction was performed in a batch high-pressure reactor (capacity = 0.7  L) at moderate oxidation conditions (temperature = 190°C and oxygen pressure = 0.9 MPa). With Cu/Ce/AC catalyst, the maximum chemical oxygen demand (COD), total organic carbon (TOC) and lignin removals of 79%, 77% and 88% were achieved compared to only 50% removal during the non-catalytic process. The 5-day biochemical oxygen demand (BOD5) to COD ratio (a measure for biodegradability) of the pulping effluent was improved to 0.52 from an initial value of 0.16. The mass balance calculations for solid recovered after CWO reaction showed 8% and 10% deduction in catalyst mass primarily attributed to the loss of carbon and metal leaching. After the CWO process, carbon deposition was also observed on the recovered catalyst which was responsible for around 3-4% TOC reduction. PMID:26508075

  19. The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

    NASA Technical Reports Server (NTRS)

    Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.

    1990-01-01

    CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

  20. Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide.

    PubMed

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

    2016-05-01

    Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240 000 at 120 °C, turnover frequency (TOF)=31 500 h(-1) at 170 °C) at an initial CO2 pressure of 1.7 MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20 °C); and was applicable to a broad range of substrates, including terminal and internal epoxides. PMID:26990557

  1. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH₃ at low temperature.

    PubMed

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo

    2016-01-15

    The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO2 and H2O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO2/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NOx conversion ranges from 196 to 300°C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO2 species responsible for fast SCR reactions. PMID:26414927

  2. Dry Reforming of Methane on a Highly-Active Ni-CeO2 Catalyst: Effects of Metal-Support Interactions on C-H Bond Breaking.

    PubMed

    Liu, Zongyuan; Grinter, David C; Lustemberg, Pablo G; Nguyen-Phan, Thuy-Duong; Zhou, Yinghui; Luo, Si; Waluyo, Iradwikanari; Crumlin, Ethan J; Stacchiola, Dario J; Zhou, Jing; Carrasco, Javier; Busnengo, H Fabio; Ganduglia-Pirovano, M Verónica; Senanayake, Sanjaya D; Rodriguez, José A

    2016-06-20

    Ni-CeO2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst. Strong metal-support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV on Ni/CeO2-x (111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CHx or C species are detected in the C 1s XPS region. The reforming of methane proceeds in a clean and efficient way. PMID:27144344

  3. The Potent Oxidant Anticancer Activity of Organoiridium Catalysts**

    PubMed Central

    Liu, Zhe; Romero-Canelón, Isolda; Qamar, Bushra; Hearn, Jessica M; Habtemariam, Abraha; Barry, Nicolas P E; Pizarro, Ana M; Clarkson, Guy J; Sadler, Peter J

    2014-01-01

    Platinum complexes are the most widely used anticancer drugs; however, new generations of agents are needed. The organoiridium(III) complex [(η5-Cpxbiph)Ir(phpy)(Cl)] (1-Cl), which contains π-bonded biphenyltetramethylcyclopentadienyl (Cpxbiph) and C∧N-chelated phenylpyridine (phpy) ligands, undergoes rapid hydrolysis of the chlorido ligand. In contrast, the pyridine complex [(η5-Cpxbiph)Ir(phpy)(py)]+ (1-py) aquates slowly, and is more potent (in nanomolar amounts) than both 1-Cl and cisplatin towards a wide range of cancer cells. The pyridine ligand protects 1-py from rapid reaction with intracellular glutathione. The high potency of 1-py correlates with its ability to increase substantially the level of reactive oxygen species (ROS) in cancer cells. The unprecedented ability of these iridium complexes to generate H2O2 by catalytic hydride transfer from the coenzyme NADH to oxygen is demonstrated. Such organoiridium complexes are promising as a new generation of anticancer drugs for effective oxidant therapy. PMID:24616129

  4. Novel catalysts for methane activation. Quarterly report No. 8, July 1, 1994--September 30, 1994

    SciTech Connect

    Hirschon, A.S.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1994-11-28

    Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with the synthesis and characterization of the fullerenes and fullerene soots, Task 2 with the testing of the catalysts, and Task 3 with the evaluation of the results and technical reporting requirements. The results and accomplishments for this quarter are summarized below. In addition, the authors recently presented work on the use of fullerene based catalysts for methane activation at the American Chemical Society in Washington, DC this Fall. The paper is found in Appendix A of this report.

  5. A Rhodium Catalyst Superior to Iridium Congeners for Enantioselective Radical Amination Activated by Visible Light.

    PubMed

    Shen, Xiaodong; Harms, Klaus; Marsch, Michael; Meggers, Eric

    2016-06-27

    A bis-cyclometalated rhodium(III) complex catalyzes a visible-light-activated enantioselective α-amination of 2-acyl imidazoles with up to 99 % yield and 98 % ee. The rhodium catalyst is ascribed a dual function as a chiral Lewis acid and, simultaneously, as a light-activated smart initiator of a radical-chain process through intermediate aminyl radicals. Notably, related iridium-based photoredox catalysts reported before were unsuccessful in this enantioselective radical C-N bond formation. The surprising preference for rhodium over iridium is attributed to much faster ligand-exchange kinetics of the rhodium complexes involved in the catalytic cycle, which is crucial to keep pace with the highly reactive and thus short-lived nitrogen-centered radical intermediate. PMID:27145893

  6. Lewis acid activation of carbodicarbene catalysts for Rh-catalyzed hydroarylation of dienes.

    PubMed

    Roberts, Courtney C; Matías, Desirée M; Goldfogel, Matthew J; Meek, Simon J

    2015-05-27

    The activation of carbodicarbene (CDC)-Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydro-heteroarylation of dienes (up to 98% yield and >98:2 γ:α). Reactions are promoted by 5 mol % of a readily available tridentate (CDC)-Rh complex in the presence of an inexpensive lithium salt. The reaction is compatible with a variety of terminal and internal dienes and tolerant of ester, alkyl halide, and boronate ester functional groups. X-ray data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. PMID:25961506

  7. A General Method for Multimetallic Platinum Alloy Nanowires as Highly Active and Stable Oxygen Reduction Catalysts.

    PubMed

    Bu, Lingzheng; Ding, Jiabao; Guo, Shaojun; Zhang, Xu; Su, Dong; Zhu, Xing; Yao, Jianlin; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2015-11-25

    An unconventional class of high-performance Pt alloy multimetallic nanowires (NWs) is produced by a general method. The obtained PtNi NWs exhibit amazingly specific and mass oxygen reduction reaction (ORR) activities with improvement factors of 51.1 and 34.6 over commercial Pt/C catalysts, respectively, and are also stable in ORR conditions, making them among the most efficient electrocatalysts for ORR. PMID:26459261

  8. Oxyhydrochlorination catalyst

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1992-01-01

    An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  9. Synthesis, Characterization, and Catalytic Oxygen Electroreduction Activities of Carbon-Supported PtW Nanoparticle Catalysts

    SciTech Connect

    Xiong, Liufeng; More, Karren Leslie; He, Ting

    2010-01-01

    Carbon-supported PtW (PtW/C) alloy nanoparticle catalysts with well-controlled particle size, dispersion, and composition uniformity, have been synthesized by wet chemical methods of decomposition of carbonyl cluster complexes, hydrolysis of metal salts, and chemical reactions within a reverse microemulsion. The synthesized PtW/C catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, and energy-dispersive spectroscopy. The catalytic oxygen electroreduction activities were measured by the hydrodynamic rotating disk electrode technique in an acidic electrolyte. The influence of the synthesis method on PtW particle size, size distribution, composition uniformity, and catalytic oxygen electroreduction activity, have been investigated. Among the synthesis methods studied, PtW/C catalysts prepared by the decomposition of carbonyl cluster complexes displayed the best platinum mass activity for oxygen reduction reaction under the current small scale production; a 3.4-fold catalytic enhancement was achieved in comparison to a benchmark Pt/C standard.

  10. Novel catalysts for methane activation. Quarterly report No. 6, January 1, 1994--March 31, 1994

    SciTech Connect

    Hirschon, A.S,; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1994-05-24

    Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with the synthesis and characterization of the fullerenes and fullerene soots, Task 2 with the testing of the catalysts, and Task 3 with the evaluation of the results and technical reporting requirements. The results and accomplishments for this quarter are as follows: A fullerene soot (obtained from Ulvick Labs) and an extracted soot (obtained from MER) were treated with carbon dioxide to obtain high surface area soots of greater than 600 m{sup 2}/g; A palladium-C{sub 60} complex was synthesized and characterized by a surface analysis by laser ionization (SALI) instrument; Fullerene soot and Norit-A carbon were tested as catalysts for methane activation and the order of reactivity was found to be Soot > Norit-A > no catalyst; Increases in surface area of the soot did not significantly alter the methane conversion activity; Hydrogen and helium were tested as diluents, with helium causing an increase in selectivity towards C{sub 2} hydrocarbons for the fullerene soot catalyzed reactions; and The MER extracted soot was found to be more reactive towards methane conversion, but less selective towards C{sub 2} hydrocarbons than the Ulvick fullerene soot.

  11. Heterogeneous copper-silica catalyst from agricultural biomass and its catalytic activity

    NASA Astrophysics Data System (ADS)

    Andas, Jeyashelly; Adam, Farook; Rahman, Ismail Ab.

    2013-11-01

    A series of highly mesoporous copper catalysts (5-20 wt.%) supported on silica rice husk were synthesized via sol-gel route at room temperature. The FT-IR and 29Si MAS NMR spectroscopic studies revealed the successful substitution of copper into the silica matrix. Copper in the +2 oxidation state was evidenced from the DR/UV-vis and XPS analyses. Introduction of copper up to 10 wt.% (RH-10Cu) results in a progressive enhancement in the BET surface area. The activity of the copper catalysts was studied in the liquid-phase oxidation of phenol with H2O2 yielding catechol (CAT) and hydroquinone (HQ). Phenol conversion was influenced by various experimental conditions such as temperature, catalyst dosage, molar ratio of reactants, nature of solvent and percentage metal loading. Excellent activity was achieved when 10 wt.% copper was used and decreased with further increase in the copper loading. RH-10Cu could be regenerated several times without significant loss in the catalytic activity.

  12. Regeneration of field-spent activated carbon catalysts for low-temperature selective catalytic reduction of NOx with NH3

    SciTech Connect

    Jeon, Jong Ki; Kim, Hyeonjoo; Park, Young-Kwon; Peden, Charles HF; Kim, Do Heui

    2011-10-15

    In the process of producing liquid crystal displays (LCD), the emitted NOx is removed over an activated carbon catalyst by using selective catalytic reduction (SCR) with NH3 at low temperature. However, the catalyst rapidly deactivates primarily due to the deposition of boron discharged from the process onto the catalyst. Therefore, this study is aimed at developing an optimal regeneration process to remove boron from field-spent carbon catalysts. The spent carbon catalysts were regenerated by washing with a surfactant followed by drying and calcination. The physicochemical properties before and after the regeneration were investigated by using elemental analysis, TG/DTG (thermogravimetric/differential thermogravimetric) analysis, N2 adsorption-desorption and NH3 TPD (temperature programmed desorption). Spent carbon catalysts demonstrated a drastic decrease in DeNOx activity mainly due to heavy deposition of boron. Boron was accumulated to depths of about 50 {mu}m inside the granule surface of the activated carbons, as evidenced by cross-sectional SEM-EDX analysis. However, catalyst activity and surface area were significantly recovered by removing boron in the regeneration process, and the highest NOx conversions were obtained after washing with a non-ionic surfactant in H2O at 70 C, followed by treatment with N2 at 550 C.

  13. Design of a high activity and selectivity alcohol catalyst

    SciTech Connect

    Foley, H.C.; Mills, G.A.

    1992-02-07

    Results of the pyridine adsorption, studies on native and K-doped alumina provide fundamental grounding for the observed methanol dehydration activity of these samples. Both the reactor studies and the pyridine adsorption studies support the conclusion that the K-doped sample had reduced Lewis acidity. Moreover, we were able to measurably alter the acidity of the support surface by our ion exchange treatment. More significantly, when reactor results for transition-metal loaded samples are reconsidered in combination with their surface characteristics suggested by our pyridine adsorption studies, our hypothesis that Rh and Mo have ultimately titrated the support surface seems all the more convincing. Hence, in light of the pyridine adsorption results, the attenuation of a transition-metal based decomposition pathway for methanol on the metal-loaded samples-as seen in the reactor testing-is all the more reasonable.

  14. Structure-Activity Relationship in Nanostructured Copper-Ceria-Based Preferential CO Oxidation Catalysts

    SciTech Connect

    Gamarra,D.; Munuera, G.; Hungria, A.; Fernandez-Garcia, M.; Conesa, J.; Midgley, P.; Wang, X.; Hanson, J.; Rodriguez, J.; Martinez-Arias, A.

    2007-01-01

    Two series of nanostructured oxidized copper-cerium catalysts with varying copper loadings, and prepared, respectively, by impregnation of ceria and by coprecipitation of the two components within reverse microemulsions, have been characterized in detail at structural and electronic levels by X-ray diffraction (XRD), Raman spectroscopy, high-resolution electron microscopy (HREM), X-ray energy dispersive spectroscopy (XEDS), X-ray photoelectron spectroscopy (XPS) (including Ar{sup +}-sputtering), and X-ray absorption fine structure (XAFS). These results have been correlated with analysis of their catalytic properties for preferential oxidation of CO in a H{sub 2}-rich stream (CO-PROX), complemented by Operando-DRIFTS. A relevant difference between the two series of catalysts concerns the nature of the support for the surface-dispersed copper oxide entities, which is essentially ceria for the samples prepared by impregnation and a Ce-Cu mixed oxide for those prepared by microemulsion-coprecipitation. The existence of copper segregation in the form of copper oxide or copper-enriched Cu-Ce mixed oxides for the latter type of samples is uniquely revealed by nanoprobe XEDS and XPS Ar{sup +}-sputtering experiments. The CO oxidation activity under CO-PROX conditions is correlated to the degree of support-promoted reduction achieved by the dispersed copper oxide particles under reaction conditions. Nevertheless, catalysts which display higher CO oxidation activity are generally more efficient also for the undesired H{sub 2} oxidation reaction. The balance between both reactions results in differences in the CO-PROX activity between the two series of catalysts which are examined on the basis of the structural differences found.

  15. MESOPOROUS IRON PHOSPHATE AS AN ACTIVE, SELECTIVE AND RECYCLABLE CATALYST FOR THE SYNTHESIS OF NOPOL BY PRINS CONDENSATION

    EPA Science Inventory


    Mesoporous iron phosphate is found to be a highly active and recyclable heterogeneous catalyst for the selective synthesis of nopol by Prins condensation of ?-pinene and paraformaldehyde in acetonitrile at 80 oC.



  16. Non-redox metal ion promoted oxidative coupling of indoles with olefins by the palladium(ii) acetate catalyst through dioxygen activation: experimental results with DFT calculations.

    PubMed

    Zhang, Sicheng; Chen, Zhuqi; Qin, Shuhao; Lou, Chenlin; Senan, Ahmed M; Liao, Rong-Zhen; Yin, Guochuan

    2016-04-26

    Developing new catalytic technologies through C-H bond activation to synthesize versatile pharmaceuticals has attracted much attention in recent decades. This work introduces a new strategy in catalyst design for Pd(ii)-catalyzed C-H bond activation in which non-redox metal ions serving as Lewis acids play significant roles. In the oxidative coupling of indoles with olefins using dioxygen, it was found that Pd(OAc)2 alone as the catalyst is very sluggish at ambient temperature which provided a low yield of the olefination product, whereas adding non-redox metal ions to Pd(OAc)2 substantially improves its catalytic efficiency. In particular, it provided bis(indolyl)methane derivatives as the dominant product, a category of pharmacological molecules which could not be synthesized by Pd(ii)-catalyzed oxidative coupling previously. Detailed investigations revealed that the reaction proceeds by heterobimetallic Pd(ii)/Sc(iii)-catalyzed oxidative coupling of an indole with an olefin followed by Sc(iii)-catalyzed addition with a second indole molecule. DFT calculations disclosed that the formation of heterobimetallic Pd(ii)/Sc(iii) species substantially decreases the C-H bond activation energy barrier, and shifts the rate determining step from C-H bond activation of indole to the olefination step. This non-redox metal ion promoted Pd(ii)-catalyzed C-H bond activation may offer a new opportunity for catalyst design in organic synthesis, which has not been fully recognized yet. PMID:27075840

  17. Constant-distance mode SECM as a tool to visualize local electrocatalytic activity of oxygen reduction catalysts

    PubMed Central

    Nebel, Michaela; Erichsen, Thomas

    2014-01-01

    Summary Multidimensional shearforce-based constant-distance mode scanning electrochemical microscopy (4D SF/CD-SECM) was utilized for the investigation of the activity distribution of oxygen reduction catalysts. Carbon-supported Pt model catalyst powders have been immobilized in recessed microelectrodes and compared to a spot preparation technique. Microcavities serve as platform for the binder-free catalyst sample preparation exhibiting beneficial properties for constant-distance mode SECM imaging concerning modified surface area and catalyst loading. The integration of the redox competition mode of SECM into the detection scheme of the 4D SF/CD mode is demonstrated for specifically adapting high-resolution SECM experiments to powder-based catalyst preparations. PMID:24600538

  18. Identifying the role of N-heteroatom location in the activity of metal catalysts for alcohol oxidation

    DOE PAGESBeta

    Chan-Thaw, Carine E.; Veith, Gabriel M.; Villa, Alberto; Prati, Laura

    2015-04-02

    Here, this work focuses on understanding how the bonding of nitrogen heteroatoms contained on/in a activated carbon support influence the stability and reactivity of a supported Pd catalyst for the oxidation of alcohols in solution. The results show that simply adding N groups via solution chemistry is insufficient to improve catalytic properties. Instead a strongly bound N moiety is required to activate the catalyst and stabilize the metal particles.

  19. Identifying the Role of N-Heteroatom Location in the Activity of Metal Catalysts for Alcohol Oxidation

    SciTech Connect

    Chan-Thaw, Carine E.; Veith, Gabriel M; Villa, Alberto; Prati, Laura

    2015-01-01

    This work focuses on understanding how the bonding of nitrogen heteroatoms contained on/in a activated carbon support influence the stability and reactivity of a supported Pd catalyst for the oxidation of alcohols in solution. The results show that simply adding N groups via solution chemistry is insufficient to improve catalytic properties. Instead a strongly bound N moiety is required to activate the catalyst and stabilize the metal particles.

  20. Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

    PubMed

    Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

    2015-04-01

    The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate. PMID:25600582

  1. Conversion of isoamyl alcohol over acid catalysts: Reaction dependence on nature of active centers

    SciTech Connect

    Babu, G.P.; Murthy, R.S.; Krishnan, V.

    1997-02-01

    Acid catalysts are known to catalyze the dehydration of alcohols. In addition some oxide catalysts with basic properties have also been shown to play an important role in such dehydration reactions. The dehydration of aliphatic alcohols to olefins has been studied in detail using alumina silica-alumina and zeolite catalysts. The olefin products further undergo isomerization in presence of acidic sites. The reaction of isoamyl alcohol on catalytic surfaces has not been investigated in greater detail. The dehydration of isoamyl alcohol is of considerable interest in fine chemicals. Isoamyl alcohol may also undergo dehydrogenation as observed in the case of n-butanol. The scope of the present work is to identify the nature of the active sites selective for dehydration and dehydrogenation of isoamyl alcohol and to modify the active sites to promote isomerization of dehydrated products. Four catalytic surfaces on which the acidic strength can be varied, as well as selectively suppressed, are chosen for this study. 17 refs., 1 fig., 3 tabs.

  2. Novel windows for "solar commodities": a device for CO2 reduction using plasmonic catalyst activation.

    PubMed

    Navarrete, Alexander; Muñoz, Sergio; Sanz-Moral, Luis M; Brandner, Juergen J; Pfeifer, Peter; Martín, Ángel; Dittmeyer, Roland; Cocero, María J

    2015-01-01

    A novel plasmonic reactor concept is proposed and tested to work as a visible energy harvesting device while allowing reactions to transform CO2 to be carried out. Particularly the reverse water gas shift (RWGS) reaction has been tested as a means to introduce renewable energy into the economy. The development of the new reactor concept involved the synthesis of a new composite capable of plasmonic activation with light, the development of an impregnation method to create a single catalyst reactor entity, and finally the assembly of a reaction system to test the reaction. The composite developed was based on a Cu/ZnO catalyst dispersed into transparent aerogels. This allows efficient light transmission and a high surface area for the catalyst. An effective yet simple impregnation method was developed that allowed introduction of the composites into glass microchannels. The activation of the reaction was made using LEDs that covered all the sides of the reactor allowing a high power delivery. The results of the reaction show a stable process capable of low temperature transformations. PMID:26392210

  3. Optical properties and photocatalytic activities of tungsten oxide (WO3) with platinum co-catalyst addition

    NASA Astrophysics Data System (ADS)

    Widiyandari, Hendri; Firdaus, Iqbal; Kadarisman, Vincencius Gunawan Slamet; Purwanto, Agus

    2016-02-01

    This research reported the optical properties and photocatalytic activities of tungsten oxide with platinum co-catalyst addition (WO3/Pt) film. The platinum was deposited on the surface of WO3 particle using photo deposition method, while the film formation of WO3/Pt on the glass substrate was prepared using spray deposition method. The addition of Pt of 0, 1, 2, and 4 wt.% resulted that the energy band gap value of the films were shifted to 2.840, 2.752, 2.623 and 2.507 eV, respectively. The as-prepared films were tested for methylene blue (MB) dye photo-degradation using the LED (light emitting diode) lamp as a visible domestic source light. The enhancement of photocatalytic activity was observed after the addition of Pt as a co-catalyst. The degradation kinetics analysis of the photo-catalyst showed that the Pt addition resulted increasing of photo-catalysis reaction rate constant, k.

  4. Porous Silica-Coated Gold Nanorods: A Highly Active Catalyst for the Reduction of 4-Nitrophenol.

    PubMed

    Mohanta, Jagdeep; Satapathy, Smithsagar; Si, Satyabrata

    2016-02-01

    The successful coating of thin porous silica layers of various thicknesses [(10±1), (12±1), and (14±1) nm] on cetyl trimethylammonium bromide (CTAB) capped gold nanorods was achieved through a modified Stöber procedure. The resulting material was applied as a novel catalyst for the reduction of 4-nitrophenol. The catalytic activities of the gold nanorods increased up to eight times after coating with a layer of porous silica and the reaction followed a zero-order kinetics, having a rate constant as high as 2.92×10(-1) mol L(-1) min(-1). The spectral changes during the reduction reaction of 4-nitrophenol were observed within a very short span of time and a complete conversion to 4-aminophenol occured within 5-6 mins, including the induction period of ≈2 mins. The reusability of the catalyst was studied by running the catalytic reaction during five consecutive cycles with good efficiency without destroying the nanostructure. The methodology can be effectively applied to the development of composite catalysts with highly enhanced catalytic activity. PMID:26663755

  5. Characterization of the surface chemical properties of activated carbons for catalyst preparation

    SciTech Connect

    Noh, J.S.

    1989-01-01

    The demands placed on activated carbon based technologies have outpaced fundamental studies of the relationship between the surface properties of carbons and their performance as adsorbents or as catalyst supports. This research is directed toward an understanding how the surface functionalities of activated carbons affect the catalytic phase impregnated onto the carbon support. The surface functionalities were characterized by acidity measurements employing gaseous base adsorption and aqueous base neutralization procedures. The results were examined with a simple amphoteric surface ionization model. An alternative technique to conventional potentiometric titration, designated mass titration, was developed. Employing this method, the point of zero charge (PZC) of the adsorbent was determined by the asymptotic pH value in the plot of pH vs. mass fraction of solid added to water. The methodology developed here for evaluating the PZC was used to investigate the effects of surface treatment with nitric acid on the PZC of carbons. The PZC decreased from 10 for the untreated carbon to 3.5 for the carbon receiving the most intense oxidation treatment. The carbon supported nickel precursors derived from the ion exchange procedures were characterized by temperature-programmed reduction (TPR), and their properties as a gasification catalyst were evaluated. The hydrogen consumption during TPR increased and the ignition temperature decreased as either the acidity of the carbon support increased or the PZC decreased. It is proposed that the PZC can be used as an index to characterize the carbon surface as a suitable support for a heterogeneous catalyst.

  6. Highly active nanoporous Pt-based alloy as anode and cathode catalyst for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoting; Jiang, Yingying; Sun, Junzhe; Jin, Chuanhong; Zhang, Zhonghua

    2014-12-01

    In this paper, we explore nanoporous PtPdAlCu (np-PtPdAlCu) quaternary alloy through ball-milling with the subsequent two-step dealloying strategy. The microstructure and catalytic performance of the np-PtPdAlCu catalyst have been characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements. The np-PtPdAlCu catalyst exhibits an open bi-continuous interpenetrating ligament/channel structure with a length scale of 2.3 ± 0.5 nm. The np-PtPdAlCu catalyst shows 2 and 3.5 times enhancement in the mass activity and area specific activity towards methanol oxidation at anode respectively, compared to the Johnson Matthey (JM) Pt/C (40 wt.%) catalyst. Moreover, the CO stripping peak of np-PtPdAlCu is 0.49 V (vs. SCE), indicating a 180 mV negative shift in comparison with the Pt/C catalyst (0.67 V vs. SCE). In addition, the np-PtPdAlCu catalyst also shows an enhanced oxygen reduction reaction (ORR) activity at cathode compared to Pt/C. The present study provides a facile and effective route to design high-performance catalysts for direct methanol fuel cells (DMFCs).

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

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

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

  8. Pt-Au/Al[sub 2]O[sub 3] catalysts: Preparation, characterization, and dehydrogenation activity

    SciTech Connect

    Rouabah, D.; Fraissard, J. )

    1993-11-01

    The physicochemical characteristics of Pt-Au catalysts, such as the dispersion, chemisorption, and thermodesorption of hydrogen, have been studied in terms of gold content. The catalysts were prepared by coimpregnation of a [gamma]-alumina by a mixture of hexachloroplatinic and tetrachloroauric acids, calcination in oxygen and slow reduction in H[sub 2]-He from 25 to 400[degrees]C. The most outstanding result is the very large increase in the dispersion with the gold concentration. For example, with the alloy containing 80% gold more than 70% of the detectable particles are below 10 [angstrom]. In the same way, the activity per site and the selectivity in the dehydrogenation of methylcyclohexane to toluene increase with the gold concentration. 26 refs., 10 figs., 2 tabs.

  9. Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts

    PubMed Central

    Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay; Fabbri, Emiliana; Levecque, Pieter; Kötz, Rüdiger; Schmidt, Thomas J.

    2015-01-01

    In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts. PMID:26178185

  10. A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts

    SciTech Connect

    Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; Huang, Xiaoqing; Guo, Shaojun; Zhang, Xu; Lu, Gang; Su, Dong; Zhu, Xing; Guo, Jun

    2015-10-13

    The production of inorganic nanoparticles (NPs) with precise control over structures has always been a central target in various fields of chemistry and physics because the properties of NPs can be desirably manipulated by their structure.[1-4] There has been an intense search for high-performance noble metal NP catalysts particular for Pt.[5-9] Precious platinum (Pt) NPs are active catalysts for various heterogeneous reactions and show particularly superior performance in both the anodic oxidation reaction and the cathodic ORR in the fuel cells, but their rare content and high cost largely impede the practical application.[10-12] A potential strategy to address this tremendous challenge is alloying Pt NPs with the transition metals (TM).[13-16]

  11. Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts

    NASA Astrophysics Data System (ADS)

    Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay; Fabbri, Emiliana; Levecque, Pieter; Kötz, Rüdiger; Schmidt, Thomas J.

    2015-07-01

    In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts.

  12. A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts

    DOE PAGESBeta

    Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; Huang, Xiaoqing; Guo, Shaojun; Zhang, Xu; Lu, Gang; Su, Dong; Zhu, Xing; Guo, Jun

    2015-10-13

    The production of inorganic nanoparticles (NPs) with precise control over structures has always been a central target in various fields of chemistry and physics because the properties of NPs can be desirably manipulated by their structure.[1-4] There has been an intense search for high-performance noble metal NP catalysts particular for Pt.[5-9] Precious platinum (Pt) NPs are active catalysts for various heterogeneous reactions and show particularly superior performance in both the anodic oxidation reaction and the cathodic ORR in the fuel cells, but their rare content and high cost largely impede the practical application.[10-12] A potential strategy to address this tremendousmore » challenge is alloying Pt NPs with the transition metals (TM).[13-16]« less

  13. Influence of the support on the activity and selectivity of high dispersion Fe catalysts in the Fischer-Tropsch reaction

    SciTech Connect

    Cagnoli, M.V.; Marchetti, S.G.; Gallegos, N.G.; Alvarez, A.M.; Mercader, R.C.; Yeramian, A.A. Facultad de Ciencias Exactas, La Plata )

    1990-05-01

    In order to study the influence of the support on high dispersion catalysts used for the CO hydrogenation reaction, two catalysts, Fe/SiO{sub 2} and Fe/Al{sub 2}O{sub 3}, were prepared by the dry impregnation method. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to determine the Fe species present as well as the metallic crystal size, the degree of dispersion, and the reduction percentage. The presence of small Fe{sup 0} crystallites with high dispersion was determined in both catalysts. Reaction rates were measured in a differential reactor and significant differences, about one order of magnitude less for the Al{sub 2}O{sub 3} than for the SiO{sub 2} supported catalysts, were found in the methane turnover frequencies. They are attributed to the interaction between the metal and the supports. The selectivity differences is also discussed in connection with distinct surface properties.

  14. The contrasting catalytic efficiency and cancer cell antiproliferative activity of stereoselective organoruthenium transfer hydrogenation catalysts.

    PubMed

    Fu, Ying; Sanchez-Cano, Carlos; Soni, Rina; Romero-Canelon, Isolda; Hearn, Jessica M; Liu, Zhe; Wills, Martin; Sadler, Peter J

    2016-05-28

    The rapidly growing area of catalytic ruthenium chemistry has provided new complexes with potential as organometallic anticancer agents with novel mechanisms of action. Here we report the anticancer activity of four neutral organometallic Ru(II) arene N-tosyl-1,2-diphenylethane-1,2-diamine (TsDPEN) tethered transfer hydrogenation catalysts. The enantiomers (R,R)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8) and (S,S)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8a) exhibited higher potency than cisplatin against A2780 human ovarian cancer cells. When the N-methyl was replaced by N-H, i.e. to give (R,R)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7) and (S,S)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7a), respectively, anticancer activity decreased >5-fold. Their antiproliferative activity appears to be linked to their ability to accumulate in cells, and their mechanism of action might involve inhibition of tubulin polymerisation. This appears to be the first report of the potent anticancer activity of tethered Ru(II) arene complexes, and the structure-activity relationship suggests that the N-methyl substituents are important for potency. In the National Cancer Institute 60-cancer-cell-line screen, complexes 8 and 8a exhibited higher activity than cisplatin towards a broad range of cancer cell lines. Intriguingly, in contrast to their potent anticancer properties, complexes 8/8a are poor catalysts for asymmetric transfer hydrogenation, whereas complexes 7/7a are effective asymmetric hydrogenation catalysts. PMID:27109147

  15. Preparation and characterization of nanosized gold catalysts supported on Co3O4 and their activities for CO oxidation.

    PubMed

    Kim, Ki-Joong; Song, Jae-Koon; Shin, Seong-Soo; Kang, Sang-Jun; Chung, Min-Chul; Jung, Sang-Chul; Jeong, Woon-Jo; Ahn, Ho-Geun

    2011-02-01

    Gold catalysts supported on Co3O4 were prepared by co-precipitation (CP), deposition-precipitation (DP), and impregnation (IMP) methods. The Au/Co3O4 catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature programmed reduction (TPR) to understand the different activities for CO oxidation with different preparation methods. Gold particles below 5 nm supported on Co3O4 by DP method were found to be more exposed to the surface than those by CP and IMP methods, and this catalyst was highly active and stable in CO oxidation. Finally, catalytic activity of Au/Co3O4 catalyst for CO oxidation was strongly dependent on the gold particle size. PMID:21456247

  16. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

    SciTech Connect

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; Schwartz, Thomas J.; Dumesic, James A.; Shanks, Brent H.; Pruski, Marek

    2015-11-20

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticles. In addition, by offering >2500-fold time savings, the technique enabled the observation of 13C-13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  17. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

    DOE PAGESBeta

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; Schwartz, Thomas J.; Dumesic, James A.; Shanks, Brent H.; Pruski, Marek

    2015-11-20

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticles. In addition, by offering >2500-fold time savings, the technique enabled the observation of 13C-13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  18. Effect of a carrier's nature on the activation of supported iron catalysts

    NASA Astrophysics Data System (ADS)

    Kazak, V. O.; Chernavskii, P. A.; Pankina, G. V.; Khodakov, A. Y.; Ordomsky, V. V.

    2015-11-01

    The effect a carrier's nature has on the activation of supported iron catalysts in a stream of pure carbon monoxide CO is investigated. It is shown that iron is mainly present in the form of magnetite Fe3O4 in case of carbon supports and in the form of hematite Fe2O3 for silica gel supports. It is shown that all activated samples are chiefly made up of the Hägg carbide χ-Fe5C2, but its concentration is higher for the carbon supports.

  19. Study of new states in visible light active W, N co-doped TiO{sub 2} photo catalyst

    SciTech Connect

    Sajjad, Ahmed Khan Leghari; Shamaila, Sajjad; Zhang, Jinlong

    2012-11-15

    Highlights: ► Visible light efficient W, N co-doped TiO{sub 2} photo catalysts are prepared by sol–gel. ► Oxygen vacancies are detected in the form of new linkages as N-Ti-O, N-W-O, Ti-O-N and W-O-N. ► W, N co-doped titania has new energy states which narrows the band gap effectively. ► Oxygen vacancies are proved to be the cause for high photo catalytic activity. ► W and N co-doping plays the major role to make the composite thermally stable. -- Abstract: The visible light efficient W, N co-doped TiO{sub 2} photo catalysts are prepared by sol–gel method. New linkages of N, W and O are formed as N-Ti-O, N-W-O, Ti-O-N and W-O-N. Electron paramagnetic resonance illustrates the presence of oxygen vacancies in W, N co-doped TiO{sub 2} acting as trapping agencies for electrons to produce active species. X-ray photoelectron spectroscopy confirms the presence of new energy states. New linkages and oxygen vacancies are proved to be the main cause for the improved photo catalytic performances. W, N co-doped TiO{sub 2} has new energy states which narrow the band gap effectively. W, N co-doped TiO{sub 2} is thermally stable and retains its anatase phase up to 900 °C. 4.5% W, N co-doped TiO{sub 2} showed superior activity for the degradation of Rhodamine B and 2,4-dichlorophenol as compared to pure titania, Degussa P-25, traditional N-doped TiO{sub 2} and pure WO{sub 3}.

  20. Counting Active Sites on Titanium Oxide-Silica Catalysts for Hydrogen Peroxide Activation through In Situ Poisoning with Phenylphosphonic Acid

    SciTech Connect

    Eaton, Todd R.; Boston, Andrew M.; Thompson, Anthony B.; Gray, Kimberly A.; Notestein, Justin M.

    2015-06-04

    Quantifying specific active sites in supported catalysts improves our understanding and assists in rational design. Supported oxides can undergo significant structural changes as surface densities increase from site-isolated cations to monolayers and crystallites, which changes the number of kinetically relevant sites. Herein, TiOx domains are titrated on TiOx–SiO2 selectively with phenylphosphonic acid (PPA). An ex situ method quantifies all fluid-accessible TiOx, whereas an in situ titration during cis-cyclooctene epoxidation provides previously unavailable values for the number of tetrahedral Ti sites on which H2O2 activation occurs. We use this method to determine the active site densities of 22 different catalysts with different synthesis methods, loadings, and characteristic spectra and find a single intrinsic turnover frequency for cis-cyclooctene epoxidation of (40±7) h-1. This simple method gives molecular-level insight into catalyst structure that is otherwise hidden when bulk techniques are used.

  1. Antifungal activity of heartwood extracts from three Juniperus species

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heartwood samples from three species of Juniperus (i.e., J. virginianna, J. occidentalis, and J. ashei) were extracted with hexane, ethanol and methanol and the hexane and ethanol extracts were tested for antifungal activity against four species of wood-rot fungi. These three species represent the ...

  2. The effect of soot on ammonium nitrate species and NO2 selective catalytic reduction over Cu-zeolite catalyst-coated particulate filter.

    PubMed

    Mihai, Oana; Tamm, Stefanie; Stenfeldt, Marie; Olsson, Louise

    2016-02-28

    interacting with the ammonium nitrate species on the CuxOy or other copper species on the surface of the zeolite particles, which reduces the ammonium nitrate blocking of the catalyst and thereby results in higher NO2 SCR activity. PMID:26755757

  3. Probe molecule studies: Active species in alcohol synthesis. Tenth quarterly report, January 1993--March 1993

    SciTech Connect

    Blackmond, D.G.; Wender, I.; Oukaci, R.; Wang, Jian

    1993-03-01

    The goal of this research is to develop a better understanding of the mechanisms of formation of alcohols and other oxygenates from syngas over supported catalysts. Probe molecules are added in situ during the reaction to help delineate reaction pathways and identify reaction intermediate species. The key of our study is to investigate how the species generated by these probe molecules interact with surface species present during oxygenate formation. The catalysts chosen for this investigation is Co/Cu/ZnO/Al{sub 2}O{sub 3}. Detailed motivations for studying this system as well as using CH{sub 3}NO{sub 2} as the probe molecule were given in a previous report. X-ray photoelectron spectroscopy (XPS) experiments were carried out on calcined and reduced samples of Co(0%)/Cu/ZnO and Co(10%)/Cu/ZnO catalysts. The extent of reduction of the copper and cobalt phases in the Co(0,5 and l0%)/Cu/ZnO catalysts was estimated from XPS, TPR, and XRD results. (C) A Co(5%) /Al/{sub 2}O{sub 3} catalyst was prepared to be used as a base catalyst for the study of probe molecule addition. CO hydrogenation under the same conditions used before was conducted over the Co(5%)/Al{sub 2}O{sub 3} catalyst as well as a Co/Cu/ZnO/Al{sub 2}O{sub 3} catalyst (ZC45) prepared by coprecipitation method.

  4. Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere

    SciTech Connect

    Jain, Avijita; Buchko, Garry W.; Reback, Matthew L.; O'Hagan, Molly J.; Ginovska-Pangovska, Bojana; Linehan, John C.; Shaw, Wendy J.

    2012-10-05

    The synthesis, catalytic activity, and structural features of a rhodium-based hydrogenation catalyst containing a phosphine ligand coupled to a 14-residue peptide are reported. Both CD and NMR spectroscopy show that the peptide adopts a helical structure in 1:1:1 TFE/MeCN/H2O that is maintained when the peptide is attached to the ligand and when the ligand is attached to the metal complex. The metal complex hydrogenates aqueous solutions of 3-butenol to 1-butanol at 360 ± 50 turnovers/Rh/h at 294 K. This peptide- based catalyst represents a starting point for developing and characterizing a peptide-based outer-coordination sphere that can be used to introduce enzyme-like features into molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AJ, JCL and WJS), the Office of Science Early Career Research Program through the Office of Basic Energy Sciences (GWB, MLR and WJS). Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy’s Office of Biolog-ical and Environmental Research (BER) program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

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

    NASA Astrophysics Data System (ADS)

    Yik, Edwin Shyn-Lo

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

  6. Novel catalysts for methane activation. Quarterly report No. 9, October 1, 1994--December 31, 1994

    SciTech Connect

    Hirschon, A.S.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1995-04-20

    Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon-based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with synthesis and characterization of the fullerenes and fullerene soots, Task 2 with testing of the catalysts, and Task 3 with evaluation of the results and technical reporting. The results and accomplishments for this quarter are as follows: Reconstituted fullerene soot was prepared by adding C{sub 60} to a toluene-extracted Terrasimco fullerene soot; K-doped fullerene soots of different potassium concentrations were prepared; Fullerene soot doped with cesium was prepared by addition of cesium carbonate; The reconstituted fullerene soot was tested for methane activation. K-doped soots at different K concentrations were tested for methane activation. K-doped soot was examined for methane activation in the presence of co-feeds of either ethane or ethylene; a higher selectivity to C{sub 3} and C{sub 4} hydrocarbons was observed for the K-soot than when these reactions were conducted using soot as a catalyst, or when thermally induced. The Cs-doped soot was tested for methane activation; the selectivity for hydrocarbons from the methane conversion catalyzed by this soot was found to be higher than catalyzed by fullerene soot but lower than by K-soot.

  7. A simple synthesis method of sulfur-free Fe-N-C catalyst witih high ORR activity

    SciTech Connect

    Ding, Zhongfen; Johnston, Christina M; Zelenay, Piotr

    2010-01-01

    To try to deconvolute which factors affect the activity and durability of metal-nitrogen-carbon (M-N-C) type non-precious catalysts for oxygen reduction reaction (ORR), M-N-C catalysts based on ion chloride, polyaniline (PANI) and Ketjen Black carbon support were synthesized using different synthetic conditions. The catalysts were characterized electrochemically and tested as cathodes for Hydrogen fuel cells. PANI is usually chemically oxidative polymerized using ammonium persulfate (APS) as oxidant. To eliminate sulfur in the synthesized catalysts, a simple synthesis method using ion chloride as oxidant for aniline polymerization was developed. Two different aniline polymerization conditions led to very different product morphologies. Synthesized at low initial proton concentration, the final product was composed of dense micrometer sized particles. A decomposable salt was found to be able to prohibit PANI cross linking during the drying and annealing process and thus led to porous product. The porous catalyst has much higher ORR activity than the dense product due to more accessible active sites. Synthesized at high proton concentration, the catalyst appeared to be porous. The decomposable salt treatment did not make too much improvement in the porous structure and electrochemical activity. However, fuel cell testing using air as cathode feeder indicates that the salt treatment improves mass transfer in the cathode layer. Catalyst synthesized using this simple method has performance comparable to our state-of-the art catalyst synthesized in a much more complicated procedure. The factor that sulfur sources are completely eliminated in the synthesis suggests that sulfur is not necessary for the ORR catalysis activity.

  8. Degradation of flumequine in aqueous solution by persulfate activated with common methods and polyhydroquinone-coated magnetite/multi-walled carbon nanotubes catalysts.

    PubMed

    Feng, Mingbao; Qu, Ruijuan; Zhang, Xiaoling; Sun, Ping; Sui, Yunxia; Wang, Liansheng; Wang, Zunyao

    2015-11-15

    In recent years, flumequine (FLU) has been ubiquitously detected in surface waters and municipal wastewaters. In light of its potential negative impacts to aquatic species, growing concern has been arisen for the removal of this antibiotic from natural waters. In this study, the kinetics, degradation mechanisms and pathways of aqueous FLU by persulfate (PS) oxidation were systematically determined. Three common activation methods, including heat, Fe(2+) and Cu(2+), and a novel heterogeneous catalyst, namely, polyhydroquinone-coated magnetite/multi-walled carbon nanotubes (Fe3O4/MWCNTs/PHQ), were investigated to activate PS for FLU removal. It was found that these three common activators enhanced FLU degradation obviously, while several influencing factors, such as solution pH, inorganic ions (especially HCO3(-) at 5 mmol/L) and dissolved organic matter extracts, exerted their different effects on FLU removal. The catalysts were characterized, and an efficient catalytic degradation performance, high stability and excellent reusability were observed. The measured total organic carbon levels suggested that FLU can be effectively mineralized by using the catalysts. Radical mechanism was studied by combination of the quenching tests and electron paramagnetic resonance analysis. It was assumed that sulfate radicals predominated in the activation of PS with Fe3O4/MWCNTs/PHQ for FLU removal, while hydroxyl radicals also contributed to the catalytic oxidation process. In addition, a total of fifteen reaction intermediates of FLU were identified, from which two possible pathways were proposed involving hydroxylation, decarbonylation and ring opening. Overall, this study represented a systematical evaluation regarding the transformation process of FLU by PS, and showed that the heterogeneous catalysts can efficiently activate PS for FLU removal from the water environment. PMID:26281959

  9. The influence of carbon support porosity on the activity of PtRu/Sibunit anode catalysts for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Rao, V.; Simonov, P. A.; Savinova, E. R.; Plaksin, G. V.; Cherepanova, S. V.; Kryukova, G. N.; Stimming, U.

    In this paper we analyse the promises of homemade carbon materials of Sibunit family prepared through pyrolysis of natural gases on carbon black surfaces as supports for the anode catalysts of direct methanol fuel cells. Specific surface area ( SBET) of the support is varied in the wide range from 6 to 415 m 2 g -1 and the implications on the electrocatalytic activity are scrutinized. Sibunit supported PtRu (1:1) catalysts are prepared via chemical route and the preparation conditions are adjusted in such a way that the particle size is constant within ±1 nm in order to separate the influence of support on the (i) catalyst preparation and (ii) fuel cell performance. Comparison of the metal surface area measured by gas phase CO chemisorption and electrochemical CO stripping indicates close to 100% utilisation of nanoparticle surfaces for catalysts supported on low (22-72 m 2 g -1) surface area Sibunit carbons. Mass activity and specific activity of PtRu anode catalysts change dramatically with SBET of the support, increasing with the decrease of the latter. 10%PtRu catalyst supported on Sibunit with specific surface area of 72 m 2 g -1 shows mass specific activity exceeding that of commercial 20%PtRu/Vulcan XC-72 by nearly a factor of 3.

  10. Active Site Dependent Reaction Mechanism over Ru/CeO2 Catalyst toward CO2 Methanation.

    PubMed

    Wang, Fei; He, Shan; Chen, Hao; Wang, Bin; Zheng, Lirong; Wei, Min; Evans, David G; Duan, Xue

    2016-05-18

    Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C). PMID:27135417

  11. Role of pH in the Formation of Structurally Stable and Catalytically Active TiO2-Supported Gold Catalysts

    SciTech Connect

    Veith, G.; Lupini, A; Dudney, N

    2008-01-01

    We report the investigation of titania (Degussa P25) supported gold catalysts prepared by magnetron sputtering. Catalysts grown on natural fumed titania were structurally unstable, resulting in the rapid coarsening of 2.4 nm gold clusters into large 20 nm gold clusters in a few days at room temperature under normal atmospheric conditions. However, treating the titania support powder to a mock deposition-precipitation process, at pH 4, followed by the subsequent deposition of gold onto this treated powder produced a remarkable enhancement in gold particle stability and a 20-fold enhancement of catalytic activity. Furthermore, it was found that treating the titania under basic conditions (pH 10) resulted in a further enhancement of structural stability and a further doubling of the reaction rate to 0.28 mol of CO/mol of Au s. This enhancement cannot be attributed to removing surface Cl- species from the titania, the formation of oxygen vacancies on the TiO2 surface, or an electronic effect. Instead, it appears to be associated with the formation of strongly bound hydroxyl species on the TiO2 surface. The formation of surface hydroxyls during the deposition-precipitation method is coincidental and contributes significantly to the properties of Au/TiO2 catalysts

  12. A comparison of the activity, selectivity and kinetics of several iron-based Fischer-Tropsch catalysts

    SciTech Connect

    Dictor, R.A.; Bell, A.T.

    1986-03-01

    Much attention in the area of Fischer-Tropsch chemistry has been directed at slurry-phase reactor systems because of facilitated temperature control and the ability to operate continuously using hydrogen-lean feeds. The ability to predict and control the behavior of bubble column Ft reactors requires a detailed understanding of the reaction kinetics and mass transfer limitations. The authors examined the effects of temperature, reactant partial pressures, gas velocity and feed ratio on catalyst activity and selectivity for a number of catalysts: Fe/sub 2/O/sub 3/, potassium-promoted Fe/sub 2/O/sub 3/, Fe, Fe/sub 3/C, and a fused iron ammonia synthesis catalyst. The goal of this communication is to determine the effects of structural features (e.g., surface area, promoters, etc.) on the activities and selectivities of these catalysts.

  13. In-line localized monitoring of catalyst activity in selective catalytic NO.sub.x reduction systems

    DOEpatents

    Muzio, Lawrence J.; Smith, Randall A.

    2009-12-22

    Localized catalyst activity in an SCR unit for controlling emissions from a boiler, power plant, or any facility that generates NO.sub.x-containing flue gases is monitored by one or more modules that operate on-line without disrupting the normal operation of the facility. Each module is positioned over a designated lateral area of one of the catalyst beds in the SCR unit, and supplies ammonia, urea, or other suitable reductant to the catalyst in the designated area at a rate that produces an excess of the reductant over NO.sub.x on a molar basis through the designated area. Sampling probes upstream and downstream of the designated area draw samples of the gas stream for NO.sub.x analysis, and the catalyst activity is determined from the difference in NO.sub.x levels between the two probes.

  14. Trimetallic Au/Pt/Rh Nanoparticles as Highly Active Catalysts for Aerobic Glucose Oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Cao, Yingnan; Lu, Lilin; Cheng, Zhong; Zhang, Shaowei

    2015-02-01

    This paper reports the findings of an investigation of the correlations between the catalytic activity for aerobic glucose oxidation and the composition of Au/Pt/Rh trimetallic nanoparticles (TNPs) with average diameters of less than 2.0 nm prepared by rapid injection of NaBH4. The prepared TNPs were characterized by UV-Vis, TEM, and HR-TEM. The catalytic activity of the alloy-structured TNPs for aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with nearly the same particle size. The catalytic activities of the TNP catalysts were dependent not only on the composition, but also on the electronic structure. The high catalytic activities of the Au/Pt/Rh TNPs can be ascribed to the formed negative-charged Au atoms due to electron donation of Rh neighboring atoms acting as catalytically active sites for aerobic glucose oxidation.

  15. Cross-Couplings Using Aryl Ethers via C-O Bond Activation Enabled by Nickel Catalysts.

    PubMed

    Tobisu, Mamoru; Chatani, Naoto

    2015-06-16

    Arene synthesis has been revolutionized by the invention of catalytic cross-coupling reactions, wherein aryl halides can be coupled with organometallic and organic nucleophiles. Although the replacement of aryl halides with phenol derivatives would lead to more economical and ecological methods, success has been primarily limited to activated phenol derivatives such as triflates. Aryl ethers arguably represent one of the most ideal substrates in terms of availability, cost, safety, and atom efficiency. However, the robust nature of the C(aryl)-O bonds of aryl ethers renders it extremely difficult to use them in catalytic reactions among the phenol derivatives. In 1979, Wenkert reported a seminal work on the nickel-catalyzed cross-coupling of aryl ethers with Grignard reagents. However, it was not until 2004 that the unique ability of a low-valent nickel species to activate otherwise unreactive C(aryl)-O bonds was appreciated with Dankwardt's identification of the Ni(0)/PCy3 system, which significantly expanded the efficiency of the Wenkert reaction. Application of the nickel catalyst to cross-couplings with other nucleophiles was first accomplished in 2008 by our group using organoboron reagents. Later on, several other nucleophiles, including organozinc reagents, amines, hydrosilane, and hydrogen were shown to be coupled with aryl ethers under nickel catalysis. Despite these advances, progress in this field is relatively slow because of the low reactivity of benzene derivatives (e.g., anisole) compared with polyaromatic substrates (e.g., methoxynaphthalene), particularly when less reactive and synthetically useful nucleophiles are used. The "naphthalene problem" has been overcome by the use of N-heterocyclic carbene (NHC) ligands bearing bulky N-alkyl substituents, which enables a wide range of aryl ethers to be coupled with organoboron nucleophiles. Moreover, the use of N-alkyl-substituted NHC ligands allows the use of alkynylmagnesium reagents, thereby realizing

  16. Promotion of the electrocatalytic activity of a bimetallic platinum-ruthenium catalyst by repetitive redox treatments for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Huang, Sheng-Yang; Yeh, Chuin-Tih

    Pt-Ru/C catalyst (12 wt%) was prepared by the incipient wetness impregnation method followed by a redox heat-treatment. Transmission electron microscopy (TEM) results revealed uniformly distributed metallic crystallites of Pt-Ru alloy nanoparticles (d PtRu = 2.1 ± 1.0 nm). The effect of redox treatments of the impregnated catalysts on methanol oxidation reaction (MOR) was examined by cyclic voltammetry (CV). The MOR activity of the PtRu/C was significantly improved after each oxidation step of the redox treatment cycles. The enhanced catalytic activity was found to be quite stable in chronoamperometry (CA) measurements. CV, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results strongly suggested that the improved catalytic activity was due to the formation of a stable c-RuO x (x = 2-3) domain during the oxidation treatments. A bifunctional based mechanism was proposed for the MOR on the oxidized PtRu/C catalysts. Formation of Ru-OH species on the surface of c-RuO x domains was suggested as stale sites for the oxidation of carbon monoxide adsorbed on the Pt catalytic sites.

  17. Highly Active and Stable Pt-Loaded Ce0.75Zr0.25O2 Yolk-Shell Catalyst for Water-Gas Shift Reaction.

    PubMed

    Shim, Jae-Oh; Hong, Young Jun; Na, Hyun-Suk; Jang, Won-Jun; Kang, Yun Chan; Roh, Hyun-Seog

    2016-07-13

    Multishelled, Pt-loaded Ce0.75Zr0.25O2 yolk-shell microspheres were prepared by a simple spray pyrolysis process for use in the water-gas shift (WGS) reaction. The Pt-loading was optimized, obtaining highly active Pt/Ce0.75Zr0.25O2 yolk-shell nanostructures for the WGS. Of the prepared catalysts, a 2% Pt loading of the Ce0.75Zr0.25O2 yolk-shell microspheres showed the highest CO conversion. The high catalytic activity of the 2% Pt/Ce0.75Zr0.2O2 catalyst was mainly due to its easier reducibility and the maintenance of active catalytic Pt species. The Pt-loaded Ce0.75Zr0.25O2 catalyst microspheres were highly resistant to Pt sintering because of their unique yolk-shell structure. Spray pyrolysis was found to be highly efficient for the production of precious-metal-loaded, multicomponent metal oxide yolk-shell microspheres for catalytic applications. PMID:27315135

  18. Doped-CuCl2/Al2O3 catalysts for ethylene oxychlorination: Influence of additives on the nature of active phase and reducibility

    NASA Astrophysics Data System (ADS)

    Gianolio, D.; Muddada, N. B.; Olsbye, U.; Lamberti, C.

    2012-08-01

    Doped CuCl2/Al2O3 is an industrial catalyst used to produce dichloroethane, key intermediate of the polyvinyl chloride (PVC) chemistry. Using in situ and operando X-ray absorption spectroscopies, combined with laboratory techniques, we succeeded in understanding the nature of the active phase and the role played by most used additives for fluid and fixed beds technologies (LiCl, KCl, CsCl, MgCl2, and LaCl3). Moreover we were able to quantify relative fraction, reducibility and dispersion of Cu-phases adjoining catalytic tests in a pulse reactor. EXAFS and XANES highlighted that all additives contribute more or less efficiently in increasing the fraction of the active species (supported CuCl2). EXAFS directly, UV-vis and IR spectroscopies indirectly proved the formation of mixed salts, when KCl or CsCl are added, so displacing the rate determining step from the CuCl oxidation to the CuCl2 reduction. Fully oxidized catalyst is inactive, so copper in the working catalyst, exhibits a I/II mixed valence state. Coupling the ethylene conversion, measured with a pulse reactor, with XANES spectra collected after interaction with C2H4, we could differentiate the ability of doped samples to be reduced by ethylene. We obtained slightly different results explainable by the different dispersion of the active phase, measured by CO chemisorption.

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

    NASA Astrophysics Data System (ADS)

    Yik, Edwin Shyn-Lo

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

  20. Use of pyrolyzed iron ethylenediaminetetraacetic acid modified activated carbon as air-cathode catalyst in microbial fuel cells.

    PubMed

    Xia, Xue; Zhang, Fang; Zhang, Xiaoyuan; Liang, Peng; Huang, Xia; Logan, Bruce E

    2013-08-28

    Activated carbon (AC) is a cost-effective catalyst for the oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). To enhance the catalytic activity of AC cathodes, AC powders were pyrolyzed with iron ethylenediaminetetraacetic acid (FeEDTA) at a weight ratio of FeEDTA:AC = 0.2:1. MFCs with FeEDTA modified AC cathodes and a stainless steel mesh current collector produced a maximum power density of 1580 ± 80 mW/m(2), which was 10% higher than that of plain AC cathodes (1440 ± 60 mW/m(2)) and comparable to Pt cathodes (1550 ± 10 mW/m(2)). Further increases in the ratio of FeEDTA:AC resulted in a decrease in performance. The durability of AC-based cathodes was much better than Pt-catalyzed cathodes. After 4.5 months of operation, the maximum power density of Pt cathode MFCs was 50% lower than MFCs with the AC cathodes. Pyridinic nitrogen, quaternary nitrogen and iron species likely contributed to the increased activity of FeEDTA modified AC. These results show that pyrolyzing AC with FeEDTA is a cost-effective and durable way to increase the catalytic activity of AC. PMID:23902951

  1. Sol-gel derived mesoporous cobalt silica catalyst: Synthesis, characterization and its activity in the oxidation of phenol

    NASA Astrophysics Data System (ADS)

    Andas, Jeyashelly; Adam, Farook; Rahman, Ismail Ab.

    2014-10-01

    Highly mesoporous cobalt silica rice husk catalysts with (5-15 wt.%) Co2+ loading were prepared via a simple sol-gel technique at room temperature. The successful insertion of cobalt ions into silica matrix was evidenced from FT-IR, NMR, XPS and AAS analyses. Preservation of the mesoporosity nature of silica upon incorporating Co2+ was confirmed from the N2-sorption studies. The topography and morphology viewed by TEM analysis differs as the cobalt concentration varies from 5 to 15 wt.%. Parallel pore channels and spherical nanoparticles of 9.44 nm were achieved for cobalt silica catalysts with 10 and 15 wt.% respectively. Cobalt catalysts were active in the liquid-phase oxidation of phenol with H2O2 as an oxygen source. The performances of the catalysts were greatly influenced by various parameters such as reaction temperature, catalyst amount, molar ratio of substrate to oxidant, nature of solvent, metal loading and homogeneous precursor salt. Water served as the best reaction medium for this oxidation system. The regeneration studies confirmed cobalt catalyst could be reused for five cycles without experiencing large loss in the conversion. Both leaching and reusability studies testified that the catalysts were truly heterogeneous.

  2. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

    SciTech Connect

    Moliner, Manuel; Roman-Leshkov, Yuriy; Davis, Mark E.

    2010-04-06

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].

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

    SciTech Connect

    Ju, Hua; Li, Zhihu; Xu, Yanhui

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  4. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst. PMID:27483759

  5. Novel catalysts for methane activation. Quarterly report No. 12, July 1, 1995--September 30, 1995

    SciTech Connect

    Hirschon, A.S.; Du, Y.; Wu, H.J.

    1995-12-01

    Fullerenes are a recently discovered allotrope of carbon that possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon-based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with synthesis and characterization of the fullerenes and fullerene soots, Task 2 with testing of the catalysts, and Task 3 with evaluation of the results and technical reporting. Due to money constraints we have not done any technical work during this period. However, we hope to continue our work and produce a final report including recommendations for future research when funds are available.

  6. Diarylrhodates as promising active catalysts for the arylation of vinyl ethers with Grignard reagents.

    PubMed

    Iwasaki, Takanori; Miyata, Yoshinori; Akimoto, Ryo; Fujii, Yuuki; Kuniyasu, Hitoshi; Kambe, Nobuaki

    2014-07-01

    Anionic diarylrhodium complexes, generated by reacting [RhCl(cod)]2 with 2 equiv of aryl Grignard reagents, were found to be effective active catalysts in cross-coupling reactions of vinyl ethers with aryl Grignard reagents, giving rise to the production of vinyl arenes. In this catalytic system, vinyl-O bonds were preferably cleaved over Ar-O or Ar-Br bonds. A lithium rhodate complex was isolated, and its crystal structure was determined by X-ray crystallography. PMID:24957673

  7. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    PubMed

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1). PMID:20362394

  8. Novel catalysts for methane activation. Quarterly report No. 2, January 1, 1993--March 31, 1993

    SciTech Connect

    Hirschon, A.S.; Malhotra, R.; Wilson, R.B.

    1993-07-07

    The objectives of this project are to test novel fullerene based catalysts for application in methane activation. Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane conversion to higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with the synthesis and characterization of the fullerenes and fullerene soots, Task 2 with the testing of the catalysts, and Task 3 with the evaluation of the results and technical reporting requirements. This quarter we prepared fullerene soot and conducted experiments to determined its reactivity towards methane, hydrogen, and ethylene. The results are summarized: (1) Soot containing approximately 12-14 wt % fullerenes was prepared by the discharge method of Haufler et al. SRI is in the process of developing methodology to produce large scale amounts of fullerenes and fullerene based materials and is working with a private company to that end. In order to provide a background of fullerene soot and describe some of these methods we have included Appendix A. (2) We conducted some preliminary experiments in order to determine the temperature regime at which fullerene based soot would begin to be active for methane activation. We also were interested to determine if the soot would interact with methane or any of the product gases to undergo hydrogenation or methanation reactions.

  9. Ixodes ticks: serum species sensitivity of anticomplement activity.

    PubMed

    Lawrie, C H; Randolph, S E; Nuttall, P A

    1999-12-01

    Ixodid ticks feed for extended periods of up to 2 weeks or more. To complete engorgement, they must overcome their host's innate immune mechanisms of which the complement system is a major component. Using in vitro assays, salivary gland extracts of the ixodid ticks, Ixodes ricinus, I. hexagonus, and I. uriae, were shown to inhibit activity of the alternative pathway of complement. The ability of the different Ixodes species to inhibit complement activity varied with the animal species used as a complement serum source. Serum species sensitivity correlates to the reported host range of the tick species tested. PMID:10600446

  10. Theoretical studies on CuCl-catalyzed C-H activation/C-O coupling reactions: oxidant and catalyst effects.

    PubMed

    Zhang, Lu-Lu; Li, Shi-Jun; Zhang, Lei; Fang, De-Cai

    2016-05-11

    Copper-complex catalyzed coupling reactions have been widely applied in the production of many important organic moieties from a synthetic perspective. In this work, a series of density functional theory (DFT) calculations, employing the B3LYP + IDSCRF/DZVP method, have been performed for a typical CuCl-catalyzed C-O cross-coupling reaction. The novel reaction mechanism was reported as four successive processes: oxidative radical generation (ORG) or oxidative addition (OA), hydrogen abstraction (HA), C-H activation/reductive elimination, and separation of product and recycling of catalyst (SP & RC). Our calculations provided a deep understanding on the dissimilar chemical activities associated with varying the oxidants used; detailed energy profile analyses suggested that the first oxidation process could proceed via either of the two competing channels (ORG and OA mechanisms) which is the basis to explain the different experimental yields. In addition, our molecular modelling gave theoretical evidence that Cu(ii) → Cu(i) reduction by solvent DMF (and a water molecule) might serve as a preliminary step to produce some more active Cu(i) species that could subsequently be oxidized into Cu(iii) favorably. In contrast, the Cu(ii) → Cu(iii) direct pathway was estimated to be prohibited from thermodynamics. All the calculation results in this work are parallel with the experimental observations. PMID:27088885

  11. Reaction of deuterium with olefins on nickel catalysts: evidence for adsorbed vinylic species

    SciTech Connect

    Mintsa-Eya, V.; Hilaire, L.; Choplin, A.; Touroude, R.; Gault, F.G.

    1983-08-01

    The interaction of deuterium with 1,2-dimethylcyclopentene, 2,3-dimethylcyclopentene, 1-methyl-2-methylenecyclopentane, 1,2-dimethylcyclobutene, 1-methyl-2-methylenecyclobutane, bicyclo(2,2,1)heptene, but-1-ene, and cis-but-2-ene was studied from -85 to 50/sup 0/C on nickel films in a static apparatus and on Ni/pumice in a flow system. Unexpected d/sub 3/ and d/sub 4/ molecules were obtained in the deuteration of bicyclo(2,2,1)heptene. The position of the double bond in the ring of the other cycloolefins was the main factor governing their behavior: in the deuteration of 1,2-dimethylcycloalkenes, the saturated products, especially the trans somers, were much more exchanged and the percentage of trans was lower than when the starting material consisted of the olefins with the double bond in 2,3 or exocyclic positions. The hyperfine distribution, obtained by microwave analysis, of the exchanged d/sub 1/ but-1-ene, revealed that the major part of the deuterium was introduced on C/sub 2/; the cis-trans isomerization was much faster than the double bond migration with the introduction of zero or one deuterium atom while the isomerized but-1-ene showed a multiple exchange up to d/sub 4/; in the isomerized d/sub 1/ but-1-ene, the deuterium atom was distributed on the three carbon atoms C/sub 1/, C/sub 2/, C/sub 3/. Most of these results clearly show that the classical Horiuti-Polanyi mechanism is not the only one taking part in the reactions. The introduction of other intermediaries, sigma-vinylic, sigma-vinylic ..pi..-olefinic, and sigma-vinylic ..pi..-allylic species, provides a coherent explanation for all our findings. It is shown that nickel and iron behave in a very similar way. 5 tables.

  12. Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal-Organic Framework Catalysts.

    PubMed

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

    2016-05-01

    A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8 (OH)6 (popha)6 (H2 O)4 ]⋅3 H2 O (InPF-16), [In(popha)(2,2'-bipy)]⋅3 H2 O (InPF-17), [In3 (OH)3 (popha)2 (4,4'-bipy)]⋅4 H2 O (InPF-18), [In2 (popha)2 (4,4'-bipy)2 ]⋅3 H2 O (InPF-19), [In(OH)(Hpopha)]⋅0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]⋅4 H2 O (InPF-21) (InPF=indium polymeric framework, H3 popha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions. PMID:27010759

  13. Stabilizing a Platinum1 Single-Atom Catalyst on Supported Phosphomolybdic Acid without Compromising Hydrogenation Activity.

    PubMed

    Zhang, Bin; Asakura, Hiroyuki; Zhang, Jia; Zhang, Jiaguang; De, Sudipta; Yan, Ning

    2016-07-11

    In coordination chemistry, catalytically active metal complexes in a zero- or low-valent state often adopt four-coordinate square-planar or tetrahedral geometry. By applying this principle, we have developed a stable Pt1 single-atom catalyst with a high Pt loading (close to 1 wt %) on phosphomolybdic acid(PMA)-modified active carbon. This was achieved by anchoring Pt on the four-fold hollow sites on PMA. Each Pt atom is stabilized by four oxygen atoms in a distorted square-planar geometry, with Pt slightly protruding from the oxygen planar surface. Pt is positively charged, absorbs hydrogen easily, and exhibits excellent performance in the hydrogenation of nitrobenzene and cyclohexanone. It is likely that the system described here can be extended to a number of stable SACs with superior catalytic activities. PMID:27240266

  14. A new iron-based carbon monoxide oxidation catalyst: structure-activity correlation.

    PubMed

    Schoch, Roland; Huang, Heming; Schünemann, Volker; Bauer, Matthias

    2014-12-01

    A new iron-based catalyst for carbon monoxide oxidation, as a potential substitute for precious-metal systems, has been prepared by using a facile impregnation method with iron tris-acetylacetonate as a precursor on γ-Al2 O3 . Light-off and full conversion temperatures as low as 235 and 278 °C can be reached. However, the catalytic activity strongly depends on the loading; lower loadings perform better than higher ones. The different activities can be explained by variations of the structures formed. The structures are thoroughly characterized by a multimethodic approach by using X-ray diffraction, Brunauer-Emmett-Teller surface areas, and Mössbauer spectroscopy combined with diffuse reflectance UV/Vis and X-ray absorption spectroscopy. Consequently, isolated tetrahedrally coordinated Fe(3+) centers and phases of AlFeO3 are identified as structural requirements for high activity in the oxidation of carbon monoxide. PMID:25212843

  15. Hierarchical Pd-Sn Alloy Nanosheet Dendrites: An Economical and Highly Active Catalyst for Ethanol Electrooxidation

    PubMed Central

    Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

    2013-01-01

    Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures. PMID:23383368

  16. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation. PMID:15330667

  17. Electrochemically active species and multielectron processes in ionic melts

    NASA Astrophysics Data System (ADS)

    Shapoval, Viktor I.; Solov'ev, Veniamin V.; Malyshev, Viktor V.

    2001-02-01

    The model concepts for the mechanisms of formation of electrochemically active species and multielectron processes in ionic nitrate-, carbonate-, boron- and titanium-containing fluoride melts are generalised. The fundamental importance of the acid-base properties of a melt in the mechanism of formation of electrochemically active species is shown for nitrate- and carbonate-containing melts. This fact is confirmed by electrochemical measurements and by calculations of force constants for oxyanions. The optimum form of electrochemically active species has been established; their reduction abilities depend on the cationic composition of a melt, the adsorption properties of the electrode surface and the electric field strength. The bibliography includes 218 references.

  18. Antimicrobial activities of silver used as a polymerization catalyst for a wound-healing matrix.

    PubMed

    Babu, Ranjith; Zhang, Jianying; Beckman, Eric J; Virji, Mohammed; Pasculle, William A; Wells, Alan

    2006-08-01

    Wound healing is a complex and orchestrated process that re-establishes the barrier and other functions of the skin. While wound healing proceeds apace in healthy individual, bacterial overgrowth and infection disrupts this process with significant morbidity and mortality. As such, any artificial matrix to promote wound healing must also control infecting microbes. We had earlier developed a two-part space-conforming gel backbone based on polyethyleneglycol (PEG) or lactose, which used ionic silver as the catalyst for gelation. As silver is widely used as an in vitro antimicrobial, use of silver as a catalyst for gelation provided the opportunity to assess its function as an anti-microbial agent in the gels. We found that these gels show bacteriostatic and bactericidal activity for a range of Gram-negative and Gram-positive organisms, including aerobic as well as anaerobic bacteria. This activity lasted for days, as silver leached out of the formed gels over a day in the manner of second-order decay. Importantly the gels did not limit either cell growth or viability, though cell migration was affected. Adding collagen I fragments to the gels corrected this effect on cell migration. We also found that the PEG gel did not interfere with hemostasis. These observations provide the basis for use of the gel backbones for incorporation of anesthetic agents and factors that promote wound repair. In conclusion, silver ions can serve dual functions of catalyzing gelation and providing anti-microbial properties to a biocompatible polymer. PMID:16635526

  19. Antimicrobial activities of silver used as a polymerization catalyst for a wound-healing matrix

    PubMed Central

    Babu, Ranjith; Zhang, Jianying; Beckman, Eric J.; Virji, Mohammed; Pasculle, William A.; Wells, Alan

    2007-01-01

    Wound healing is a complex and orchestrated process that re-establishes the barrier and other functions of the skin. While wound healing proceeds apace in healthy individual, bacterial overgrowth and infection disrupts this process with significant morbidity and mortality. As such, any artificial matrix to promote wound healing must also control infecting microbes. We had earlier developed a two-part space-conforming gel backbone based on polyethyleneglycol (PEG) or lactose, which used ionic silver as the catalyst for gelation. As silver is widely used as an in vitro antimicrobial, use of silver as a catalyst for gelation provided the opportunity to assess its function as an anti-microbial agent in the gels. We found that these gels show bacteriostatic and bactericidal activity for a range of Gram-negative and Gram-positive organisms, including aerobic as well as anaerobic bacteria. This activity lasted for days, as silver leached out of the formed gels over a day in the manner of second-order decay. Importantly the gels did not limit either cell growth or viability, though cell migration was affected. Adding collagen I fragments to the gels corrected this effect on cell migration. We also found that the PEG gel did not interfere with hemostasis. These observations provide the basis for use of the gel backbones for incorporation of anesthetic agents and factors that promote wound repair. In conclusion, silver ions can serve dual functions of catalyzing gelation and providing anti-microbial properties to a biocompatible polymer. PMID:16635526

  20. Isoselenazolones as catalysts for the activation of bromine: bromolactonization of alkenoic acids and oxidation of alcohols.

    PubMed

    Balkrishna, Shah Jaimin; Prasad, Ch Durga; Panini, Piyush; Detty, Michael R; Chopra, Deepak; Kumar, Sangit

    2012-11-01

    Isoselenazolones were synthesized by a copper-catalyzed Se-N bond forming reaction between 2-halobenzamides and selenium powder. The catalytic activity of the various isoselenazolones was studied in the bromolactonization of pent-4-enoic acid. Isoselenazolone 9 was studied as a catalyst in several reactions: the bromolactonization of a series of alkenoic acids with bromine or N-bromosuccinimide (NBS) in the presence of potassium carbonate as base, the bromoesterification of a series of alkenes using NBS and a variety of carboxylic acids, and the oxidation of secondary alcohols to ketones using bromine as an oxidizing reagent. Mechanistic details of the isoselenazolone-catalyzed bromination reaction were revealed by (77)Se NMR spectroscopic and ES-MS studies. The oxidative addition of bromine to the isoselenazolone gives the isoselenazolone(IV) dibromide, which could be responsible for the activation of bromine under the reaction conditions. Steric effects from an N-phenylethyl group on the amide of the isoselenazolone and electron-withdrawing fluoro substituents on the benzo fused-ring of the isoselenazolone appear to enhance the stability of the isoselenazolone as a catalyst for the bromination reaction. PMID:23046286

  1. Active sites and mechanisms for H2O2 decomposition over Pd catalysts.

    PubMed

    Plauck, Anthony; Stangland, Eric E; Dumesic, James A; Mavrikakis, Manos

    2016-04-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2 We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O-O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O-O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  2. Active hydrogen species on TiO2 for photocatalytic H2 production.

    PubMed

    Wu, Zongfang; Zhang, Wenhua; Xiong, Feng; Yuan, Qing; Jin, Yuekang; Yang, Jinlong; Huang, Weixin

    2014-04-21

    Photocatalytic H2 production over TiO2 has attracted tremendous attention and achieved great progress, but the active hydrogen species is still unknown. Employing a rutile TiO2(110) surface as a model catalyst we report here for the first time the direct observation of photocatalytic H2 production under ultrahigh vacuum conditions during UV-light irradiation at 115 K and the identification of negatively-charged hydride-type H-Ti species as the corresponding photoactive surface species by means of thermal desorption spectroscopy, photon-stimulated desorption spectroscopy, X-ray photoelectron spectroscopy and DFT calculations. The formation and stability of H-Ti species are closely related to available surplus electrons on the rutile TiO2(110) surface that can be created by the formation of surface BBO vacancies or by the formation of surface hydroxyls via the adsorption of atomic H or molecular H2 on O sites. The photocatalytic H2 production from H-Ti species is hole-mediated and co-existing water exerts a negative effect on this process. PMID:24614827

  3. Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides and Iodides: Scope and Structure-Activity Relationships

    PubMed Central

    Shen, Qilong; Ogata, Tokutaro; Hartwig, John F.

    2010-01-01

    We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes. PMID:18444639

  4. Effect of carriers on physico-chemical properties and activity of Pd nano-catalyst in n-hexane isomerization

    NASA Astrophysics Data System (ADS)

    Loc Luu, Cam; Thoa Dao, Thi Kim; Nguyen, Tri; Huong Bui, Thanh; Yen Dang, Thi Ngoc; Hoang, Minh Nam; Thoang Ho, Si

    2013-12-01

    In this work zeolites HY, HZSM-5 and mixes of zeolites with γ-Al2O3 in different ratios were taken as carriers for 0.8 wt% Pd catalysts. Physico-chemical characteristics of the catalysts were determined by methods of Brunauer-Emmett-Teller (BET)-N2 adsorption, x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), hydrogen pulse chemisorption (HPC) and NH3 adsorption-desorption. The activity of catalysts was studied at 225-450 °C, at 0.1 and 0.7 MPa with molar ratio of H2:n-C6H14 = 5.92 and n-hexane concentration 9.2 mol%. Mixing of γ-Al2O3 with zeolite made acidity of catalyst weaken and led to a decrease of Pd cluster size, to an increase of Pd dispersity and a reduction of the extent of Pd in the case of catalyst Pd/HY; but for the catalyst Pd/HZSM-5 such mixing led to the reverse effect. That is why the increase of activity in the first case and the decrease of activity in the second case have been observed. It has been found that the optimal ratio of mixed carrier is γ-Al2O3:HY = 2.5:1 and the optimal calcined temperature of NH4ZSM-5 to obtain HZSM-5 is 500-550 °C. An increase of reaction pressure from 0.1 to 0.7 MPa remarkably increased the activity, selectivity and stability of Pd-based catalysts.

  5. Sport Fields as Potential Catalysts for Physical Activity in the Neighbourhood

    PubMed Central

    Cutumisu, Nicoleta; Spence, John C.

    2012-01-01

    Physical activity is associated with access to recreational facilities such as sports fields. Because it is not clear whether objectively- or subjectively-assessed access to facilities exerts a stronger influence on physical activity, we investigated the association between the objective and perceived accessibility of sport fields and the levels of self-reported physical activity among adults in Edmonton, Canada. A sample of 2879 respondents was surveyed regarding their socio-demographics, health status, self-efficacy, levels of physical activity, as well as their perceptions of built environment in relation to physical activity. Neighbourhood-level data were obtained for each respondent based on their residence. Accessibility to facilities was assessed using the enhanced Two-Step Floating Catchment Area method. Geographic Information Systems were employed. A logistic regression was performed to predict physical activity using individual- and neighbourhood-level variables. Women, older individuals, and individuals with higher educational attainment were less likely to be physically active. Also, individuals with higher self-efficacy and higher objectively-assessed access to facilities were more likely to be physically active. Interventions that integrate provision of relevant programs for various population groups and of improved recreational facilities may contribute to sport fields becoming catalysts for physical activity by generating movement both on the site and in the neighbourhood. PMID:22470293

  6. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and the solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will be performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing.

  7. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing. 5 refs., 1 tab.

  8. A ternary Cu2O-Cu-CuO nanocomposite: a catalyst with intriguing activity.

    PubMed

    Sasmal, Anup Kumar; Dutta, Soumen; Pal, Tarasankar

    2016-02-21

    In this work, the syntheses of Cu2O as well as Cu(0) nanoparticle catalysts are presented. Copper acetate monohydrate produced two distinctly different catalyst particles with varying concentrations of hydrazine hydrate at room temperature without using any surfactant or support. Then both of them were employed separately for 4-nitrophenol reduction in aqueous solution in the presence of sodium borohydride at room temperature. To our surprise, it was noticed that the catalytic activity of Cu2O was much higher than that of the metal Cu(0) nanoparticles. We have confirmed the reason for the exceptionally high catalytic activity of cuprous oxide nanoparticles over other noble metal nanoparticles for 4-nitrophenol reduction. A plausible mechanism has been reported. The unusual activity of Cu2O nanoparticles in the reduction reaction has been observed because of the in situ generated ternary nanocomposite, Cu2O-Cu-CuO, which rapidly relays electrons and acts as a better catalyst. In this ternary composite, highly active in situ generated Cu(0) is proved to be responsible for the hydride transfer reaction. The mechanism of 4-nitrophenol reduction has been established from supporting TEM studies. To further support our proposition, we have prepared a compositionally similar Cu2O-Cu-CuO nanocomposite using Cu2O and sodium borohydride which however displayed lower rate of reduction than that of the in situ produced ternary nanocomposite. The evolution of isolated Cu(0) nanoparticles for 4-nitrophenol reduction from Cu2O under surfactant-free condition has also been taken into consideration. The synthetic procedures of cuprous oxide as well as its catalytic activity in the reduction of 4-nitrophenol are very convenient, fast, cost-effective, and easily operable in aqueous medium and were followed spectrophotometrically. Additionally, the Cu2O-catalyzed 4-nitrophenol reduction methodology was extended further to the reduction of electronically diverse nitroarenes. This

  9. Catalyst increases COS conversion

    SciTech Connect

    Goodboy, K.P.

    1985-02-18

    Increasingly stringent air quality legislation is placing greater emphasis on conversion of COS and CS/sub 2/ in Claus plants for the maximum sulfur recovery. Overall sulfur recovery goals are dependent upon outstanding service from the Claus catalyst in each reactor because catalyst activity is a major factor influencing plant performance. Today's catalyst are much improved over those used 10 years ago for the Claus (H/sub 2/S/SO/sub 2/) reaction. Recent technical efforts have focused on the conversion of COS and CS/sub 2/. These carbon-sulfur compounds can account for as much as 50% of the sulfur going to the incinerator, which essentially converts all remaining sulfur species to SO/sub 2/ for atmospheric dispersion. Previously, the mechanism of Claus COS conversion, i.e., hydrolysis or oxidation by SO/sub 2/, was studied and the conclusion was that oxidation by SO/sub 2/ appears to be the predominate mode of COS conversion on sulfated alumina catalysts.

  10. C-H Bond Activation by Pd-substituted CeO2: Substituted Ions versus Reduced Species

    SciTech Connect

    Misch, Lauren M; Kurzman, Joshua A; Derk, Alan R; Kim, Young-Il; Seshadri, Ram; Metiu, Horia; McFarland, Eric W; Stucky, Galen D

    2012-02-07

    Substituted metal oxides containing ionic species have been attracting a great deal of attention because of their potential ability to reduce the usage of precious metals in heterogeneous catalysts. We investigate Pd-substituted CeO2 for C-H bond activation reactions including the partial oxidation and dry reforming of CH4. This catalyst has been previously studied for CO oxidation, NOx reduction, and the water-gas shift reaction. Pd-substituted CeO2, Ce1-xPdxO2-δ, was prepared as a powder with high surface area and a hollow sphere morphology using ultrasonic spray pyrolysis. The catalysts were extensively characterized using synchrotron X-ray diffraction and other techniques, confirming phase pure samples up to 10 mol % Pd substitution. Ce0.95Pd0.05O2-δ was found to be active for partial oxidation of CH4 around 500 °C and higher. Our studies, including postcatalytic synchrotron diffraction, suggest that the single-phase Ce1-xPdxO2-δ material is not the active species and that catalysis occurs instead over the reduced two-phase Pd0/CeO2. This observation has been further confirmed by verifying the activity of the reduced Pd0/CeO2 catalysts for ethylene hydrogenation, a reaction that is known to require Pd0.

  11. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    PubMed Central

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank

    2016-01-01

    Summary A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC) “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  12. Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition.

    PubMed

    Reddy Enakonda, Linga; Zhou, Lu; Saih, Youssef; Ould-Chikh, Samy; Lopatin, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

    2016-08-01

    Activation of Fe2 O3 -Al2 O3 with CH4 (instead of H2 ) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx -free H2 . In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2 O3 by CH4 proceeds in three steps: Fe2 O3 →Fe3 O4 →FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3 C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. PMID:27345621

  13. Dinuclear thiazolylidene copper complex as highly active catalyst for azid-alkyne cycloadditions.

    PubMed

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank; Straub, Bernd F

    2016-01-01

    A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide-alkyne cycloaddition (CuAAC) "click" reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  14. Nonactivated and Activated Biochar Derived from Bananas as Alternative Cathode Catalyst in Microbial Fuel Cells

    PubMed Central

    Yuan, Haoran; Deng, Lifang; Qi, Yujie; Kobayashi, Noriyuki; Tang, Jiahuan

    2014-01-01

    Nonactivated and activated biochars have been successfully prepared by bananas at different thermotreatment temperatures. The activated biochar generated at 900°C (Biochar-act900) exhibited improved oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performances in alkaline media, in terms of the onset potential and generated current density. Rotating disk electron result shows that the average of 2.65 electrons per oxygen molecule was transferred during ORR of Biochar-act900. The highest power density of 528.2 mW/m2 and the maximum stable voltage of 0.47 V were obtained by employing Biochar-act900 as cathode catalyst, which is comparable to the Pt/C cathode. Owning to these advantages, it is expected that the banana-derived biochar cathode can find application in microbial fuel cell systems. PMID:25243229

  15. Promoting Active Species Generation by Plasmon-Induced Hot-Electron Excitation for Efficient Electrocatalytic Oxygen Evolution.

    PubMed

    Liu, Guigao; Li, Peng; Zhao, Guixia; Wang, Xin; Kong, Jintao; Liu, Huimin; Zhang, Huabin; Chang, Kun; Meng, Xianguang; Kako, Tetsuya; Ye, Jinhua

    2016-07-27

    Water splitting represents a promising technology for renewable energy conversion and storage, but it is greatly hindered by the kinetically sluggish oxygen evolution reaction (OER). Here, using Au-nanoparticle-decorated Ni(OH)2 nanosheets [Ni(OH)2-Au] as catalysts, we demonstrate that the photon-induced surface plasmon resonance (SPR) excitation on Au nanoparticles could significantly activate the OER catalysis, specifically achieving a more than 4-fold enhanced activity and meanwhile affording a markedly decreased overpotential of 270 mV at the current density of 10 mA cm(-2) and a small Tafel slope of 35 mV dec(-1) (no iR-correction), which is much better than those of the benchmark IrO2 and RuO2, as well as most Ni-based OER catalysts reported to date. The synergy of the enhanced generation of Ni(III/IV) active species and the improved charge transfer, both induced by hot-electron excitation on Au nanoparticles, is proposed to account for such a markedly increased activity. The SPR-enhanced OER catalysis could also be observed over cobalt oxide (CoO)-Au and iron oxy-hydroxide (FeOOH)-Au catalysts, suggesting the generality of this strategy. These findings highlight the possibility of activating OER catalysis by plasmonic excitation and could open new avenues toward the design of more-energy-efficient catalytic water oxidation systems with the assistance of light energy. PMID:27380539

  16. Reactivity of atomically dispersed Pt(2+) species towards H2: model Pt-CeO2 fuel cell catalyst.

    PubMed

    Lykhach, Yaroslava; Figueroba, Alberto; Camellone, Matteo Farnesi; Neitzel, Armin; Skála, Tomáš; Negreiros, Fabio R; Vorokhta, Mykhailo; Tsud, Nataliya; Prince, Kevin C; Fabris, Stefano; Neyman, Konstantin M; Matolín, Vladimír; Libuda, Jörg

    2016-03-01

    The reactivity of atomically dispersed Pt(2+) species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt(2+) sites are found to be inactive towards H2 dissociation due to high activation energy required for H-H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt-CeO2 films. H2 dissociation triggers the reduction of Ce(4+) cations which, in turn, is coupled with the reduction of Pt(2+) species. The mechanism of Pt(2+) reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt-CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt(2+) reduction. PMID:26908194

  17. Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO2 supports

    DOE PAGESBeta

    Kim, Mi -Young; Kyriakidou, Eleni A.; Choi, Jae -Soon; Toops, Todd J.; Binder, Andrew J.; Thomas, Cyril; Schwartz, Viviane; Chen, Jihua; Hensley, Dale K.; Parks, II, James E.

    2016-01-18

    In this study, we investigated the impact of ZrO2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO2 and SiO2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO2 surface area and improve sulfur tolerance, a Pd support with ZrO2-dispersed onto SiO2 was studied. The physicochemical properties of the catalysts were examined using ICP, N2 sorption, XRD, SEM, TEM, and NH3-, CO2-, and NOx-TPD. The activity of the Pd catalysts were measured from 60 to 600 °C in a flow of 4000 ppmmore » CO, 500 ppm NO, 1000 ppm C3H6, 4% O2, 5% H2O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO2-containing catalysts showed considerably higher CO and C3H6 oxidation activity than Pd/SiO2 under the reaction conditions studied.« less

  18. Novel catalysts for methane activation. Quarterly report No. 4, July 1, 1993--September 30, 1993

    SciTech Connect

    Hirschon, A.S.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1993-12-03

    The objectives of this project are to test novel fullerene based catalysts for application in methane activation. Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane conversion to higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with the synthesis and characterization of the fullerenes and fullerene soots, Task 2 with the testing of the catalysts, and Task 3 with the evaluation of the results and technical reporting requirements. This quarter the authors concentrated on Task 2. In this task they expanded the capabilities of the system so they can include the effect of diluents during the methane activation experiments and continued work on evaluating the fullerene soot. They investigated the base-line conditions for both thermal reactions and soot-catalyzed reactions of methane. They also added the capability to add diluents such as hydrogen and helium into the reaction system to determine their respective effects on selectivity during the methane activation experiments. They found that the fullerene soot significantly decreased the threshold for the methane activation and C{sub 2} products at temperatures as low as 800{degrees}C, whereas the pure thermal reaction required temperatures in the range of 900 to 950{degrees}C. However, under their conditions the selectivity to C{sub 2} was much lower for the fullerene soot, than for the thermal case. They found that the presence of H{sub 2} helped the selectivity to some degree at a given temperature, but still formed a considerable amount of coke under these condition.

  19. Potassium effects on activated-carbon-supported iron catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Wenping Ma; Edwin L. Kugler; Dady B. Dadyburjor

    2007-08-15

    The effect of potassium on the activity, selectivity, and distribution of products (hydrocarbons and oxygenates) was studied over iron catalysts supported on activated carbon (AC) for Fischer-Tropsch synthesis (FTS). This is part of a wider study on the incremental effects of components (including the support) of a multicomponent (Fe-Cu-Mo-K/AC) FTS catalyst. The range of potassium loading used was 0-2 wt%. A fixed-bed reactor was used under the conditions of 260-300{sup o}C, 300 psig, and 3 Nl/g cat/h, using syngas with a H{sub 2}/CO molar feed ratio of 0.9. Both FTS and water-gas shift activities increase after the addition of 0.9 wt % potassium, whereas an opposite trend is observed with the addition of 2 wt % potassium. This is shown to be the result of interaction between the decrease of both the activation energy (E{sub a}) and the pre-exponental factor (k{sub 0}) with the amount of potassium promoter added. Detectable hydrocarbons up to C{sub 34} and oxygenates up to C{sub 5} are formed on the Fe/AC catalysts with or without potassium. The potassium promoter significantly suppresses formation of methane and methanol and shifts selectivities to higher-molecular-weight hydrocarbons (C{sub 5+}) and alcohols (C{sub 2}-C{sub 5}). Meanwhile, the potassium promoter changes paraffin and olefin distributions. At least for carbon numbers of 25 or less, increasing the K level to 0.9 wt % greatly decreases the amount of n-paraffins and internal olefins (i.e., those with the double bond in other than the terminal positions) and dramatically increases branched paraffins and 1-olefins, but a further increase in the K level shows little additional improvement. The addition of potassium changes the effect of temperature on the selectivity to oxygenates. In the absence of K, oxygenate selectivity decreases with temperature. However, when K is present, the selectivity is almost independent of the temperature. 71 refs., 13 figs., 3 tabs.

  20. Identification of the haemolytic activity of Malassezia species.

    PubMed

    Juntachai, Weerapong; Kummasook, Aksarakorn; Mekaprateep, Malee; Kajiwara, Susumu

    2014-03-01

    Malassezia species are part of the normal skin flora and are associated with a number of human and animal skin diseases. However, the mechanisms that mediate infection and host-fungal interactions are poorly understood. The haemolytic activity of several microorganisms is considered a factor that contributes to pathogenicity of the organism to humans and animals. This virulence factor was previously identified in several pathogenic fungi that cause systemic mycoses, such as Aspergillus and Candida. In this study, the haemolytic activity of six major Malassezia species, including M. furfur, M. globosa, M. pachydermatis, M. restricta, M. slooffiae and M. sympodialis, was investigated. The haemolytic activity of these species was tested on tryptone soya agar with 5% sheep blood. All the examined Malassezia species produced a halo zone of complete haemolysis. A quantitative analysis of the haemolytic activity was performed by incubating sheep erythrocytes with the extraction from culture of each Malassezia species. Interestingly, M. globosa and M. restricta showed significantly high haemolytic activity compared with the other Malassezia species. In addition, M. globosa also exhibited stable haemolytic activity after treatment at 100 °C and in the presence of some proteases, indicating that this haemolytic factor is different from those of other fungi. PMID:24028702

  1. Synergistic "ping-pong" energy transfer for efficient light activation in a chromophore-catalyst dyad.

    PubMed

    Quaranta, Annamaria; Charalambidis, Georgios; Herrero, Christian; Margiola, Sofia; Leibl, Winfried; Coutsolelos, Athanassios; Aukauloo, Ally

    2015-10-01

    The synthesis of a porphyrin-Ru(II) polypyridine complex where the porphyrin acts as a photoactive unit and the Ru(II) polypyridine as a catalytic precursor is described. Comparatively, the free base porphyrin was found to outperform the ruthenium based chromophore in the yield of light induced electron transfer. Mechanistic insights indicate the occurrence of a ping-pong energy transfer from the (1)LC excited state of the porphyrin chromophore to the (3)MCLT state of the catalyst and back to the (3)LC excited state of the porphyrin unit. The latter, triplet-triplet energy transfer back to the chromophore, efficiently competes with fast radiationless deactivation of the excited state at the catalyst site. The energy thus recovered by the chromophore allows improved yield of formation of the oxidized form of the chromophore and concomitantly of the oxidation of the catalytic unit by intramolecular charge transfer. The presented results are among the rare examples where a porphyrin chromophore is successfully used to drive an oxidative activation process where reductive processes prevail in the literature. PMID:26327298

  2. Factors affecting activated carbon-based catalysts for selective hydrogen sulfide oxidation

    SciTech Connect

    Li, Huixing; Monnell, J.D.; Alvin, M.A.; Vidic, R.D.

    2008-09-01

    The primary product of coal gasification processes is synthesis gas (syngas), a mixture of CO, H2, CO2, H2O and a number of minor components. Among the most significant minor components in syngas is hydrogen sulfide (H2S). In addition to its adverse environmental impact, H2S poisons the catalysts and hydrogen purification membranes, and causes severe corrosion in gas turbines. Technologies that can remove H2S from syngas and related process streams are, therefore, of considerable practical interest. To meet this need, we work towards understanding the mechanism by which prospective H2S catalysts perform in simulated fuel gas conditions. Specifically, we show that for low-temperature gas clean-up (~1408C) using activated carbon fibers and water plays a significant role in H2S binding and helps to prolong the lifetime of the material. Basic surface functional groups were found to be imperative for significant conversion of H2S to daughter compounds, whereas metal oxides (La and Ce) did little to enhance this catalysis. We show that although thermal regeneration of the material is possible, the regenerated material has a substantially lower catalytic and sorption capacity.

  3. Structure-activity relationships of ruthenium Fischer-Tropsch catalysts (metal particle size effects)

    SciTech Connect

    White, M.W. Jr.

    1989-01-01

    In the group VIII transition metal catalytic conversion of hydrogen/carbon monoxide mixtures to hydrocarbons, it is known that certain catalysts catalyze the production of a narrow boiling range (C{sub 6}-C{sub 12}) product which does not fit the traditional Anderson-Schulz-Flory (ASF) chain growth model. Among the proposed explanations for this selectivity is one based on control of hydrocarbon chain propagation by metal particle size. The focus of this work was to study the effect of metal particle size on catalytic activity for the F-T synthesis. The silica-supported and unsupported Ru catalysts catalyzed the production of a hydrocarbon product which followed the ASF chain growth model and which consisted primarily of n-aklanes and linear 1-alkenes. An equation was derived relating the weight fraction of alkenes and alkanes to the residence times of the alkenes in the reactor and this equation produced a reasonable fit to the experimental data. It was observed that hydrocarbon, CO{sub 2} and CH{sub 4} production increased with time apparently reaching steady state after {approximately}200H. It was also found that increasing reactant gas space velocities (SHSV's) increased the steady state turnover numbers for hydrocarbon, CO{sub 2} and CH{sub 4} production, while at the same time, the AFS probabilities of chain growth and alkene/alkane ratios remained effectively constant.

  4. Selectivity, activity, and metal-support interactions of Rh bimetallic catalysts. Progress report, 15 November 1981-15 August 1982

    SciTech Connect

    Haller, G L

    1982-08-01

    We report on a detailed investigation of the effect of TiO/sub 2/ support on Rh-Ag interaction as exhibited in catalytic activity. The temporal evolution of activity over Rh-Ag/TiO/sub 2/ for ethane hydrogenolysis and hydrogen chemisorption as a function of temperature, Ag to Rh ratio, the Rh particle size, Rh loading, and ambient gas were studied. Preliminary extended x-ray absorption fine structure (EXAFS) analysis of Rh/TiO/sub 2/ catalysts indicate that 100% exposed (dispersed) catalyst prepared by ion exchange may be atomically dispersed after low temperature reduction. 7 figures, 1 table.

  5. Steroid-Derived Naphthoquinoline Asphaltene Model Compounds: Hydriodic Acid Is the Active Catalyst in I2-Promoted Multicomponent Cyclocondensation Reactions.

    PubMed

    Schulze, Matthias; Scott, David E; Scherer, Alexander; Hampel, Frank; Hamilton, Robin J; Gray, Murray R; Tykwinski, Rik R; Stryker, Jeffrey M

    2015-12-01

    A multicomponent cyclocondensation reaction between 2-aminoanthracene, aromatic aldehydes, and 5-α-cholestan-3-one has been used to synthesize model asphaltene compounds. The active catalyst for this reaction has been identified as hydriodic acid, which is formed in situ from the reaction of iodine with water, while iodine is not a catalyst under anhydrous conditions. The products, which contain a tetrahydro[4]helicene moiety, are optically active, and the stereochemical characteristics have been examined by VT-NMR and VT-CD spectroscopies, as well as X-ray crystallography. PMID:26584791

  6. Volatile species in halide-activated-diffusion coating packs

    NASA Technical Reports Server (NTRS)

    Bianco, Robert; Rapp, Robert A.; Jacobson, Nathan S.

    1992-01-01

    An atmospheric pressure sampling mass spectrometer was used to identify the vapor species generated in a halide-activated cementation pack. Pack powder mixtures containing a Cr-Al binary masteralloy powder, an NH4Cl activator salt, and either ZrO2 or Y2O3 (or neither) were analyzed at 1000 C. Both the equilibrium calculations for the pack and mass spectrometer results indicated that volatile AlCl(x) and CrCl(y) species were generated by the pack powder mixture; in packs containing the reactive element oxide, volatile ZrCl(z) and YCl(w) species were formed by the conversion of their oxide sources.

  7. ''KN'' series cracking catalysts

    SciTech Connect

    Klapstov, V.F.; Khlebrikova, M.A.; Maslova, A.A.; Nefedov, B.K.

    1986-09-01

    The basic directions in improving high-activity zeolitic cracking catalysts at the present stage are improvements in the resistance to attrition and increases in the bulk density of the catalysts, along with a changeover to relatively waste-free catalyst manufacturing technology. Catalysts of the ''KN'' series have been synthesized recently with improved quality characteristics. Low-waste technology is used in manufacturing them. Data are presented which show that the KN catalysts are better than the other Soviet catalysts. The starting materials and reagents in preparing the KN catalysts are technical alumina, rare-earth element nitrates, a natural component (such as clay conforming to specification TU-21-25-146-75), sodium hydroxide, and granulated sodium silicate. The preparation of the KN catalysts is described and no silica gel is used in manufacturing the KN series catalyst, in contrast to the RSG-6Ts catalyst. The use of KN series catalysts in place of KMTsR in catalytic cracking units will result in an increase in the naphtha yield by at least 20% by weight, as well as a reduction of the catalyst consumption by a factor of 2-3. A changeover to the commerical production of this catalyst will make it possible to reduce saline waste by a factor of 8-10 and reduce the catalyst cost by a factor of 1.5-2.

  8. Activated Carbon Catalysts for the Production of Hydrogen for the Sulfur-Iodine Thermochemical Water Splitting Cycle

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Harry W. Rollins; Kyle C Burch; Cristina Deiana; Hugo S. Silva; Maria F. Sardella; Dolly Granados

    2009-05-01

    Seven activated carbon catalysts obtained from a variety of raw material sources and preparation methods were examined for their catalytic activity to decompose hydroiodic acid (HI) to produce hydrogen; a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. Within the group of ligno-cellulosic steam-activated carbon catalysts, activity increased with surface area. However, both a mineral-based steam-activated carbon and a ligno-cellulosic chemically-activated carbon displayed activities lower than expected based on their higher surface areas. In general, ash content was detrimental to catalytic activity while total acid sites, as determined by Bohem’s titrations, seemed to favor higher catalytic activity within the group of steam-activated carbons. These results suggest, one more time, that activated carbon raw materials and preparation methods may have played a significant role in the development of surface characteristics that eventually dictated catalyst activity and stability as well.

  9. Controlled leaching with prolonged activity for Co-LDH supported catalyst during treatment of organic dyes using bicarbonate activation of hydrogen peroxide.

    PubMed

    Jawad, Ali; Li, Yibing; Lu, Xiaoyan; Chen, Zhuqi; Liu, Weidong; Yin, Guochuan

    2015-05-30

    The effluents from industries are commonly non-biodegradable and produce various hazardous intermediate products by chemical reactions that have direct impact on environment. In the present investigation, a series of Co-Mg/AL ternary LDH catalysts with fixed Mg/Al ratio were prepared by co-precipitation method. The effect of Co on the activity of the catalyst was monitored on the degradation of methylene blue (MB) as model compound at batch level using bicarbonate activation of H2O2 (BAP) system. On bench level, the best CoMgAl-4 catalyst can completely decolorize both methylene blue (MB) and methylene orange (MO) in short time, while in fixed bed, the catalyst was found stable for over 300 h with nearly 100% decolorization and excellent chemical oxygen demand (COD) removal. No leaching of Co was detected for the entire fixed experiment which may be accounted for long life stability and good activity of the catalyst. The ternary LDH catalysts were characterized by AES, XRD, FTIR, BET, and SEM for its compositional, phase structure, optical properties, textural, and surface morphology respectively. The XRD analysis confirmed characteristic pattern of hydrotalcite like structures without impurity phases. The formation of superoxide and hydroxyl radical as ROS was proposed with CoMgAl-4 by radical's scavengers. PMID:25725338

  10. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste material in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-12-31

    Recently, carbonaceous materials including activated carbon were proven to be effective catalysts for hazardous waste gasification in supercritical water. Using coconut shell activated carbon catalyst, complete decomposition of industrial organic wastes including methanol and acetic acid was achieved. During this process, the total mass of the activated carbon catalyst changes by two competing processes: a decrease in weight via gasification of the carbon by supercritical water, or an increase in weight by deposition of carbonaceous materials generated by incomplete gasification of the biomass feedstocks. The deposition of carbonaceous materials does not occur when complete gasification is realized. Gasification of the activated carbon in supercritical water is often favored, resulting in changes in the quality and quantity of the catalyst. To thoroughly understand the hazardous waste decomposition process, a more complete understanding of the behavior of activated carbon in pure supercritical water is needed. The gasification rate of carbon by water vapor at subcritical pressures was studied in relation to coal gasification and generating activated carbon.

  11. Electron donor properties of claus catalysts--1. Influence of NaOH on the catalytic activity of silica gel

    SciTech Connect

    Dudzik, Z.; George, Z.M.

    1980-05-01

    ESR spectroscopy showed that SO/sub 2/ adsorbed on silica gel impregnated with NaOH formed the SO/sub 2//sup -/ anion radical. With increasing NaOH concentration, the SO/sub 2/ adsorption and the activity for the reaction of H/sub 2/S with SO/sub 2/ (Claus reaction) went through a maximum at 1.0-1.4% NaOH. The SO/sub 2/ anion radical apparently formed by electron transfer from the catalyst surface and was a reaction intermediate which reacted rapidly with H/sub 2/S. The NaOH catalyst had similar stability and activity as commercial alumina catalyst in five-day tests under Claus conditions.

  12. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste materials in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-10-01

    Recently, carbonaceous materials were proved to be effective catalysts for hazardous waste decomposition in supercritical water. Gasification of the carbonaceous catalyst itself is also expected, however, under supercritical conditions. Thus, it is essential to determine the gasification rate of the carbonaceous materials during this process to determine the active lifetime of the catalysts. For this purpose, the gasification characteristics of granular coconut shell activated carbon in supercritical water alone (600-650{degrees}C, 25.5-34.5 MPa) were investigated. The gasification rate at subatmospheric pressure agreed well with the gasification rate at supercritical conditions, indicating the same reaction mechanism. Methane generation under these conditions is via pyrolysis, and thus is not affected by the water pressure. An iodine number increase of 25% was observed as a result of the supercritical water gasification.

  13. XAFS study on structure-activity correlations of α-Co(OH)2 nanosheets water oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Huang, Junheng; Liu, Qinghua; Yao, Tao; Pan, Zhiyun; Wei, Shiqiang

    2016-05-01

    Understanding the structure-activity of the metal hydroxide materials is critical to the design of an efficient oxygen evolution reaction (OER) catalyst for water oxidation. A challenge is to identify and collect surface active site relative to bulk. Here, we have prepared an ultrathin α-Co(OH)2 nanosheet with large exposed surface Co sites as an high-efficiency O2 evolution catalyst. Using XAFS technique, we have investigated the oxidation state and local structural evolutions of the α-Co(OH)2 nanosheets catalyst. A coordination-miss Co sites (CoO6-x) with oxidation state of +3.3 on the nanosheet surface is revealed after the OER procedure, indicating the in situ formation of y-CoOOH nanosheet is a key factor leading to an enhanced water oxidation performance.

  14. Methane conversion to aromatics on Mo/H-ZSM5: Structure of molybdenum species in working catalysts

    SciTech Connect

    Ding, Weiping; Li, Senzi; Meitzner, George D.; Iglesia, Enrique

    2000-10-27

    The structure and density of Mo species in Mo/H-ZSM5 during catalytic CH4 reactions was investigated using in-situ X-ray absorption spectroscopy (XAS), temperature-programmed oxidation after reaction, and the isotopic exchange of D2 with OH groups in H-ZSM5 before and after CH4 reactions. These methods reveal that CH4 reactions cause exchanged Mo2O52+ dimers, formed from physical mixtures of MoO3 and H-ZSM5, to reduce and carburize to form small (0.6-1 nm) MoCx clusters with the concurrent regeneration of the bridging OH groups that were initially replaced by Mo oxo dimers during exchange. In this manner, catalytically inactive Mo oxo species activate in contact with CH4 to form the two sites required for the conversion of CH4 to aromatics: MoCx for C-H bond activation and initial C-C bond formation and acid sites for oligomerization and cyclization of C2+ hydrocarbons to form stable aromatics. These MoCx clusters resist agglomeration during methane reactions at 950 K for > 10 h. The Bronsted acid sites formed during carburization and oligomerization of MoCx species ultimately become covered with hydrogen-deficient reaction intermediates (H/C{sup X} 0.2) or unreactive deposits. The highly dispersed nature of the MoCx clusters was confirmed by detailed simulations of the XAS radial structure function and by the low temperatures required for the complete oxidation of these MoCx species compared with bulk Mo2C. Initial CH4 reactions with MoOx precursors are stoichiometric and lead first to the removal of oxygen as CO, CO2, and H2O and to the introduction of carbidic carbons into the reduced structures. As carbidic carbon passivates the surface, C-H bond activation reactions become catalytic by the coupling of this activation step with the removal of the resulting CHx species to form C2 hydrocarbons, which desorb to re-form the MoCx sites required for C-H bond activation steps.

  15. Fe3-xCuxO4 as highly active heterogeneous Fenton-like catalysts toward elemental mercury removal.

    PubMed

    Zhou, Changsong; Sun, Lushi; Zhang, Anchao; Wu, Xiaofeng; Ma, Chuan; Su, Sheng; Hu, Song; Xiang, Jun

    2015-04-01

    A series of novel spinel Fe3-xCuxO4 (0active heterogeneous Fenton-like catalysts to remove elemental mercury (Hg0) from the simulated flue gases. Inductively coupled plasma-Atomic emission spectrometry (ICP-AES), X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and X-ray photoelectron spectrometer (XPS) were used to characterize the catalysts. The catalysts were confirmed the presence of the redox pairs Fesurf2+/Fesurf3+ and Cusurf+/Cusurf2+ on the surface of the cubic structure. The performance of heterogeneous Fenton-like reactions for Hg0 removal was evaluated in a lab-scale bubbling reactor at the solution temperature of 50°C. The systematic studies on the effects of different catalysts, H2O2 concentration and solution pH values on Hg0 removal efficiencies were performed. The recycling of the Fe3-xCuxO4 catalysts in Fenton-like solution is stable and Hg0 removal efficiency remain above 90% after 3 cycles. The active hydroxyl radical (OH) generated during heterogeneous Fenton-like reactions was confirmed through electron spin resonance (ESR) spin-trapping technique. The Hg0 removal mechanism has been discussed based on the experimental and analytical results. PMID:25655441

  16. Preliminary results from screening tests of commercial catalysts with potential use in gas turbine combustors. Part 1: Furnace studies of catalyst activity

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1976-01-01

    Thirty commercially produced monolith and pellet catalysts were tested as part of a screening process to select catalysts suitable for use in a gas turbine combustor. The catalysts were contained in a 1.8 centimeter diameter quartz tube and heated to temperatures varying between 300 and 1,200 K while a mixture of propane and air passed through the bed at space velocities of 44,000 to 70,000/hour. The amount of propane oxidized was measured as a function of catalyst temperature. Of the samples tested, the most effective catalysts proved to be noble metal catalysts on monolith substrates.

  17. Preliminary results from screening tests of commercial catalysts with potential use in gas turbine combustors. I - Furnace studies of catalyst activity

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1976-01-01

    Thirty commercially produced monolith and pellet catalysts were tested as part of a screening process to select catalysts suitable for use in a gas turbine combustor. The catalysts were contained in a 1.8 centimeter diameter quartz tube and heated to temperatures varying between 300 and 1200 K while a mixture of propane and air passed through the bed at space velocities of 44,000 to 70,000 per hour. The amount of propane oxidized was measured as a function of catalyst temperature. Of the samples tested, the most effective catalysts proved to be noble metal catalysts on monolith substrates.

  18. Catalyst Additives to Enhance Mercury Oxidation and Capture

    SciTech Connect

    Jared W. Cannon; Thomas K. Gale

    2004-12-31

    Preliminary research has shown that SCR catalysts employed for nitrogen-oxide reduction can effectively oxidize mercury. This report discusses initial results from fundamental investigations into the behavior of mercury species in the presence of SCR catalysts at Southern Research Institute. Three different SCR catalysts are being studied. These are honeycomb-type, plate-type, and a hybrid-type catalyst. The catalysts are manufactured and supplied by Cormetech Inc., Hitachi America Ltd., and Haldor-Topsoe Inc., respectively. Test methods and experimental procedures were developed for current and future testing. The methods and procedures equalize factors influencing mercury adsorption and oxidation (surface area, catalyst activity, and pore structure) that normally differ for each catalyst type. Initial testing was performed to determine the time necessary for each catalyst to reach surface-adsorption equilibrium. In addition, the fraction of Hg oxidized by each of the SCR catalyst types is being investigated, for a given amount of catalyst and flow rate of mercury and flue gas. The next major effort will be to examine the kinetics of mercury oxidation across the SCR catalysts with respect to changes in mercury concentration and with respect to HCl concentration. Hg-sorption equilibrium times will also be investigated with respect to ammonia concentration in the simulated flue gas.

  19. Active transposable elements recover species boundaries and geographic structure in Madagascan coffee species.

    PubMed

    Roncal, Julissa; Guyot, Romain; Hamon, Perla; Crouzillat, Dominique; Rigoreau, Michel; Konan, Olivier N'Guessan; Rakotomalala, Jean-Jacques; Nowak, Michael D; Davis, Aaron P; de Kochko, Alexandre

    2016-02-01

    The completion of the genome assembly for the economically important coffee plant Coffea canephora (Rubiaceae) has allowed the use of bioinformatic tools to identify and characterize a diverse array of transposable elements (TEs), which can be used in evolutionary studies of the genus. An overview of the copy number and location within the C. canephora genome of four TEs is presented. These are tested for their use as molecular markers to unravel the evolutionary history of the Millotii Complex, a group of six wild coffee (Coffea) species native to Madagascar. Two TEs from the Gypsy superfamily successfully recovered some species boundaries and geographic structure among samples, whereas a TE from the Copia superfamily did not. Notably, species occurring in evergreen moist forests of eastern and southeastern Madagascar were divergent with respect to species in other habitats and regions. Our results suggest that the peak of transpositional activity of the Gypsy and Copia TEs occurred, respectively, before and after the speciation events of the tested Madagascan species. We conclude that the utilization of active TEs has considerable potential to unravel the evolutionary history and delimitation of closely related Coffea species. However, the selection of TE needs to be experimentally tested, since each element has its own evolutionary history. Different TEs with similar copy number in a given species can render different dendrograms; thus copy number is not a good selection criterion to attain phylogenetic resolution. PMID:26231981

  20. Design strategies for the molecular level synthesis of supported catalysts.

    PubMed

    Wegener, Staci L; Marks, Tobin J; Stair, Peter C

    2012-02-21

    Supported catalysts, metal or oxide catalytic centers constructed on an underlying solid phase, are making an increasingly important contribution to heterogeneous catalysis. For example, in industry, supported catalysts are employed in selective oxidation, selective reduction, and polymerization reactions. Supported structures increase the thermal stability, dispersion, and surface area of the catalyst relative to the neat catalytic material. However, structural and mechanistic characterization of these catalysts presents a formidable challenge because traditional preparations typically afford complex mixtures of structures whose individual components cannot be isolated. As a result, the characterization of supported catalysts requires a combination of advanced spectroscopies for their characterization, unlike homogeneous catalysts, which have relatively uniform structures and can often be characterized using standard methods. Moreover, these advanced spectroscopic techniques only provide ensemble averages and therefore do not isolate the catalytic function of individual components within the mixture. New synthetic approaches are required to more controllably tailor supported catalyst structures. In this Account, we review advances in supported catalyst synthesis and characterization developed in our laboratories at Northwestern University. We first present an overview of traditional synthetic methods with a focus on supported vanadium oxide catalysts. We next describe approaches for the design and synthesis of supported polymerization and hydrogenation catalysts, using anchoring techniques which provide molecular catalyst structures with exceptional activity and high percentages of catalytically significant sites. We then highlight similar approaches for preparing supported metal oxide catalysts using atomic layer deposition and organometallic grafting. Throughout this Account, we describe the use of incisive spectroscopic techniques, including high

  1. Novel catalysts for methane activation. Quarterly report number 10, January 1--March 31, 1995

    SciTech Connect

    Hirschon, A.S.; Du, Y.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1995-06-10

    Fullerenes are a recently discovered allotrope of carbon that possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon-based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks: synthesis and characterization of the fullerenes and fullerene soots; testing of catalysts; and evaluation of the results and technical reporting. The authors had two objectives for this quarter. The first objective was to complete their study of the K-doped fullerene soots to include the selectivity of these materials as a function of methane conversion. The second objective was to identify and evaluate other metal promoters, and the combination of transition and alkali metals to enhance the selectivity of the methane conversion process and hopefully reduce the temperature of reaction. Results from these two tasks are discussed.

  2. Sphalerite is a geochemical catalyst for carbon−hydrogen bond activation

    PubMed Central

    Shipp, Jessie A.; Gould, Ian R.; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

    2014-01-01

    Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth’s deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon−hydrogen bond in the dimethylcyclohexanes. PMID:25071186

  3. Distinguishing molecular environments in supported Pt catalysts and their influences on activity and selectivity

    NASA Astrophysics Data System (ADS)

    Jones, Louis Chin

    This thesis entails the synthesis, automated catalytic testing, and in situ molecular characterization of supported Pt and Pt-alloy nanoparticle (NP) catalysts, with emphasis on how to assess the molecular distributions of Pt environments that are affecting overall catalytic activity and selectivity. We have taken the approach of (a) manipulating nucleation and growth of NPs using oxide supports, surfactants, and inorganic complexes to create Pt NPs with uniform size, shape, and composition, (b) automating batch and continuous flow catalytic reaction tests, and (c) characterizing the molecular environments of Pt surfaces using in situ infrared (IR) spectroscopy and solid-state 195Pt NMR. The following will highlight the synthesis and characterization of Ag-doped Pt NPs and their influence on C 2H2 hydrogenation selectivity, and the implementation of advanced solid-state 195Pt NMR techniques to distinguish how distributions of molecular Pt environments vary with nanoparticle size, support, and surface composition.

  4. Active and Durable Hydrogen Evolution Reaction Catalyst Derived from Pd-Doped Metal-Organic Frameworks.

    PubMed

    Chen, Jitang; Xia, Guoliang; Jiang, Peng; Yang, Yang; Li, Ren; Shi, Ruohong; Su, Jianwei; Chen, Qianwang

    2016-06-01

    The water electrolysis is of critical importance for sustainable hydrogen production. In this work, a highly efficient and stable PdCo alloy catalyst (PdCo@CN) was synthesized by direct annealing of Pd-doped metal-organic frameworks (MOFs) under N2 atmosphere. In 0.5 M H2SO4 solution, PdCo@CN displays remarkable electrocatalytic performance with overpotential of 80 mV, a Tafel slope of 31 mV dec(-1), and excellent stability of 10 000 cycles. Our studies reveal that noble metal doped MOFs are ideal precursors for preparing highly active alloy electrocatalysts with low content of noble metal. PMID:27112733

  5. [Nocturnal flight activities of Culicoides (Diptera: Ceratopogonidae) species in Konya].

    PubMed

    Dik, Bilal; Ergül, Recep

    2006-01-01

    This study was carried out in order to determine the nocturnal flight activities of Culicoides species during July, 1997 in Konya. Light traps were used for the collection of Culicoides specimens. They were placed in or nearby pens of poultry, sheep and cattle between the hours 20:00-22:00, 22:00-24:00, 24:00-02:00, 02:00-04:00, 04:00-06:00, and 06:00-08:00. A total of 4084 specimens were caught. Twelve species (C. puncticollis, C. maritimus, C. circumscriptus, C. punctatus, C. newsteadi, C. flavipulicaris, C. obsoletus, C. pulicaris, C. simulator, C. gejgelensis, C. salinarius, and C. vexans) were identified. C. puncticollis, C. maritimus, C. circumscriptus and C. punctatus were the most abundant species. It was found that the Culicoides species fly at night and their numbers decrease in the morning. The different species were observed to have different flight activities. A maximum number of C. puncticollis was captured in between the hours 20:00-22:00. A relatively high number of C. maritimus were caught between the hours of 20.00-22.00. Flight activity of this species peaked between the hours 22:00-24:00. The maximum number of C. circumscriptus was captured between the hours of 22:00-24:00 and 24:00-02:00. Flight activity of C. punctatus increased regularly from the hours of 20:00-22:00 until 02:00-04:00. PMID:17160855

  6. Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

    PubMed Central

    Oveisi, Ali R.; Zhang, Kainan; Khorramabadi-zad, Ahmad; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880 m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity. PMID:26177563

  7. Effect of surface oxidation of the support on the thiophene hydrodesulfurization activity of Mo, Ni, and NiMo catalysts supported on activated carbon

    SciTech Connect

    Calafat, A. |; Lopez-Agudo, A.; Palacios, J.M.

    1996-08-01

    The present investigation attempts to provide a better understanding of the influence of the nature of the carbon support on the HDS activity of Mo, Ni, and NiMo catalysts. For this purpose a high purity activated carbon was subjected to oxidative treatments with HNO{sub 3} to modify its surface properties. NiMo catalysts supported on the resulting activated carbons were prepared and characterized by TPR, XRD, and SEM-EDX, and their activity for HDS of thiophene at 30 bars and 375{degrees}C was evaluated. The results obtained showed that oxidation of the carbon surface does not affect the HDS activity and other characteristics of the supported Mo phase. In contrast, the HDS activity of the Ni catalysts is enhanced by acid treatments of the carbon support. In this case, introduction of oxygen-containing functional groups (O{sub (s)}) leads to a strong interaction of O{sub (s)}-Ni during impregnation, which becomes essential to achieving and preserving high nickel dispersion. This effect on NiMo/C catalysts. The synergistic effect of the bimetallic catalysts is observed only when oxygen functional groups are present on the carbon surface, which are necessary for a good HDS activity, mainly because they enhance Ni-Mo interactions that produce the highly active Ni-Mo-S phase. A NiMoO{sub 4}-like phase formed during impregnation seems to be the precursor for the active sulfide phase over the present NiMo/C catalysts. 34 refs., 6 figs., 5 tabs.

  8. Impact of carbon on the surface and activity of silica-carbon supported copper catalysts for reduction of nitrogen oxides

    NASA Astrophysics Data System (ADS)

    Spassova, I.; Stoeva, N.; Nickolov, R.; Atanasova, G.; Khristova, M.

    2016-04-01

    Composite catalysts, prepared by one or more active components supported on a support are of interest because of the possible interaction between the catalytic components and the support materials. The supports of combined hydrophilic-hydrophobic type may influence how these materials maintain an active phase and as a result a possible cooperation between active components and the support material could occur and affects the catalytic behavior. Silica-carbon nanocomposites were prepared by sol-gel, using different in specific surface areas and porous texture carbon materials. Catalysts were obtained after copper deposition on these composites. The nanocomposites and the catalysts were characterized by nitrogen adsorption, TG, XRD, TEM- HRTEM, H2-TPR, and XPS. The nature of the carbon predetermines the composite's texture. The IEPs of carbon materials and silica is a force of composites formation and determines the respective distribution of the silica and carbon components on the surface of the composites. Copper deposition over the investigated silica-carbon composites leads to formation of active phases in which copper is in different oxidation states. The reduction of NO with CO proceeds by different paths on different catalysts due to the textural differences of the composites, maintaining different surface composition and oxidation states of copper.

  9. Active low-valent niobium catalysts from NbCl5 and hydrosilanes for selective intermolecular cycloadditions.

    PubMed

    Satoh, Yasushi; Obora, Yasushi

    2011-10-21

    An active niobium catalyst was developed via a simple and nontoxic reduction method from NbCl(5)/hydrosilane and utilized for the selective [2 + 2 + 2] cycloaddition reaction of terminal alkynes and alkenes/α,ω-dienes, to give 1,3-cyclohexadiene derivatives in high yields with excellent chemo- and regioselectivity. PMID:21919436

  10. Effects of plasmochemical treatments and cerium additions on the structural characteristics and activity of copper catalyst particles in isopropanol dehydrogenation

    NASA Astrophysics Data System (ADS)

    Platonov, E. A.; Lobanov, N. N.; Galimova, N. A.; Protasova, I. A.; Yagodovskii, V. D.

    2012-08-01

    The effect of the treatment of the 5 wt % Cu/SiO2 (I) and (5 wt % Cu + 0.5 wt % Ce)/SiO2 (II) catalysts with glow discharge plasma in O2, H2, and Ar on their structural characteristics was studied by X-ray phase analysis; the influence of cerium additions and plasmochemical treatments on the catalyst activity in isopropanol dehydrogenation was also investigated. Under the plasmochemical treatment, the diameters of Cu particles in catalyst I nearly doubled and microstresses in the metal particles also changed. Catalyst II was X-ray amorphous both before and after plasmochemical treatments. The activity of I after plasmochemical treatment increased because of the increase in the number of centers and changes in their composition. Growth of the activity of I compared with the activity of II was explained by the formation of new catalytic centers due to positive charging of the Ce+α adatom on the surface of the copper particle.

  11. A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    DOE PAGESBeta

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-02-19

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superiormore » activity for hydrogen evolution, achieving current densities of 10 mA cm–2 and 100 mA cm–2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.« less

  12. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    NASA Astrophysics Data System (ADS)

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-02-01

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm-2 and 100 mA cm-2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.

  13. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide.

    PubMed

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I; Wang, Hailiang

    2016-01-01

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm(-2) and 100 mA cm(-2) at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation. PMID:26892437

  14. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  15. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    PubMed Central

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-01-01

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm−2 and 100 mA cm−2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation. PMID:26892437

  16. Structure and Activity of Pt-Ni Catalysts Supported on Modified Al2O3 for Ethanol Steam Reforming.

    PubMed

    Navarro, R M; Sanchez-Sanchez, M C; Fierro, J L G

    2015-09-01

    Modification of alumina with La-, Ce-, Zr- and Mg-oxides was studied with the aim to use them as supports of bimetallic Pt-Ni catalysts for the steam reforming of ethanol. Activity results showed that modifications of Al2O3 support with the incorporation of La, Ce, Zr or Mg oxides play an essential role in the catalytic behaviour of PtNi catalysts. Bimetallic PtNi catalyst supported on bare Al2O3 showed evolution of the reaction products with time on stream consisting in the increase of C2H4 production with concomitant decrease of CH4 and CO2 production. The addition of Mg or Zr to γ-A1203 did not inhibit the appearance of ethylene but delayed its production. In the case of Ce- or La-supported catalysts, the product selectivities were stable with time-on-stream, with no changes being observed in the product distribution for 24 h. Characterization results showed that La- and Ce-containing supports improves the Pt and Ni metal exposure values. The better stability achieved for Ce and La containing catalysts was inferred to be related with a participation/assistance of lanthanum and cerium entities in the gasification of coke deposits together with a modification of Pt and Ni dispersion which lower the probability of the nucleation of coke precursors on their surfaces. PMID:26716216

  17. Comparison of Cas9 activators in multiple species.

    PubMed

    Chavez, Alejandro; Tuttle, Marcelle; Pruitt, Benjamin W; Ewen-Campen, Ben; Chari, Raj; Ter-Ovanesyan, Dmitry; Haque, Sabina J; Cecchi, Ryan J; Kowal, Emma J K; Buchthal, Joanna; Housden, Benjamin E; Perrimon, Norbert; Collins, James J; Church, George

    2016-07-01

    Several programmable transcription factors exist based on the versatile Cas9 protein, yet their relative potency and effectiveness across various cell types and species remain unexplored. Here, we compare Cas9 activator systems and examine their ability to induce robust gene expression in several human, mouse, and fly cell lines. We also explore the potential for improved activation through the combination of the most potent activator systems, and we assess the role of cooperativity in maximizing gene expression. PMID:27214048

  18. Effects of CeO 2-ZrO 2 present in Pd/Al 2O 3 catalysts on the redox behavior of PdO x and their combustion activity

    NASA Astrophysics Data System (ADS)

    Zhou, Renxian; Zhao, Bo; Yue, Baohua

    2008-05-01

    The ceria-zirconium-modified alumina-supported palladium catalysts are prepared using impregnation method with H 2PdCl 4 as Pd source, hydrazine hydrate as reducing agent. The physicochemical properties of these catalysts are characterized by BET surface area (BET), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (H 2-TPR) and temperature programmed oxidation (O 2-TPO) techniques, and their catalytic activities for the combustion of methane are examined. The results show that the palladium mainly exist in a highly dispersed PdO species on Ce-Zr-rich grains as well as Al 2O 3-rich grains surfaces, and a stable PdO species due to the strong interaction between PdO and CeO 2-ZrO 2 on the Ce-Zr/Al 2O 3 surfaces. The catalytic activity is strongly related to the redox behavior of PdO species highly dispersed on Ce-Zr-rich grains and Al 2O 3-rich grains surfaces, and the higher the reducibility of the PdO species, the higher the catalytic activity. The presence of Ce-Zr in Pd/Al 2O 3 catalyst would inhibit the site growth of PdO x particles and decomposition of PdO to Pd 0, and the reoxidation property of Pd 0 to PdO x is significantly improved, which obviously increases thermal stability and catalytic activity of Pd/Ce-Zr/Al 2O 3 catalyst for the methane combustion.

  19. Ti or Sn doping as a way to increase activity and sulfur tolerance of Mn/CeO2 catalyst for low temperature NH3 selective catalytic reduction of NO

    NASA Astrophysics Data System (ADS)

    Xiong, Yan; Tang, Changjin; Dong, Lin

    2015-04-01

    Mn/CeO2 catalysts modified by doping of Ti or Sn were investigated for low temperature selective catalytic reduction (SCR) of NO by NH3 with the aim of studying the effects of Ti, Sn doping on the catalytic performance. Ceria-based solid solutions (Ce0.8Ti0.2O2 and Ce0.8Sn0.2O2) were synthesized via inverse co-precipitation, and used as supports to prepare MnOx/Ce0.8M0.2O2 (M =Ti4+, Sn4+) catalysts through wetness impregnation method. The results showed that doping of Ti or Sn to the CeO2 support increase the NO removal efficiency. A NO conversion of more than 90 % was obtained over the Mn/CeTi catalyst at the temperature window of 175 ~ 300 °C under a gas hourly space velocity (GHSV) of 60,000 mL•g-1•h-1. Catalysts modified by Ti and Sn were also found to obtain higher SO2 resistance than Mn/CeO2 catalyst. More than 90% NO conversion and 95% N2 selectivity could be provided by Mn/CeTi catalyst in the presence of 100 ppm SO2 at 250 °C for 10 h. A series of characterization techniques, namely XRD, BET, H2-TPR, XPS, NH3-TPD and in situ DRIFTS were used to elucidate the structure and surface properties of the obtained supports and catalysts. The results indicate that doping of Ti or Sn brings about catalysts with favorable properties such as higher BET surface area, better oxygen storage capacity and stronger surface acidity. The relative amount of Mn4+, Ce3+, adsorbed oxygen species and oxygen vacancies on the surface of catalysts are in the order of Mn/CeTi>Mn/CeSn>Mn/CeO2, which is thought to make positive a contribution to the low-temperature SCR activity. The promoted SCR activity is considered as well to be related to the dual redox cycles in Mn/CeTi (Mn4+ + Ce3+ ↔ Mn3+ + Ce4+, Ce4+ + Ti3+ ↔ Ce3+ + Ti4+) and Mn/CeSn (Mn4+ + Ce3+ ↔ Mn3+ + Ce4+, Ce4+ + Sn2+ ↔ Ce3+ + Sn4+ ) catalysts.

  20. Production of biodiesel fuel from canola oil with dimethyl carbonate using an active sodium methoxide catalyst prepared by crystallization.

    PubMed

    Kai, Takami; Mak, Goon Lum; Wada, Shohei; Nakazato, Tsutomu; Takanashi, Hirokazu; Uemura, Yoshimitsu

    2014-07-01

    In this study, a novel method for the production of biodiesel under mild conditions using fine particles of sodium methoxide formed in dimethyl carbonate (DMC) is proposed. Biodiesel is generally produced from vegetable oils by the transesterification of triglycerides with methanol. However, this reaction produces glycerol as a byproduct, and raw materials are not effectively utilized. Transesterification with DMC has recently been studied because glycerol is not formed in the process. Although solid-state sodium methoxide has been reported to be inactive for this reaction, the catalytic activity dramatically increased with the preparation of fine catalyst powders by crystallization. The transesterification of canola oil with DMC was studied using this catalyst for the preparation of biodiesel. A conversion greater than 96% was obtained at 65°C for 2h with a 3:1M ratio of DMC and oil and 2.0 wt% catalyst. PMID:24813567

  1. Evaluation of the Two-Dimensional Performances of Low Activity Planar Catalysts: Development and Validation of a True Scanning Reactor.

    PubMed

    Marelli, M; Nemenyi, A; Dal Santo, V; Psaro, R; Ostinelli, L; Monticelli, D; Dossi, C; Recchia, S

    2016-01-11

    The development of a scanning reactor for planar catalysts is presented here. With respect to other existing models, this reactor is able to scan catalysts even with low turnover frequencies with a minimum sensed circular area of approximately 6 mm in diameter. The downstream gas analysis is performed with a quaprupole mass spectrometer. The apparatus performances are presented for two different reactions: the hydrogenation of butadiene over palladium films and the oxidation of CO over a gold/titania catalyst. With the final setup, true scans in both X and Y directions (or even in a previously defined complex directional pattern) are possible within a scan speed ranging from 0.1 to 5.0 mm/min. Finally, this apparatus aims at becoming a valuable tool for high throughput and combinatorial experimentation to test patterned active surfaces and catalytic libraries. PMID:26616670

  2. Effect of a catalyst on the kinetics of reduction of celestite (SrSO{sub 4}) by active charcoal

    SciTech Connect

    Sonawane, R.S.; Kale, B.B.; Apte, S.K.; Dongare, M.K.

    2000-02-01

    Reduction of celestite (SrSO{sub 4}) powder with particles of active charcoal has been studied extensively in the absence and presence of catalysts. The optimum temperature at the charging zone has been optimized to get a maximum water-soluble strontium sulfide value. The strontium value has been analyzed using a chemical method, which was verified by the instrumental method using an inductively coupled plasma-optical emission spectrophotometer (ICP-OES). The conversion-time data have been analyzed by using a modified volume-reaction (MVR) model, and the effect of the catalyst on kinetic parameters has been elucidated. It was found that potassium carbonate, potassium dichromate, sodium carbonate, and sodium dichromate catalysts were found to enhance the reaction rate quite satisfactorily in the reduction of the celestite (SrSO{sub 4}).

  3. Ultrasound enhanced heterogeneous activation of peroxymonosulfate by a bimetallic Fe-Co/SBA-15 catalyst for the degradation of Orange II in water.

    PubMed

    Cai, Chun; Zhang, Hui; Zhong, Xing; Hou, Liwei

    2015-01-01

    Mesoporous silica SBA-15 supported iron and cobalt (Fe-Co/SBA-15) was prepared and used as catalyst in the ultrasound (US) enhanced heterogeneous activation of peroxymonosulfate (PMS, HSO5(-)) process. The effects of some important reaction parameters on the removal of Orange II by US/Fe-Co/SBA-15/PMS process were investigated. The results indicated that the removal rate of Orange II was not significantly affected by the initial pH, and it increased with the higher PMS concentration, reaction temperature, Fe-Co/SBA-15 dosage and ultrasonic power. Furthermore, sulfate radicals (SO4(-)) were assumed to be the dominating reactive species for the Orange II decolorization. Moreover, the Fe-Co/SBA-15 catalyst showed high activity during the repeated experiments. The intermediate products were identified by GC-MS, thereby a plausible degradation pathway is proposed. In addition, the chemical oxygen demand (COD) removal efficiencies at 2 and 24h were 56.8% and 80.1%, respectively and the corresponding total organic carbon (TOC) removal efficiencies were 33.8 and 53.3%. Finally, toxicity tests with activated sludge showed that the toxicity of the solution increased during the first stage and then decreased significantly with the progress of the oxidation. PMID:25262480

  4. Halogen-Bonding-Assisted Iodosylbenzene Activation by a Homogenous Iron Catalyst.

    PubMed

    de Sousa, David P; Wegeberg, Christina; Vad, Mads Sørensen; Mørup, Steen; Frandsen, Cathrine; Donald, William A; McKenzie, Christine J

    2016-03-01

    The iron(III) complex of hexadentate N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate (tpena(-) ) is a more effective homogenous catalyst for selective sulfoxidation and epoxidation with insoluble iodosylbenzene, [PhIO]n , compared with soluble methyl-morpholine-N-oxide (NMO). We propose that two molecules of [Fe(tpena)](2+) cooperate to solubilize PhIO, extracting two equivalents to form the halogen-bonded dimeric {[Fe(tpena)OIPh]2 }(4+) . The closest intradimeric I⋅⋅⋅O distance, 2.56 Å, is nearly 1 Å less than the sum of the van de Waals radii of these atoms. A correlation of the rates of the reaction of {[Fe(tpena)OIPh]2 }(4+) with para-substituted thioanisoles indicate that this species is a direct metal-based oxidant rather than a derived ferryl or perferryl complex. A study of gas-phase reactions indicate that an ion at m/z=231.06100 originates from solution-state {[Fe(tpena)OIPh]2 }(4+) and is ascribed to [Fe(III) (tpenaO)](2+) , derived from an intramolecular O atom insertion into an Fe-tpena donor bond. Proposed ion pairs, {[Fe(tpena)OIPh]Cl}(+) and {[Fe(tpena)OIPh]ClO4 }(+) , are more stable than native [Fe(tpena)OIPh](2+) ions, suggesting that halogen-bonding, as for the solution and solid states, operates also in the gas phase. PMID:26598789

  5. Increasing FCC regenerator catalyst level

    SciTech Connect

    Wong, R.F. )

    1993-11-01

    A Peruvian FCC unit's operations were improved by increasing the regenerator's catalyst level. This increase resulted in lower stack losses, an improved temperature profile, increased catalyst activity and a lower catalyst consumption rate. A more stable operation saved this Peruvian refiner over $131,000 per year in catalyst alone. These concepts and data may be suitable for your FCC unit as well.

  6. Searching for active binary rutile oxide catalyst for water splitting from first principles.

    PubMed

    Chen, Dong; Fang, Ya-Hui; Liu, Zhi-Pan

    2012-12-28

    Water electrolysis is an important route to large-scale hydrogen production using renewable energy, in which the oxygen evolution reaction (OER: 2H(2)O → O(2) + 4H(+) + 4e(-)) causes the largest energy loss in traditional electrocatalysts involving Ru-Ir mixed oxides. Following our previous mechanistic studies on the OER on RuO(2)(110) (J. Am. Chem. Soc. 2010, 132, 18214), this work aims to provide further insight into the key parameters relevant to the activity of OER catalysts by investigating a group of rutile-type binary metal oxides, including RuNiO(2), RuCoO(2), RuRhO(2), RuIrO(2) and OsIrO(2). Two key aspects are focused on, namely the surface O coverage at the relevant potential conditions and the kinetics of H(2)O activation on the O-covered surfaces. The O coverage for all the oxides investigated here is found to be 1 ML at the concerned potential (1.23 V) with all the exposed metal cations being covered by terminal O atoms. The calculated free energy barrier for the H(2)O dissociation on the O covered surfaces varies significantly on different surfaces. The highest OER activity occurs at RuCoO(2) and RuNiO(2) oxides with a predicted activity about 500 times higher than pure RuO(2). On these oxides, the surface bridging O near the terminal O atom has a high activity for accepting the H during H(2)O splitting. It is concluded that while the differential adsorption energy of the terminal O atom influences the OER activity to the largest extent, the OER activity can still be tuned by modifying the electronic structure of surface bridging O. PMID:22941355

  7. Wilsonville Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama. Topical report No. 14. Catalyst activity trends in two-stage coal liquefaction

    SciTech Connect

    Not Available

    1984-02-01

    The Two Stage Coal Liquefaction process became operational at Wilsonville in May 1981, with the inclusion of an H-OIL ebullated-bed catalytic reactor. The two stage process was initially operated in a nonintegrated mode and has recently been reconfigurated to fully integrate the thermal and the catalytic stages. This report focuses on catalyst activity trends observed in both modes of operation. A literature review of relevant catalyst screening studies in bench-scale and PDU units is presented. Existing kinetic and deactivation models were used to analyze process data over an extensive data base. Based on the analysis, three separate, application studies have been conducted. The first study seeks to elucidate the dependence of catalyst deactivation rate on type of coal feedstock used. A second study focuses on the significance of catalyst type and integration mode on SRC hydrotreatment. The third study presents characteristic deactivation trends observed in integrated operation with different first-stage thermal severities. In-depth analytical work was conducted at different research laboratories on aged catalyst samples from Run 242. Model hydrogenation and denitrogenation activity trends are compared with process activity trends and with changes observed in catalyst porosimetric properties. The accumulation of metals and coke deposits with increasing catalyst age, as well as their distribution across a pellet cross-section, are discussed. The effect of catalyst age and reactor temperature on the chemical composition of flashed bottoms product is addressed. Results from regenerating spent catalysts are also presented. 35 references, 31 figures, 18 tables.

  8. Amorphous Silicate Smokes as Catalysts for the Production of Complex Organic Species in the Primitive Solar Nebula

    NASA Astrophysics Data System (ADS)

    Nuth, J. A., III; Hill, H. G. M.

    2002-03-01

    Amorphous Mg-silicates are excellent Fischer-Tropsch catalysts that convert H2 and CO into hydrocarbons almost as well as Fe-silicates. Mg-silicates do not catalyze formation of ammonia. N is incorporated into the organics if CO, N2 and H2 are used.

  9. Amorphous Silicate Smokes as Catalysts for the Production of Complex Organic Species in the Primitive Solar Nebula

    NASA Technical Reports Server (NTRS)

    Nuth, J. A., III; Hill, H. G. M.

    2002-01-01

    Amorphous Mg-silicates are excellent Fischer-Tropsch catalysts that convert H2 and CO into hydrocarbons almost as well as Fe-silicates. Mg-silicates do not catalyze formation of ammonia. N is incorporated into the organics if CO, N2 and H2 are used. Additional information is contained in the original extended abstract.

  10. New catalysts active for the mild oxidation of hydrogen sulfide to sulfur

    SciTech Connect

    Laperdrix, E.; Costentin, G.; Guyen, N.N.; Saur, O.; Lavalley, J.C.

    1999-10-25

    Nickel iron phosphates were studied for the selective oxidation of hydrogen sulfide to sulfur. Nickel iron phosphate and Fe/Cr samples were more active than simple iron, chromium, and mixed iron-chromium oxides, which has been previously studied. Nickel iron phosphate catalyst prepared by solid-solid method with, consequently, a very low specific surface area was intrinsically active and selective to sulfur (conversion 17%, S{sub n} selectivity 97%); no rapid deactivation was observed. Even though higher specific surface area samples, prepared according to a solution method at various calcination temperatures, showed better performance (conversion 76%, S{sub n}selectivity {gt}90%), the specific activity depended on the crystallinity of the samples. The reaction is apparently structure sensitive. The structure of the catalytic material must facilitate electronic exchange, evidence by Moessbauer characterization. The establishment of the mixed valency Fe{sub 2+}/Fe{sup 3+} under catalytic feed was shown to be an essential factor in this reaction.

  11. Pd-embedded graphene: An efficient and highly active catalyst for oxidation of CO

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Nematollahi, Parisa; Nurazar, Roghaye

    2016-04-01

    Despite numerous efforts performed on the elimination of toxic gases from the air, the oxidation of carbon monoxide (CO) with metal-embedded nanostructures still remains a challenge. The geometry, electronic structure and catalytic properties of Pd-doped graphene (Pd-graphene) are investigated by means of density functional theory (DFT) calculations. The large atomic radius of Pd dopant in graphene can induce the local surface curvature and modulate the electronic structure of the sheet through the charge redistribution effects. Also, Pd-graphene can facilitate the O2 adsorption. Therefore, the catalytic activity of the Pd-graphene for CO oxidation reaction is enhanced. Moreover, the complete CO oxidation reactions on the Pd-graphene include a two-step process of the Langmuir-Hinshelwood (LH) reaction, in which the first step is almost barrier-less (Eact = 0.002 eV) and the second step exhibits an energy barrier of 0.2 eV. The results indicate that the surface activity of graphene-based materials can be drastically improved by introducing the Pd dopants, so Pd-graphene can be a clue for fabricating graphene-based catalysts with high activity toward the oxidation of CO molecule.

  12. Novel catalysts for methane activation. Final progress report, September 30, 1992--April 30, 1996

    SciTech Connect

    Hirschon, A.S.; Du, Y.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1996-06-11

    This final report summarizes the results of our research under Contract No. DE-AC22-92PC92112, Novel Catalysts for Methane Activation. In this research we prepared and tested fullerene soots for converting methane into higher hydrocarbons. We conducted the methane conversions using dehydrocoupling conditions, primarily in the temperature regimes of 600{degrees}-1000{degrees}C and atmospheric pressures. The research was divided into three sections. The first section focused on comparing fullerene soots with other forms of carbon such as acetylene black and Norit-A. We found that the fullerene soot was indeed more reactive than the other forms of carbon. However, due to its high reactivity, it was not selective. The second section focused on the effect of metals on the reactivity of the soots, including both transition metals and alkali metals. We found that potassium could enhance the selectivities of fullerene soot to higher hydrocarbons, but the effect was unique to fullerene soot and did not improve the performance of other forms of carbon. The third part focused on the use of co-feeds for methane activation to enhance the selectivities and lower the temperature threshold of methane activation.

  13. In-situ activation of CuO/ZnO/Al.sub.2 O.sub.3 catalysts in the liquid phase

    DOEpatents

    Brown, Dennis M.; Hsiung, Thomas H.; Rao, Pradip; Roberts, George W.

    1989-01-01

    The present invention relates to a method of activation of a CuO/ZnO/Al.sub.2 O.sub.3 catalyst slurried in a chemically inert liquid. Successful activation of the catalyst requires the use of a process in which the temperature of the system at any time is not allowed to exceed a certain critical value, which is a function of the specific hydrogen uptake of the catalyst at that same time. This process is especially critical for activating highly concentrated catalyst slurries, typically 25 to 50 wt %. Activation of slurries of CuO/ZnO/Al.sub.2 O.sub.3 catalyst is useful in carrying out the liquid phase methanol or the liquid phase shift reactions.

  14. Microwave enhanced alcoholysis of non-edible (algal, jatropha and pongamia) oils using chemically activated egg shell derived CaO as heterogeneous catalyst.

    PubMed

    Joshi, Girdhar; Rawat, Devendra S; Sharma, Amit Kumar; Pandey, Jitendra K

    2016-11-01

    Microwave enhanced fast and efficient alcoholysis (methanolysis and ethanolysis) of non-edible oils (algal, jatropha and pongamia) is achieved using chemically activated waste egg shell derived CaO (i.e. CaO(cesp)) as heterogeneous catalyst. CaO(cesp) was extracted from waste chicken egg shell and further activated chemically by supporting transition metal oxide. The maximum conversion was achieved using 3wt% catalysts under 700W microwave irradiation and 10:1 alcohol/oil ratio in 6min. Alcoholysis using ZnO activated CaO(cesp) catalyst has shown higher reaction yields in comparison to other modified catalysts. Methanolysis has shown better biodiesel conversion in comparison to ethanolysis. The catalyst has shown longer lifetime and sustained activity after being used for four cycles. Due to more saturated fatty acid content; algal biodiesel has shown improved fuel properties in comparison to other biodiesels. PMID:27521785

  15. Unraveling the role of support surface hydroxyls and its effect on the selectivity of C2 species over Rh/γ-Al2O3 catalyst in syngas conversion: A theoretical study

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Duan, Tian; Wang, Baojun; Ling, Lixia

    2016-08-01

    The supported Rh-based catalysts exhibit the excellent catalytic performances for syngas conversion to C2 species. In this study, all possible elementary steps leading to C2 species from syngas have been explored to identify the role of support and its surface hydroxyls over Rh/γ-Al2O3 catalyst; Here, the results are obtained using density functional theory (DFT) method. Two models: Rh4 cluster supported on the dry γ-Al2O3(110) surface, D(Rh4), and on the hydroxylated γ-Al2O3(110) surface, H(Rh4), have been used to model Rh/γ-Al2O3 catalyst. Our results show that CO prefers to be hydrogenated to CHO, subsequently, starting from CHO species, CH and CH2 species are the dominate monomers among CHx(x = 1-3) species rather than CH3 and CH3OH on D(Rh4) and H(Rh4) surfaces, suggesting that γ-Al2O3-supported Rh catalyst exhibits the high selectivity towards CHx formation compared to the pure Rh catalyst. On the other hand, D(Rh4) is more favorable for C2 hydrocarbon (C2H2) formation, whereas H(Rh4) surface easily produces C2 hydrocarbon (C2H2) and C2 oxygenates (CHCO,CH2CHO), indicating that the surface hydroxyls of support can affect the selectivity of C2 species over Rh/γ-Al2O3 catalyst in syngas conversion. Moreover, compared to the pure Rh(111) surface, Rh/γ-Al2O3 catalyst can achieve the excellent catalytic performances for syngas conversion to C2 species.

  16. Activity testing of fine-particle size, iron catalysts for coal liquefaction

    SciTech Connect

    Stohl, F.V.; Diegert, K.V.; Gugliotta, T.P.

    1993-10-01

    The use of fine-particle size (< 40 nm) unsupported catalysts in direct coal liquefaction may result in improved economics due to possible enhanced yields of desired products, the potential for decreasing reaction severity, and the possibility of using less catalyst. Sandia has developed a standard testing procedure for evaluating and comparing the fine-particle catalysts. The test procedure uses phenanthrene as the reaction solvent, the DECS-17 Blind Canyon Coal, and a statistical experimental design to enable evaluation of the catalysts over ranges of temperature (350 to 400{degrees}C), time (20 to 60 minutes), and catalyst loading (0 to 1 wt % on a dmmf coal basis). Product analyses include tetrahydrofuran (THF) conversion, heptane conversion, solvent recovery, and gas analyses. Phenanthrene as the solvent in the testing procedure yielded significant differences between thermal and catalytic reactions, whereas using a good hydrogen donor such as 9,10-dihydrophenanthrene (DHP) showed no catalytic effects.

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

    PubMed

    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. PMID:22372510

  18. Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Wang, Ziyun; Liu, Xinyi; Rooney, D. W.; Hu, P.

    2015-10-01

    The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

  19. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion.

    PubMed

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones. PMID:26074206

  20. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    NASA Astrophysics Data System (ADS)

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-06-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones.

  1. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    PubMed Central

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones. PMID:26074206

  2. Amorphous molybdenum sulfides as hydrogen evolution catalysts.

    PubMed

    Morales-Guio, Carlos G; Hu, Xile

    2014-08-19

    Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

  3. What are the active carbon species during graphene chemical vapor deposition growth?

    NASA Astrophysics Data System (ADS)

    Shu, Haibo; Tao, Xiao-Ming; Ding, Feng

    2015-01-01

    The dissociation of carbon feedstock is a crucial step for understanding the mechanism of graphene chemical vapor deposition (CVD) growth. Using first-principles calculations, we performed a comprehensive theoretical study for the population of various active carbon species, including carbon monomers and various radicals, CHi (i = 1, 2, 3, 4), on four representative transition-metal surfaces, Cu(111), Ni(111), Ir(111) and Rh(111), under different experimental conditions. On the Cu surface, which is less active, the population of CH and C monomers at the subsurface is found to be very high and thus they are the most important precursors for graphene CVD growth. On the Ni surface, which is more active than Cu, C monomers at the subsurface dominate graphene CVD growth under most experimental conditions. In contrast, on the active Ir and Rh surfaces, C monomers on the surfaces are found to be very stable and thus are the main precursors for graphene growth. This study shows that the mechanism of graphene CVD growth depends on the activity of catalyst surfaces and the detailed graphene growth process at the atomic level can be controlled by varying the temperature or partial pressure of hydrogen.The dissociation of carbon feedstock is a crucial step for understanding the mechanism of graphene chemical vapor deposition (CVD) growth. Using first-principles calculations, we performed a comprehensive theoretical study for the population of various active carbon species, including carbon monomers and various radicals, CHi (i = 1, 2, 3, 4), on four representative transition-metal surfaces, Cu(111), Ni(111), Ir(111) and Rh(111), under different experimental conditions. On the Cu surface, which is less active, the population of CH and C monomers at the subsurface is found to be very high and thus they are the most important precursors for graphene CVD growth. On the Ni surface, which is more active than Cu, C monomers at the subsurface dominate graphene CVD growth under most

  4. A novel Pt-Co alloy hydrogen anode catalyst with superlative activity, CO-tolerance and robustness.

    PubMed

    Shi, G Y; Yano, H; Tryk, D A; Watanabe, M; Iiyama, A; Uchida, H

    2016-08-01

    PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations. PMID:26952735

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

    PubMed

    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 (Al2 O3 , Fe2 O3 , ZnO, SnO2 , TiO2 and WO3 ) precursors, two series of such catalysts are prepared by wet impregnation, oven-drying at 120ºC, and subsequent heat treatment at 200ºC or 850ºC 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 850ºC. PMID:26457467

  6. Diversity and Activity of Lysobacter Species from Disease Suppressive Soils

    PubMed Central

    Gómez Expósito, Ruth; Postma, Joeke; Raaijmakers, Jos M.; De Bruijn, Irene

    2015-01-01

    The genus Lysobacter includes several species that produce a range of extracellular enzymes and other metabolites with activity against bacteria, fungi, oomycetes, and nematodes. Lysobacter species were found to be more abundant in soil suppressive against the fungal root pathogen Rhizoctonia solani, but their actual role in disease suppression is still unclear. Here, the antifungal and plant growth-promoting activities of 18 Lysobacter strains, including 11 strains from Rhizoctonia-suppressive soils, were studied both in vitro and in vivo. Based on 16S rRNA sequencing, the Lysobacter strains from the Rhizoctonia-suppressive soil belonged to the four species Lysobacter antibioticus, Lysobacter capsici, Lysobacter enzymogenes, and Lysobacter gummosus. Most strains showed strong in vitro activity against R. solani and several other pathogens, including Pythium ultimum, Aspergillus niger, Fusarium oxysporum, and Xanthomonas campestris. When the Lysobacter strains were introduced into soil, however, no significant and consistent suppression of R. solani damping-off disease of sugar beet and cauliflower was observed. Subsequent bioassays further revealed that none of the Lysobacter strains was able to promote growth of sugar beet, cauliflower, onion, and Arabidopsis thaliana, either directly or via volatile compounds. The lack of in vivo activity is most likely attributed to poor colonization of the rhizosphere by the introduced Lysobacter strains. In conclusion, our results demonstrated that Lysobacter species have strong antagonistic activities against a range of pathogens, making them an important source for putative new enzymes and antimicrobial compounds. However, their potential role in R. solani disease suppressive soil could not be confirmed. In-depth omics'–based analyses will be needed to shed more light on the potential contribution of Lysobacter species to the collective activities of microbial consortia in disease suppressive soils. PMID:26635735

  7. Diversity and Activity of Lysobacter Species from Disease Suppressive Soils.

    PubMed

    Gómez Expósito, Ruth; Postma, Joeke; Raaijmakers, Jos M; De Bruijn, Irene

    2015-01-01

    The genus Lysobacter includes several species that produce a range of extracellular enzymes and other metabolites with activity against bacteria, fungi, oomycetes, and nematodes. Lysobacter species were found to be more abundant in soil suppressive against the fungal root pathogen Rhizoctonia solani, but their actual role in disease suppression is still unclear. Here, the antifungal and plant growth-promoting activities of 18 Lysobacter strains, including 11 strains from Rhizoctonia-suppressive soils, were studied both in vitro and in vivo. Based on 16S rRNA sequencing, the Lysobacter strains from the Rhizoctonia-suppressive soil belonged to the four species Lysobacter antibioticus, Lysobacter capsici, Lysobacter enzymogenes, and Lysobacter gummosus. Most strains showed strong in vitro activity against R. solani and several other pathogens, including Pythium ultimum, Aspergillus niger, Fusarium oxysporum, and Xanthomonas campestris. When the Lysobacter strains were introduced into soil, however, no significant and consistent suppression of R. solani damping-off disease of sugar beet and cauliflower was observed. Subsequent bioassays further revealed that none of the Lysobacter strains was able to promote growth of sugar beet, cauliflower, onion, and Arabidopsis thaliana, either directly or via volatile compounds. The lack of in vivo activity is most likely attributed to poor colonization of the rhizosphere by the introduced Lysobacter strains. In conclusion, our results demonstrated that Lysobacter species have strong antagonistic activities against a range of pathogens, making them an important source for putative new enzymes and antimicrobial compounds. However, their potential role in R. solani disease suppressive soil could not be confirmed. In-depth omics'-based analyses will be needed to shed more light on the potential contribution of Lysobacter species to the collective activities of microbial consortia in disease suppressive soils. PMID:26635735

  8. Liquid-phase hydrogenation of citral over Pt/SiO{sub 2} catalysts. 1. Temperature effects on activity and selectivity

    SciTech Connect

    Singh, U.K.; Vannice, M.A.

    2000-04-01

    Liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) over Pt/SiO{sub 2} catalysts was studied in the temperature and pressure ranges 298--423 K and 7--21 atm, respectively. The reaction kinetics were shown to be free of artifacts arising from transport limitations and poisoning effects. The reaction rate in hexane at the solvent exhibited an activity minimum at 373 K. The initial turnover frequency for citral disappearance over 1.44% Pt/SiO{sub 2} catalyst at 20 atm H{sub 2} pressure decreased from 0.19 s{sup {minus}1} at 298 K to 0.02 s{sup {minus}1} at 373 K, but exhibited normal Arrhenius behavior between 373 and 423 K with an activation energy of 7 kcal/mol. Reaction at 298 K produced substantial deactivation, with the rate decreasing by more than an order of magnitude during the first 4 h of reaction; however, reaction at temperatures greater than 373 K exhibited negligible deactivation and a constant rate up to citral conversions greater than 70%. These unusual temperature effects were modeled using Langmuir-Hinshelwood kinetics invoking dissociative adsorption of hydrogen, competitive adsorption between hydrogen and the organic compounds, and addition of the second hydrogen atom to each reactant as the rate-determining step. Decomposition of the unsaturated alcohol (either geraniol or nerol) was proposed to occur concurrently with the hydrogenation steps to yield adsorbed CO and carbonaceous species which cause the deactivation, but at higher temperatures these species could be removed from the Pt surface by desorption or rapid hydrogenation, respectively. The activity minimum observed in the present study is attributed to the relative rates of the alcohol decomposition reaction and CO desorption, with the decomposition reaction having an activation barrier lower than that for CO desorption.

  9. Are intramolecular frustrated Lewis pairs also intramolecular catalysts? A theoretical study on H2 activation.

    PubMed

    Zeonjuk, Lei Liu; St Petkov, Petko; Heine, Thomas; Röschenthaler, Gerd-Volker; Eicher, Johannes; Vankova, Nina

    2015-04-28

    We investigate computationally a series of intramolecular frustrated Lewis pairs (FLPs), with the general formula Mes2PCHRCH2B(C6F5)2, that are known from the literature to either activate molecular hydrogen (FLPs with R = H (1) or Me (4)), or remain inert (FLPs with R = Ph (2) or SiMe3 (3)). The prototypical system Mes2PCH2CH2B(C6F5)2 (1) has been described in the literature (Grimme et al., Angew. Chem., Int. Ed., 2010; Rokob et al., J. Am. Chem. Soc., 2013) as an intramolecular reactant that triggers the reaction with H2 in a bimolecular concerted fashion. In the current study, we show that the concept of intramolecular H2 activation by linked FLPs is not able to explain the inertness of the derivative compounds 2 and 3 towards H2. To cope with this, we propose an alternative intermolecular mechanism for the investigated reaction, assuming stacking of two open-chain FLP conformers, and formation of a dimeric reactant with two Lewis acid–base domains, that can split up to two hydrogen molecules. Using quantum-chemical methods, we compute the reaction profiles describing these alternative mechanisms, and compare the derived predictions with earlier reported experimental results. We show that only the concept of intermolecular H2 activation could explain both the activity of the FLPs having small substituents in the bridging molecular region, and the inertness of the FLPs with a bulkier substitution, in a consistent way. Importantly, the intermolecular H2 activation driven by intramolecular FLPs indicates the key role of steric factors and noncovalent interactions for the design of metal-free systems that can efficiently split H2, and possibly serve as metal-free hydrogenation catalysts. PMID:25812167

  10. Boron-doped graphene as promising support for platinum catalyst with superior activity towards the methanol electrooxidation reaction

    NASA Astrophysics Data System (ADS)

    Sun, Yongrong; Du, Chunyu; An, Meichen; Du, Lei; Tan, Qiang; Liu, Chuntao; Gao, Yunzhi; Yin, Geping

    2015-12-01

    We report the synthesis of boron-doped graphene by thermally annealing the mixture of graphene oxide and boric acid, and its usage as the support of Pt catalyst towards the methanol oxidation reaction. The composition, structure and morphology of boron-doped graphene and its supported Pt nanoparticles (Pt/BG) are characterized by transmission electron microscopy, inductively coupled plasma mass spectrometry, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It is revealed that boron atoms are doped into graphene network in the form of BC2O and BCO2 bonds, which lead to the increase in defect sites and facilitate the subsequent deposition of Pt nanoparticles. Therefore, the Pt/BG catalyst presents smaller particle size and narrower size distribution than the graphene supported Pt (Pt/G) catalyst. When evaluated as the electrocatalyst for the methanol oxidation reaction, the Pt/BG catalyst exhibits excellent electrochemical activity and stability demonstrated by cyclic voltammetry and chronoamperometry tests. The enhanced activity is mainly ascribed to the electronic interaction between boron-doped graphene and Pt nanoparticles, which lowers the d-band center of Pt and thus weakens the absorption of the poisoning intermediate CO. Our work provides an alternative approach of improving the reaction kinetics for the oxidation of small organic molecules.

  11. Preparation of N-doped ZnO-loaded halloysite nanotubes catalysts with high solar-light photocatalytic activity.

    PubMed

    Cheng, Zhi-Lin; Sun, Wei

    2015-01-01

    N-doped ZnO nanoparticles were successfully assembled into hollow halloysite nanotubes (HNTs) by using the impregnation method. The catalysts based on N-doped ZnO-loaded HNTs nanocomposites (N-doped ZnO/HNTs) were characterized by X-ray diffraction (XRD), transmission electron microscopy-energy dispersive X-ray (TEM-EDX), scanning electron microscopy-energy dispersive X-ray (SEM-EDX), UV-vis and Fourier transform infrared spectroscopy (FT-IR) techniques. The XRD pattern showed ZnO nanoparticles with hexagonal structure loaded on HNTs. The TEM-EDX analysis indicated ZnO particles with the crystal size of ca.10 nm scattered in hollow structure of HNTs, and furthermore the concentration of N atom in nanocomposites was up to 2.31%. The SEM-EDX verified most of N-ZnO nanoparticles existing in hollow nanotubes of HNTs. Besides containing an obvious ultraviolet absorbance band, the UV-vis spectra of the N-doped ZnO/HNTs catalysts showed an available visible absorbance band by comparing to HNTs and non-doped ZnO/HNTs. The photocatalytic activity of the N-doped ZnO/HNTs catalysts was evaluated by the degradation of methyl orange (MO) solution with the concentration of 20 mg/L under the simulated solar-light irradiation. The result showed that the N-doped ZnO/HNTs catalyst exhibited a desirable solar-light photocatalytic activity. PMID:26540544

  12. In Situ Detection of Active Edge Sites in Single-Layer MoS2 Catalysts.

    PubMed

    Bruix, Albert; Füchtbauer, Henrik Gøbel; Tuxen, Anders K; Walton, Alexander S; Andersen, Mie; Porsgaard, Søren; Besenbacher, Flemming; Hammer, Bjørk; Lauritsen, Jeppe V

    2015-09-22

    MoS2 nanoparticles are proven catalysts for processes such as hydrodesulfurization and hydrogen evolution, but unravelling their atomic-scale structure under catalytic working conditions has remained significantly challenging. Ambient pressure X-ray Photoelectron Spectroscopy (AP-XPS) allows us to follow in situ the formation of the catalytically relevant MoS2 edge sites in their active state. The XPS fingerprint is described by independent contributions to the Mo 3d core level spectrum whose relative intensity is sensitive to the thermodynamic conditions. Density Functional Theory (DFT) is used to model the triangular MoS2 particles on Au(111) and identify the particular sulphidation state of the edge sites. A consistent picture emerges in which the core level shifts for the edge Mo atoms evolve counterintuitively toward higher binding energies when the active edges are reduced. The shift is explained by a surprising alteration in the metallic character of the edge sites, which is a distinct spectroscopic signature of the MoS2 edges under working conditions. PMID:26203593

  13. Isobutanol coupling with ethanol and methanol to ethers over sulfonated resin catalysts: Activities and selectivities

    SciTech Connect

    Herman, R.G.; Klier, K.; Feeley, O.C.

    1994-12-31

    The synthesis of C{sub 5}-C{sub 8} ethers from mixtures of C{sub 1}-C{sub 4} alcohols over strong acid Amberlyst resin catalysts has been initiated, and the overall activity pattern of the resins was found to be Amberlyst-35 > Amberlyst-36 > Amberlyst-15 > Amberlyst-1010, all of which were more active than Nafion-H. With methanol/isobutanol reactants, it was observed that increasing the reaction pressure strongly decreased the space time yield and selectivity of the butenes, principally isobutene, while tending to increase the space time yield of the ethers methylisobutylether (MIBE), methyl tertiarybutyl ether (MTBE), and dimethylether (DME). Other reactant mixtures utilized at high flow rates included ethanol/isobutanol, where EIBE and ETBE were products. Upon increasing the isobutanol/ethanol ratio above 1/1, it was shown that diethylether (DEE) formation decreased but the synthesis of tertiarybutyl isobutylether (TBIBE) increased. A reactant mixture of ethanol/isopropanol was also investigated, and dehydration of the isopropanol readily occurred to form propene and coupling gave diisoproplyether (DIPE) as the dominant product at 90{degrees}C.

  14. Antioxidant, Antimicrobial and Antiproliferative Activities of Five Lichen Species

    PubMed Central

    Mitrović, Tatjana; Stamenković, Slaviša; Cvetković, Vladimir; Tošić, Svetlana; Stanković, Milan; Radojević, Ivana; Stefanović, Olgica; Čomić, Ljiljana; Đačić, Dragana; Ćurčić, Milena; Marković, Snežana

    2011-01-01

    The antioxidative, antimicrobial and antiproliferative potentials of the methanol extracts of the lichen species Parmelia sulcata, Flavoparmelia caperata, Evernia prunastri, Hypogymnia physodes and Cladonia foliacea were evaluated. The total phenolic content of the tested extracts varied from 78.12 to 141.59 mg of gallic acid equivalent (GA)/g of extract and the total flavonoid content from 20.14 to 44.43 mg of rutin equivalent (Ru)/g of extract. The antioxidant capacities of the lichen extracts were determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals scavenging. Hypogymnia physodes with the highest phenolic content showed the strongest DPPH radical scavenging effect. Further, the antimicrobial potential of the lichen extracts was determined by a microdilution method on 29 microorganisms, including 15 strains of bacteria, 10 species of filamentous fungi and 4 yeast species. A high antimicrobial activity of all the tested extracts was observed with more potent inhibitory effects on the growth of Gram (+) bacteria. The highest antimicrobial activity among lichens was demonstrated by Hypogymnia physodes and Cladonia foliacea. Finally, the antiproliferative activity of the lichen extracts was explored on the colon cancer adenocarcinoma cell line HCT-116 by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) viability assay and acridine orange/ethidium bromide staining. The methanol extracts of Hypogymnia physodes and Cladonia foliacea showed a better cytotoxic activity than the other extracts. All lichen species showed the ability to induce apoptosis of HCT-116 cells. PMID:21954369

  15. Metabolomic profiling and antioxidant activity of some Acacia species

    PubMed Central

    Abdel-Farid, I.B.; Sheded, M.G.; Mohamed, E.A.

    2014-01-01

    Metabolomic profiling of different parts (leaves, flowers and pods) of Acacia species (Acacia nilotica, Acacia seyal and Acacia laeta) was evaluated. The multivariate data analyses such as principal component analysis (PCA) and partial least square-discriminant analysis (PLS-DA) were used to differentiate the distribution of plant metabolites among different species or different organs of the same species. A.nilotica was characterized with a high content of saponins and A.seyal was characterized with high contents of proteins, phenolics, flavonoids and anthocyanins. A.laeta had a higher content of carbohydrates than A. nilotica and A. seyal. On the basis of these results, total antioxidant capacity, DPPH free radical scavenging activity and reducing power of the methanolic extracts of studied parts were evaluated. A.nilotica and A.seyal extracts showed less inhibitory concentration 50 (IC50) compared to A.laeta extracts which means that these two species have the strongest radical scavenging activity whereas A. laeta extracts have the lowest radical scavenging activity. A positive correlation between saponins and flavonoids with total antioxidant capacity and DPPH radical scavenging activity was observed. Based on these results, the potentiality of these plants as antioxidants was discussed. PMID:25313274

  16. Clean Donor Oxidation Enhances the H2 Evolution Activity of a Carbon Quantum Dot-Molecular Catalyst Photosystem.

    PubMed

    Martindale, Benjamin C M; Joliat, Evelyne; Bachmann, Cyril; Alberto, Roger; Reisner, Erwin

    2016-08-01

    Carbon quantum dots (CQDs) are new-generation light absorbers for photocatalytic H2 evolution in aqueous solution, but the performance of CQD-molecular catalyst systems is currently limited by the decomposition of the molecular component. Clean oxidation of the electron donor by donor recycling prevents the formation of destructive radical species and non-innocent oxidation products. This approach allowed a CQD-molecular nickel bis(diphosphine) photocatalyst system to reach a benchmark lifetime of more than 5 days and a record turnover number of 1094±61 molH2  (molNi )(-1) for a defined synthetic molecular nickel catalyst in purely aqueous solution under AM1.5G solar irradiation. PMID:27355200

  17. A self-reductive mesoporous CuO(x)/Fe/silicate nanocomposite as a highly active and stable catalyst for methanol reforming.

    PubMed

    Li, Chien-Cheng; Chen, Yan-Wun; Lin, Ran-Jin; Chang, Ching-Chun; Chen, Kuei-Hsien; Lin, Hong-Ping; Chen, Li-Chyong

    2011-09-01

    A simple and convenient one-pot synthetic route to directly prepare a self-reductive mesoporous copper-iron-silicate (CuO(x)-Fe-silicate)-based catalyst has been developed. The resultant catalyst is highly active and stable in methanol reforming without needing a pre-reduction procedure. PMID:21773606

  18. Highly active and stable iron Fischer-Tropsch catalyst for synthesis gas conversion to liquid fuels

    SciTech Connect

    Bukur, D.B.; Lang, X.

    1999-09-01

    A precipitated iron Fischer-Tropsch (F-T) catalyst (100 Fe/3 Cu/4 K/16 SiO{sub 2} on mass basis) was tested in a stirred tank slurry reactor under reaction conditions representative of industrial practice using CO-rich synthesis gas (260 C, 1.5--2.2 MPa, H{sub 2}/CO = 2/3). Repeatability of performance and reproducibility of catalyst preparation procedure were successfully demonstrated on a laboratory scale. Catalyst productivity was increased by operating at higher synthesis pressure while maintaining a constant contact time in the reactor and through the use of different catalyst pretreatment procedures. In one of the tests (run SA-2186), the catalyst productivity was 0.86 (g hydrocarbons/g Fe/h) at syngas conversion of 79%, methane selectivity of 3% (weight percent of total hydrocarbons produced), and C{sub 5}+ hydrocarbon selectivity of 83 wt %. This represents a substantial improvement in productivity in comparison to state-of-the-art iron F-T catalysts. This catalyst is ideally suited for production of high-quality diesel fuels and C{sub 2}-c{sub 4} olefins from a coal-derived synthesis gas.

  19. In situ UV-vis-NIR diffuse reflectance and Raman spectroscopy and catalytic activity studies of propane oxidative dehydrogenation over supported CrO3/ZrO2 catalysts.

    PubMed

    Malleswara Rao, T V; Deo, Goutam; Jehng, Jih-Mirn; Wachs, Israel E

    2004-08-17

    The molecular structures, oxidation states, and reactivity of 3 and 6% CrO3/ZrO2 catalysts prepared by incipient wetness impregnation were examined under different conditions. The in situ Raman spectroscopic studies under dehydrated conditions reveal that the 3 and 6% CrO3/ZrO2 catalysts possess equal amounts of monochromate and polychromate species. Consequently, monolayer coverage on this ZrO2 support is about 3% CrO3. The 6% CrO3/ZrO2 possesses an additional Raman band due to Cr2O3 crystals corresponding to the remaining 3% CrO3. Furthermore, during reaction conditions the polychromate species is preferentially reduced, the monochromate species are slightly affected, and the Cr2O3 crystals are not affected. The in situ UV-vis-NIR diffuse reflectance spectroscopy results reveal that under steady-state reaction conditions the extent of reduction and edge energy position of surface Cr6+ cations increase with an increase in reduction environment for the 3 and 6% CrO3/ZrO2 samples. Propane oxidative dehydrogenation (ODH) studies reveal that the catalytic activity expressed in moles of propane converted per gram catalyst per second is similar for the two catalysts, which is consistent with equal amounts of molecularly dispersed chromia present. The turnover frequency for the 6% CrO3/ZrO2 catalyst is, however, smaller than that for the 3% CrO3/ZrO2 sample due to the presence of Cr2O3 crystals, which are relatively inactive for propane ODH. For this catalytic system and for the experimental conditions used, propene, CO, and CO2 are primary products. Furthermore, the 33-39% propene selectivity is not affected by the C3H8/O2 ratio for both catalysts. Structure-reactivity studies suggest that the molecularly dispersed species are present in equal amounts in the 3 and 6% CrO3/ZrO2 samples as Cr6+ monochromate and polychromate species are the most effective catalytic active sites taking part in the propane ODH reaction. PMID:15301500

  20. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

  1. Novel catalysts for methane activation. Quarterly report No. 7, April 1, 1994--June 30, 1994

    SciTech Connect

    Hirschon, A.S.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1994-09-01

    Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with the synthesis and characterization of the fullerenes and fullerene soots, Task 2 with the testing of the catalysts, and Task 3 with the evaluation of the results and technical reporting requirements. The results and accomplishments for this quarter are summarized below; soots were prepared either by extraction in toluene or sublimation of the lower fullerenes (such as C{sub 60}/C{sub 70}); a fullerene soot was prepared by adding C{sub 60} to an extracted soot; fullerene soot was doped with platinum and nickel by incipient wetness techniques, and a nickel fullerene complex was synthesized using organometallic techniques; soot from three manufactures were tested for methane activation and found to exhibit small but notable differences in reactivity; increasing the surface area of soots by partial oxidation with C0{sub 2} did not cause significant changes in the reactivities; the effect of the extraction and sublimation of C{sub 60}/C{sub 70} was determined to be minor; the effect of added C{sub 60} to an extracted MER soot was determined to be beneficial; acetylene black was tested and found to have higher activity and lower selectivity than a Norit-A carbon; and nickel and platinum doped soots were found to be more active than the undoped soots.

  2. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  3. Catalyst enhances Claus operations

    SciTech Connect

    Dupin, T.; Voizin, R.

    1982-11-01

    An improved Claus catalyst offers superior activity that emphasizes hydrolysis of CS/sub 2/ in the first converter. The catalyst is insensitive to oxygen action at concentrations generally found in Claus gas feeds. It also has an excellent resistance to hydrothermal shocks that may occur during shutdown of the sulfur line. Collectively, these properties make this catalyst the most active formula now available for optimum Claus yields and COS/CS/sub 2/ hydrolysis conversion.

  4. Distinguishing Candida Species by β-N-Acetylhexosaminidase Activity

    PubMed Central

    Niimi, Kyoko; Shepherd, Maxwell G.; Cannon, Richard D.

    2001-01-01

    A variety of fungi produce the hydrolytic enzyme β-N-acetylhexosaminidase (HexNAcase), which can be readily detected in assays by using p-nitrophenyl-N-acetyl-β-d-glucosaminide as a substrate. In the present study we developed a microtiter plate-based HexNAcase assay for distinguishing Candida albicans and Candida dubliniensis strains from other yeast species. HexNAcase activity was detected in 89 of 92 (97%) C. albicans strains and 4 of 4 C. dubliniensis strains but not in 28 strains of eight other Candida species, 4 Saccharomyces cerevisiae strains, or 2 Cryptococcus neoformans strains. The HexNAcase activity in C. albicans and C. dubliniensis was strain specific. All except three clinical C. albicans isolates among the C. albicans strains tested produced enzyme activity within 24 h. These strains did produce enzyme activity, however, after a prolonged incubation period. For two of these atypical strains, genomic DNA at the C. albicans HEX1 gene locus, which encodes HexNAcase, showed nucleotide differences from the sequence of control strains. Among the other Candida species tested, only C. dubliniensis had a DNA sequence that hybridized with the HEX1 probe under low-stringency conditions. The microtiter plate-based assay used in the present study for the detection of HexNAcase activity is a simple, relatively inexpensive method useful for the presumptive identification of C. albicans and C. dubliniensis. PMID:11376040

  5. Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

    SciTech Connect

    Cronauer, D. C.

    2011-04-15

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry - specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first

  6. CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

    PubMed Central

    Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

    2014-01-01

    Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8–1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study. PMID:25491655

  7. Iron(II) Active Species in Iron-Bisphosphine Catalyzed Kumada and Suzuki-Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides.

    PubMed

    Daifuku, Stephanie L; Kneebone, Jared L; Snyder, Benjamin E R; Neidig, Michael L

    2015-09-01

    While previous studies have identified FeMes2(SciOPP) as the active catalyst species in iron-SciOPP catalyzed Kumada cross-coupling of mesitylmagnesium bromide and primary alkyl halides, the active catalyst species in cross-couplings with phenyl nucleophiles, where low valent iron species might be prevalent due to accessible reductive elimination pathways, remains undefined. In the present study, in situ Mössbauer and magnetic circular dichroism spectroscopic studies combined with inorganic syntheses and reaction studies are employed to evaluate the in situ formed iron species and identify the active catalytic species in iron-SciOPP catalyzed Suzuki-Miyaura and Kumada cross-couplings of phenyl nucleophiles and secondary alkyl halides. While reductive elimination to form Fe(η(6)-biphenyl)(SciOPP) occurs upon reaction of FeCl2(SciOPP) with phenyl nucleophiles, this iron(0) species is not found to be kinetically competent for catalysis. Importantly, mono- and bis-phenylated iron(II)-SciOPP species that form prior to reductive elimination are identified, where both species are found to be reactive toward electrophile at catalytically relevant rates. The higher selectivity toward the formation of cross-coupled product observed for the monophenylated species combined with the undertransmetalated nature of the in situ iron species in both Kumada and Suzuki-Miyaura reactions indicates that Fe(Ph)X(SciOPP) (X = Br, Cl) is the predominant reactive species in cross-coupling. Overall, these studies demonstrate that low-valent iron is not required for the generation of highly reactive species for effective aryl-alkyl cross-couplings. PMID:26266698

  8. Iron(II) Active Species in Iron–Bisphosphine Catalyzed Kumada and Suzuki–Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides

    PubMed Central

    2015-01-01

    While previous studies have identified FeMes2(SciOPP) as the active catalyst species in iron–SciOPP catalyzed Kumada cross-coupling of mesitylmagnesium bromide and primary alkyl halides, the active catalyst species in cross-couplings with phenyl nucleophiles, where low valent iron species might be prevalent due to accessible reductive elimination pathways, remains undefined. In the present study, in situ Mössbauer and magnetic circular dichroism spectroscopic studies combined with inorganic syntheses and reaction studies are employed to evaluate the in situ formed iron species and identify the active catalytic species in iron–SciOPP catalyzed Suzuki–Miyaura and Kumada cross-couplings of phenyl nucleophiles and secondary alkyl halides. While reductive elimination to form Fe(η6-biphenyl)(SciOPP) occurs upon reaction of FeCl2(SciOPP) with phenyl nucleophiles, this iron(0) species is not found to be kinetically competent for catalysis. Importantly, mono- and bis-phenylated iron(II)–SciOPP species that form prior to reductive elimination are identified, where both species are found to be reactive toward electrophile at catalytically relevant rates. The higher selectivity toward the formation of cross-coupled product observed for the monophenylated species combined with the undertransmetalated nature of the in situ iron species in both Kumada and Suzuki–Miyaura reactions indicates that Fe(Ph)X(SciOPP) (X = Br, Cl) is the predominant reactive species in cross-coupling. Overall, these studies demonstrate that low-valent iron is not required for the generation of highly reactive species for effective aryl-alkyl cross-couplings. PMID:26266698

  9. Quality assessment and antiplasmodial activity of West African Cochlospermum species.

    PubMed

    Lamien-Meda, Aline; Kiendrebeogo, Martin; Compaoré, Moussa; Meda, Roland N T; Bacher, Markus; Koenig, Karin; Pacher, Thomas; Fuehrer, Hans-Peter; Noedl, Harald; Willcox, Merlin; Novak, Johannes

    2015-11-01

    The present study focuses on development of phytochemical methods for quality assessment of two West-African Cochlospermum species (Cochlospermum planchonii and Cochlospermum tinctorium) traditionally used for malaria treatment in Burkina Faso. Antimalarial activity of preparations from dried rhizomes (decoction) was tested against the chloroquine-sensitive Plasmodium strain 3D7 using the histidine-rich protein II (HRP2) drug susceptibility assay and compared with extract preparations using organic solvents of different polarity. Two main apocarotenoids were isolated from rhizomes of C. planchonii and unambiguously identified as dihydrocochloxanthine and cochloxanthine by spectroscopic methods. Comparative HPLC analyses of thirty-nine (39) samples from markets and from collections in natural habitats of both species showed a high variability in the accumulation of cochloxanthines and related carotenoids which were proven to be characteristic for rhizomes of both species and generally absent in leaves. Furthermore, content of total phenolics and antioxidant activities (DPPH and FRAP) as well as haemolytic activity of various extracts was tested. The HPLC method presented here was validated and provides a good separation of both compounds including 10 minor carotenoids. Extracts from both species and pure cochloxanthine offered pronounced antioxidant activities and weak haemolytic activity while, in contrast, dihydrocochloxanthine had a strong haemolytic effect at the highest concentration analysed. However, cochloxanthine as well as dihydrocochloxanthine showed erythroprotective effects against the haemolytic activity of the reference saponin. Moderate antiplasmodial activity between 16 and 63 μg/ml were observed with all tested extracts, and lower IC50 values were obtained with pure dihydrocochloxanthine (IC50=6.9 μg/ml), cochloxanthine (IC50=6.8 μg/ml), the DCM fraction (IC50=2.4 μg/ml) and the ethyl acetate fraction (IC50=11.5μg/ml) derived from a methanolic

  10. Progress in Synthesis of Highly Active and Stable Nickel-Based Catalysts for Carbon Dioxide Reforming of Methane.

    PubMed

    Kawi, Sibudjing; Kathiraser, Yasotha; Ni, Jun; Oemar, Usman; Li, Ziwei; Saw, Eng Toon

    2015-11-01

    In recent decades, rising anthropogenic greenhouse gas emissions (mainly CO2 and CH4 ) have increased alarm due to escalating effects of global warming. The dry carbon dioxide reforming of methane (DRM) reaction is a sustainable way to utilize these notorious greenhouse gases. This paper presents a review of recent progress in the development of nickel-based catalysts for the DRM reaction. The enviable low cost and wide availability of nickel compared with noble metals is the main reason for persistent research efforts in optimizing the synthesis of nickel-based catalysts. Important catalyst features for the rational design of a coke-resistant nickel-based nanocatalyst for the DRM reaction are also discussed. In addition, several innovative developments based on salient features for the stabilization of nickel nanocatalysts through various means (which include functionalization with precursors, synthesis by plasma treatment, stabilization/confinement on mesoporous/microporous/carbon supports, and the formation of metal oxides) are highlighted. The final part of this review covers major issues and proposed improvement strategies pertaining to the rational design of nickel-based catalysts with high activity and stability for the DRM reaction. PMID:26440576

  11. Activation of Single-Component Nickel(II) Polyethylene Catalysts via Phase Transfer of Fluorous Phosphine Ligands.

    PubMed

    Xi, Zhenxing; Bazzi, Hassan S; Gladysz, John A

    2015-09-01

    The nickel salicylaldiminato phosphine complexes [1,2,3-C6H3(9-anthracenyl)O(CH═N(2,6-C6H3(iPr)2)]Ni(Me)[P(4-C6H4R)3] (4; R = a, (CH2)2Rf8; b, (CH2)3Rf8; c, H (Rf8 = (CF2)7CF3)) are prepared from the corresponding phosphines 3a-c and nickel NCMe adduct (46-68%). These are applied as catalysts for ethylene polymerization in toluene and fluorous/toluene liquid/liquid biphasic mixtures. Under the latter conditions, the fluorous phosphines 3a,b that must dissociate to generate the active catalyst migrate to the fluorous phase (partition coefficients 97.5:2.5 and 66.6:33.4 vs <0.5:>99.5 for 4a,b). Catalysts 4a,b show marked accelerations under biphasic conditions, but 4c (which has a lipophilic phosphine ligand) does not. Under all conditions, 4a,b are faster catalysts than the Ni(Ph)(PPh3) analogue, a previously reported benchmark. PMID:26300472

  12. [Towards computer-aided catalyst design: Three effective core potential studies of C-H activation]. Final report

    SciTech Connect

    1998-12-31

    Research in the initial grant period focused on computational studies relevant to the selective activation of methane, the prime component of natural gas. Reaction coordinates for methane activation by experimental models were delineated, as well as the bonding and structure of complexes that effect this important reaction. This research, highlighted in the following sections, also provided the impetus for further development, and application of methods for modeling metal-containing catalysts. Sections of the report describe the following: methane activation by multiple-bonded transition metal complexes; computational lanthanide chemistry; and methane activation by non-imido, multiple-bonded ligands.

  13. Mechanically activated catalyst mixing for high-yield boron nitride nanotube growth.

    PubMed

    Li, Ling; Li, Lu Hua; Chen, Ying; Dai, Xiujuan J; Xing, Tan; Petravic, Mladen; Liu, Xiaowei

    2012-01-01

    Boron nitride nanotubes (BNNTs) have many fascinating properties and a wide range of applications. An improved ball milling method has been developed for high-yield BNNT synthesis, in which metal nitrate, such as Fe(NO3)3, and amorphous boron powder are milled together to prepare a more effective precursor. The heating of the precursor in nitrogen-containing gas produces a high density of BNNTs with controlled structures. The chemical bonding and structure of the synthesized BNNTs are precisely probed by near-edge X-ray absorption fine structure spectroscopy. The higher efficiency of the precursor containing milling-activated catalyst is revealed by thermogravimetric analyses. Detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations disclose that during ball milling the Fe(NO3)3 decomposes to Fe which greatly accelerates the nitriding reaction and therefore increases the yield of BNNTs. This improved synthesis method brings the large-scale production and application of BNNTs one step closer. PMID:22827911

  14. Mechanically activated catalyst mixing for high-yield boron nitride nanotube growth

    PubMed Central

    2012-01-01

    Boron nitride nanotubes (BNNTs) have many fascinating properties and a wide range of applications. An improved ball milling method has been developed for high-yield BNNT synthesis, in which metal nitrate, such as Fe(NO3)3, and amorphous boron powder are milled together to prepare a more effective precursor. The heating of the precursor in nitrogen-containing gas produces a high density of BNNTs with controlled structures. The chemical bonding and structure of the synthesized BNNTs are precisely probed by near-edge X-ray absorption fine structure spectroscopy. The higher efficiency of the precursor containing milling-activated catalyst is revealed by thermogravimetric analyses. Detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations disclose that during ball milling the Fe(NO3)3 decomposes to Fe which greatly accelerates the nitriding reaction and therefore increases the yield of BNNTs. This improved synthesis method brings the large-scale production and application of BNNTs one step closer. PMID:22827911

  15. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    DOEpatents

    Angelici, Robert J.; Gao, Hanrong

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

  16. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    DOEpatents

    Angelici, R.J.; Gao, H.

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

  17. Nanosized IrO(x)-Ir Catalyst with Relevant Activity for Anodes of Proton Exchange Membrane Electrolysis Produced by a Cost-Effective Procedure.

    PubMed

    Lettenmeier, Philipp; Wang, Li; Golla-Schindler, Ute; Gazdzicki, Pawel; Cañas, Natalia A; Handl, Michael; Hiesgen, Renate; Hosseiny, Seyed S; Gago, Aldo S; Friedrich, Kaspar A

    2016-01-11

    We have developed a highly active nanostructured iridium catalyst for anodes of proton exchange membrane (PEM) electrolysis. Clusters of nanosized crystallites are obtained by reducing surfactant-stabilized IrCl3 in water-free conditions. The catalyst shows a five-fold higher activity towards oxygen evolution reaction (OER) than commercial Ir-black. The improved kinetics of the catalyst are reflected in the high performance of the PEM electrolyzer (1 mg(Ir) cm(-2)), showing an unparalleled low overpotential and negligible degradation. Our results demonstrate that this enhancement cannot be only attributed to increased surface area, but rather to the ligand effect and low coordinate sites resulting in a high turnover frequency (TOF). The catalyst developed herein sets a benchmark and a strategy for the development of ultra-low loading catalyst layers for PEM electrolysis. PMID:26616747

  18. Ultrasound enhanced heterogeneous activation of peroxydisulfate by bimetallic Fe-Co/GAC catalyst for the degradation of Acid Orange 7 in water.

    PubMed

    Cai, Chun; Wang, Liguo; Gao, Hong; Hou, Liwei; Zhang, Hui

    2014-06-01

    Bimetallic Fe-Co/GAC (granular activated carbon) was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate (PS, S2O(2-)8) process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 (AO7) was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles. PMID:25079835

  19. Conformational Control of Chiral Amido-Thiourea Catalysts Enables Improved Activity and Enantioselectivity.

    PubMed

    Lehnherr, Dan; Ford, David D; Bendelsmith, Andrew J; Kennedy, C Rose; Jacobsen, Eric N

    2016-07-01

    While aryl pyrrolidinoamido-thioureas derived from α-amino acids are effective catalysts in a number of asymmetric transformations, they exist as mixtures of slowly interconverting amide rotamers. Herein, the compromising role of amide bond isomerism is analyzed experimentally and computationally. A modified catalyst structure that exists almost exclusively as a single amide rotamer is introduced. This modification is shown to result in improved reactivity and enantioselectivity by minimizing competing reaction pathways. PMID:27294369

  20. Ruthenium(0) nanoparticles supported on multiwalled carbon nanotube as highly active catalyst for hydrogen generation from ammonia-borane.

    PubMed

    Akbayrak, Serdar; Ozkar, Saim

    2012-11-01

    Ruthenium(0) nanoparticles supported on multiwalled carbon nanotubes (Ru(0)@MWCNT) were in situ formed during the hydrolysis of ammonia-borane (AB) and could be isolated from the reaction solution by filtration and characterized by ICP-OES, XRD, TEM, SEM, EDX, and XPS techniques. The results reveal that ruthenium(0) nanoparticles of size in the range 1.4-3.0 nm are well-dispersed on multiwalled carbon nanotubes. They were found to be highly active catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value of 329 min⁻¹. The reusability experiments show that Ru(0)@MWCNTs are isolable and redispersible in aqueous solution; when redispersed they are still active catalyst in the hydrolysis of AB exhibiting a release of 3.0 equivalents of H₂ per mole of NH₃BH₃ and preserving 41% of the initial catalytic activity even after the fourth run of hydrolysis. The lifetime of Ru(0)@MWCNTs was measured as 26400 turnovers over 29 h in the hydrolysis of AB at 25.0 ± 0.1 °C before deactivation. The work reported here also includes the kinetic studies depending on the temperature to determine the activation energy of the reaction (E(a) = 33 ± 2 kJ/mol) and the effect of catalyst concentration on the rate of the catalytic hydrolysis of AB, respectively. PMID:23113804

  1. A novel Pt-Co alloy hydrogen anode catalyst with superlative activity, CO-tolerance and robustness

    NASA Astrophysics Data System (ADS)

    Shi, G. Y.; Yano, H.; Tryk, D. A.; Watanabe, M.; Iiyama, A.; Uchida, H.

    2016-07-01

    PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations.PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations. Electronic supplementary information (ESI) available: Experimental details, TEM images and particle size distribution histograms of all catalysts, and details of the DFT calculations. See DOI: 10.1039/c6nr00778c

  2. Plant species richness increases phosphatase activities in an experimental grassland

    NASA Astrophysics Data System (ADS)

    Hacker, Nina; Wilcke, Wolfgang; Oelmann, Yvonne

    2014-05-01

    Plant species richness has been shown to increase aboveground nutrient uptake requiring the mobilization of soil nutrient pools. For phosphorus (P) the underlying mechanisms for increased P release in soil under highly diverse grassland mixtures remain obscure because aboveground P storage and concentrations of inorganic and organic P in soil solution and differently reactive soil P pools are unrelated (Oelmann et al. 2011). The need of plants and soil microorganisms for P can increase the exudation of enzymes hydrolyzing organically bound P (phosphatases) which might represent an important release mechanism of inorganic P in a competitive environment such as highly diverse grassland mixtures. Our objectives were to test the effects of i) plant functional groups (legumes, grasses, non-leguminous tall and small herbs), and of (ii) plant species richness on microbial P (Pmic) and phosphatase activities in soil. In autumn 2013, we measured Pmic and alkaline phosphomonoesterase and phosphodiesterase activities in soil of 80 grassland mixtures comprising different community compositions and species richness (1, 2, 4, 8, 16, 60) in the Jena Experiment. In general, Pmic and enzyme activities were correlated (r = 0.59 and 0.46 for phosphomonoesterase and phosphodiesterase activities, respectively; p

  3. Identification of Active Radical Species in Alkaline Persulfate Oxidation.

    PubMed

    Liang, Chenju; Lei, Jung-Hsuan

    2015-07-01

    A proposed mechanism for alkaline activation of persulfate involves generation of sulfate (SO(4)(-)), hydroxyl (HO·), and superoxide radicals (O(2)(-)). The present study investigated the feasibility of chloroform (CF) degradation using alkaline activated persulfate and identified the active radical species using a radical inhibition technique. 2-propanol (PrOH) (preferentially reacted with HO·), phenol (preferentially reacted with both HO· and SO(4)(-)), and carbon tetrachloride (CT) (preferentially reacted with O(2)(-)) were used to inhibit the degradation of CF, and the extent of inhibited degradation was used to indicate the predominant radical species. Additions of PrOH and phenol appeared to significantly scavenge SO(4)(-) and HO· and resulted in inhibited CF degradation. Here, the authors demonstrated that SO(4)(-) and HO· were predominant radicals in the alkaline activated persulfate system. The presence of O(2)(-) scavengers (i.e., CT) resulted in a partial inhibition of CF degradation and, hence, one can speculate that O(2)(-) is a minor radical species. PMID:26163502

  4. A nickel iron diselenide-derived efficient oxygen-evolution catalyst

    NASA Astrophysics Data System (ADS)

    Xu, Xiang; Song, Fang; Hu, Xile

    2016-08-01

    Efficient oxygen-evolution reaction catalysts are required for the cost-effective generation of solar fuels. Metal selenides have been reported as promising oxygen-evolution catalysts; however, their active forms are yet to be elucidated. Here we show that a representative selenide catalyst, nickel selenide, is entirely converted into nickel hydroxide under oxygen-evolution conditions. This result indicates that metal selenides are unstable during oxygen evolution, and the in situ generated metal oxides are responsible for their activity. This knowledge inspired us to synthesize nanostructured nickel iron diselenide, a hitherto unknown metal selenide, and to use it as a templating precursor to a highly active nickel iron oxide catalyst. This selenide-derived oxide catalyses oxygen evolution with an overpotential of only 195 mV for 10 mA cm-2. Our work underscores the importance of identifying the active species of oxygen-evolution catalysts, and demonstrates how such knowledge can be applied to develop better catalysts.

  5. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    SciTech Connect

    Peng, X.D.; Toseland, B.A.; Underwood, R.P.

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  6. Environmentally benign heterogeneous nano-particle catalysts: synthesis, characterization and catalytic activity of 4-nitrophenol.

    PubMed

    Murugan, Eagambaram; Jebaranjitham, J Nimita

    2011-02-01

    Pollution free catalyst is an attractive area of current interest. The p-Aminophenol is one of the most significant catalyst, because it involves the manufacture of various pharmaceuticals. Crosslinked poly(styrene)-co-poly(4-vinylimidazole) (PSPVIM) was prepared by varying the crosslinked monomer ratio as 2% and 10% respectively. The 2 (w%) of DVB, 25 (w%) of N-VIm as functional monomer and 73 (w%) of styrene as support monomer as organic phase and gelatin, boric acid and polyvinyl alcohol as aqueous phase was used to prepare cross-linked poly(styrene)-co-poly(N-vinyl imidazole) (PVIM) beads (Type-I). Similarly, Type II beads were also prepared by fixing the 10% as a cross linking ratio (DVB). The immobilization of Ag NPs onto the PS-VIm polymer matrix was performed using AgNO3 as a metal precursor solution. The k(obs) determined from UV-Vis results, reveals that the degree of reduction of 4-nitrophenol using Type-I catalysts is more effective than Type-II catalyst due to lower immobilization of AgNPs at higher cross-linked bead matrix. It was found that on increasing the amount of catalyst i.e., type-I PS-PVIm-AgNPs, the rate constant also increases. Therefore, PS-PVIm-AgNPs (Type-I) heterogeneous catalyst is superior for the reduction of 4-NP. PMID:21485850

  7. Heterogeneous adsorption and catalytic oxidation of benzene, toluene and xylene over spent and chemically regenerated platinum catalyst supported on activated carbon

    NASA Astrophysics Data System (ADS)

    Shim, Wang Geun; Kim, Sang Chai

    2010-06-01

    The heterogeneous adsorption and catalytic oxidation of benzene, toluene and o-xylene (BTX) over the spent platinum catalyst supported on activated carbon (Pt/AC) as well as the chemically treated spent catalysts were studied to understand their catalytic and adsorption activities. Sulfuric aqueous acid solution (0.1N, H 2SO 4) was used to regenerate the spent Pt/AC catalyst. The physico-chemical properties of the catalysts in the spent and chemically treated states were analyzed by using nitrogen adsorption-desorption isotherm and elemental analysis (EDX). The gravimetric adsorption and the light-off curve analysis were employed to study the BTX adsorption and oxidation on the spent catalyst and its modified Pt/AC catalysts. The experimental results indicate that the spent Pt/AC catalyst treated with the H 2SO 4 aqueous solution has a higher toluene adsorption and conversion ability than that of the spent Pt/AC catalyst. A further studies of H 2SO 4 treated Pt/AC catalyst on their catalytic and heterogeneous adsorption behaviours for BTX revealed that the activity of the H 2SO 4 treated Pt/AC catalyst follows the sequence of benzene > toluene > o-xylene. The adsorption equilibrium isotherms of BTX on the H 2SO 4 treated Pt/AC were measured at different temperatures ranging from 120 to 180 °C. To correlate the equilibrium data and evaluate their adsorption affinity for BTX, the two sites localized Langmuir (L2m) isotherm model was employed. The heterogeneous surface feature of the H 2SO 4 treated Pt/AC was described in detail with the information obtained from the results of isosteric enthalpy of adsorption and adsorption energy distributions. Furthermore, the activity of H 2SO 4 treated Pt/AC about BTX was found to be directly related to the Henry's constant, isosteric enthalpy of adsorption and adsorption energy distribution functions.

  8. A Simple, Efficient Synthesis of 2-Aryl Benzimidazoles Using Silica Supported Periodic Acid Catalyst and Evaluation of Anticancer Activity

    PubMed Central

    Sontakke, Vyankat A.; Ghosh, Sougata; Lawande, Pravin P.; Chopade, Balu A.; Shinde, Vaishali S.

    2013-01-01

    A new, efficient method for the synthesis of 2-aryl substituted benzimidazole by using silica supported periodic acid (H5IO6-SiO2) as a catalyst has been developed. The salient feature of the present method includes mild reaction condition, short reaction time, high yield and easy workup procedure. The synthesized benzimidazoles exhibited potent anticancer activity against MCF7 and HL60 cell lines. PMID:24052861

  9. Highly active, chemo- and regioselective Yb(II) and Sm(II) catalysts for the hydrophosphination of styrene with phenylphosphine.

    PubMed

    Basalov, Ivan V; Dorcet, Vincent; Fukin, Georgy K; Carpentier, Jean-François; Sarazin, Yann; Trifonov, Alexander A

    2015-04-13

    Stable heteroleptic amido Yb(II) and Sm(II) complexes bearing aminoether-phenolate ligands and devoid of coordinated solvent have been structurally characterized. They afford highly active, chemoselective and, in the case of monoadditions, 100 % anti-Markovnikov regiospecific catalysts (down to 0.04 mol % loading) for the hydrophosphination of styrene with PhPH2 under mild conditions. PMID:25760678

  10. A highly active and coke-resistant steam reforming catalyst comprising uniform nickel-iron alloy nanoparticles.

    PubMed

    Koike, Mitsuru; Li, Dalin; Nakagawa, Yoshinao; Tomishige, Keiichi

    2012-12-01

    Doing fine with Ni-Fe: The calcination and reduction of a hydrotalcite precursor containing Ni and Fe ions gives uniform Ni-Fe alloy nanoparticles mixed with Mg(Ni, Fe, Al)O particles. The uniformity of the Ni-Fe alloy nanoparticles is connected to the catalyst's high activity and resistance to coke formation in toluene and phenol steam reforming reactions. PMID:23135797

  11. Design and preparation of highly active carbon nanotube-supported sulfated TiO 2 and platinum catalysts for methanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Song, Huanqiao; Xiao, Pu; Qiu, Xinping; Zhu, Wentao

    A novel electrocatalyst structure of carbon nanotube-supported sulfated TiO 2 and Pt (Pt-S-TiO 2/CNT) is reported. The Pt-S-TiO 2/CNT catalysts are prepared by a combination of improved sol-gel and ethylene glycol reduction methods. Transmission electron microscopy and X-ray diffraction show that the sulfated TiO 2 is amorphous and is coated uniformly on the surface of the CNTs. Pt nanoparticles of about 3.6 nm in size are homogenously dispersed on the sulfated TiO 2 surface. Fourier transform infrared spectroscopy analysis proves that the CNT surfaces are modified with sulfated TiO 2 and a high concentration of SO x, and adsorbed OH species exist on the surface of the sulfated TiO 2. Electrochemical studies are carried out using chronoamperometry, cyclic voltammetry, CO stripping voltammetry and impedance spectroscopy. The results indicate that Pt-S-TiO 2/CNT catalysts have much higher catalytic activity and CO tolerance for methanol electrooxidation than Pt/TiO 2/CNTs, Pt/CNTs and commercial Pt/C.

  12. Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

    PubMed

    Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

    2016-06-25

    Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%. PMID:26902668

  13. Novel ebullated bed catalyst regeneration technology improves regenerated catalyst quality

    SciTech Connect

    Neuman, D.J.

    1995-09-01

    Regeneration of spent hydroprocessing catalysts has long been practiced by the refining industry. With increased pressures on refiners to reduce catalyst expenditures and waste generation, refiners are more frequently reusing spent hydroprocessing catalysts after ex-situ regeneration to restore catalytic activity. By reusing regenerated catalyst for at least two cycles, the refiner reduces catalyst waste by at least one-half. As environmental laws become more restrictive, spent hydroprocessing catalyst is more likely to be classified as hazardous waste. Disposal of spent catalyst, which was previously accomplished by landfilling, now requires more expensive reclamation techniques. TRICAT has introduced the TRICAT Regeneration Process (TRP), a novel ebullated bed regeneration plant, to improve the catalyst regeneration process. The ebullated bed design allows for better control of heat release during the regeneration process. As a result, the regeneration can be accomplished in a single-pass, with improved catalyst activity retention. Catalyst losses are also minimized due to reduced catalyst handling. Commercial results from the TRP have demonstrated successful scale-up of the technology from pilot scale. The plant has achieved complete recovery of the available catalyst activity with little or no losses in catalyst yield or extrudate length. The flexibility of the TRP to process a variety of catalysts is also discussed.

  14. Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO2 hydrogenation

    DOE PAGESBeta

    Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; Illas, Francesc

    2015-02-02

    Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO2 decomposition, thiophene hydrodesulfurization, O2 and H2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO2 + H2 → CO + H2O) and CO2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalytic activity of Au/TiC towards the hydrogenation ofmore » CO or CO2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO2/H2/H2O), CO could be transformed into CO2 through the water gas shift reaction with subsequent hydrogenation of CO2 to methanol.« less

  15. Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO2 hydrogenation

    NASA Astrophysics Data System (ADS)

    Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; Illas, Francesc

    2015-10-01

    Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO2 decomposition, thiophene hydrodesulfurization, O2 and H2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water-gas shift (CO2 + H2 → CO + H2O) and CO2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalytic activity of Au/TiC towards the hydrogenation of CO or CO2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO2 involves the hydrogenation of a HOCO-like intermediate. When dealing with mixtures of syngas (CO/CO2/H2/H2O), CO could be transformed into CO2 through the water gas shift reaction with subsequent hydrogenation of CO2 to methanol.

  16. Nature, density, and catalytic role of exposed species on dispersed VOx/CrOx/Al2O3 catalysts.

    PubMed

    Yang, Shuwu; Iglesia, Enrique; Bell, Alexis T

    2006-02-16

    The structure and surface composition of binary oxides consisting of CrO(x) and VO(x) dispersed on alumina and their effects on the rate and selectivity of oxidative dehydrogenation (ODH) of propane were examined and compared with those for CrO(x) and VO(x) dispersed on alumina. VO(x) deposition on an equivalent CrO(x) monolayer on alumina and deposition of CrO(x) on an equivalent monolayer of VO(x) deposited on alumina led to CrVO(4) species during thermal treatment with concomitant reduction of Cr(6+) to Cr(3+). Autoreduction of Cr(6+) to Cr(3+) is also detected for CrO(x), even without the presence of VO(x). Infrared spectroscopy of NO adsorbed at 153 K probes the relative abundance of alumina and of V(5+), Cr(3+), and Cr(6+) at surfaces. This technique detects differences in the surface composition of VO(x)/CrO(x)()/Al(2)O(3) and CrO(x)/VO(x)/Al(2)O(3). The first of these samples is enriched in VO(x) relative to CrO(x) compared with the second sample. Consistent with this finding, VO(x)/CrO(x)/Al(2)O(3) and CrO(x)/VO(x)/Al(2)O(3) are distinguishable in their ODH activities and propene selectivities. The highest ODH activity and propene selectivity is observed for VO(x)/CrO(x)/Al(2)O(3), which exhibits a surface enriched in VO(x) and having a low surface concentration of Cr(6+). PMID:16471878

  17. Synergistic effects of Ir-Au/TiO₂ catalysts in the total oxidation of propene: influence of the activation conditions.

    PubMed

    Aguilar-Tapia, Antonio; Zanella, Rodolfo; Calers, Christophe; Louis, Catherine; Delannoy, Laurent

    2015-11-14

    Iridium was added to the Au/TiO2 system to try to enhance its catalytic activity in the reaction of propene oxidation, performed under conditions close to those used in the studies of decomposition of volatile organic compounds (1200 ppm propene and 9 vol% O2 in He). Titania supported Ir-Au (Ir/Au = 1) was prepared by sequential deposition-precipitation with urea (DPU) of Ir then Au. The effect of the activation conditions (hydrogen or air at 400 °C) was investigated. The study of the activation conditions of Ir-Au/TiO2 showed that activation under hydrogen at 400 °C generated a catalyst more active than the monometallic ones, while Ir-Au/TiO2 activated in air remained as poorly active as Au/TiO2. TEM characterization showed the formation of metallic particles of similar size (2-3 nm) in both monometallic Au/TiO2 and bimetallic Ir-Au/TiO2. Characterization especially by DRIFTS using CO as a probe molecule suggests the presence of Ir-Au interaction, IrO2-Au(0) interaction when the sample is calcined and Ir(0)-Au(0) bimetallic particles when it is reduced. XPS and TPR characterization techniques showed that gold hinders to some extent the reoxidation of iridium in the reduced bimetallic Ir-Au/TiO2 catalyst. The enhanced catalytic activity of the reduced bimetallic Ir-Au/TiO2 catalyst is attributed to a surface Ir(0)-Au(0) synergism. PMID:25785784

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

    PubMed

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

    2016-04-01

    Correction for 'Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions' by Riny Y. Parapat et al., Nanoscale, 2013, 5, 796-805. PMID:26961853

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  20. Comparative Study of CuO Species on CuO/Al2O3, CuO/CeO2-Al2O3 and CuO/La2O-Al2O3 Catalysts for CO Oxidation

    NASA Astrophysics Data System (ADS)

    Jin, Ling-yun; He, Mai; Lu, Ji-qing; Luo, Meng-fei; Fang, Ping; Xie, Yun-long

    2007-10-01

    CuO/Al2O3, CuO/CeO2-Al2O3, and CuO/La2O3-Al2O3 (denoted as Cu/Al, Cu/CeAl, and Cu/LaAl) catalysts were prepared by an impregnation method. CuO species and CuO/Al2O3 thermal solid-solid interaction were characterized by in situ XRD, Raman spectroscopy and H2-TPR techniques. For the Cu/Al catalyst, a CuAl2O4 phase exists between the CuO and Al2O3 layer and the CuO phase exists on the surface in both highly dispersed and bulk forms. For the Cu/CeAl catalyst, there is highly dispersed and bulk CuO on the surface, but most of the CuO has transferred into the internal layer of CeO2 as bulk CuO and CuAl2O4. For the Cu/LaAl catalyst, only bulk CuO is present on the surface of the catalyst and no CuAl2O4 is formed. The catalytic activity order for CO oxidation is Cu/CeAl>Cu/Al>Cu/LaAl. The highly dispersed CuO on the catalyst surface may be the active phase for CO oxidation. The results show that the addition of CeO2 not only promotes both the transference of CuO and the formation of CuAl2O4 but also favors the CO oxidation due to the association of highly dispersed CuO with CeO2, while La2O3 hinders the transference of CuO and the formation of CuAl2O4.

  1. Examination of alternative catalysts for biomass direct liquefaction

    SciTech Connect

    Tran, A.D.; Rogers, D.Z.

    1985-08-01

    We have now completed a survey study of several water-soluble salts of transition metals that are deemed likely to have utility as catalysts for direct biomass liquefaction in a carbon monoxide steam process. Certain salts of molybdenum and nickel are the most effective catalysts, and are the only species for which some catalytic activity independent of the ligand can be shown. The most effective forms of the nickel and molybdenum are cyanide and oxyanion complexes. 30 refs., 5 figs., 4 tabs.

  2. Pincer Ligand Modifications To Tune the Activation Barrier for H2 Elimination in Water Splitting Milstein Catalyst.

    PubMed

    Sandhya, Karakkadparambil S; Remya, Geetha S; Suresh, Cherumuttathu H

    2015-12-01

    Modifications on the ligand environment of Milstein ruthenium(II) pincer hydride catalysts have been proposed to fine-tune the activation free energy, ΔG(⧧) for the key step of H2 elimination in the water splitting reaction. This study conducted at the B3LYP level of density functional theory including the solvation effect reveals that changing the bulky t-butyl group at the P-arm of the pincer ligand by methyl or ethyl group can reduce the ΔG(⧧) by a substantial margin, ∼ 10 kcal/mol. The reduction in the steric effect of the pincer ligand causes exothermic association of the water molecule to the metal center and leads to significant stabilization of all the subsequent reaction intermediates and the transition state compared to those of the original Milstein catalyst that promotes endothermic association of the water molecule. Though electron donating groups on the pyridyl unit of the pincer ligand are advantageous for reducing the activation barrier in the gas phase, the effect is only 1-1.4 kcal/mol compared to that of an electron withdrawing group. The absolute minimum of the electrostatic potential at the hydride ligand and carbonyl stretching frequency of the catalyst are useful parameters to gauge the effect of ligand environment on the H2 elimination step of the water splitting reaction. PMID:26575086

  3. A highly active and magnetically recoverable tris(triazolyl)-Cu(I) catalyst for alkyne-azide cycloaddition reactions.

    PubMed

    Wang, Dong; Etienne, Laetitia; Echeverria, María; Moya, Sergio; Astruc, Didier

    2014-04-01

    Nanoparticle-supported tris(triazolyl)-CuBr, with a diameter of approximately 25 nm measured by TEM spectroscopy, has been easily prepared, and its catalytic activity was evaluated in the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In initial experiments, 0.5 mol % loading successfully promoted the CuAAC reaction between benzyl azide and phenylacetylene, in water at room temperature (25 °C). During this process, the iron oxide nanoparticle-supported tris(triazolyl)-CuBr displayed good monodispersity, excellent recoverability, and outstanding reusability. Indeed, it was simply collected and separated from the reaction medium by using an external magnet, then used for another five catalytic cycles without significant loss of catalytic activity. Inductively coupled plasma (ICP) analysis for the first cycle revealed that the amount of copper leached from the catalyst into the reaction medium is negligible (1.5 ppm). The substrate scope has been examined, and it was found that the procedure can be successfully extended to various organic azides and alkynes and can also be applied to the one-pot synthesis of triazoles, through a cascade reaction involving benzyl bromides, alkynes, and sodium azide. In addition, the catalyst was shown to be an efficient CuAAC catalyst for the synthesis of allyl- and TEG-ended (TEG=triethylene glycol) 27-branch dendrimers. PMID:24574335

  4. Modification of Pd-CeO 2 catalyst by different treatments: Effect on the structure and CO oxidation activity

    NASA Astrophysics Data System (ADS)

    Wang, Bin; Weng, Duan; Wu, Xiaodong; Ran, Rui

    2011-02-01

    To investigate the interaction between noble metal and CeO2, a Pd-doped CeO2 catalyst was prepared by sol-gel method, and the catalyst was then treated in static air and a H2/O2 alternating flow at 800 °C, respectively. It is found by step-scanning XRD that Pd ions migrate out of the ceria lattice during the redox treatment, while the exudation of Pd is not so obvious after the oxidative treatment. For the CO oxidation activity, the redox treated catalyst is seriously weakened compared with the oxidative-treated one. This difference is ascribed to the encapsulation of Pd crystallites by the CeO2 support during the redox treatment, which is confirmed by XPS and CO-TPR. Based on the activity and FTIR results, it is proposed that, CO oxidation at low temperatures proceeds mainly via the reaction between the adsorbed CO on Pd sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface.

  5. High catalytic activity and pollutants resistivity using Fe-AAPyr cathode catalyst for microbial fuel cell application

    NASA Astrophysics Data System (ADS)

    Santoro, Carlo; Serov, Alexey; Villarrubia, Claudia W. Narvaez; Stariha, Sarah; Babanova, Sofia; Artyushkova, Kateryna; Schuler, Andrew J.; Atanassov, Plamen

    2015-11-01

    For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm-2 and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm-2 by day 13, achieving similar values of an activated carbon based cathode. The presence of S2- and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater.

  6. High catalytic activity and pollutants resistivity using Fe-AAPyr cathode catalyst for microbial fuel cell application

    PubMed Central

    Santoro, Carlo; Serov, Alexey; Villarrubia, Claudia W. Narvaez; Stariha, Sarah; Babanova, Sofia; Artyushkova, Kateryna; Schuler, Andrew J.; Atanassov, Plamen

    2015-01-01

    For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm−2 and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm−2 by day 13, achieving similar values of an activated carbon based cathode. The presence of S2− and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater. PMID:26563922

  7. Anionic group 6B metal carbonyls as homogeneous catalysts for carbon dioxide/hydrogen activation: the production of alkyl formates

    SciTech Connect

    Darensbourg, D.J.; Ovalles, C.

    1984-06-27

    The production of alkyl formates from the hydrocondensation of carbon dioxide in alcohols utilizing anionic group 6B carbonyl hydrides as catalysts is herein reported. HM(CO)/sub 5//sup -/ (M = Cr, W; derived from ..mu..-H(M/sub 2/(CO)/sub 10/)/sup -/) and their products of carbon dioxide insertion, HCO/sub 2/M(CO)/sub 5//sup -/, have been found to be effective catalysts for the hydrogenation of CO/sub 2/ in alcohols under rather mild conditions (loading pressures of CO/sub 2/ and H/sub 2/, 250 psi each, and 125/sup 0/C) to provide alkyl formates. The only metal carbonyl species detected in solution via spectroscopy, both at the end of a catalytic period and during catalysis, were M(CO)/sub 6/ and HCO/sub 2/M(CO)/sub 5//sup -/. The metal hexacarbonyls were independently shown to be catalytically inactive. A catalytic cycle is proposed which initially involves release of formic acid from the metal center, either by reductive elimination of the hydrido formato ligands or ligand-assisted heterolytic splitting of dihydrogen with loss of formic acid. In a rapid subsequent process HCOOH reacts with alcohols to yield HCOOR. The addition of carbon monoxide retards alkyl formate production, strongly implying CO/sub 2/ to be the primary source of the carboxylic carbon atom in HCOOR. This was verified by carrying out reactions in the presence of HCO/sub 2/W(/sup 13/CO)/sub 5//sup -/ which provided only H/sup 12/COOR after short reaction periods. However, in the absence of hydrogen and carbon dioxide ..mu..-H(M/sub 2/(CO)/sub 10/)/sup -/ species were observed to be effective catalyst precursors for converting CO and methanol into methyl formate. 36 references, 2 figures, 2 tables.

  8. Plasmonic Nanorattles as Next-Generation Catalysts for Surface Plasmon Resonance-Mediated Oxidations Promoted by Activated Oxygen.

    PubMed

    da Silva, Anderson G M; Rodrigues, Thenner S; Correia, Valquírio G; Alves, Tiago V; Alves, Rafael S; Ando, Rômulo A; Ornellas, Fernando R; Wang, Jiale; Andrade, Leandro H; Camargo, Pedro H C

    2016-06-13

    Nanorattles, comprised of a nanosphere inside a nanoshell, were employed as the next generation of plasmonic catalysts for oxidations promoted by activated O2 . After investigating how the presence of a nanosphere inside a nanoshell affected the electric-field enhancements in the nanorattle relative to a nanoshell and a nanosphere, the SPR-mediated oxidation of p-aminothiophenol (PATP) functionalized at their surface was investigated to benchmark how these different electric-field intensities affected the performances of Au@AgAu nanorattles, AgAu nanoshells and Au nanoparticles having similar sizes. The high performance of the nanorattles enabled the visible-light driven synthesis of azobenzene from aniline under ambient conditions. As the nanorattles allow the formation of electromagnetic hot spots without relying on the uncontrolled aggregation of nanostructures, it enables their application as catalysts in liquid phase under mild conditions using visible light as the main energy input. PMID:27159199

  9. Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Shen, Chengmin; Liang, Yanyu; Tong, Hao; He, Wei; Shi, Xuezhao; Zhang, Xiaogang; Gao, Hong-jun

    2011-08-01

    A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized by in situ chemical oxidation polymerization. Palladium nanoparticles (NPs) with a diameter of 4.0 nm were loaded on the reduced graphene oxide(RGO)-PPy composites by a microwave-assisted polyol process. Microstructure analysis showed that a layer of coated PPy film with monodisperse Pd NPs is present on the RGO surface. The Pd/RGO-PPy catalysts exhibit excellent catalytic activity and stability for formic acid electro-oxidation when the weight feed ratio of GO to pyrrole monomer is 2:1. The superior performance of Pd/RGO-PPy catalysts may arise from utilization of heterogeneous nucleation sites for NPs and the greatly increased electronic conductivity of the supports. PMID:21713273

  10. Selectivity loss of Pt/CeO{sub 2} PROX catalysts at low CO concentrations: mechanism and active site study.

    SciTech Connect

    Polster, C. S.; Zhang, R.; Cyb, M. T.; Miller, J. T.; Baertsch, C. D.

    2010-07-01

    CO and H{sub 2} oxidation were studied over a series of Pt/CeO{sub 2} catalysts with differing Pt loadings and dispersions. Kinetic rate analysis confirms the presence of dual Langmuir-Hinshelwood (L-H) and Mars and van Krevelen (M-vK) pathways and is used to explain the loss in CO oxidation selectivity at low CO concentrations. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) shows the strong CO coverage dependence on both CO and O{sub 2} concentrations and explains the transition from L-H to M-vK reaction character. Redox site measurements are performed on Pt/CeO{sub 2} catalysts by anaerobic titrations under conditions where the M-vK pathway dominates the reaction rate. Similar redox site densities per interfacial Pt atom suggest that interfacial Pt-O-Ce sites are responsible for M-vK redox activity.

  11. On the design of Pt based catalysts. Combining porous architecture with surface modification by Sn for electrocatalytic activity enhancement

    NASA Astrophysics Data System (ADS)

    Flórez-Montaño, Jonathan; García, Gonzalo; Rodríguez, José L.; Pastor, Elena; Cappellari, Paula; Planes, Gabriel A.

    2015-05-01

    Metallic mesoporous (MP) catalysts with large surface area can be obtained in-situ, in a single step, by electrochemical reduction. In this work, the electrochemical behavior of MPPt and Sn modified mesoporous Pt (MPPt/Sn) was studied and compared with commercial carbon supported PtSn alloy (3:1). The electrochemical activity toward carbon monoxide and methanol oxidation reactions were evaluated by cyclic voltammetry and chronoamperometry, whereas X-ray photoelectron spectroscopy was used to determine the surface composition and oxidation state of the atoms in the top layers of the catalysts. The analysis of methanol conversion to CO2 was performed with aid of differential electrochemical mass spectrometry (DEMS). Results reveal a better performance of the MPPt/Sn, which shows higher current density and energy conversion efficiency of fuel to CO2 than conventional carbon supported PtSn alloy (3:1).

  12. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    SciTech Connect

    Jackson, N.B.; Kohler, S.; Harrington, M.

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  13. Whole Blood Cholinesterase Activity in 20 Species of Wild Birds.

    PubMed

    Horowitz, Igal H; Yanco, Esty G; Landau, Shmulik; Nadler-Valency, Rona; Anglister, Nili; Bueller-Rosenzweig, Ariela; Apelbom-Halbersberg, Tal; Cuneah, Olga; Hanji, Vera; Bellaiche, Michel

    2016-06-01

    Clinical signs of organophosphate and carbamate intoxication in wild birds can be mistaken for those of other diseases, thus potentially delaying diagnosis and implementation of life-saving treatment. The objective of this study was to determine the reference interval for blood cholinesterase activity in 20 different wild avian species from 7 different orders, thereby compiling a reference database for wildlife veterinarians. Blood was collected from birds not suspected of having organophosphate or carbamate toxicosis, and the modified Michel method, which determines the change in blood pH that directly correlates with cholinesterase activity, was used to measure blood cholinesterase levels. Results of change in blood pH values ranged from 0.11 for the white-tailed eagle ( Haliaeetus albicilla ) to 0.90 for the honey buzzard ( Pernis apivorus ). The results showed that even within the same family, interspecies differences in normal cholinesterase blood activity were not uncommon. The findings emphasized the importance of determining reference intervals for avian blood cholinesterase activity at the species level. PMID:27315378

  14. Phytochemical profiles, antioxidant and antimicrobial activities of three Potentilla species

    PubMed Central

    2013-01-01

    Background Extracts from Potentilla species have been applied in traditional medicine and exhibit antioxidant, hypoglycemic, anti-inflammatory, antitumor and anti-ulcerogenic properties, but little has been known about the diversity of phytochemistry and pharmacology on this genus. This study investigated and compared the phytochemical profiles, antioxidant and antimicrobial activities of leaf extracts from three Potentilla species (Potentilla fruticosa, Potentilla glabra and Potentilla parvifolia) in order to discover new resources for lead structures and pharmaceutical products. Methods Chemical composition and content of six phenolic compounds were evaluated and determined by RP-HPLC; Total phenolic and total flavonoid content were determined using Folin-Ciocalteau colourimetric method and sodium borohydride/chloranil-based method (SBC); Antioxidant activities were determined using DPPH, ABTS and FRAP assays; Antimicrobial properties were investigated by agar dilution and mycelial growth rate method. Results The results showed hyperoside was the predominant phenolic compound in three Potentilla species by RP-HPLC assay, with the content of 8.86 (P. fruticosa), 2.56 (P. glabra) and 2.68 mg/g (P. parvifolia), respectively. The highest content of total identified phenolic compounds (hyperoside, (+)-catechin, caffeic acid, ferulic acid, rutin and ellagic acid) was observed in P. parvifolia (14.17 mg/g), follow by P. fruticosa (10.01 mg/g) and P. glabra (7.01 mg/g). P. fruticosa possessed the highest content of total phenolic (84.93 ± 0.50 mmol gallic acid equivalent/100 g) and total flavonoid (84.14 ± 0.03 mmol quercetin equivalent/100 g), which were in good correlation with its significant DPPHIC50 (16.87 μg/mL), ABTS (2763.48 μmol Trolox equivalent/g) and FRAP (1398.70 μmol Trolox equivalent/g) capacities. Furthermore, the effective methodology to distinguish the different species of Potentilla was also established by chromatographic fingerprint analysis for

  15. Solvent-Induced Reversal of Activities between Two Closely Related Heterogeneous Catalysts in the Aldol Reaction

    SciTech Connect

    Kandel, Kapil; Althaus, Stacey M; Peeraphatdit, Chorthip; Kobayashi, Takeshi; Trewyn, Brian G; Pruski, Marek; Slowing, Igor I

    2013-01-11

    The relative rates of the aldol reaction catalyzed by supported primary and secondary amines can be inverted by 2 orders of magnitude, depending on the use of hexane or water as a solvent. Our analyses suggest that this dramatic shift in the catalytic behavior of the supported amines does not involve differences in reaction mechanism, but is caused by activation of imine to enamine equilibria and stabilization of iminium species. The effects of solvent polarity and acidity were found to be important to the performance of the catalytic reaction. This study highlights the critical role of solvent in multicomponent heterogeneous catalytic processes.

  16. Bioreductively Activated Reactive Oxygen Species (ROS) Generators as MRSA Inhibitors.

    PubMed

    Khodade, Vinayak S; Sharath Chandra, Mallojjala; Banerjee, Ankita; Lahiri, Surobhi; Pulipeta, Mallikarjuna; Rangarajan, Radha; Chakrapani, Harinath

    2014-07-10

    The number of cases of drug resistant Staphylococcus aureus infections is on the rise globally and new strategies to identify drug candidates with novel mechanisms of action are in urgent need. Here, we report the synthesis and evaluation of a series of benzo[b]phenanthridine-5,7,12(6H)-triones, which were designed based on redox-active natural products. We find that the in vitro inhibitory activity of 6-(prop-2-ynyl)benzo[b]phenanthridine-5,7,12(6H)-trione (1f) against methicillin-resistant Staphylococcus aureus (MRSA), including a panel of patient-derived strains, is comparable or better than vancomycin. We show that the lead compound generates reactive oxygen species (ROS) in the cell, contributing to its antibacterial activity. PMID:25050164

  17. Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

    PubMed Central

    Patterson, Joseph P.; Cotanda, Pepa; Kelley, Elizabeth G.; Moughton, Adam O.; Lu, Annhelen; Epps, Thomas H.; O’Reilly, Rachel K.

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity. PMID:23539324

  18. Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

    NASA Astrophysics Data System (ADS)

    Pan, Yuan; Yang, Na; Chen, Yinjuan; Lin, Yan; Li, Yanpeng; Liu, Yunqi; Liu, Chenguang

    2015-11-01

    Development of hybrid catalysts with high activity, good stability and low cost is extremely desirable for hydrogen production by electrolysis of water. In this work, a hybrid composed of Ni2P nanoparticles (NPs) on N-doped reduced graphene oxide (NRGO) is synthesized via an in situ thermal decomposition approach for the first time and investigated as a catalyst for the hydrogen evolution reaction (HER). The as-synthesized Ni2P/NRGO hybrid exhibits an enhanced catalytic activity with low onset overpotential (37 mV), a small Tafel slope (59 mV dec-1), a much larger exchange current density (4.9 × 10-5 A cm-2), and lower HER activation energy (46.9 kJ mol-1) than Ni2P/RGO hybrid. In addition, the Ni2P/NRGO hybrid maintains its catalytic activity for at least 60‧000 s in acidic media. The enhanced catalytic activity is attributed to the synergistic effect of N-doped RGO and Ni2P NPs, the charged natures of Ni and P, as well as the high electrical conductivity of Ni2P/NRGO hybrid. This study may offer a new strategy for improving the electrocatalytic activity for hydrogen production.

  19. Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C.

    PubMed

    Hu, Jue; Wu, Lijun; Kuttiyiel, Kurian A; Goodman, Kenneth R; Zhang, Chengxu; Zhu, Yimei; Vukmirovic, Miomir B; White, Michael G; Sasaki, Kotaro; Adzic, Radoslav R

    2016-07-27

    We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxide-free core atoms. The oxide on edges and vertexes induces high catalyst stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low-coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those of commercial Pt/C catalysts. The durability tests show no activity loss after 10 000 potential cycles from 0.6 to 1.0 V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective titanium oxide located at the most dissolution-prone edge and vertex sites and Au-supported active and stable Pt shell. PMID:27362731

  20. Large roads reduce bat activity across multiple species.

    PubMed

    Kitzes, Justin; Merenlender, Adina

    2014-01-01

    Although the negative impacts of roads on many terrestrial vertebrate and bird populations are well documented, there have been few studies of the road ecology of bats. To examine the effects of large roads on bat populations, we used acoustic recorders to survey bat activity along ten 300 m transects bordering three large highways in northern California, applying a newly developed statistical classifier to identify recorded calls to the species level. Nightly counts of bat passes were analyzed with generalized linear mixed models to determine the relationship between bat activity and distance from a road. Total bat activity recorded at points adjacent to roads was found to be approximately one-half the level observed at 300 m. Statistically significant road effects were also found for the Brazilian free-tailed bat (Tadarida brasiliensis), big brown bat (Eptesicus fuscus), hoary bat (Lasiurus cinereus), and silver-haired bat (Lasionycteris noctivagans). The road effect was found to be temperature dependent, with hot days both increasing total activity at night and reducing the difference between activity levels near and far from roads. These results suggest that the environmental impacts of road construction may include degradation of bat habitat and that mitigation activities for this habitat loss may be necessary to protect bat populations. PMID:24823689

  1. Large Roads Reduce Bat Activity across Multiple Species

    PubMed Central

    Kitzes, Justin; Merenlender, Adina

    2014-01-01

    Although the negative impacts of roads on many terrestrial vertebrate and bird populations are well documented, there have been few studies of the road ecology of bats. To examine the effects of large roads on bat populations, we used acoustic recorders to survey bat activity along ten 300 m transects bordering three large highways in northern California, applying a newly developed statistical classifier to identify recorded calls to the species level. Nightly counts of bat passes were analyzed with generalized linear mixed models to determine the relationship between bat activity and distance from a road. Total bat activity recorded at points adjacent to roads was found to be approximately one-half the level observed at 300 m. Statistically significant road effects were also found for the Brazilian free-tailed bat (Tadarida brasiliensis), big brown bat (Eptesicus fuscus), hoary bat (Lasiurus cinereus), and silver-haired bat (Lasionycteris noctivagans). The road effect was found to be temperature dependent, with hot days both increasing total activity at night and reducing the difference between activity levels near and far from roads. These results suggest that the environmental impacts of road construction may include degradation of bat habitat and that mitigation activities for this habitat loss may be necessary to protect bat populations. PMID:24823689

  2. Lectin activity in mycelial extracts of Fusarium species.

    PubMed

    Bhari, Ranjeeta; Kaur, Bhawanpreet; Singh, Ram S

    2016-01-01

    Lectins are non-immunogenic carbohydrate-recognizing proteins that bind to glycoproteins, glycolipids, or polysaccharides with high affinity and exhibit remarkable ability to agglutinate erythrocytes and other cells. In the present study, ten Fusarium species previously not explored for lectins were screened for the presence of lectin activity. Mycelial extracts of F. fujikuroi, F. beomiformii, F. begoniae, F. nisikadoi, F. anthophilum, F. incarnatum, and F. tabacinum manifested agglutination of rabbit erythrocytes. Neuraminidase treatment of rabbit erythrocytes increased lectin titers of F. nisikadoi and F. tabacinum extracts, whereas the protease treatment resulted in a significant decline in agglutination by most of the lectins. Results of hapten inhibition studies demonstrated unique carbohydrate specificity of Fusarium lectins toward O-acetyl sialic acids. Activity of the majority of Fusarium lectins exhibited binding affinity to d-ribose, l-fucose, d-glucose, l-arabinose, d-mannitol, d-galactosamine hydrochloride, d-galacturonic acid, N-acetyl-d-galactosamine, N-acetyl-neuraminic acid, 2-deoxy-d-ribose, fetuin, asialofetuin, and bovine submaxillary mucin. Melibiose and N-glycolyl neuraminic acid did not inhibit the activity of any of the Fusarium lectins. Mycelial extracts of F. begoniae, F. nisikadoi, F. anthophilum, and F. incarnatum interacted with most of the carbohydrates tested. F. fujikuroi and F. anthophilum extracts displayed strong interaction with starch. The expression of lectin activity as a function of culture age was investigated. Most species displayed lectin activity on the 7th day of cultivation, and it varied with progressing of culture age. PMID:27237111

  3. Reduction of Pt2+ species in model Pt-CeO2 fuel cell catalysts upon reaction with methanol

    NASA Astrophysics Data System (ADS)

    Neitzel, Armin; Johánek, Viktor; Lykhach, Yaroslava; Skála, Tomáš; Tsud, Nataliya; Vorokhta, Mykhailo; Matolín, Vladimír; Libuda, Jörg

    2016-11-01

    The stability of atomically dispersed Pt2+ species on the surface of nanostructured CeO2 films during the reaction with methanol has been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The isolated Pt2+ species were prepared at low Pt concentration in Pt-CeO2 film. Additionally, Pt2+ species coexisting with metallic Pt particles were prepared at high Pt concentration. We found that adsorption of methanol yields similar decomposition products regardless of Pt concentration in Pt-CeO2 films. A small number of oxygen vacancies formed during the methanol decomposition can be replenished in the Pt-CeO2 film with low Pt concentration by diffusion of oxygen from the bulk. In the presence of supported Pt particles, a higher number of oxygen vacancies leads to a partial reduction of the Pt2+ species. The isolated Pt2+ species are reduced under rather strongly reducing conditions only, i.e. during annealing under continuous exposure to methanol. Reduction of isolated Pt2+ species results in the formation of ultra-small Pt particles containing around 25 atoms per particle or less. Such ultra-small Pt particles demonstrate excellent stability against sintering during annealing of Pt-CeO2 film with low Pt concentration under reducing conditions.

  4. Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

    PubMed

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes. PMID:18657902

  5. Catalyst design based on agostic interactions: synthesis, characterization, and catalytic activity of bis(pyrazolyl)borate copper complexes.

    PubMed

    Cao, Hou-Ji; Zhao, Qianyi; Zhang, Qian-Fan; Li, Jiaxuan; Hamilton, Ewan J M; Zhang, Jie; Wang, Lai-Sheng; Chen, Xuenian

    2016-06-21

    Agostic interactions are often used to activate inert C-H bonds, and thus facilitate new reactions. We report the first example of designed catalysts based on the agostic interaction. Novel copper(i) complexes [BBN(pz(x))2]Cu(PPh3)n (BBN = 9-borabicyclo[3.3.1]nonane; pz(x) = 3-substituted pyrazole; x = H, n = 2; x = Me, n = 1) and {[BBN(pz(iPr))2]Cu}2 have been synthesized and characterized. Single crystal studies of the three compounds show weak intramolecular C-HCu interactions which can be assigned as agostic or anagostic interactions. Catalytic studies of these complexes toward carbenoid insertion into N-H bonds indicate these weak interactions act as a "switch" which will be turned "on" if interacting with the substrate and "off" if eliminating the product and regenerating the weak interaction. The process of the "switch" turning "on" or "off", which is related to the catalytic effect, is found to be influenced by both steric effects and the solvent: a less sterically hindered catalyst in non-coordinating benzene results in high yield, while a more sterically hindered catalyst in coordinating THF results in relatively low yield. PMID:27171346

  6. Highly active Ce 1- xCu xO 2 nanocomposite catalysts for the low temperature oxidation of CO

    NASA Astrophysics Data System (ADS)

    Mai, Hailing; Zhang, Dengsong; Shi, Liyi; Yan, Tingting; Li, Hongrui

    2011-06-01

    A series of Ce 1- xCu xO 2 nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N 2 adsorption, H 2-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce 1- xCu xO 2 nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce 0.80Cu 0.20O 2 nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10 -4 mmol g -1 s -1 and high turnover frequency of 7.53 × 10 -2 s -1 (1% CO balanced with air at a rate of 40 mL min -1, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce 0.80Cu 0.20O 2 nanocomposite catalyst.

  7. Fischer-Tropsch Catalysts

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Taylor, Jesse W. (Inventor)

    2008-01-01

    Catalyst compositions and methods for F-T synthesis which exhibit high CO conversion with minor levels (preferably less than 35% and more preferably less than 5%) or no measurable carbon dioxide generation. F-T active catalysts are prepared by reduction of certain oxygen deficient mixed metal oxides.

  8. Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

    DOE PAGESBeta

    Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; Olarte, Mariefel V.; Armstrong, Beth L.; Meyer, III, Harry M.; Schwartz, Viviane; Soykal, I. Ilgaz

    2016-05-19

    This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

  9. Mo-Fe catalysts supported on activated carbon for synthesis of liquid fuels by the Fischer-Tropsch process: effect of Mo addition on reducibility, activity, and hydrocarbon selectivity

    SciTech Connect

    Wenping Ma; Edwin L. Kugler; James Wright; Dady B. Dadyburjor

    2006-12-15

    The effects of Mo loading (0-12 wt %) on the properties of activated-carbon- (AC-) supported Fe-Cu-K catalysts and their performance for Fischer-Tropsch synthesis are studied. Physicochemical properties studied include particle size, reducibility, and dispersion, and catalytic properties include activity, selectivity, and stability. Catalysts were characterized by N{sub 2} adsorption, energy-dispersive spectroscopy, X-ray diffraction (XRD), H{sub 2} temperature-programmed reduction (TPR), and CO chemisorption. Catalyst performance was studied at 310-320{sup o}C, 2.2 MPa, 3 Nl/g-cat/h, and H{sub 2}/CO = 0.9. Reaction results in a fixed-bed reactor show that addition of 6% Mo into the Fe-Cu-K/AC catalyst improves catalyst stability without sacrificing activity, but activity is suppressed dramatically on a 12% Mo-loaded catalyst. Detectable hydrocarbons of C{sub 1} to C{sub 34} are produced on the Fe-Cu-K/AC catalysts with or without Mo. However, the addition of Mo results in the production of more CH{sub 4} and less C{sub 5+} hydrocarbons. The Mo promoter greatly enhances secondary reactions of olefins, leading to a large amount of internal olefins (i.e., other than 1-olefins) in the product. TPR shows that a strong interaction between Fe and Mo oxides is present, and the extent of reduction of Fe is suppressed after addition of Mo to the Fe-Cu-K catalyst. CO-chemisorption and XRD studies show increased iron dispersion and decreased particle size of the iron carbide and iron oxide after the addition of Mo. Segregation of iron active sites, thereby preventing them from agglomerating, and a larger number of active sites on the 6% Mo catalyst are possible reasons for the improved stability and higher activity of Mo-promoted catalysts. 54 refs., 5 figs., 6 tabs.

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

    SciTech Connect

    Wickham, David; Cook, Ronald

    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).

  11. Influence of reductive pretreatments on the activity and selectivity of vanadium-phosphorus oxide catalysts for n-butane partial oxidation

    SciTech Connect

    Hodnett, B.K.; Delmon, B.

    1984-11-01

    The catalytic activities for n-butane conversion to maleic anhydride of two series of vanadium-phosphorus oxide catalysts with phosphorus:vanadium ratios in the range 0.94 to 1.10 and calcined at 773 or 923 K were compared before and after reduction by hydrogen. In almost all cases studied, reduction gave rise to increased conversion, and for catalysts with low phosphorus:vanadium ratios increased selectivity was also noted. When n-butane was contacted with these catalysts in the absence of gas phase oxygen, maleic anhydride and total oxidation products continued to be formed until changes in average oxidation state of vanadium of up to -1.5 were recorded. From considerations of the dynamic state of the catalysts during catalysis, it was concluded that a morphology consisting of oxidized surface layers on a reduced core favors high activities and selectivities for this process.

  12. Effect of the conditions of preparing mixed oxide catalyst of Mo-V-Te-Nb-O composition on its activity in the oxidative dehydrogenation of ethane

    NASA Astrophysics Data System (ADS)

    Finashina, E. D.; Kucherov, A. V.; Kustov, L. M.

    2013-12-01

    It is shown that catalytic activity of mixed oxide catalyst of Mo-V-Te-Nb-O composition in oxidative dehydrogenation (OD) of ethane is determined to a substantial degree by the Nb-to-(C2O4)2- ratio in niobium-containing precursors. A pH value of 2.8 to 3.0 for a mixture is optimal when conducting the hydrothermal synthesis of a mixed oxide catalyst; this is achieved by using oxaloniobic acid as a niobium-containing precursor. It is determined that substituting antimony for tellurium results in a loss of catalyst activity during the OD of ethane. The optimum Te content in a catalyst is 0.17 mol %.

  13. Reactive oxygen species-activated nanomaterials as theranostic agents.

    PubMed

    Kim, Kye S; Lee, Dongwon; Song, Chul Gyu; Kang, Peter M

    2015-01-01

    Reactive oxygen species (ROS) are generated from the endogenous oxidative metabolism or from exogenous pro-oxidant exposure. Oxidative stress occurs when there is excessive production of ROS, outweighing the antioxidant defense mechanisms which may lead to disease states. Hydrogen peroxide (H2O2) is one of the most abundant and stable forms of ROS, implicated in inflammation, cellular dysfunction and apoptosis, which ultimately lead to tissue and organ damage. This review is an overview of the role of ROS in different diseases. We will also examine ROS-activated nanomaterials with emphasis on hydrogen peroxide, and their potential medical implications. Further development of the biocompatible, stimuli-activated agent responding to disease causing oxidative stress, may lead to a promising clinical use. PMID:26328770

  14. Reactive oxygen species-activated nanomaterials as theranostic agents

    PubMed Central

    Kim, Kye S; Lee, Dongwon; Song, Chul Gyu; Kang, Peter M

    2015-01-01

    Reactive oxygen species (ROS) are generated from the endogenous oxidative metabolism or from exogenous pro-oxidant exposure. Oxidative stress occurs when there is excessive production of ROS, outweighing the antioxidant defense mechanisms which may lead to disease states. Hydrogen peroxide (H2O2) is one of the most abundant and stable forms of ROS, implicated in inflammation, cellular dysfunction and apoptosis, which ultimately lead to tissue and organ damage. This review is an overview of the role of ROS in different diseases. We will also examine ROS-activated nanomaterials with emphasis on hydrogen peroxide, and their potential medical implications. Further development of the biocompatible, stimuli-activated agent responding to disease causing oxidative stress, may lead to a promising clinical use. PMID:26328770

  15. Periodic density functional theory studies of the VOx/TiO2 (anatase) catalysts: Structure and stability of monomeric species

    NASA Astrophysics Data System (ADS)

    Du, Yu-Jue; Li, Zhen Hua; Fan, Kang-Nian

    2012-06-01

    Periodic density functional theory has been utilized to investigate the structure and stability of monomeric HVOx species on anatase support. The three most stable surfaces of anatase were investigated, namely the (001), (100) and (101) surfaces. Unlike previous theoretical studies it was found that on the (001) surface vanadia species with five-coordinated vanadium atom are more stable than those with tetrahedrally coordinated vanadium atom. On the other hand, on the (100) and (101) surfaces, the vanadium atom in the vanadia species is still tetrahedrally coordinated. The stability of different VOx/TiO2 structures which are not fully dehydrated has been systematically studied and the results show that the vanadia species on the three surfaces follow an order of TiO2 (001) > TiO2 (100) > TiO2 (101). This can be understood from the acidity and basicity of the three anatase surfaces. The results suggest that monomeric VOx species may be better stabilized if the support exposes more (001) surfaces. Our analyses on electronic structure of the most stable VOx/TiO2 structure (D001) suggest that its bridging V-O-Ti oxygen atoms may have higher reactivity than the terminal vanadyl oxygen atoms.

  16. Antimicrobial activity of Amazonian oils against Paenibacillus species.

    PubMed

    Santos, Roberto Christ Vianna; dos Santos Alves, Camilla Filippi; Schneider, Taiane; Lopes, Leonardo Quintana Soares; Aurich, Carlos; Giongo, Janice Luehring; Brandelli, Adriano; de Almeida Vaucher, Rodrigo

    2012-03-01

    The Gram-positive, spore-forming bacterium Paenibacillus larvae is the primary bacterial pathogen of honeybee brood and the causative agent of American foulbrood disease (AFB). One of the feasible alternative treatments being used for their control of this disease is essential oils. In this study in vitro antimicrobial activity of Andiroba and Copaíba essential oils against Paenibacillus species, including P. larvae was evaluated. Minimal inhibitory concentration (MIC) in Mueller-Hinton broth by the microdilution method was assessed. Andiroba registered MIC values of 1.56-25%, while the MICs values obtained for Copaíba oil were of 1.56-12.5%. In order to determine the time-response effect of essential oils on P. larvae, this microorganism was exposed to the oils for up to 48 h. After 24 h treatment with Andiroba oil and after 48 h treatment with Copaíba oil no viable cells of P. larvae ATCC 9545 were observed. The possible toxic effect of essential oils were assessed by the spraying application method of the same concentrations of MICs. Bee mortality was evident only in treatment with Andiroba oil and the Copaíba oil shows no toxic effects after 10 days of observation. Taking together ours results showed for the first time that these oils presented a high activity against Paenibacillus species showing that Copaíba oil may be a candidate for the treatment or prevention of AFB. PMID:22200645

  17. Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

    NASA Astrophysics Data System (ADS)

    Dade, William N.

    Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

  18. From surface science to catalysis: The importance of methoxy and formate species on Cu single crystals and industrial catalysts

    NASA Astrophysics Data System (ADS)

    Bowker, M.; Waugh, K. C.

    2016-08-01

    Early work from the Madix group identified a number of simple surface intermediate species which have proved to be of significance for industrial catalytic processes. Two of these intermediates are the methoxy and formate surface species. We discuss the formation and behavior of these on copper surfaces, and go on to highlight their role in two important industrial reactions, namely methanol synthesis and the selective oxidation of methanol to formaldehyde. The formate is the pivotal intermediate for methanol synthesis and is formed from the reaction of CO2 and H2, whereas it is important to avoid the formation of that intermediate for selective methanol oxidation, which proceeds through dehydrogenation of the methoxy species.

  19. Multiply twinned AgNi alloy nanoparticles as highly active catalyst for multiple reduction and degradation reactions.

    PubMed

    Kumar, Mukesh; Deka, Sasanka

    2014-09-24

    Size dependent surface characteristics of nanoparticles lead to use of these nanomaterials in many technologically important fields, including the field of catalysis. Here Ag(1-x)Ni(x) bimetallic alloy nanoparticles have been developed having a 5-fold twinned morphology, which could be considered as an important alloy because of their excellent and unique catalytic and magnetic properties. Alloying between Ag and Ni atoms on a nanoscale has been confirmed with detailed X-ray diffraction, high resolution transmission electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, and magnetization measurements. Although introduced for the first time as a catalyst due to having high active surface sites, the as-synthesized nanoparticles showed one of the best multiple catalytic activity in the industrially important (electro)-catalytic reduction of 4-nitrophenol (4-NP) and 4-nitroaniline (4-NA) to corresponding amines with noticeable reduced reaction time and increased rate constant without the use of any large area support. Additionally the same catalyst showed enhanced catalytic activity in degradation of environment polluting dye molecules. The highest ever activity parameter we report here for Ag0.6Ni0.4 composition is 156 s(-1)g(-1) with an apparent rate constant of 31.1 × 10(-3) s(-1) in a 4-NP reduction reaction where the amount of catalyst used was 0.2 mg and the time taken for complete conversion of 4-NP to 4-aminophenol was 60 s. Similarly, an incredible reaction rate constant (115 s(-1)) and activity parameter (576.6 s(-1)g(-1)) were observed for the catalytic degradation of methyl orange dye where 15 s is the maximum time for complete degradation of the dye molecules. The high catalytic performance of present AgNi alloy NPs over the other catalysts has been attributed to size, structural (twinned defect) and electronic effects. This study may lead to use of these bimetallic nanostructures with excellent recyclable catalytic

  20. Two stage leaching of activated spent HDS catalyst and solvent extraction of aluminium using organo-phosphinic extractant, Cyanex 272.

    PubMed

    Park, Kyung Ho; Mohapatra, Debasish; Nam, Chul-Woo

    2007-09-01

    Spent catalyst generally contains valuable metals like Mo, Co, Ni on a supporting material, such as gamma-A1(2)O(3). In the present study, a two stage alkali/acid leaching process is proposed to selectively target molybdenum and cobalt/nickel separately to facilitate the downstream processing. Prior to the leaching, the spent catalyst was calcined at 500 degrees C to remove C and S; and to convert metal sulphides to metal oxides. 98% Mo, 93% Co and 90% Ni was effectively recovered by this process. The sulphuric acid leaching of spent catalyst, previously treated by alkali solutions to remove Mo, yielded a solution rich in Ni, Co and Al. In order to recover Co and Ni, the Al impurity must be eliminated. The extraction and stripping of Al has been carried out using the organo-phosphinic extractant, Cyanex 272 diluted in carbon tetrachloride. Quantitative Al extraction efficiency was achieved with 1.0M Cyanex 272 in two stages at an aqueous:organic (A:O) phase ratio of 1:1 and equilibrium pH of 3.2. Complete stripping of Al from the loaded organic was carried out using 2M H(2)SO(4) at an A:O phase ratio of 1:1. The extraction reaction proceeded via the cation exchange mechanism and the extracted species was assumed to be AlA(3).3HA. The extraction of Al was carried out in the presence of various ions to ascertain the tolerance limit of individual ions. The regenerated solvent was successfully used for 8 cycles without any significant loss of extraction efficiency, suggesting that Cyanex 272 is extremely stable under present experimental conditions. PMID:17363155